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ICBZM 2019
4th International Conference on
Bioinspired and Zwitterionic Materials
Program Book
June 16-19, 2019
Rolduc Abbey, Kerkrade, the Netherlands
www.icbzm-conferences.org
ICBZM 2019
4th International Conference on
Bioinspired and Zwitterionic Materials
Program Book
June 16-19, 2019
Rolduc Abbey, Kerkrade, the Netherlands
2
Table of Contents
Sponsor Acknowledgement ..................................................................................... 3
ICBZM 2019 ............................................................................................................ 4
ICBZM 2019 Organizing Committee ....................................................................... 5
General Information ................................................................................................. 6
Presentation Information ......................................................................................... 7
Poster Prizes ........................................................................................................... 7
Social Program ....................................................................................................... 8
Scientific Program .................................................................................................. 9
List of Posters ........................................................................................................ 14
Abstracts of Oral Presentations ............................................................................. 16
Abstracts of Posters .............................................................................................. 65
Author Index .......................................................................................................... 99
3
Sponsor Acknowledgement
4
ICBZM 2019
Scope Understanding the sophisticated functionalities offered by objects and processes found in nature will guide the design of materials with desirable properties to meet challenging applications. Zwitterionic materials, inspired by cell membranes and proteins, are excellent examples of bioinspired materials and have emerged as a new class of biomaterials. As the fourth meeting in the successful row of the ICBZM conferences, ICBZM2019 aims to capture the excitement of this emerging field. This conference will focus on zwitterionic materials as polymers, hybrids and molecular assemblies. Tone of the objectives is to provide an update regarding the latest developments in zwitterionic materials and identify challenges and opportunities in biomaterials. Attention will be given to the fundamentals, as well as innovative technologies and applications. The conference will provide an excellent opportunity for researchers from different fields in biomaterials, polymers, chemistry and bioengineering to discuss recent advances, share innovative ideas, and promote international collaborations.
Earlier ICBZM Meetings
ICBZM 2017 - http://www.mpc.t.u-tokyo.ac.jp/icbzm2017/index.html
ICBZM 2015 - http://depts.washington.edu/jgroup/ICBZM/index.html ICBZM 2013 - http://depts.washington.edu/jgroup/ICBZM/ICBZM2013.html
5
ICBZM 2019 Organizing Committee
Chair
G. Julius Vancso University of Twente the Netherlands
Co-Chair
Shaoyi Jiang University of Washington USA
Co-Chair Short Course
Sissi de Beer University of Twente the Netherlands
Committee Members
Jian Ji, Zhejiang University, China
Han Zuilhof, Wageningen University, the Netherlands
Kazuhiko Ishihara, University of Tokio, Japan
Yasuhiko Iwasaki, Kansai University, Japan
Clemens Padberg - Treasurer
Marion Steenbergen - Meeting secretary
Klara Vancso - Webmaster
6
General Information
Conference Venue The venue of ICBZM 2019 is Rolduc Abbey Hotel, Kerkrade, the Netherlands. Heyendallaan 82 6464 EP Kerkrade
Telephone: +31 (0)45 54 66 888 Email: [email protected]
Registration
Participants can register during the following periods: Short course registration: Saturday: 5:00 PM - 7:00 PM Sunday: 8:00 AM - 9:00 AM
Conference registration: Saturday: 5:00 PM - 7:00 PM Sunday: 5:00 PM - 7:00 PM Monday: 8:00 AM - 9:00 AM
Registration fee is all-in (includes):
lodging (3 nights, June 16, Sunday afternoon - June 19, Wednesday morning),
meals, coffee breaks and, meeting registration, Book of Abstracts.
Opening Times of the Conference Secretariat Sunday-Monday-Tuesday:
8:00 AM – 10:00 AM 12:00 PM – 1:30 PM 5:30 PM – 7:00 PM
Wednesday: 8:00 AM – 10:00 AM
7
Oral Presentations
Location of lectures
Plenary and Keynote Invited lectures: Aula Minor Contributed lectures: Room 1 and Room 2 (Zaal 1 and Zaal 2)
Length
Plenary lectures are 45 minutes long (including Q&A). Keynote Invited lectures are 30 minutes long (including Q&A). Invited lectures are 20 minutes long (including Q&A). Contributed lectures are 15 minutes long (including Q&A).
Poster Presentations
Poster sessions are scheduled on
Monday, 18:30 – 22:00, June 17, 2019 and Tuesday, 11:50 – 13:00, June 18, 2019.
Posters will be ordered by poster number. Please, mount your poster before the first poster session starts. Please, remove your poster at the end of the conference.
Poster Prizes Langmuir Poster Prize € 300 Poster Prize will be given for the best poster in the area of fundamental surface science.
Elsevier Poster Prizes Three Elsevier Poster Prizes will be given to the three best posters valued € 300,
€ 200 and € 100.
8
Social Program
Welcome reception
Sunday 6:00 PM, dinner included. Location: Big Dining Room (Grote Eetzaal)
Organ concert
Date and time: Tuesday, June 18, 2019, 15:30 - 16:30 Location: Abbey Church (Abdijkerk, Rolduc) Organist: Tjeu Zeijen
Banquet
Date and time: Tuesday, June 18, 2019, 19:00 The conference banquet will be accompanied by piano music, played by Vincent Snackers. We are sure you will enjoy the fabulous meal and music performance.
Excursion to Maastricht
On Wednesday, June 19th, after lunch there is the opportunity to visit Maastricht, capital of the province Limburg, beautifully situated along the river Maas. Not included in the registration fee, places are limited.
9
Scientific Program
June 17, Monday
Time Event Name Title
8:00 - Registration desk opens
8:45 - 9:00
Opening – Vancso, Julius; Jiang, Shaoyi - Location: Aula Minor
9:00 - 9:45
Plenary lecture Chair: Jiang, Shaoyi
Ishihara, Kazuhiko Biocompatibility of phosphorylcholine group bearing polymers
Chair: Vancso, Julius – Location: Aula Minor
9:45 - 10:15
Keynote invited lecture
Jiang, Shaoyi Recent Advances in Zwitterionic Materials
10:15 - 10:45
Keynote invited lecture
Moroni, Lorenzo Engineering Biomaterials to Steer the Foreign Body Response towards Tissue Regeneration
10:45 - 11:00
Break
Chair: Ishihara, Kazuhiko - Location: Aula Minor
11:00 - 11:30
Keynote invited lecture
Yuan, Jiayin Soft actuators derived from poly(ionic liquid)s
11:30 - 11:50
Invited lecture Steele, Terry Zwitterionic, Voltage Initiated Tissue Adhesives
11:50 - 12:10
Invited lecture Smulders, Maarten Romantic surfaces with a bead – functional antifouling polymer brushes on polymer beads
12:10 - 13:00
Lunch – Location: Big Dining Room (Grote Eetzaal)
Chair: Steele, Terry - Location: Aula Minor
13:00 - 13:30
Keynote invited lecture
Liu, Danqing Coating as two-dimensional soft robotics
13:30 - 13:50
Invited lecture Yusa, Shin-ichi Thermo-responsive Behaviours of Amphoteric Copolymers
13:50 - 14:10
Invited lecture Benetti, Edmondo Chemical and Topological Evolution of Polymer Biointerfaces
14:10 - 14:30
Invited lecture Sui, Xiaofeng Enzyme-Mediated Graft Polymerization of Zwitterionic Polymers from Cellulose Nanofiber - derived Porous Materials
14:30 - 14:50
Invited lecture White, Andrew Computational design of peptide-based materials with maximum entropy molecular simulation and data-driven modeling
14:50 - 15:10
Break
10
Contributed lectures, Chair: Smulders, Maarten -
Location: Room 1 (Zaal 1) Contributed lectures, Chair: Benetti, Edmondo - Location:
Room 2 (Zaal 2)
Time Name Title Name Title
15:10 - 15:25
Appelhans, Dietmar
Functional principles of polymeric vesicles for mimicking cell functions
Li , Xu
Lactobionic acid modified mixed-charge self-assembled monolayer modified gold nanoparticles as smart carries for active targeting
15:25 - 15:40
Biehl, Philip Polyampholytic hybrid nanoparticles as platform for reversible adsorption processes
Lienkamp, Karen
Antimicrobially Active Polyzwitterions - A Paradigm Change?
15:40 - 15:55
Ederth, Thomas
Pseudozwitterionic polymers and their potential for antifouling applications
Lísalová, Hana
Functionalizable Ultra-Low Fouling Nonionic and Zwitterionic Surfaces: Effects of Surface Physico-Chemical Properties on Living Cells
15:55 - 16:10
Huang, Chun-Jen
Responsive Interpenetrating Network Hydrogels with Reversibly Switchable Killing/ Releasing Bacteria
Liu, Mingjie
Bio-inspired mechano-functional gels through multi-phase order-structure engineering
16:10 - 16:25
Leonida, Mihaela
Molecular “Wiring”: Ionic Liquids versus High Pressure
Münch, Alexander
Multi-functional polymer coatings based on zwitterionic phosphorylcholines
16:25 - 16:40
Koc, Julian Thin Hydrogel Coatings for marine applications made of Photocrosslinked Polyzwitterions
Panzer, Matthew
Zwitterionic Copolymer Scaffolds for Nonaqueous, Ionic Liquid-Based Gel Electrolytes
17:30 - 18:30
Dinner – Location: Big Dining Room (Grote Eetzaal)
18:30 - 22:00
Poster session I. + wine
11
June 18, Tuesday
Time Event Name Title
Chair: Zuilhof, Han - Location: Aula Minor
8:30 - 9:15
Plenary lecture Ratner, Buddy RF-Plasma Deposition to Create Non-Fouling, Zwitterionic and Other Surfaces
9:15 - 9:45
Keynote invited lecture
de Vos, Wiebe Polyzwitterions in Membrane Separations: Beyond Anti-fouling
9:45 - 10:15
Keynote invited lecture
Laschewsky, Andre
Designing Zwitterionic Polymer for Thin Film Hydrogels and Low-Fouling Surfaces
10:15 - 10:30
Break
10:30 - 11:00
Keynote invited lecture
Bintinger, Johannes
Towards a biomimetic smell sensor
11:00 - 11:30
Keynote invited lecture
Wu, Peiyi ZwitterIonic skin
11:30 - 11:50
Invited lecture Iwasaki, Yasuhiko
Zwitterionic thiol-protected nanoparticles and nanoclusters
11:50 - 13:00
Lunch and Poster Session II. – Location: Big Dining Room (Grote Eetzaal)
Chair: de Beer, Sissi - Location: Aula Minor
13:00 -13:45
Plenary lecture Gleason, Karen Chemical Vapor Deposition (CVD) of Zwitterionic Surfaces
13:45 - 14:05
Invited lecture Wang, Yapei Spider-Inspired Multicomponent 3D Printing for Tissue Engineering
14:05 - 14:35
Invited lecture Bernards, Matthew
Evaluating the Role of Electrostatic Interactions on Macroscale Properties of Polyampholyte Hydrogels
14:35-14:55
Invited lecture Cao, Zhiqiang Zwitterionic Materials for Nanomedicine
14:55 - 15:15
Invited lecture Chang, Yung Impacts of Zwitterionic Membranes in Medical Applications
15:15 - 16:45
Break - Organ Concert – Location: Abbey Church (Abdijkerk)
Chair: de Vos, Wiebe - Location: Aula Minor
16:45 - 17:05
Invited lecture Zheng, Jie Multifunctional Zwitterionic Materials for Engineering
17:05-17:25
Invited lecture Chen, Shengfu Ultra-high Bio-affinity Recovery of RGDS peptide through protein mimicking based on the zwitterionic PAMAM-5
17:25 - 17:45
Invited lecture Wang, Zhanhua Water-Repairable Zwitterionic Polymer Coatings for Anti-Biofouling Surfaces
12
19:00 - 21:30
Banquet, dinner, Poster price award – Location: Big Dining Room (Grote Eetzaal)
21:30 - Bar “Verloren Zoon” – Location: Cellar (Kelder)
13
June 19, Wednesday
Time Event Name Title
Chair: Jiang, Shaoyi - Location: Aula Minor
9:00 - 9:45
Plenary lecture Lei, Jiang Smart Interfacial Materials from Super-Wettability to Binary Cooperative Complementary Systems
9:45 - 10:15
Keynote invited lecture
Ji, Jian Polyelectrolyte Complex Coatings: From Bioinspired Method to Real Coating Technology
10:15 - 10:45
Keynote invited lecture
de Beer, Sissi Tribo-Mechanics of Vapor-Hydrated Polymer Brushes
10:45 - 11:00
Break
Contributed lectures, Chair: Sui, Xiaofeng; Location -
Room 1 (Zaal 1) Contributed lectures, Chair: Feng, Xueling; Location -
Room 2 (Zaal 2)
Time Name Title Name Title
11:00 - 11:15
Roeven, Esther
Design, Synthesis and Characterization of Fully Zwitterionic, Functionalized Dendrimers
Yu, Qiuming
PEDOT-based Zwitterionic Conducting Polymer for Organic Electrochemical Transistor Biosensors
11:15 - 11:30
Shen, Yizhou
Rationally design nanostructure features on superhydrophobic surfaces for enhancing self-propelling dynamics of condensed droplets
Zhou, Jian
Computer Simulations on the Structure-Property Relationship of the Zwitterionic Drug Delivery System
11:30 - 11:45
Takemoto, Hiroyasu
Polyzwitterion comprising 1,2-diaminoethane that recognizes tumorous pH for effective delivery of the coated nanoparticles
Baggerman, Jacob
Bioactive Zwitterionic Surfaces for Biosensing
11:45 - 12:00
Farewell - Vancso, Julius; Location - Room 1 (Zaal 1)
13:00 - 14:00
Lunch – Location: Big Dining Room (Grote Eetzaal)
14:00 - Optional excursion to Maastricht. Sign up.
14
Poster Presentations
P1 AI ITO Influence of ion structures of zwitterions on the cellulose dissolution ability and toxicity to microorganisms
P2 Al-Muallem, Hasan Synthesis of a pH-Responsive Polyampholytic Maleic Acid-alt- Methyldiallylamine Copolymer and its Application as Antiscalant
P3 Amoako, Kagya Antifouling Activity of Graft-to Poly(carboxybetaine) Pre and Post Flow
P4 Beyer, Cindy Parallelized microfluidic accumulation assay to test zwitterionic fouling release coatings for marine applications
P5 Cabanach, Pol Zwitterionic self-assembled nanoparticles for drug delivery
P6 Cheng, Bohan One-step surface zwitterionization by bio-inspired polyphenolic coating
P7 Feliciano, Antonio Designing Corneal Implants with Zwitterionic and Supramolecular Materials
P8 Haag, Stephanie Biocompatibility of Polyampholyte Polymers for Tissue Engineering Applications
P9 He, Huacheng Zwitterionic Supplement in Poly(ethylene glycol) Hydrogel Dressings Accelerating Wound Healing by Anti-inflammation and Enhanced Cell Proliferation, Angiogenesis and Collagen Deposition
P10 Hong, Daewha Achieving Antifouling under Air Condition via Controlled Radical Polymerization of Carboxybetaine
P11 Jin, Qiao Zwitterionic supramolecular prodrug micelles for photodynamic cancer therapy
P12 Koschitzki, Florian Photoinduced Amphiphilic Zwitterionic Carboxybetaine Polymer Coatings with Marine Antifouling Properties
P13 Kuzmyn, Andriy Diblock antifouling-bioactive polymer brushes for the next generation of biosensors
P14 Laschewsky, Andre “Schizophrenic” Micellar Self-organization of Twofold Switchable Zwitterionic Block Copolymers
P15 Martinez Guajardo, Alejandro
Long-Term Stability of Zwitterionic Polymers against Hydrolysis
P16 McMullen, Patrick Alternating Charge Peptides Confers Stability to Proteins
P17 Nagy, Bela Swelling of pseudo-zwitterionic co-polymer hydrogels
P18 Palitza, Patricia Synthesis and characterisation of zwitterionic siloxanes as marine antifouling coatings
P19 Paschke, Stefan A Simultaneously Protein-repellent and Antimicrobially Active Zwitterionic Polymer Network
P20 Saha, Pabitra Stimuli-responsive polyzwitterionic microgels by RAFT precipitation polymerization
P21 Shao, Qing Molecular Simulations of Zwitterionic Electrolytes for Lithium Ion Batteries
P22 Shiomoto, Shohei Thermal Analysis of Bound Water Restrained by Poly(2-methacryloyloxyethyl inverse-phosphorylcholine)
15
P23 Surman, František Efficient Initiator for Grafting Polymer Brushes Based on Carboxybetaine (Meth)acrylamide
P24 Tsao, Caroline Zwitterionic-based Platforms for Biopharmaceutics
P25 Védie, Elora Fabrication and characterization of biomimetic texture for antifouling applications
P26 Virga, Ettore Multifarious Zwitterions applications: from low fouling membrane coatings to excellent surfactants for enhanced oil recovery
P27 Víšová, Ivana Spectroscopic Ellipsometry of Zwitterionic and Nonionic Polymer Coatings in Liquid Environment
P28 Wang Ruochun Zwitterionic Poly(sulfobetaine methacrylate) Grafted Cellulose Acetoacetate via Enzyme-Mediated Polymerization
P29 Wu, Jiang Soft Tissue Mimicking Zwitterionic Hydrogels through Reversible Strain-Induced Anisotropic Polar Filament Bundles to Achieve Hyperelasticity for Healthy Implantation
P30 Yang, Rong Vapor-Deposited Zwitterionic Coatings for Seawater Desalination
P31 Yu, Wenfa Polyelectrolyte Multilayers reinforced by Zwitterionic Silanes as Marine Protective Coatings
P32 Teunissen, Lucas Tailoring Zwitterionic, Antifouling Polymer Brushes
P33 Ren, Ke-Feng Dynamic Microporous Coating for On-demand Encapsulation of Functional Agents
P34 Roeven, Esther Synthesis and characterization of functionalized zwitterionic dendrimers
ICBZM 2019 - Plenary lecture
16
Biocompatibility of phosphorylcholine group bearing polymers
Kazuhiko Ishihara2
Affiliation: Department of Materials Engineering, The University of Tokyo
Tokyo 113-8656, Japan, E-mail: [email protected]
For the acquisition of blood-compatible materials, various hydrophilic polymers for surface
modification have been examined. Among them, polymers with a representative
phospholipid polar group, the phosphorylcholine (PC) group, are a successful example.
These polymers with 2-methacryloyloxyethyl phosphorylcholine (MPC) were designed
from inspiration of the cell membrane surface and industrial production of the MPC
polymers has in progress since later 1990’s.
The MPC polymers provide protein adsorption resistance even following contact with
plasma and whole blood. This important property is based on the unique hydration state of
water molecules surrounding hydrated polymer; in other words, water molecules weakly
interact with the polymers and maintain their favorable cluster structure through hydrogen
bonding. These polymers are not only hydrophilic, but also electrically neutral, important
characteristics which make hydrogen bonding with water molecules less likely to occur
and avoid hydrophobic interactions. The PC groups and other zwitterionic structures are
significant as hydrophilic functional groups meeting these important requirements.
In this communication, blood compatibility of a polymer having a PC group is introduced
in relation to its hydration structure, followed by a description of the applications of this
polymer to medical devices.
Figure 1: Molecular design of MPC polymers and industrialization.
References
[1] K. Ishihara, J Biomed Mater Res A. published on WEB (2019) doi:10.1002/jbm.a.36635.
[2] S. Asif, K. Asawa, Y. Inoue, K. Ishihara, B. Lindell, R. Holmrgren, R. Nilsson, A. Rydén, M. K. Ishihara,
Jensen-Waern, Y. Teramura, KN Ekdahl, Macromol Biosci., published on WEB (2019) doi:
10.1002/mabi.201800485.
[3] K. Ishihara, Langmuir, 35(5), 1778-1787 (2019) doi:10.1021/acs.langmuir.8b01565.
ICBZM 2019 - Keynote invited lecture
17
Recent Advances in Zwitterionic Materials
Shaoyi Jiang
Boeing-Roundhill Professor
Department of Chemical Engineering
University of Washington, Seattle
Abstract
In this talk, I will update recent developments in zwitterionic materials, surfaces.
hydrogels and nanoparticles for biomedical and engineering applications. New classes of
zwitterionic materials will be presented. The development of universal zwitterionic surface
coatings for blood-contact devices, injectable zwitterionic hydrogels for cell storage and
expansion and long-lasting zwitterionic coatings for ship hulls will be discussed. Finally, the
immunogenicity of PEGylated proteins and the replacement of poly(ethylene glycol) (PEG)
polymers with zwitterionic counterparts will be highlighted. At present, zwitterionic materials
have been applied to a wide range of applications, including medical devices, drug delivery
carriers, cell media, antimicrobial coatings, and marine coatings.
ICBZM 2019 - Keynote invited lecture
18
Engineering Biomaterials to Steer the Foreign Body Response towards
Tissue Regeneration
L Moroni1
MERLN Institute for Technology-Inspired Regenerative Medicine, Complex Tissue Regeneration,
Maastricht University, Universiteitsingel 40, 6229ER, Maastricht, the Netherlands; e-mai:
In situ tissue regeneration has been shown a promising tissue engineering and regenerative
medicine strategy for several applications, spanning from hard to soft tissues. Typically, in
this approach a biomaterial with designed surface properties is implanted in a host, which
acts as an in vivo bioreactor for tissue maturation. After maturation, the engineered graft can
remain in the implanted location if coincident with the final one or can be transplanted into
the final site of interest.
Here, we present an in situ tissue regeneration approach for the biofabrication of vascular
grafts. The graft was engineered through the design of the surface properties of a polymeric
rod that was used as a template for tissue regeneration. Different surface properties of the
polymeric rods were screened in vitro and in vivo for enhanced vascular extracellular matrix
(ECM) formation and macrophage polarization towards a tissue healing phenotype. Rods
with optimal ECM formation and macrophage polarization showed to support also vascular
tissue maturation in small and large animal models.
ICBZM 2019 - Keynote invited lecture
19
Soft actuators derived from poly(ionic liquid)s
Jianke Sun,1 Weiyi Zhang,1 Atefeh Khorsand Kheirabad,1 Qiang Zhao,2 Jiayin Yuan1
1Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University,
Svante Arrheniusväg 16C, Stockholm 10691, Sweden 2School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan
430074 China
*E-mail: [email protected]
Poly(ionic liquid)s (PILs) are the polymerization products of ionic liquids (ILs). They
combine certain properties and functions of polymeric materials (e.g. shape durability and
good processability) and that of ILs (e.g. ion conductivity and thermal stability). We have
exploited these favorable properties in the fabrication of porous membrane actuators from
imidazolium based PILs through electrostatic complexation.[1] The porous structure forms
as a result of microphase separation of the hydrophobic PIL chains from the surrounding
aqueous environment, which is simultaneously stabilized by ionically crosslinked networks
produced between the cationic PIL and the negatively charged neutralized polyacids. The
as-obtained porous ionic membrane features a gradient profile in the cross-linking density
along the membrane cross-section, triggered by the diffusive penetration of a base species
(NH3 or KOH) from the top to the bottom into the PIL-polyacid physical blend film. The
membrane pore sizes can be tuned from nano- to micrometer scale by varying the degree of
electrostatic complexation. Such membrane actuator features a high actuation speed that is
comparable to or faster than the Venus flytrap in response to external stimuli on account of
its gradient in cross-linking density and its intrinsic porous nature that enhances the internal
mass transport.[2,3] By tailoring the type and combination of different gradient elements
(tandem gradients), more complex actuation can be realized to respond to an entire multi-
step event that mimics a true, complex environment in our physical world .[4]
Figure 1: A porous poly(ionic liquid) membrane with tandem gradients to respond individually to multiple
stimuli.
References
[1] Q. Zhao, M. Yin, A. P. Zhang, S. Prescher, M. Antonietti, and J. Yuan, J. Am. Chem. Soc. 135 (2013),
5549.
[2] Q. Zhao, J. W. C. Dunlop, X. Qiu, F. Huang, Z. Zhang, J. Heyda, J. Dzubiella, M. Antonietti, and J. Yuan,
Nat. Commun. 5 (2014), 4293.
[3] Q. Zhao, J. Heyda, J. Dzubiella, J. W. C. Dunlop, and J. Yuan, Adv. Mater. 27 (2015), 2913.
[4] J.-K. Sun, W. Zhang, R. Guterman, H. Lin, J. Yuan, Nat. Commun. 9 (2018), 1717.
porous membrane
solvent
(physical stimuli)
weak acid (a.q.)
(chemical stimuli)
concave membraneconvex membrane
NH3(a.q.)
tandem-gradient
ICBZM 2019 - Invited lecture
20
Zwitterionic, Voltage Initiated Tissue Adhesives
Authors are cited first and underlined, in Times 12, centred, as in the following:
T.W.J. Steele1, M. Singh1, N. Tan1, G. Wicaksono1, O. Pokholenko1
1School of Materials Science & Engineering Nanyang Technological University
N4.1-01-29, 50 Nanyang Avenue, Singapore 639798, [email protected]
Implantable tissue adhesives typically fall within two categories, being activated by either
two-part mixing or photo-initiated designs. These curing strategies limit applications to
superficial sites and prevent incorporation into minimally invasive surgeries. An unmet
clinical need exists for adhesives that allow for manipulation and subsequent adhesive
activation in wet or inaccessible locations. Herein, the latest developments towards an
instant curing adhesive through zwitterionic polymers and on-demand activation is
presented. The zwitterionic adhesives are synthesized by grafting donor/acceptor ionic
internal additives on dendrimers to form conductive one-pot adhesives that crosslink upon
energetic activation [1-5]. AC and DC voltages allow tunable material properties, which are
evaluated in real-time with electro-rheology. The novel zwitterionic dendrimers aim to
mimic anisotropic tissue moduli while retaining antimicrobial properties. Crosslinking
initiation and propagation are observed to be ampere dependent, enabling tuning of both
elasticity and adhesive strength. Adhesion bond strengths on a variety of natural and
synthetic substrates will be presented to showcase cosmetic and clinical applications.
[1] - Singh S, Nanda HS, O’Rorke R, Jakus A, Shah AE, Shah AH, Shah RN, Webster DW, Steele TWJ
Voltaglue Bioadhesives Energized with Interdigitated 3D-graphene Electrodes. Advanced Healthcare
Materials. https://doi.org/10.1002/adhm.201800538
[2] - Lu, G; Tan, CS; Shah AH, Webster RD, Steele TWJ. Voltage Activated Adhesion Through Donor-
Acceptor Dendrimers. ACS Macromolecules. http://dx.doi.org/10.1021/acs.macromol.8b01000
[3] - Gao, F.; Djordjevic, I.; Pokholenko, O.; Zhang, H.; Zhang, J.; Steele, T., On-Demand Bioadhesive
Dendrimers with Reduced Cytotoxicity. MDPI Molecules 2018, 23 (4), 796, doi:10.3390/molecules23040796
[4] - Nanda HS, Shah AH, Wicaksono G, Pokholenko O, Gao F, Djordjevic I, Steele TWJ, Nonthrombogenic
Hydrogel Coatings with Carbene-Cross-Linking Bioadhesives. ACS Biomacro. DOI:10.1021/
acs.biomac.8b00074
[5] - Gao F., Mogal V., O’Rorke R., Djordjevic I., Steele, T.W.J. Elastic Light Tunable Tissue Adhesive
Dendrimers Macromol Biosci. 2016 Jul;16(7):1072-82. doi: 10.1002/mabi.201600033
ICBZM 2019 - Invited lecture
21
Romantic surfaces with a bead – functional antifouling polymer brushes
on polymer beads
M. M. J. Smulders1, E. van Andel1,2, E. J. Tijhaar2, H. F. J. Savelkoul2, H. Zuilhof1
1Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6708 WE Wageningen, NL 2Cell Biology and Immunology Group, Wageningen University, De Elst 1, 6709 PG Wageningen, NL
Micron- and nano-sized particles are extensively used in various biomedical applications.
However, their performance is often drastically hampered by the non-specific adsorption of
biomolecules, a process called biofouling, which can cause false-positive and false-negative
outcomes in diagnostic tests. Although antifouling coatings have been extensively studied
on flat surfaces,[1] their use on micro- and nanoparticles remains largely unexplored, despite
the widespread experimental (specifically, clinical) uncertainties that arise because of
biofouling. In this contribution, the preparation of magnetic micron-sized beads coated with
zwitterionic sulfobetaine polymer brushes that display strong antifouling characteristics is
presented.[2] These coated beads can then be equipped with recognition elements of choice,
to enable the specific binding of target molecules (Figure 1).
Figure 1: Schematic representation of a romantic bead that combines selective binding to its target protein
with generic protein repellence.[2]
A proof of principle is presented with biotin-functionalized beads that are able to specifically
bind fluorescently labelled streptavidin from a complex mixture of serum proteins. Also, the
versatility of the method is shown by demonstrating that it is possible to functionalize the
beads with mannose moieties to specifically bind the carbohydrate-binding protein
concanavalin A. Flow cytometry was used to show that thus-modified beads only bind
specifically targeted proteins, with minimal/near-zero nonspecific protein adsorption.
These antifouling zwitterionic polymer-coated beads, therefore, provide a significant
advancement for the many bead-based diagnostic and other biosensing applications that
require stringent antifouling conditions. In addition, using flow cytometry as read-out
system, these beads offer a platform for the systematic comparison of zwitterionic and non-
zwitterionic antifouling polymer brushes.[3]
References
[1] – J. Baggerman, M. M. J. Smulders and H. Zuilhof, Langmuir 35, 1072 (2019).
[2] – E. van Andel, I. de Bus, E. J. Tijhaar, M. M. J. Smulders, H. F. J. Savelkoul and H. Zuilhof, ACS Appl.
Mater. Interfaces 9, 38211 (2017).
[3] – E. van Andel, S. C. Lange, S. P. Pujari, E. J. Tijhaar, M. M. J. Smulders, H. F. J. Savelkoul, H. Zuilhof,
Langmuir 35, 1181 (2019).
ICBZM 2019 - Keynote invited lecture
22
Coating as two-dimensional soft robotics
Danqing Liu
1 Group Functional Organic Materials & Devices (SFD), Department of Chemical Engineering &Chemistry,
Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven, The Netherlands
2Institute for Complex Molecular Systems (ICMS), P.O. Box 513, 5600 MB Eindhoven, The Netherlands
E-mail: [email protected]
In the past decade, liquid-crystal network (LCN) technology has been used for the
development of soft actuators based on the controlled reversible changes of the order
parameter of the oriented polymer network. Various deformations ranging from simply
bending or curling to complex origami type of morphing are demonstrated to lift weights,
mimic nature in shape and color, or transport materials. Herein, we propose the use of a
liquid crystal network for soft robotics where the various molecular accessories are
assembled in the two dimensions of a coating. For instance, the LCN surface deforms
dynamically into a variety of pre-designed topographic patterns by means of various triggers,
such as temperature, light and the input of electric field. These microscopic deformations
exhibit macroscopic impact on, for instance, tribology, haptics, laminar mixing of fluids in
microchannels and directed cell growth. Another robotic-relevant function we brought into
the LCN coating is its capability to secret liquids under UV irradiation or by an AC field.
This controlled release is associated with many potential applications, including lubrication,
controlled adhesion, drug delivery, agriculture, antifouling in marine and biomedical
devices, personal care and cosmetics. With this we bring together a tool box to form two-
dimensional soft robots designed to operate in area where man and machine come together.
ICBZM 2019 - Invited lecture
23
Thermo-responsive Behaviours of Amphoteric Copolymers
S. Yusa1 and K. K. Sharker1
Department of Applied Chemistry, Graduate School of Engineering, University of Hyogo, 2167 Shosha,
Himeji, Hyogo 671-2280, Japan, [email protected] (S.Y.), [email protected] (K.K.S.)
It is well-known that sulfobetaine polymers show an upper critical solution temperature
(UCST) in aqueous solutions [1]. We would like to introduce some amphoteric copolymers
show UCST and lower critical solution temperature (LCST) behaviours in aqueous solutions.
Amphoteric diblock copolymers (S82An) composed of anionic poly(2-acrylamido-2-
methylpropanesulfonic acid sodium salt) (PAMPS) and poly(3-(acrylamido)propyl
trimethylammonium chloride) (PAPTAC) blocks were prepared via controlled radical
polymerization (Figure 1). Three kinds of S82An were
prepared with fixed degree of polymerization (DP) for the
PAMPS block (= 82) and different DP of the PAPTAC
blocks (n = 37, 83, and 183). Solubility of S82An was
studied at varying NaCl concentrations. S82A83
precipitated in pure water due to electrostatic attractive
interactions between polymer chains [2]. In contrast,
S82A37 and S82A183 can dissolve in pure water. S82An
showed LCST type thermo-responsive behaviour at
certain NaCl concentrations. The LCST increased with
increasing the NaCl concentration. The mechanism of
LCST behaviour is affected hydrogen bonding
interactions between water and the pendant amide groups.
Strong polyampholytes comprising cationic vinylbenzyl trimethylammonium chloride
(VBTAC) bearing a pendant quaternary ammonium group and anionic sodium p-
styrenesulfonate (NaSS) bearing a pendant sulfonate group
were prepared via controlled radical polymerization (Figure
2). The resultant polymers are labelled P(VBTAC/NaSS)n,
where n (= 20 or 97) indicates DP. The percentage VBTAC
content in P(VBTAC/NaSS)n is always about 50 mol%.
Although P(VBTAC/NaSS)n cannot dissolve in pure water
at room temperature, the addition of NaCl or heating
solubilizes the polymers [3]. Furthermore,
P(VBTAC/NaSS)n exhibits UCST behaviour in aqueous
NaCl solutions. The UCST is shifted to higher temperatures
by increasing the polymer concentration and molecular
weight, and by decreasing the NaCl concentration. The
UCST behaviour was measured ranging the polymer
concentrations from 0.5 to 5.0 g/L.
References
[1] D.N.Schulz, D.G.Peiffer, P.K.Agarwal, J.Larabee, J.J.Kaladas, L.Soni, B.Handwerker, and R.T.Garner,
Polymer 27, 1734 (1986).
[2] Y.Kawata, S.Kozuka, and S.Yusa, Langmuir 35, 1458 (2019).
[3] K.K.Sharker, Y.Ohara, Y.Shigeta, S.Ozoe, and S.Yusa, Polymers 11, 265 (2019).
Figure 1. Chemical structures
of amphoteric block copolymers
(S82An).
Figure 2. Chemical structures of
amphotric random copolymers
(VBTAC/NaSS50)n.
ICBZM 2019 - Invited lecture
24
Chemical and Topological Evolution of Polymer Biointerfaces
Edmondo M. Benetti
Polymer Surfaces Group, Laboratory for Surface Science and Technology, ETH Zürich, Vladimir-Prelog-
Weg 5, 8093 Zürich, Switzerland.
The application of cyclic polymers in surface functionalization enables an extremely broad
modulation of interfacial physicochemical properties, surpassing the attractive
characteristics provided by commonly applied, linear polymer “brushes”. This is valid on
macroscopic, inorganic surfaces, where cyclic polymer brushes provide an enhanced steric
stabilization of the interface and a superlubricious behavior [1-3]. Alternatively, when cyclic
brushes form shells on inorganic nanoparticles (NPs), their highly compact and ultradense
character make them impenetrable and long-lasting shields, which extend the stability of NP
dispersions and hinder any interaction with serum proteins [4].
The translation of topology effects typically observed in solution on interfacial properties,
can be further exploited to design highly branched, surface-reactive comb-like polymers
(CLPs) including cyclic segments, which can assemble on inorganic and organic surfaces,
protect them from the surrounding biological environment and significantly reduce friction.
These unique characteristics can be exploited to formulate biocompatible surface modifiers
for human cartilage, which are capable of binding to the tissue, and generating a bioinert and
highly lubricious polymer layer that halt the progression of degenerative syndromes
affecting articular joints [5,6].
Polymer topology effects are amplified by adding an additional boundary such as a grafting
surface. Their precise tuning translates into materials with unprecedented properties and
extremely high applicability.
References
[1] Morgese G, & Benetti EM, Angew. Chem. Int. Ed. 55, 15583 (2016). [2] Divandari M, &
Benetti EM, Macromolecules 50, 7760 (2017). [3] Divandari M, & Benetti EM, ACS Macro Lett.,
7, 1455 (2018). [4] Morgese G, & Benetti EM, Angew Chem Int Ed. 56, 4507 (2017). [5] Morgese
G, & Benetti EM, ACS Nano 11, 2794 (2017). [6] Morgese G, & Benetti EM, Angew Chem Int Ed.
57, 1621 (2018).
ICBZM 2019 - Invited lecture
25
Enzyme-Mediated Graft Polymerization of Zwitterionic Polymers from
Cellulose Nanofiber - derived Porous Materials
X. Sui, R. Wang, H. Cheng
Key Lab of Science & Technology of Eco-textile, Ministry of Education, College of Chemistry, Chemical
Engineering and Biotechnology, Donghua University, Shanghai, 201620, People’s Republic of China.
The cellulose nanofiber (CNF)-derived porous materials have drawn numerous
attentions in the fields of environment, biomaterials, energy materials, etc., by cooperating
the advantages of superior strength, low density, high porosity and easy chemical
modification. Furthermore, in order to broaden their practical applications, CNF-derived
porous materials decorated with functional polymers are desirable.[1-5] In this work,
acetoacetate groups anchored CNF-derived porous materials with controllable structure and
properties were obtained by adjusting the proportion and drying method of cellulose
nanofibers, 3-aminopropyltriethoxysilane and acetoacetate cellulose (CAA). Zwitterionic
polymers were grafted onto the surface of porous materials through enzymatic
polymerization, contributing to a further surface modification and porosity tailoring as well
as an extension on their potential applications. Overall, we present a versatile method of
tailoring CNF-derived porous materials with functional polymers, which might play a vital
role in development of value-added cellulosic materials.
References
[1] - Y. Li, L. Zhu, B. Wang, Z. Mao*, H. Xu, Y. Zhong, L. Zhang, and X. Sui*. ACS Appl. Mater. Inter.
10, 27831 (2018).
[2] - H. Cheng, Y. Du, B. Wang, Z. Mao, H. Xu, L. Zhang, Y. Zhong, W. Jiang, L.Wang*, and X. Sui*.
Chem. Eng. J. 338, 1 (2018).
[3] - H. Cheng#, C. Li#, Y. Jiang, B. Wang, F. Wang, Z. Mao, H. Xu, L. Wang*, and X.Sui*. J. Mater.
Chem. B. 6, 634 (2018).
[4] - L. Rong, H. Liu, B. Wang, Z. Mao, H. Xu, L. Zhang, Y. Zhong, J. Yuan, and X. Sui*. ACS Sustain.
Chem. Eng. 6, 9028 (2018).
[5] - Y. Li, L. Xu, B. Xu, Z. Mao*, H. Xu, Y. Zhong, L. Zhang, B. Wang, and X. Sui*. ACS Appl. Mater.
Inter. 9, 17155 (2017).
ICBZM 2019 - Invited lecture
26
Computational design of peptide-based materials with maximum entropy
molecular simulation and data-driven modeling
A. D. White1
Affiliation: University of Rochester, USA, [email protected]
Peptides are small proteins built from monomer units called amino acids. Peptides can be
precisely synthesized using solid-phase peptide synthesis and their constituent amino acids
can provide functional groups ranging from hydrogen bond-donors to aromatics. Peptides
can be immobilized onto surfaces, nanoparticles, or formed into hydrogels. This flexibility
and precise control give a wide-range of potential applications including self-assembling
antifouling surface coatings, antimicrobial therapeutics, hydrogel vaccines, and nucleating
crystal structures. I will present computational methods my group has used to design peptides
for antifouling, antimicrobial, and self-assembly. Our approach is to use insight from nature
through data-driven informatics methods and maximum entropy molecular simulation.
Molecular simulation seeks to model the dynamics of peptides at the atomic level. Maximum
entropy methods minimally modify molecular simulations to match experimental data. This
enables better accuracy, which is critical for modeling self-assembly of peptides, which is a
complex multiscale process. Broadly our goal in methods development is to combine
physics-based simulation with modern machine learning methods to create interpretable and
accurate models. Most of our tools and methods are freely available and this work will
describe how they can be used for systems beyond peptides.
Figure 1: A comparison of our designed antifouling peptides along with other biologically relevant molecules
in nanomedicine.
References
[1] - Classifying Antimicrobial and Multifunctional Peptides with Bayesian Network Models. R Barrett, S
Jiang, AD White . (2018) Peptide Science. 110: e24079
ICBZM 2019 - Contributed lecture
27
Functional principles of polymeric vesicles for mimicking cell functions
Dietmar Appelhans1, Silvia Moreno,1 Xueyi Wang,1,2 Brigitte Voit1,2
1Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, 01069 Dresden, Germany. E-mail :
[email protected] 2Organic Chemistry of Polymers, Technische Universität Dresden, 01062 Dresden, Germany.
Engineering of multifunctional vesicular (multi)compartments for mimicking specific
cellular functions [1] is one promising approach for overcoming protein lack in organ tissues
and human diseases. These vesicular compartments have to fulfil various key characteristics
(e.g. tuneable by external stimuli, controlling membrane functions for exchanging
biomolecules, controlled release of biomolecules, retaining cargo inside of vesicular cavity),
while multicompartments should also possess orthogonal-responsive membrane properties
to control spatiotemporal and spatially separated biological pathways for establishing
protocells [2]. Overall, this would result in, for example, the establishment of next-
generation therapeutics and bio-nanotechnology.
Figure 1: Cell-like uptake of nanometer-sized proteins by swollen polymersome membrane
[3].
This talk will present the use of pH-/T-responsive and crosslinked polymersomes and hollow
capsules as versatile supramolecular tool for mimicking cell functions and for out-of-
equilibrium approach to fabricate self-regulated on/off enzymatic nanoreactors. In line with
this there is a requirement to understand following key characteristics of crosslinked
polymersomes and hollow capsules: (i) the pH-dependent molecular switch of membrane
properties, (ii) the membrane permeability against cargo (macro)molecules from outside to
inside (Figure 1) and vice versa, (iii) membrane integration of proteins, (iv) (un)docking
processes on polymersome surface, and (v) light-triggered proton transfer against
polymersomes membrane, using cyclic isomerization of merocyanine/spiropyran pair. From
this various functional principles (e.g. post encapsulation of swollen polymersome
membrane upon in-situ encapsulation by polymersome formation) [3-7 and unpublished] are
shown to being adaptable for mimicking cell functions and protocells [1,2].
References
[1] – P. Schwille, Science 33, 1252 (2011).
[2] – S. Mann, Acc. Chem. Res. 45, 2131 (2012).
[3] – H. Gumz et al., Adv. Sci., accepted (2018).
[4] – J. Gaitzsch et al., Angew. Chem. Int. Ed. 51, 4448 (2012).
[5] – D. Gräfe et al., Nanoscale 6, 10752 (2014).
[6] – X. Liu et al., Angew. Chem. Int. Ed. 56, 16233 (2017).
[7] – X. Liu et al., J. Am. Chem. Soc., https://doi.org/10.1021/jacs.8b07980 (2018).
ICBZM 2019 - Contributed lecture
28
Lactobionic acid modified mixed-charge self-assembled monolayer
modified gold nanoparticles as smart carries for active targeting
Xu Li1, Huan Li1, Jian Ji1*
1MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science
and Engineering, Zhejiang University, Hangzhou 310027, China, with *Email: [email protected]
Nanocarriers could accumulate drug in tumor site to improve the efficacy and decrease the
side effects. Passive targeting nanocarriers have the ability of escaping from the elimination
of the immune system but supress the cellular uptake, which limited the usage of the drug
which only take effects inside the cell. Active targeting nanocarriers could enhance the
cellular uptake while easy to be cleaned by the immune system due to the high biological
activity of the active targeting ligands. In order to get rid of the disadvantages of the passive
targeting and the active targeting nanocarriers, we modified the active targeting ligand
lactobionic acid (LA) on the pH-sensitive mixed-charge self-assembled monolayer (MC-
SAM) modified gold nanoparticles (MC-AuNPs) to make a kind of nanoparticle which could
keep “stealth” in normal tissue while show biological activity in the tumor site. In normal
tissue, the LA loaded on the nanoparticles could be protected by the hydration shell formed
by the MC-SAM, while in tumor site with mild acid environment, the hydration shell would
be destroyed, and the LA would expose to combine the receptor on the hepatocellular
carcinoma cell to improve the cellular uptake of the nanoparticles.
Figure 1: Schematic illustration of the pH-sensitive behaviors of the LA@MC-GNPs and active cell targeting
at pH 6.5.
References
[1]Liu XS, et al. Enhanced Retention and Cellular Uptake of Nanoparticles in Tumors by Controlling Their
Aggregation Behavior. Acs Nano, 2013, 7 (7):6244-6257.
[2]Liu H, et al. Lactobionic acid-modified dendrimer-entrapped gold nanoparticles for targeted computed
tomography imaging of human hepatocellular carcinoma. ACS Appl. Mater. Interfaces. 2014, 6(9):6944–
6953.
ICBZM 2019 - Contributed lecture
29
Polyampholytic hybrid nanoparticles as platform for reversible
adsorption processes
P. Biehl1,2, M. von der Lühe1,2, A. Weidner3, S. Dutz3, F. H. Schacher1,2
Affiliation: 1 Institute of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, 2 Jena
Center for Soft Matter, Friedrich Schiller University Jena, 3 Institute of Biomedical Engineering and
Informatics, Technische Universität Ilmenau
Polyelectrolytes are a highly interesting class of polymers considering their properties at
interfaces. We use polyampholytes as coating material for magnetic nanoparticles which
leads to hybrid systems which respond to a variety of external triggers. The magnetic core
of the system is of great interest for a broad field of applications, including selective transport
at the nanoscale, tissue targeting in biomedical applications, as well as adsorption processes
in solution for heterogeneous catalysis and wastewater treatment. Using polyampholytes as
surface coating here is beneficial as it increases dispersion stability, antifouling behavior,
and applies a rather high charge densities.[1] As we are using polyampholytes with weak
electrolytes this enables the response to an external pH leading to a hybrid system which can
react to both, magnetic fields and pH values.
Our system consists of 40 nm multicore magnetic nanoparticles (MCNPs) featuring a
polyampholytic coating, which depending on the pH exhibits polycationic, polyzwitterionic
or polyanionic net charge.[2] This enables the selective adsorption and release of different
charged molecules within a certain pH range at the interface of the nanoparticles.
We can show that a broad variety of charged molecules like (fluorescent-) dyes,
macromolecules, and antibiotics can bind to our system and also be released in a narrow pH
regime. In first attempts we adsorbed the cationic dye Methylenblue (MB) as a model system
under neutral pH conditions and showed that a rapid release under acidified conditions is
possible. This process was repeatable multiple times and thus allowed a recycling of the
system.[3] Furthermore charged macromolecules namely poly((N,N-dimethylamino)ethyl
methacrylate), poly(styrenesulfonic acid) and bovine serum albumin were shown to adsorb
reversible to our system.[4] Currently we are expanding on the one hand the range of host
molecules to anionic dyes, fluorescent dyes and drugs and on the other hand expand our
system to different polyampholytic shells to get an insight into the role of functional groups
which determine the pH dependent adsorption and release of molecules.
Our systems allow the specific loading of magnetic nanoparticles with different materials
by attractive electrostatic interactions and the subsequent release upon external changes in
pH and thus give insight in an interesting field at the interface of polyampholytic coatings.
In that way, these hybrid materials simultaneously allow diagnostic approaches
(fluorescent labelling), controlled release (mediated by pH) and ideally specific targeting
of areas of interest.
ICBZM 2019 - Contributed lecture
30
Figure 1: A) Schematic representation of the adsorption and release of hostmolecules. B) Nine consecutive
cycles of a MB solution before and after dispersion of PDha@MCNP (black squares) and solutions after
desorption of MB (red dots).
References
[1] Biehl, P.; von der Lühe, M.; Dutz, S.; Schacher, F. Synthesis, Characterization, and Applications of
Magnetic Nanoparticles Featuring Polyzwitterionic Coatings. Polymers 2018, 10 (1), 91.
[2] von der Lühe, M.; Günther, U.; Weidner, A.; Gräfe, C.; Clement, J. H.; Dutz, S.; Schacher, F. H.
SPION@polydehydroalanine hybrid particles. RSC Adv. 2015, 5 (40), 31920.
[3] Philip, B.; Moritz, v. d. L.; H., S. F. Reversible Adsorption of Methylene Blue as Cationic Model
Cargo onto Polyzwitterionic Magnetic Nanoparticles. Macromolecular Rapid Communications
2018, 39 (14), 1800017.
[4] von der Lühe, M.; Weidner, A.; Dutz, S.; Schacher, F. H. Reversible Electrostatic Adsorption of
Polyelectrolytes and Bovine Serum Albumin onto Polyzwitterion-Coated Magnetic Multicore
Nanoparticles: Implications for Sensing and Drug Delivery. ACS Applied Nano Materials 2018, 1
(1), 232.
ICBZM 2019 - Contributed lecture
31
Antimicrobially Active Polyzwitterions - A Paradigm Change?
K. Lienkamp,*,1,2 M. Kurowska,1,2 A. Al Ahmad3
Albert-Ludwigs-Universität Freiburg 1 Freiburg Center for Interactive Materials and Bioinspired Technologies (FIT)
2 Department of Microsystems Engineering (IMTEK) 3 Department of Operative Dentistry and Periodontology, Center for Dental Medicine
Polyzwitterions have been extensively explored as non-fouling coatings in the contexts of
biomaterials and the prevention of biofilm formation on technical products.[1] They are
highly cell-compatible and resist the adhesion of proteins, bacteria and other biological
entities.[2] It is believed so far that this is a passive property related to the strong water-
binding of polyzwitterions, which otherwise have no intrinsic bioactivity. Indeed, the
polyzwitterions that were explicitly tested so far showed no antimicrobial activity.[3]
Surprisingly, we recently found two polyzwitterions from which intrinsically antimicrobial
polymer coatings could be obtained.[4] Additionally, they were protein-repellent, cell-
compatible and reduced the growth of bacterial biofilms on surfaces.[4] The coatings were
made from poly(oxonorbornene)-based carboxybetaines, which were surface-attached and
cross-linked in one step by simultaneous UV-activated C,H insertion and thiol-ene reaction.
Importantly, this process was applicable to both laboratory surfaces like silicon, glass and
gold, and real life surfaces like polyurethane foam wound dressings. Thus, the materials are
promising candidates for biomedical applications.
Is this a change in paradigm in the way we have to think about the bioactivity of
polyzwitterions? And what makes some polyzwitterions antimicrobial and others inactive?
To explore these questions, the chemical structure and physical properties of the two
polyzwitterions and two reference surfaces (an antimicrobial but protein-adhesive cationic
polymer coating, and a protein-repellent but not antimicrobial sulfobetaine polyzwitterion
coating), were characterized using a number of surface characterization techniques, and
correlated to their bioactivity. From this data, we begin to understand the factors that govern
antimicrobial activity of polyzwitterions.
References
[1] a) A. Laschewsky, Polymers 6, 1544 (2014); b) J. B. Schlenoff, Langmuir 30, 9625 (2014), c) S. Lowe,
N. M. O'Brien-Simpson and L. A. Connal, Polymer Chem. 6, 198 (2015); d) S. Jiang, Z. Cao, Adv. Mater.
22, 920 (2010); e) Z. Zhang, J. A. Finlay, L. Wang, Y. Gao, J. A. Callow, M. E. Callow, S. Jiang,
Langmuir 25, 13516 (2009).
[2] G. Cheng, G. Li, H. Xue, S. Chen, J. D. Bryers and S. Jiang, Biomaterials 30, 5234 (2009).
[3] a) P. Sobolciak, M. Spirek, J. Katrlik, P. Gemeiner, I. Lacik, P. Kasak, Macromol Rapid Commun. 34,
635 (2013); b) Z. Cao, L. Mi, J. Mendiola, J.-R. Ella-Menye, L. Zhang, H. Xue, S. Jiang, Angew. Chem.,
Int. Ed. 51, 2602 (2012).
[4] a) M. Kurowska, A. Eickenscheidt, D. L. Guevara-Solarte, V. T. Widyaya, F. Marx, A. Al-Ahmad, K.
Lienkamp, Biomacromolecules 18, 1373 (2017); b) M. Kurowska, A. Eickenscheidt, A. Al-Ahmad and
K. Lienkamp, ACS Applied Bio Materials 1, 613 (2018).
ICBZM 2019 - Contributed lecture
32
Pseudozwitterionic polymers
and their potential for antifouling applications
T. Ederth1, W. Yandi1, A. Skallberg2, K.Uvdal2, B. Nagy1, B. Liedberg1,3
1 Division of Molecular Physics, IFM, Linköping University, SE-581 83 Linköping, Sweden
2 Division of Molecular Surface Physics and Nanoscience, IFM, Linköping University, SE-581 83 Linköping,
Sweden 3 Centre for Biomimetic Sensor Science, School of Materials Science and Engineering, Nanyang
Technological University, Singapore 637553,
Zwitterionic materials incorporating strong acidic and basic residues maintain resistance to
biofouling under various conditions by retaining charge neutrality over a wide pH range.
Pseudozwitterionic polymers (polyampholytes) give greater flexibility in polymer design,
and the use of weak acidic or basic groups allow for tuning the polymer properties in
response to environmental changes, but at the expense of more complex behaviour. To this
end, we have explored a range of pseudowzitterionic and polyampholytic polymer systems,
with the aim to understanding their structure, behaviour and antifouling properties under
various conditions.
Here, we show that pseudozwitterionic poly(2-aminoethyl methacrylate-co-sulfopropyl
methacrylate) (p(AEMA-co-SPMA)) hydrogel thin films, prepared by self-initiated
photografting and photopolymerization (SIPGP), are potential alternatives to films prepared
from zwitterionic poly(sulfobetaine methacrylate) (pSBMA) for biofouling applications.
The antibiofouling properties of these two materials, as well as those of single-component
pAEMA and pSPMA films, were compared via adsorption of fibrinogen, settlement of
zoospores, and the growth of sporelings, of the marine alga Ulva lactuca. Wettabilities and
surface energies were studied by contact angle goniometry, and the compositions of the films
determined by infrared and X-ray photoelectron spectroscopy. The fouling of the p(AEMA-
co-SPMA) copolymer was close to that of the zwitterionic pSBMA hydrogel. The hydration
and viscoelastic properties of p(AEMA-co-SPMA) films at ionic strengths ranging from 0.1
to 2 M were assessed by quartz crystal microbalance with dissipation, and indicate clear
variations with changes of ionic strength, confirming anti-polyelectrolyte properties. This
makes them potentially suitable for applications under high-salinity conditions, such as
marine or physiological environments.
ICBZM 2019 - Contributed lecture
33
Functionalizable Ultra-Low Fouling Nonionic and Zwitterionic Surfaces:
Effects of Surface Physico-Chemical Properties on Living Cells
H. Vaisocherová-Lísalová1, O. Lunov1, B. Smolková1, M. Uzhytchak1, I.
Víšová1, M. Vrabcová1, M. Houska1, F. Surman2, A. de los Santos2, A.
Dejneka1
1Institute of Physics CAS, Na Slovance 2, 182 21 Prague, Czech Republic, 2Institute of Macromolecular
Chemistry CAS, Heyrovského nám. 2, 162 00 Prague, Czech Republic, [email protected]
Ultra-low fouling and functionalizable surfaces represent emerging platforms to examine
various biomolecular and cellular interactions in native environments as well as possess a
high potential for novel biochip and bioanalytical technologies towards rapid and accurate
analysis of real-world biological samples [1]. In this work, we report a study of behaviour of
living cells at ultra-low fouling functionalizable surfaces in dependence on different contents
of surface charges and hydrophilicity. Surface-grafted polymer brushes of carboxybetaine
acrylamide (pCBAA) and random brushes of copolymers of N-(2-hydroxypropyl)
methacrylamide and carboxybetaine methacrylamide (pHPMAA-CBMAA) with easily
tunable molar contents of CBMAA and HPMAA were used [2]. The surface thickness,
fouling resistance, wettability, or chemical composition were characterized by means of wet
spectral ellipsometry, SPR, contact angle measurements, and FTIR spectroscopy. The Huh7
cells were selected as a model system due to its high sensitivity to external stresses [3]. The
tendency of cell adhesion and grow as well as cell shapes and cytoskeleton distribution were
analysed via high-resolution spinning disk confocal microscopy. The results revealed that
despite no cytotoxicity and low-fouling capabilities of all used coatings, apparent trends in
cell tendency to grow at surfaces in dependence of charge content and hydrophilicity was
revealed. It was found that presence of zwitterionic moieties at higher contents promotes cell
vitality compared to nonionic pHPMAA and pHPMAA-CBMAA with a CBMAA molar
content lower than 65%. Furthermore, a surface with optimized properties was
functionalized with cell adhesion-promoting peptides. This unique surface platform was
employed to investigate cellular interactions with YAP/TAZ proteins [4] as important
effectors of signalling pathways involved in organ regeneration.
Figure 1: Differences in Huh7 cellular shape obtained by high-resolution spinning disk confocal
microscopy indicate strong effect of nonionic and zwitterionic surface physico-chemical properties. Cells
were incubated with different substrates for 4 days. The cell organelles were labeled according to standard
procedures..
References
[1] – Q.Shao and S.Jiang. Adv Mater, 27, 15-26 (2015).
[2] – H.Vaisocherova-Lisalova et al, Anal Chem, 88, 10533-10539 (2016).
[3] – B.Smolkova et al, Cell Physiol Biochem. 52, 119-140 (2019).
[4] – I.M.Moya and G.Halder, Nat Rev Mol Cell Biol. 20, 211-226 (2019).
ICBZM 2019 - Contributed lecture
34
Responsive Interpenetrating Network Hydrogels with Reversibly
Switchable Killing/ Releasing Bacteria
Kang-Ting Huang1, Kazuhiko Ishihara3, Chun-Jen Huang1,2,*
1Department of Biomedical Sciences and Engineering, National Central University, Taoyuan, Taiwan.
2Department of Chemical & Materials Engineering, National Central University, Taoyuan, Taiwan. 3Department of Materials Engineering, School of Engineering, The University of Tokyo, Tokyo, Japan.
In this study, we propose a responsive interpenetrating network (IPN) hydrogel,
which was composed of a bactericidal poly((trimethylamino)ethyl methacrylate chloride)
(pTMAEMA) hydrogel as the first network and a polyzwitterionic poly(sulfobetaine
vinylimidazole) (pSBVI) hydrogel as the second network. Mechanical performances of the
hydrogels were significantly enhanced as double network hydrogels. Moreover, we
demonstrated that these two independent polymer networks of pTMAEMA and pSBVI not
only exhibited completely opposite salt-responsive swelling and shrinkage properties in their
single network hydrogels respectively but also within the IPN hydrogel, which was due to
the polyelectrolyte effect and anti-polyelectrolyte effect. Therefore, the surface properties of
IPN hydrogel can be reversibly switched between pTMAEMA and pSBVI networks by
manipulating the ionic-strength in aqueous solution. The results showed that the IPN
hydrogel exhibited high antibacterial effectiveness by contact-killing attached bacteria of
both E. coli and S. epidermidis in PBS solution after 24 h, and regeneration of surface by
releasing adherent live or dead bacteria from the surface upon a simple treatment of 1.0 M
NaCl solution for 10 min. The physicochemical properties of IPN hydrogel were
characterized using a Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron
spectroscopy (XPS) and a small-angle X-ray scattering (SAXS). The repetitive killing and
releasing actions of IPN hydrogel between PBS solution and 1.0 M NaCl solution were
demonstrated, indicating the highly efficient regeneration and long-term reusability of this
system. This work demonstrates a new design for a salt-responsive IPN hydrogel to
effectively achieve antimicrobial and surface regeneration properties, making this hydrogel
very promising for antimicrobial applications.
ICBZM 2019 - Contributed lecture
35
Bio-inspired mechano-functional gels through multi-phase
order-structure engineering
Mingjie Liu*
Beihang University, Xueyuan Road #37, Haidian District, Beijing, China
E-mail: [email protected]
Adaptive gel materials can greatly change shape and volume in response to diverse stimuli,
and thus have attracted considerable attention due to their promising applications in soft
robots, flexible electronics and sensors. In biological soft tissues, the dynamic coexistence
of opposing components (for example, hydrophilic and oleophilic molecules, organic and
inorganic species) is crucial to provide biological materials with complementary
functionalities (for example, elasticity, freezing tolerance and adaptivity). Taking
inspiration from nature, we developed a series of high mechanical performance soft active
materials, so-called organohydrogels, based on multiphase synergistic strategy. Traditional
techniques such as post-polymerization modification, interpenetrating network and
controlled micro-phase separation are combined with binary complementary concept to
design and fabricate new organohydrogels with diverse topology of heteronetworks.
Meanwhile, the synergistic effect of heteronetworks provided the organohydrogels with
unprecedented mechanical functions such as freeze-tolerance, programmed high-strain
shape memory and shaking insulation. Their applications in anti-biofouling, thin-film
fabrication, flexible electronics and actuators are also explored.
References
[1] H. N. Gao et al., Nat. Commu. 8 (2017).
[2] Z. G. Zhao et al., Adv. Mater. 29, 33 (2017)
[3] Q. F. Rong et al., Angew. Chem. Int. Ed. 56 (2017)
[4] Z. G. Zhao et al., Adv. Mater. 29, 45 (2017)
[5] M. J. Liu et al., Nat. Rev. Mater. 2, 7 (2017)
[6] M. J. Liu et al., Nature, 517 (2015)
ICBZM 2019 - Contributed lecture
36
Molecular “Wiring”: Ionic Liquids versus High Pressure
M.D. Leonida, T-H Kim, E. Kang
Fairleigh Dickinson University, Teaneck, NJ, USA, [email protected]
Copper-containing amine oxidases occur in many organisms both prokaryotic and
eukaryotic. The interest in them stems from their present and potential applications in
therapy (in heart ischemia, allergic reactions, ulcerative colitis) and in biosensors for clinical
lab and the food industry. Their use presents two hurdles: poor stability and slow rate of
electron transfer (due to redox centers deeply buried in insulating protein/glycoprotein shell).
Since electron transfer in proteins is an electron tunneling process, its rate decays
exponentially with the donor-acceptor distance. A strategy for enhancing the kinetics of
these reactions has been the use of bioconjugation, binding covalently redox-active
molecules (mediators) to sites on the enzyme. This approach is known in the chemical
literature as enzyme “wiring” [1] and it typically results in an important loss in enzyme
activity, besides the inconvenience of being labor-intensive and using organic solvents.
Our approach to “wiring” redox enzymes is environmentally-friendly and it is done at the
molecular level. The working hypothesis is that partially unfolding the protein under mild
conditions, in the presence of enzyme-friendly species, and subsequent removal of the
denaturant, will result in refolding with new moieties embedded in the 3-D structure of the
protein (modified enzyme, ME). These moieties would confer beneficial properties to the
enzyme, such as enhanced kinetics and stability. The model enzyme on which we tested our
method was amine oxidase (AO, EC 1.4.3.6.).
One procedure used to modify AO was by transient exposure to a room temperature ionic
liquid (RTIL, 1-ethyl-3-methylimidazolium tetrafluoroborate) in the presence of enzyme-
friendly modifiers (FAD – prosthetic group of some AOs, Cu2+ (II) ions, pyrroquinoline
quinone (PQQ, closely related to topaquinone prosthetic group of other AOs). Based on new
literature mentioning the cardioprotective effect of AOs, a strong antioxidant lipoic acid
(LA) was tested as a modifier as well. In another green procedure, AO was reversibly
unfolded/refolded using high hydraulic pressure (325 MPa), in the presence of the same
modifiers, and using various compression times. All ME were assayed and showed
enhancement compared to the native AO. The highest enhancement was afforded by
“wiring” at short compression times (30 min) compared to longer times or to exposure to
RTIL. Encapsulation efficiency values were high for all modifiers while entrapment of Cu2+
(II) ions, intrinsic cofactor of AO, resulted in the highest activity. The antioxidant effect of
the MEs was also evaluated. The activity of all ME was retained over several months. The
most enhanced enzyme from each procedure was tested, respectively, in a biosensor for
amine detection. Both sensors showed good catalytic effect. The linearity of the biosensor
response to amine concentration extended over a larger range of concentrations for the RTIL-
ME in the presence of two “wires” (FAD and Cu2+ (II) ions). A comparative discussion of
the two procedures is presented as is a comparison with other redox enzymes [2] enhanced
by using RTIL.
References
[1] – A.W. Bott, Curr. Sepns. 21,1 (2004).
[2] – M.D. Leonida and B. Aurian-Blajeni, The Protein J., 34, 1, 68-72 (2015).
ICBZM 2019 - Contributed lecture
37
Multi-functional polymer coatings based on zwitterionic
phosphorylcholines
Alexander S. Münch1, Petra Uhlmann1,2
1Leibniz-Institut für Polymerforschung Dresden e.V., Germany, 2University of Nebraska-Lincoln, Lincoln,
NE 68588, USA, corresponding authors: [email protected], [email protected]
Functional polymer films, like stimuli-responsive polymer brushes, comb-like polymers or
cross-linked polymer networks, are a group of smart surface coatings for the design of
intelligent interfaces. Such innovative surface coatings will have to adopt additional
intelligent functions preferentially simultaneously. These films are generated by a one step
“grafting-to” approach of specifically designed and synthesized co-polymers allowing the
modification of surfaces with preformed and most notably well-defined macromolecules.
The formed transparent thin films can adjust and modulate the properties of the interface as
a result of the current environmental conditions. As an example for such a system a novel
multi-functional coating with simultaneous easy-to-clean, non-fouling as well as anti-fog
properties based on co-polymers consisting of zwitterionic phosphorylcholine groups (MPC)
and benzophenone units (BPO) as anchor and UV cross-linking agent will be presented.[1-4]
A series of co-polymers with different contents of BPO were synthesized by atom transfer
radical polymerisation to investigate the influence of the degree of cross-linking. To
determine this ratio and to understand the influence of the polymer composition on the easy-
to-clean, anti-fouling and anti-fog properties a combined study of infrared and UV-Vis
spectroscopy, contact angle as well as in-situ ellipsometry measurements was performed.
The study demonstrates that an exactly balanced ratio between thickness of the dry films,
degree of swelling, and water contact angle, which can be controlled by the amount of the
cross-linker, is necessary to create multi-functional surface coatings with tailored properties.
Figure 1: Illustration of anti-fouling easy-to-clean as well as anti-fog performance of a zwitterionic
phosphorylcholine coating.
Financial support by the Federal Ministry for Economic Affairs and Energy (BMWi) of
Germany is gratefully acknowledged (AiF-IGF 18696 BR; AiF-IGF 18573 BG/1).
References
[1] – A.S.Münch, […] and P.Uhlmann, J. Mater. Chem. 6, 830 (2018).
[2] – A.S.Münch, […] and P.Uhlmann, J. Coat. Technol. Res. 15, 703 (2018).
[3] – A.S.Münch, […] and P.Uhlmann, J. Coat. Technol. Res. under review (2019).
[4] – A.S.Münch, […] and P.Uhlmann, ACS Appl. Mater. Interfaces in preparation (2019).
ICBZM 2019 - Contributed lecture
38
Thin Hydrogel Coatings for marine applications made of
Photocrosslinked Polyzwitterions
J. Koc1, E. Schoenemann2, J.A. Finlay3, N. Aldred3, A.S. Clare3, A. Laschewsky2,4, A.
Rosenhahn1
Affiliation: 1Analytical Chemistry – Biointerfaces, Ruhr University Bochum, 2Department of Chemistry,
University Potsdam, 3School of Natural and Environmental Sciences, Newcastle University, 4Fraunhofer
Insitute of Applied Polymer Research IAP, [email protected], [email protected]
The development of materials with the capability to resist the accumulation of biomass on
surfaces in contact with seawater is both, economically and ecologically desired.
Zwitterionic polymers show high resistance against differently charged proteins, bacteria
[1], and marine organisms [2]. While self-assembled monolayers enabled us to understand
the relevance of charge neutrality and to reveal the effect of different anionic and cationic
groups [3], the zwitterionic functionality has ultimately to be embedded into polymers for
technical applications. [4] Zwitterionic methacrylates were co-polymerized with
benzophenonemethacrylate to fabricate photocrosslinkable zwitterionic polymers. [5] To
correlate the molecular structure of the zwitterionic moieties with antifouling activity, the
polymers were applied by spin-coating and subsequently photocrosslinked. The obtained
coatings were characterized by AFM, IR, and XPS prior to biological testing. All surfaces
were characterized with respect to protein resistance by SPR, exposed to microfluidic diatom
tests and tested against colonization of zoospores of the green alga Ulva linza and barnacle
cyprids of B. improvisus. The results of the biological assays reveal that apparently minor
chemical changes in the polymer structure affect the antifouling performance markedly,
although the density of zwitterionic groups is virtually the same in all coatings. Furthermore,
varying the crosslinker ratio reveals the impact of swelling on antifouling performance.
References
[1] – G. Cheng, G. Li, H. Xue, S. Chen, J.D Bryers and S. Jiang, Biomaterials 30, 5234 (2009).
[2] – W. Yang, P. Lin, D. Cheng, L. Zhang, Y. Wu, Y. Liu, X. Pei and F Zhou, ACS Appl. Mater. Interfaces
9, 18295 (2017).
[3] – S. Bauer, J.A. Finlay, I. Thome, K. Nolte, S. C. Franco, E. Ralston, G. E. Swain, A. S. Clare, and A.
Rosenhahn, Langmuir 32, 5663 (2016).
[4] – S. Jiang and Z. Cao, Adv. Mater. 22, 920 (2010).
[5] – J. Koc, E. Schoenemann, A. Amuthalingam, J. Clarke, J.A. Finlay, A.S. Clare, A Laschewsky and A.
Rosenhahn, Langmuir 35, 1552-1562 (2019).
ICBZM 2019 - Contributed lecture
39
Zwitterionic Copolymer Scaffolds for Nonaqueous, Ionic Liquid-Based
Gel Electrolytes
A. J. D’Angelo,1 F. Lind,1 L. Rebollar,1 M. E. Taylor,1 and M. J. Panzer1
1Department of Chemical & Biological Engineering, Tufts University, [email protected]
Polymers featuring zwitterionic pendant groups have been widely reported to offer unique
advantages for developing several classes of novel materials, including improved anti-
fouling coatings and biocompatible, self-healing hydrogels. Recently, our group has been
exploring the use of zwitterionic (co)polymers within nonaqueous, ion-dense electrolytes
(ionic liquids) to develop polymer-supported ionogel composites, which offer excellent
tunability of the gel mechanical properties while also promoting high room temperature ionic
conductivity values.[1, 2] Ionogel electrolytes are an emerging class of nonvolatile,
nonflammable ion conductors that can enable safer electrochemical energy storage devices,
wearable sensors, as well as other applications. In this presentation, I will describe the
synthesis and characterization of a variety of novel zwitterionic copolymer-supported
ionogels that are readily formed via in situ photopolymerization within various ionic liquid
electrolytes, some of which are also facile lithium ion conductors.[3] Varying the chemical
nature of the zwitterionic monomer(s) (e.g. sulfobetaine vs. phosphorylcholine) facilitates
the creation of polymer-supported ionogels that exhibit room temperature ionic
conductivities as high as 12 mS/cm and compressive elastic modulus values that can be tuned
between ~1 kPa and >10 MPa. Experimental evidence of increased ion pair dissociation, as
well as the formation of dipole-dipole physical cross-links that enhance gel stiffness due to
the presence of zwitterionic groups, has been obtained. Fully-zwitterionic copolymer
scaffolds offer exquisite control over ionogel physical and electrochemical properties; in
some cases, self-healing behavior can also be observed. While the discovery of zwitterionic
functional group behaviors in nonaqueous electrolytes is still in its infancy, these findings
serve as early stepping stones towards building an understanding of the largely unexplored
realm of zwitterion/ionic liquid intermolecular interactions and the properties of zwitterionic
copolymer-based ionogel composites.
References
[1] – F. Lind, L. Rebollar, P. Bengani-Lutz, A. Asatekin, and M. J. Panzer, Chem. Mater. 28, 8480 (2016).
[2] – M. E. Taylor and M. J. Panzer, J. Phys. Chem. B 122, 8469 (2018).
[3] – A. J. D’Angelo and M. J. Panzer, Adv. Energy Mater. 8, 1801646 (2018).
ICBZM 2019 - Plenary lecture
40
RF-Plasma Deposition to Create Non-Fouling, Zwitterionic and Other Surfaces
Marvin Mecwan and Buddy Ratner
Department of Bioengineering
University of Washington
Seattle, Washington 98195 USA
Polymeric chains containing units with an equal balance of + and – charges (zwitterionic
polymers) have dominated the evolving field of non-fouling polymers. However, many other
classes of polymers also demonstrate non-fouling behavior. This talk will focus on generalities
important for non-fouling and strategies enhancing our abilities to apply non-fouling coatings to
real-world medical and biological devices. The plasma-deposition of poly(ethylene glycol)-like
surfaces and N-isopropyl acrylamide surfaces will be presented and their non-fouling ability
discussed. Recent work on using the plasma vapor phase to mix equal ratios of + and - charges
on surfaces will then be presented. The ease of processing and the durability of the films will be
discussed.
ICBZM 2019 - Keynote invited lecture
41
Polyzwitterions in Membrane Separations: Beyond Anti-fouling
Wiebe M. de Vos
Membrane Surface Science, University of Twente, MESA+ institute for Nanotechnology, Enschede, The
Netherlands, [email protected]
Polyzwitterions have rightly taken up a key position in membrane science and technology as
the anti-fouling agent of choice for the most difficult to treat feed streams [1]. But zwitterions
can do even more! In this lecture we discuss a very simple approach, based on layer-by-layer
deposition, to prepare polyzwitterion based coatings on membrane surfaces. As expected
these layers show good anti-fouling properties, but they also show other beneficial behaviour
such a responsive behaviour (figure 1, [2]) and enhanced separation properties [3].
The discussed work opens the door to new membrane coatings where a single polyzwitterion
coating is used to achieve multiple beneficial functionalities.
Figure 1: A membrane coating prepared from the polyzwitterion PSBMA and the cationic polymer
PDADMAC in a layer-by-layer fashion leads to a unique salt responsive membrane [2].
References
1. M. He, K. Gao, L. Zhou, Z. Jiao, M. Wu, J. Cao, X. You, Z. Cai, Y. Su, Z. Jiang, Acta Biomaterialia, 40,
142-152 (2016).
2. J. de Grooth, M. Dong, W.M. de Vos, K. Nijmeijer, Langmuir, 30, 5152 (2014).
3. J. de Grooth, D.M. Reurink, J. Ploegmakers, W.M. de Vos, Nijmeijer, K, ACS Applied Materials and
Interfaces, 6, 17009–17017, (2016).
ICBZM 2019 - Keynote invited lecture
42
Designing Zwitterionic Polymer for Thin Film Hydrogels and Low-
Fouling Surfaces
A. Laschewsky1,2 , A. Rosenhahn3
1 University of Potsdam, Inst. Chemistry, 14476 Potsdam-Golm, Germany; [email protected]
2 Fraunhofer Institute of Applied Polymer Research IAP, 14476 Potsdam-Golm, Germany 3 Ruhr-Universität Bochum, Institute of Analytical Chemistry, 44801 Bochum, Germany;
The widespread occurrence of zwitterionic compounds in nature has stimulated the use of
polyzwitterions [1] for designing biomimetic materials [2]. A particular interest for this
particular polymer class has currently focused on their use for the construction of
biocompatible as well as of low-fouling surfaces [3,4,5]. Surprisingly, the structural variety
of quenched polyzwitterions, as desirable for model studies and presumably also for most
applications , is rather limited up to now [6]. We present our recent efforts to diversify the
structure of zwitterionic monomers, and the polymers derived therefrom.
Figure 1: Blueprint of the polyzwitterions studied, highlighting the structural variables of the underlying
monomers:: (i) nature of polymerizable group (here shown: methacryl residue), (ii) hetero element at
junction to backbone ( E ), (iii) length of spacer between backbone and zwitterionic moiety ( x ), (iv)
fixation point and orientation of zwitterionic moiety relative to the polymerizable group/polymer
backbone (here shown: via the ammonium moiety), (v) length of spacer between cationic and anionic
groups ( y ), (vi) nature of substituents on ammonium group ( R1, R2 ), (vii) nature of the anionic
group (Q- = -SO3- , = -O-SO3
-).
We identify key structural variables (cf. Figure 1), synthesize polymers in which these are
systematically varied, and consider their influence on essential properties such as overall
hydrophilicity and long-term chemical stability [5,6]. Furthermore, the performance of thin
hydrogel coatings made by spin-coating in protein adsorption and marine organisms fouling
laboratory assays is investigated [7]. Emphasis is given to the classes of polymeric
sulfobetaines and sulfabetaines, employing free radical polymerization methods for their
synthesis, and the use of photo-crosslinking methods to stabilize thin polymer hydrogel films
on diverse supports.
References
[1] S. Kudaibergenov, W. Jaeger and A. Laschewsky, Adv. Polym. Sci., 2006, 201, 157-224.
[2] B. Hall, R. L. R. Bird and D. Chapman, Angew. Makromol. Chem., 1989, 166, 169-178.
[3] Z. Cao and S. Jiang, Nano Today, 2012, 7, 404-413.
[4] D. W. Grainger, Nature Biotechnol., 2013, 31, 507-509.
[5] A. Laschewsky and A. Rosenhahn, Langmuir, 2019, 35, 1056-1071.
[6] A. Laschewsky, Polymers, 2014, 6, 1544-1601.
[7] J. Koc, E. Schönemann, A. Amuthalingam, J. Clarke, J. A. Finlay, A. S. Clare, A. Laschewsky and
A. Rosenhahn, Langmuir, 2019, 35, 1552-1562.
ICBZM 2019 - Keynote invited lecture
43
Towards a biomimetic smell sensor
J. Bintinger1, J. Andersson1, P. Aspermair2,3, F. Fedi1, U. Ramach2, P. Pelosi1, W. Knoll1
Authors are cited first and underlined, in Times 12, centred, as in the following:
R.A. Grant , H. Bethier1, G. Gauthier2
Affiliation: 1Austrian Institute of Technology - AIT, Vienna, Austria; 2Center for Electrochemical Surface
Technology (CEST), Wiener Neustadt, Austria; 3Université de Lille, Lille, France
Three of our five senses, namely, seeing, hearing, and touching, have been commercialized
in small powerful sensors and are present in almost every electronic device (smartphone etc).
Odor and taste, due to their fundamentally different detection mechanism, represent an
extreme challenge for the technical implementation. In contrast to readily attainable
mechano- or photoreceptors, chemoreceptors which are capable of translating a chemical-
biological signal into an electronic one and are a prerequisite for odor and taste sensors. In
this presentation we will highlight our research efforts using three different biomimetic
approaches (Figure 1): A) an array of ultra-low cost chemiresistors based on conductive
polymers1 is used to mimic the combinatorial code of the olfactory process. The conductive
polymers respond to odorants with changes in their electronic performance and by tuning
their chemical side groups they can be more specifically tailored to different chemical
classes. B) In order to improve the specificity of the sensors we also use odor-binding
proteins – derived from insects - as a biological recognition unit for fragrances.2 The binding
of an odorant to an odor-binding protein alters its three-dimensional structure. This
conformational change is then converted into an electronic signal because the structural
variation also causes a change in the electronic properties of the underlying transistor
material. C) Finally, we present our newest efforts in using artificial membrane structures3
(tethered lipid membranes) to better mimic the cell membranes which, host the olfactory
receptors in the real world and which are essential to take advantage of the signal
amplification process in olfaction.
The aim of our research is to produce, characterize, compare and benchmark these systems
with other methods, tools and finally mother nature itself (electroantennography) to create a
better understanding of the olfactory process.
Figure 1: Schematic illustration of our biomimetic smell sensor efforts. Left: Schematic of a field-effect
transistor endowed with odorant binding proteins; Middle: Logo: illustration of the use of insect odorant
binding proteins for smell sensing; Right: difference between human- and electronic nose concepts
References
[1] Yang, S.; Bintinger, J.; Park, S.; Jain, S.; Alexandrou, K.; Fruhmann, P.; Besar, K.; Katz, H.;
Kymissis, I. IEEE Sens. Lett. 2017, PP (99), 1–1
[2] Larisika, M.; Kotlowski, C.; Steininger, C.; Mastrogiacomo, R.; Pelosi, P.; Schütz, S.; Peteu, S. F.;
Kleber, C.; Reiner-Rozman, C.; Nowak, C.; Knoll, W.; Angew. Chem. 2015, 127 (45), 13443–13446..
[3] Andersson, J.; Köper, I. Membranes 2016, 6 (2).
ICBZM 2019 - Keynote invited lecture
44
ZwitterIonic skin
Peiyi Wu
College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai, People’s
Republic of China, [email protected]
Intrinsically stretchable conductors have undergone rapid development in the past few years
and a variety of strategies have been established to improve their electro-mechanical
properties. However, ranging from electronically to ionically conductive materials, they are
usually vulnerable either to large deformation or in harsh environments, mainly due to the
fact that conductive domains are generally incompatible with neighboring elastic networks.
This is a problem that is usually overlooked and remains challenging to address. Herein, we
introduce synergistic effect between conductive nanochannels created by zwitterionic
polymers and dynamic networks to break the limitations. The as-prepared conductor is
highly transparent (>90% transmittance), ultra-stretchable (> 10000% strain), with high-
strength (> 2MPa Young’s modulus), self-healing, and capable of maintaining stable
conductivity during large deformation and in harsh environments. Transparent integrated
sensory systems are further demonstrated via 3D printing of its precursor and could achieve
diverse sensations simultaneously towards strain, temperature, humidity, etc., and even
recognition of different liquids. This work may break the electro-mechanical limitations
encountered with current stretchable conductors, opens up a horizon for the rational designs
of their nanostructures, and could promote the development of next-generation of sensory
systems for entirely soft robots which may require high transparence, large deformation, and
environmental stability.
ICBZM 2019 - Invited lecture
45
Zwitterionic thiol-protected nanoparticles and nanoclusters
Y. Iwasaki1,2, A. Sangsuwan3,4, S. Noree3, H. Kawasaki1,2
1Department of Chemistry and Materials Engineering, 2ORDIST, 3Graduate School of Science and
Engineering, Kansai University, 3-3-35 Yamate, Suita, Osaka 564-8680, Japan. 4 Faculty of Education,
Khon Kaen University, 123 Mittraphap Rd., Muang, Khon Kaen 40002, Thailand.
E-mail: [email protected]
Metallic nanoparticles and nanoclusters have recently attracted interest in biosensor,
imaging, photodynamic therapies etc. The surface modification of these nanomaterials to
improve their dispersion stability is still an important issue and reliable immobilization
techniques are required. We have synthesized thiol-terminated phosphorylcholine (PC-SH,
Figure 1) by the Michael addition of 1,6-hexanedithiol to 2-methacryloyloxyethyl
phosphorylcholine (MPC). It has been clarified that PC-SH can enable functionalization of
a noble metal electrode and is useful for preparing antifouling self-assembled monolayers
(SAMs) against proteins and cells [1]. Recently, we have used PC-SH as a protecting ligand
for the nanomaterials to promote their application in biomedical fields.
PC-SH protected silver nanoparticles (PC-
AgNPs) are prepared as cell-killing agents under UV
irradiation [2]. PC-AgNPs were synthesized in
formic acid aqueous solutions containing PC-SH.
The surface plasmon resonance band of PC-AgNPs
is observed at 404 nm, and the average diameter of the particles is determined at 13.4 ± 2.2
nm through transmission electron microscopy (TEM) and at 18.4 nm (PDI = 0.18) through
dynamic light scattering. Cell viability in contact with PC-AgNPs is relatively high, and PC-
AgNPs also exhibit a cell-killing effect under UV irradiation.
To improve the biocompatibility of silver antimicrobial agents, PC-SH has been used for
protection of silver nanoclusters (PC−AgNCs) [3]. A change in plasmon-like optical
absorption was studied to affirm the successful synthesis of small thiolated AgNCs through
the absorption spectra that become molecular-like for the AgNCs.
PC−AgNCs were spherical with an average diameter of <2 nm
(Figure 2) . The ultra small size clusters were exceedingly
immobilized by the PC-SH on the surface, resulting in excellent
biocompatibility and antibacterial activity simultaneously.
PC-SH was also useful for the size focusing synthesis of gold
nanoclusters [4]. Au25(PC)18 and Au4(PC)4 NCs were selectively
synthesized, without the need for electrophoretic or chromatographic
isolation of size mixed products, by including ethanol or not in the
solvent. The Au4(PC)4 NCs emitted at yellow wavelengths (580−600
nm) with a quantum yield (3.6%) and an average lifetime of 1.5 μs. Also, Au4(PC)4 could be
applied for C-reactive protein (CRP) sensing with a detection limit (5 nM) low enough for
the clinical diagnosis of inflammation.
PC-SH would be then a powerful capping agents for colloidal nanomaterials in
biomedical applications.
References
[1] T. Goda, Y. Iwasaki, Y. Miyahara et al., Chem. Commun. 49, 8683 (2013).
[2] A. Sangsuwan, H. Kawasaki, Y. Iwasaki, Colloids and Surfaces B: Biointerfaces 140, 128 (2016).
[3] A. Sangsuwan, H. Kawasaki, Y. Iwasaki et al., Bioconjugate Chem. 27, 2527 (2016).
Figure 1. Chemical structure of PC-SH.
Figure 2. TEM image
of PC-AgNCs.
ICBZM 2019 - Invited lecture
46
[4] J. Yoshimoto, Y. Iwasaki, H. Kawasaki et al., J. Phys. Chem. C 119, 14319 (2015).
ICBZM 2019 - Plenary lecture
47
Chemical Vapor Deposition (CVD) of Zwitterionic Surfaces
K.K. Gleason
Department of Chemical Engineering, MIT, [email protected]
Utilizing strategies which preserve chemical functionality enables the development of
Chemical Vapor Deposition (CVD) processes for by zwitterionic materials. The CVD
surface modification approach is particularly valuable for fabricating durable, conformal,
and ultrathin (i.e. thicknesses < 30 nm) layers having the zwitterionic moieties concentrated
near the surface (i.e. top < 2 nm) [1]. The variety of surface compositions achievable by
CVD will be illustrated along with their antifouling performance in molecular force probe
(MFP) testing [2]. The first CVD zwitterionic chemistries were based on acrylate polymers.
To improve durability, a method to rapidly graft the CVD layers to reverse osmosis
desalination membranes was developed [3]. Antibiofouling was achieved without significant
loss of water permeation through the membrane. Next, pyridine-based CVD materials were
demonstrated as chlorine resistant zwitterionic materials [4]. These surfaces also exhibited
underwater superhydrophobicity which were found to be stable in high salinity environments
[5]. Conformal coating of stainless steel meshes allowed rapid gravity-driven separation of
oil from water [6]. Most recently, surfaces displaying both electrical conductivity (>500
S/cm) and zwitterionic-based antibiofouling were reported. These multifunctional surfaces
are of particular interest for electrochemical devices [7].
References
[1] – R.Yang and K.K.Gleason, Langmuir 28, 12266 (2012).
[2] – R.Yang, E.Gokteken, M.Wang and K.K.Gleason, J. Biomater. Sci., Polym. Ed. 25, 1687 (2014).
[3] – R.Yang, J.Xu, G.Ince, S.Y.Wong and K.K. Gleason, Chem. Mater. 23, 1263 (2011).
[4] – R.Yang, H. Jang, R.Stocker and K.K.Gleason, Adv. Mater. 26, 1711 (2014).
[5] – R.Yang, E.Goktekin and K.K.Gleason, Langmuir 31, 11895 (2015).
[6] – R.Yang, P. Moni, K.K. Gleason, Adv. Mater. Interfaces 2, 1400489 (2015).
[7] – M.Wang, P.Kovacik, K.K.Gleason, Langmuir 33, 10623 (2017).
ICBZM 2019 - Invited lecture
48
Spider-Inspired Multicomponent 3D Printing for Tissue Engineering
Yapei Wang*
Department of Chemistry, Renmin University of China, Beijing, 100872, China
Email: [email protected]
The shortage of tissue resources is currently a serious challenge that limits the clinical
therapy to patients with tissue loss or end-stage organ failure. The booming development of
3D printing offers unprecedented hope for tissue engineering since it can construct cells and
biomaterials into a 3D tissue-mimicking object with precise control over size and shape.
However, it is still challenging to fabricate artificial living tissues or organs due to the
extreme complexity of biological tissues. Herein, we propose a new concept of spider-
inspired 3D printing technique (SI-3DP) for continuous multicomponent 3D printing based
on in situ gelation at a multibarrel printing nozzle. The printing process allows for rapid
construction of 3D architectures composed of different inks in the desired position. To
present the potential in biomedical applications, the SI-DIP also prints vessel-like hollow
hydrogel microfibers and cell-laden hollow fibers, indicating good biocompatibility of this
technique. The newly developed SI-3DP technique is envisioned to promote the
development of next-generation complex biofabrication
Figure 1: A diagram for demonstrating the spinning mechanism by natural spiders (left) ; and Schematic illustration of
spider-inspired 3D printing (right).
References
[1] S. Liao, Y. He, D. Wang, L. Dong, W. Du, Y. Wang, Adv. Mater. Technol. 1, 1600021 (2016).
[2] S. Liao, Y. Tao, W. Du, Y. Wang, Langmuir 34, 11655 (2018).
[3] Y. Zhou, S. Liao, X. Tao, X.-Q. Xu, Q. Hong, D. Wu, Y. Wang, ACS Appl. Bio Mater. 1, 502 (2018).
ICBZM 2019 - Invited lecture
49
Evaluating the Role of Electrostatic Interactions on Macroscale
Properties of Polyampholyte Hydrogels
E. Mariner, 1 S.L. Haag,1 and M.T. Bernards1
1Department of Chemical and Materials Engineering, University of Idaho, Moscow, ID
Polyampholytes are a subclass of zwitterionic materials formed from equimolar mixtures of
oppositely charged monomer subunits. These materials have been shown to replicate the
multifunctional nonfouling and biochemical delivery capabilities of their zwitterionic
analogues [1-2]. However, polyampholytes present additional beneficial features based on
control of the underlying monomer composition. For example, the mechanical properties
have been demonstrated to be tuneable based solely on monomer composition [3] and the
drug delivery kinetics have been shown to be mediated by electrostatic interactions [4].
Therefore, polyampholyte polymer systems have great promise for biomedical applications.
Our recent efforts have focused on understanding the role of electrostatic interactions
between charged monomer subunits to gain further control over the macroscale properties
of polyampholyte hydrogels. One approach for controlling the electrostatic interactions is to
vary the length of the cross-linker species used during the synthesis of polyampholyte
hydrogels. Di-, tri-, and tetra-ethylene glycol dimethacrylate (DEGDMA, TEGDMA, Tetra-
EGDMA) cross-linkers were used to gain insight into the influence of cross-linker length on
both the mechanical properties and degradation behaviour of hydrogels formed from
homogeneous mixtures of [2-(acryloyloxy) ethyl] trimethylammonium chloride (TMA) and
2-carboxyethyl acrylate (CAA) monomers. Even at low monomer to cross-linker ratios
(26:1), the length of the cross-linker was shown to have a significant impact on the resulting
hydrogel properties (Figure 1) and the implications of this on the application of
polyampholyte hydrogels in tissue engineering will be discussed.
Figure 1: Degradation behavior of polyampholyte hydrogels with different cross-linker species under acidic
conditions.
References
[1] – T.Tah and M.T. Bernards, Colloids Surf. B Biointerfaces. 93, 195 (2012).
[2] – M. Schroeder, K. Zurick, D. McGrath, and M.T. Bernards, Biomacromolecules. 14, 3112 (2013).
[3] – S. Cao, M. Barcellona, F. Pfeiffer, and M.T. Bernards, J. Appl. Polym. Sci. 133, 13985 (2016).
[4] – M. Barcellona, N. Johnson, and M.T. Bernards, Langmuir. 31, 13402 (2015).
ICBZM 2019 - Invited lecture
50
Zwitterionic Materials for Nanomedicine
Z.Q. Cao 1
1Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI, USA,
Zwitterionic polymers emerged as a new generation of materials with excellent non-fouling
properties. Their novel use as surface coatings has shown efficient resistance to the adhesion
from proteins, cells, and full blood. When the materials were contacted with tissues such as
through subcutaneous implantation, a level of tissue compatibility was achieved by resisting
foreign body reaction with surrounding tissues. When the materials were contacted with
blood such as serving a surface coating for nanoparticles, blood compatibility was achieved
resulting long blood circulation time of the modified nanoparticles. These excellent
properties were attributed to the unique superhydrophilicity of these polymers providing
strong hydration effects. Our lab focuses on exploring novel zwitterionic polymer materials,
and studying their translational potentials in healthcare. I will highlight our zwitterionic-
based technology for nanoparticles and nanomedicine. In particular, I will introduce a so-
called sharp contrast zwitterionic polymer surfactant system. Each surfactant molecule
composes of a superhydrophilic zwitterionic polymer block and a superhydrophobic lipid
block. The polarity contrast between the two domains is drastically “sharper” than most
conventional surfactant molecules. We will discuss the special synthetic route that led to the
reaction between the two polarity distinct blocks to form the sharp contrast surfactant. We
will further discuss the unique behavior of this sharp contrast surfactant in stabilizing drug
payloads in blood serum and an improved drug delivery outcome. This research was
supported financially by US National Science Foundation (NSF) and the US National
Institute of Diabetes and Digestive and Kidney Diseases of the National Institutes of Health.
Prof. Zhiqiang Cao received his Ph.D. in Chemical Engineering from the University of
Washington in 2011 under the guidance of Prof. Shaoyi Jiang. He was a research fellow in
Prof. Robert Langer’s lab at David H. Koch Institute for Integrative Cancer Research at
Massachusetts Institute of Technology, and the Department of Anesthesiology at Children’s
Hospital Boston and Harvard Medical School from 2011 to 2012. He received his B.Eng. in
Polymer Materials and Engineering and M.Eng. in Biomedical Engineering from Tianjin
University, China in 2004 and 2007, respectively. He joined the Department of Chemical
Engineering and Materials Science at Wayne State University in January 2013 and was
promoted to Associate Professor with tenure in April 2017. His research is supported by
National Science Foundation (NSF), National Institutes of Health (NIH) and multiple
programs from Juvenile Diabetes Research Foundation (JDRF). He receives the 2016 NIH
NIDDK Type 1 Diabetes Pathfinder Award (DP2).
ICBZM 2019 - Invited lecture
51
Impacts of Zwitterionic Membranes in Medical Applications
Yung Chang R&D Center for Membrane Technology and Department of Chemical Engineering, Chung Yuan Christian
University, Taiwan R.O.C, [email protected]
Zwitterionic materials are the latest generation of materials for nonfouling interfaces and
membranes. They outperform poly(ethylene glycol) derivatives because they form tighter
bonds with water molecules and can trap more water molecules. This talk summarizes our
laboratory’s fundamental developments related to the functionalization of interfaces and
membranes using zwitterionic materials. Our molecular designs of zwitterionic polymers
and copolymers, sulfobetaine-based, carboxybetaine-based, or phosphobetaine-based, will
be reviewed. Then, the strategies used to functionalize surfaces/membranes by coating,
grafting onto, grafting from, or in situ modification will be introduced, and the important
part of this talk will be the focus to key medical applications of zwitterionic membranes.
Finally, some potential future directions for molecular designs, functionalization processes,
and applications will be summarized.
References [1] C. C. Lien, L. C.Yeh, A. Venault, S. C. Tsai, C. H. Hsu, G. V. Dizon,Y. T. Huang, A. Higuchi and Y.
Chang, Journal of Membrane Science, 565, 119-130 (2018).
[2] A. Venault, C. Y. Chang, T. C. Tsai, H.Y. Chang, D. Bouyer, K. R. Lee, Y. Chang, Journal of Membrane
Science, 563, 54-64 (2018).
[3] A. Venault, C. H. Hsu, K. Ishihara, Y. Chang, Journal of Membrane Science, 550, 337-388 (2018).
[4] A. Venault, Y. N. Chou, Y. H. Wang, C. H. Hsu, Y. Chang, Journal of Membrane Science, 547, 134-145
(2018).
[5] Y. W. Chen, A. Venault, J. F. Jhong, H. T. Ho, Y. Chang, Journal of Membrane Science, 537, 355-369
(2017).
[6] A. Venault, T. C. Wei, H. L. Shih, C. C. Yeh, Y. Chang, Journal of Membrane Science, 516, 13-25
(2016).
[7] A. Venault, K. M. Trinh, Y. Chang, Journal of Membrane Science, 501, 68-78 (2016).
[8] A. Venault, M. R. B. Ballad, Y. H. Liu, P. Aimar, Y. Chang, Journal of Membrane Science, 477, 101-114
(2015).
[9] S. H. Chen, Y. Chang, K. R. Lee, J. Y. Lai, Journal of Membrane Science, 450, 224-234 (2014).
[10] A. Venault, Y. Chang, H. H. Hsu, J. F. Jhong, J. Huang, Journal of Membrane Science, 439, 48-57
(2013).
ICBZM 2019 - Invited lecture
52
Multifunctional Zwitterionic Materials for Engineering Applications
Jie Zheng
Dept. Chemical and Biomolecular Engineering
The University of Akron
Zwitterionic materials have been considered as one of the most promising and emerging soft-
materials platforms, which enable to seamlessly integrate its unique structural/chemical
features with other molecules (e.g. polymers, nanoparticles, organic molecules, nanofillers,
etc) for achieving multiple functions in a wide range of biomedical and engineering
applications. Here, we will present different design strategies and synthesis methods to
prepare different multifunctional zwitterionic materials in different forms of hydrogels,
coatings, brushes with unconventional polymer network structures and extraordinary
properties. The resultant zwitterionic materials boast tissue-like softness together with
superior mechanical robustness, low-friction, antifouling performance, and ionic
conductivity. Guided by our design principles, we will present a number of presentative
applications of zwitterionic materials for wound dressings, optical devices, soft actuators,
protein separation, regenerative antifouling coatings, and reversible lubricant/friction
surfaces.
ICBZM 2019 - Invited lecture
53
Ultra-high Bio-affinity Recovery of RGDS peptide through protein
mimicking based on the zwitterionic PAMAM-5
Liangbo Xu, Yihan Li, Haofeng Qian, Nan Xu, Ziyin Xiang, longgang Wang,
Weifeng Lin, Yi He* and Shengfu Chen *
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and
Biological Engineering, Zhejiang University, Hangzhou 310027, China. E-mail: [email protected]
Short peptides originated from specific functional proteins are consider as an ideal
protein alternative for targeted therapy due to convenient production and less side
effects1. However, most short peptides will be much less effective than them on the
original protein2. In this work, short arginine-glycine-asparagine-serine (RGDS)
peptide, which is a common intergrin binding peptide originated from various
extracellular matrix (ECM) proteins, is conjugated on a zwitterionic surface-modified
poly(amido amine) dendrimers generation 5.0 (PAMAM-5) to investigate the affinity
enhancement. The results indicated the single RGDS peptide conjugated zwitterionic
PAMAM-5 could improve over 120 times affinity than free RGDS in in vitro
experiments, which is about 44% percent higher than the affinity between platelets and
fibrinogen3. Moreover, the conjugates with single charge enhanced
CEKEKEKKKKRGDS peptide shows more than 470 times enhancement than free
RGDS. The molecular dynamics simulation shows the conjugated RGDS forms loop
structure as cyclic RGD peptides, such as c(RGDfC) peptide, at lowest free energy
through the hydrogen bond between the carboxyl group of serine residue and amino
group on the surface groups of zwitterionic PAMAM-5. The RMSD expected value of
the conjugated RGDS is 1.404 Å, which is less than half of the value of free RGDS at
2.941Å. This indicated the conjugation of RGDS on zwitterionic PAMAM-5 can make
RGDS adapt to the nature bio-active conformation on the ECM proteins and also reduce
the entropy of RGDS to gain high affinity recovery. Furthermore, the zwitterionic
conjugates showed high biocompatibility through resembling the characteristics of
blood proteins in a slightly negative charge, high resistance to nonspecific protein
adsorption and low interaction with cells at physiological pH. This indicated that
zwitterionic PAMAM-5 is a potential platform for highly biofunctional protein
mimicking for therapeutic purpose.
1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-30
20
40
60
80
100
Ad
he
ns
ion
ra
te (
%)
Concentration (mol·L-1)
PAM-CR
c(RGDfC)
Figure 1: The cell adhension assay of HepG2 cells vs Fibronectin-coated surface the picture(left). Free
energy contour map versus the structure’s Radius of gyration (Rg) and the RMSD to average structures
(right).
ICBZM 2019 - Invited lecture
54
Water-Repairable Zwitterionic Polymer Coatings for Anti-Biofouling
Surfaces
Z. Wang1, H. Xia1, H. Zhilhof2
1 State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute, Sichuan University,
Chengdu 610065, China, [email protected]. 2 Laboratory of Organic Chemistry, Wageningen
University, Stippeneng 4, 6708 WE Wageningen, The Netherlands.
The established methods of choice to prepare anti-biofouling coatings are mainly based on
grafting zwitterionic polymer brushes from surfaces by surface-initiated living
polymerizations, using Cu(I)-catalyzed atom transfer radical polymerization. A major
drawback of that method is the complicated set-up of the reaction due to the sensitivity of
the Cu(I) catalysts to oxygen and leads to high cost, which limits its application in large-
scale use. Moreover, due to the highly restricted mobility of the brush which is covalently
bonded onto the surface, this coating is very difficult to be repaired under wear or upon
mechanical damage. We present a new approach to develop new types of zwitterionic
polymer network coatings, which combine trivial attachment requirements, robust films that
are stable in air and water, excellent protein repellence and self-healing properties. Both the
mechanical properties and the anti-biofouling characteristics are repaired within 1 minute
after water-induced healing from a mechanical scratch, also for thin films (<100 nm)[1].
There we found that the maximum width and depth that can be repaired is related to the
coating thickness, as for large degree damage, the coatings cannot be repaired and the protein
adsorption still happens. Up to now, to the best of our knowledge, there is no report about
anti-biofouling coatings which can repair both the nano/micro scratches and macro damage,
and substantially regenerate the anti-biofouling properties after healing process. This is
linked to the balance between flexible enough to allow molecular mobility on the one hand,
with sufficient structural strength to withstand substantial abrasion and surface restructuring
on the other hand. Since the sort and extent of material damage typically cannot be predicted
upon long-term day-to-day use, new kinds of anti-biofouling polymer materials that integrate
a self-healing structure, mechanical strength and optimal surface properties are in high
demand. In order to further improve the self-healing and anti-biofouling properties of the
zwitterionic coatings and overcome all of the issues mentioned above, we developed a new
kind of dual self-healing anti-biofouling coating, which can repair both macro and
nano/micro-scale damage and regenerate the surface wetting and anti-biofouling
properties.[2]
ICBZM 2019 - Invited lecture
55
Figure 1: Schematic illustration of the monomer structures used to prepare the zwitterionic polymer networks
and the protein adhesion behavior on the freshly prepared, damaged and repaired zwitterionic polymer
networks.
References
[1] – Z. Wang, E. V. Andel, S. P. Pujari, H. Feng, J. A. Dijksman, M. M. J.Smulders and H. Zuilhof*, J.
Mater. Chem. B., 5, 6728 (2017).
[2] – Z. Wang, G. Fei., H. Xia and H. Zuilhof*, J. Mater. Chem. B., 6, 6930 (2018).
Damage
Original: anti-fouling Damage: fouling Repair: anti-fouling
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ICBZM 2019 - Plenary lecture
56
Smart Interfacial Materials from Super-Wettability
to Binary Cooperative Complementary Systems
Lei Jiang
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
School of Chemistry and Environment, Beihang University, Beijing 100191, China
E-mail: [email protected]
Learning from nature and based on lotus leaves and fish scale, we developed super-
wettability system: superhydrophobic, superoleophobic, superhydrophilic, superoleophilic
surfaces in air and superoleophobic, superareophobic, superoleophilic, superareophilic
surfaces under water [1]. Further, we fabricated artificial materials with smart switchable
super-wettability [2]. The concept was extended into 1D system. Energy conversion systems
that based on artificial ion channels have been fabricated [3]. Also, we discovered the spider
silk’s and cactus's amazing water collection and transportation capability, and based on these
nature systems, artificial water collection fibers and oil/water separation system have been
designed successfully [5]. We also extended the superwettability system to interfacial
chemistry, including basic chemical reactions, crystallization, and nanofabrication arrays
[6].
References
[1] Nat. Rev. Mater., 2017, 2, 17036; J. Am. Chem. Soc. 2016, 138, 1727-1748.
[2] Adv. Mater. 2008, 20, 2842-2858.
[3] Chem. Soc. Rev., 2018, 47, 322.
[4] Nat Commun 2013, 4, 2276;
[5] Adv. Mater. 2010, 22 (48), 5521-5525.
[6] Chem. Soc. Rev. 2012, 41 (23), 7832-7856; Nat. Electron.. 2018, 1, 404.
ICBZM 2019 - Keynote invited lecture
57
Polyelectrolyte Complex Coatings:
From Bioinspired Method to Real Coating Technology
Jian Ji
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science
and Engineering, Zhejiang University, Hangzhou 310027, China , e-mail:[email protected]
Bio-inspired thin films built up by oppositely charged polyelectrolytes have drawn
tremendous interests for mimicking extracellular matrix (ECM) membranes [1,2]. We report
herein a straightforward strategy to generate polyelectrolyte complex (PEC) films by a
humidity-triggered relaxation of PEC NPs. The Poly(L-lysine)/hyaluronan NPs were pre-
complexed and sprayed onto a surface to form an initial film, which, via a post-annealing
process, can be transited into an even and stable film. We demonstrated that spontaneous
polymer chain interfusion was activated at 100% relative humidity, which not only improved
film morphology, but also promoted a conformation transition of PLL from α-helix to 310-
helix that is more similar to LBL approach. Based on this strategy, we present a one-pot
loading approach for adding functions to mimic the complexity of extracellular matrix.
Compared to LBL approach, our method is superior in generating biomimetic extracellular
matrix membranes because 1) significantly high efficiency, 2) applicable to various PEC
NPs, and 3) feasibility for diversified functionalities, such as drug coating, high-throughput
array, and programmed pattern with heterogeneous and gradients.
References
[1] Ren, K.-f.; Hu, M.; Zhang, H.; Li, B.-c.; Lei, W.-x.; Chen, J.-y.; Chang, H.; Wang, L.-m.; Ji, J. Layer-by-
layer assembly as a robust method to construct extracellular matrix mimic surfaces to modulate cell behavior.
Progress in Polymer Science 2019, DOI: https://doi.org/10.1016/j.progpolymsci.2019.02.004, in press.
[2] Chen, X.-C.; Ren, K.-F.; Zhang, J.-H.; Li, D.-D.; Zhao, E.; Zhao, Z. J.; Xu, Z.-K.; Ji, J. Humidity-Triggered
Self-Healing of Microporous Polyelectrolyte Multilayer Coatings for Hydrophobic Drug Delivery. Advanced
Functional Materials 2015, 25, 7470-7477; Zhang, H.; Ren, K.-f.; Chang, H.; Wang, J.-l.; Ji, J. Surface-
mediated transfection of a pDNA vector encoding short hairpin RNA to downregulate TGF-β1 expression for
the prevention of in-stent restenosis. Biomaterials 2017, 116, 95-105; Hu, M.; Chang, H.; Zhang, H.; Wang, J.;
Lei, W.-x.; Li, B.-c.; Ren, K.-f.; Ji, J. Mechanical Adaptability of the MMP-Responsive Film Improves the
Functionality of Endothelial Cell Monolayer. Advanced Healthcare Materials 2017, 6, 1601410; Chang, H.;
Ren, K.-f.; Wang, J.-l.; Zhang, H.; Wang, B.-l.; Zheng, S.-m.; Zhou, Y.-y.; Ji, J. Surface-mediated functional
gene delivery: An effective strategy for enhancing competitiveness of endothelial cells over smooth muscle
cells. Biomaterials 2013, 34, 3345-3354;
ICBZM 2019 - Keynote invited lecture
58
Tribo-Mechanics of Vapor-Hydrated Polymer Brushes
I. de Vries, L. van der Velden, B. ten Brug, J.-W. Nijkamp, G. Ritsema van Eck, G. J.
Vancso, S. de Beer
Materials Science and Technology of Polymers, University of Twente, Enschede, the Netherlands
Polymer Brushes are well known for their excellent lubricious properties when completely
immersed in water. However, for many applications complete water immersion is
impractical and hydration via condensed water vapor in the brush is preferred. We show
using friction force microscopy that the dissipation within vapor-hydrated polymer brushes
is qualitatively different from the frictional response of water-immersed polymer brushes.
By atomic force spectroscopy combined with neutron reflectivity and molecular dynamics
simulations, we unravel and quantify the surface and bulk dynamic relaxations that built up
the dissipative response of vapor-hydrated polymer brushes. The fundamental insights
obtained by this study will aid in optimizing brush-design for employment as lubricious
coatings in air, which can find application e.g. on tubular medical devices.
ICBZM 2019 - Contributed lecture
59
Design, Synthesis and Characterization of
Fully Zwitterionic, Functionalized Dendrimers
E. Roeven,1,2 L. Scheres,2 M.M.J. Smulders,1 H. Zuilhof 1
1 Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6708 WE Wageningen, The
Netherlands.
2 Surfix BV, Bronland 12 B-1, 6708 WH Wageningen, The Netherlands.
Dendrimers are interesting candidates for various applications due to the high level of control
over their architecture, the presence of internal cavities and the possibility for multivalent
interactions have made dendrimers interesting candidates for various applications [1]. More
specifically, zwitterionic dendrimers modified with an equal number of oppositely charged
groups have found use in in vivo biomedical applications. However, the design and control
over the synthesis of these dendrimers remains challenging, in particular with respect to
achieving full modification of the dendrimer.
In this work we show the design and subsequent synthesis of dendrimers that are highly
charged whilst having zero net charge, i.e. zwitterionic dendrimers that are potential
candidates for biomedical applications [2]. First we designed and fully optimized the
synthesis of charge-neutral carboxybetaine and sulfobetaine zwitterionic dendrimers.
Following their synthesis, the various zwitterionic dendrimers were extensively
characterized. In this study we also report for the first time the use of X-ray photoelectron
spectroscopy (XPS) as an easy-to-use and quantitative tool for the compositional analysis of
this type of macromolecules that can complement e.g. NMR and GPC. Finally, we designed
and synthesized zwitterionic dendrimers that contain a variable number of alkyne and azide
groups that allow straightforward (bio)functionalization via click chemistry.
Figure 1: Schematic representation of fully zwitterionic, functionalized zwitterionic dendrimers.
[1] – C.C. Lee, J.A. MacKay, J.M.J. Fréchet, F.C. Szoka; Nat. Biotechnol. 23, 12 (2005)
[2] – E. Roeven, L. Scheres, M.M.J. Smulders, H. Zuilhof; ACS Omega. 4, 2 (2019)
ICBZM 2019 - Contributed lecture
60
PEDOT-based Zwitterionic Conducting Polymer for Organic
Electrochemical Transistor Biosensors
Shin-Ya Chen, Erjin Zheng, Priyesh Jain, Shukun Zhong and Qiuming Yu
Department of Chemical Engineering, University of Washington, Seattle, WA 98195, USA, [email protected]
Organic electrochemical transistors (OECTs) represent a very promising class of organic
thin film transistors (OTFTs) that have recently attracted scientific interest as performing
transducers in sensing applications [1]. OECTs offer the advantages of simple electrical
readout, low operation voltage, inherent signal amplification, straightforward
miniaturization, and ease of fabrication on flexible substrates including paper. Therefore,
they are excellent candidates for disposable biosensors. However, the commonly used
conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate)
PEDOT:PSS lacks of functionality and non-fouling properties, which limits the application
as the active layer for OECT biosensors.
In this work, we present the development of zwitterionic carboxybetaine PEDOT conducting
polymer (PEDOT-CB) and print it on PET substrate to form a planar OECT and link
biorecognition element on the gate to realize biosensing (Figure 1). PEDOT-CB offers both
functionalibility to chemically link antibody to the sensor surface and non-fouling properties
to allow direct detection in complex media. The UV-Vis absorption spectroscopy and Raman
scattering spectroscopy are used to determine polaron and bipolaron populations in the
oxidized PEDOT-CB. The dimension of channel length/width and gate length/width are
optimized to achieve high transconductance under certain gate voltage (VG) and source-drain
voltage (VD). The drain current (ID) is recorded with time after a certain concentration
colorectal cancer (CRC) biomarker solution is flowed through the PDMS microfluidic
channel under the VG and VD that produced the maximum transconductance. The limits of
detection are determined for CRC biomarkers in buffer solution and undiluted human plasma
to demonstrate the ultra-low fouling capability.
Figure 1: (A) From monomer to the final oxidized PEDOT-CB. (B) Schematics of OECT sensor with fluidic
channel and surface functionalization. (C) Planar OECT printed on a glass slide with silver contacts. (D)
Arrays of planar OECTs printed on a piece of PET sheet. (E) Photograph of an experimental setup.
References
[1] J. Rivnay, S. Inal, A. Salleo, R. M. Owens, M. Berggren, and G. G. Malliaras. Nat. Rev. Mater. 3, 17086 (2018).
ICBZM 2019 - Contributed lecture
61
Rationally design nanostructure features on superhydrophobic surfaces
for enhancing self-propelling dynamics of condensed droplets
Y. Shen, J. Tao, Y. Xie
College of Materials Science and Technology,
Nanjing University of Aeronautics and Astronautics, Nanjing 210016, P. R. China
[email protected]; [email protected]; [email protected];
Self-propelling ability towards achieving more efficient dropwise condensation intensively
appeals to researchers due to its academic significance to explain some basic wetting
phenomena. Herein we designed and fabricated the two types of microstructure
superhydrophobic surfaces, i.e., sealed layered nanoporous structures (SLP-surface) and
open nanocone structures (OC-surface). As a consequence, the resultant surfaces exhibit the
robust water repellency, and the water droplet nearly suspends on the superhydrophobic
surfaces (CA=158.8°±0.5°, SA=4°±0.5° for SLP-surface and CA=160.2°±0.4°, SA=1°±0.5°
for OC-surface, respectively). Meanwhile, the impacting droplets can be rapidly rebounded
off with shorter contact time of 11.2 ms and 10.4 ms (impact velocity V0 = 1 m/s). The
excellent static-dynamic superhydrophobicity is mainly attributed to the air pockets captured
by the both microscopic rough structures. Regarding the self-propelling ability of condensed
droplets, it is found that the droplet microscopic pining effect of SLP-surface severely
weakens dynamic self-propelling ability of condensed droplets. The capillary adhesive force
induced by the sealed layered nanoporous structures is up to 16.0 μN. However, the open
nanocone structures cause lower water adhesive force (~4.1 μN) under the action of flowing
air pockets, producing higher dynamic self-propelling ability of condensed droplets. As a
consequence, the open nanocone structure superhydrophobic surface displays a huge
potential of inhibiting attachment of condensed droplets.
Figure 1: Two types of nanostructure superhydrophobic surfaces were designed to investigate the self-
propelling dynamics of the condensed droplets for a potential application of water-harvesting
References
[1] - The heading “References” follows one double space below the body text in times 10 bold. Reference
citations are shown in the text by a numeral in brackets and cited under the heading “References” in times 10.
[2] – P.Noble and B.Collin, J. Polym. Sci. 132, 425 (1975).
ICBZM 2019 - Contributed lecture
62
Computer Simulations on the Structure-Property Relationship of
the Zwitterionic Drug Delivery System
Lingxia Hao†, Wenfeng Min†, Delin Sun, Jian Zhou
† L.X. Hao and W.F. Min contribute equally to this work.
E-mail: [email protected]
Cancers pose serious threats to human being due to their high mortality. Enormous
research efforts are devoted to developing new therapeutic methods for the treatment of
cancers. In this work, dissipative particle dynamics (DPD) simulations were performed to
study the drug-loading and drug release mechanism of zwitterionic polycarboxybetaine
(PCB)-based polymer prodrug. In addition, the difference between the PCB-based
system and the PEGylated system, in terms of their different drug release mechanisms
were discussed.
Simulation results show that the polymer prodrug system can form a well-defined core-
shell structure at a proper condition. With the increase of polymer concentration, the self-
assembled morphology exhibits a transition from spherical to columnar, perforated and
finally to lamellar micelles in aqueous solutions. Besides, doxorubicin (DOX) is distributed
from ring-like to evenly distributed in the micelle’s nucleus with the increase of drug content.
The self-assembled loading process follows the nucleation-growth mechanism of
“aggregation, mutual attraction, fusion and growth”. According to the comparison between
the PCB-based system and the PEGylated system, we find that the PCB drug-loaded
micelle reaches the dynamic equilibrium faster than the traditional PEGylated system. Under
the acidic condition, spherical micelles are disassembled and can effectively release drug
molecules due to the protonation of carboxyl groups.
These findings give a molecular level interpretation for the drug release process of DOX
in the zwitterionic system. The structure-property relationship can provide meaningful
guidance for the rational design of drug delivery systems.
References
[1] M. Liao, H. Liu, H. Guo, J. Zhou, Langmuir 33, 7575 (2017).
[2] W. Min, D. Zhao, X. Quan, D. Sun, L. Li, J. Zhou, Colloids & Surfaces B: Biointerfaces 152, 260 (2017).
[3] L. Hao, L. Lin, J. Zhou, Langmuir 35,1944 (2019).
ICBZM 2019 - Contributed lecture
63
Polyzwitterion comprising 1,2-diaminoethane that recognizes tumorous
pH for effective delivery of the coated nanoparticles
Hiroyasu Takemoto, Nobuhiro Nishiyama2
Affiliation: Tokyo Institute of Technology, [email protected]
Polyzwitterions offer an antifouling property when the net charge is neutral, and have been
often utilized as a coating polymer for biomaterials, in order to circumvent non-specific
interaction with biological components. For this purpose, polyzwitterions that are neutral in
a wide pH range have been extensively investigated. However, precisely regulated
protonation in the betaine structure in principle produces smart polyzwitterions with a
switchable property to be interactive with surrounding substances in response to a site-
specific pH (i.e., tumor in the present study). Herein, we report a polyzwitterion comprising
1,2-diaminoethane-based carboxybetaine with polyglutamate backbone (termed as
PGlu(DET-Car)) which switches antifouling property to be tissue-interactive in response to
tumorous pH (~6.5), on the basis of the unique protonation behavior of 1,2-diaminoethane
moiety (Fig. 1) [1].
To investigate the pH-responsive
behaviour of PGlu(DET-Car), the
hydrodynamic size was measured in the
presence of anionic heparin in
fluorescence correlation spectroscopy
(FCS). As a result, PEG system kept
original size in the presence of heparin
at the treated pH values (pH 6.0-8.0),
because of the neutral property.
PGlu(DET-Car) system also showed
original size at physiological pH 7.4,
but the size was increased below pH 7.0, indicating the interaction with heparin. The
interaction with heparin below pH 7.0 demonstrates the cationic behavior of PGlu(DET-Car)
selectively at tumorous acidic pH, potentially leading to the interaction with tissue
components after entering the tumor site. Indeed, when quantum dots (QDs) coated with
PGlu(DET-Car) was intravenously administered for the tumor-bearing mice, 3.2 times more
QDs accumulated in the tumor tissues, relative to PEG system. Note that the blood
circulation property and distribution in normal tissues were comparable for the two systems,
suggesting that the effective tumor accumulation for PGlu(DET-Car) system should be
attributed to the event within the tumor tissue, such as cationic behavior of the system for
tissue interaction.
The present study suggests that the performance of polyzwitterions can be tuned by the
ionizable moieties in betaine structure. Thus, polyzwitterion has huge potential with
switchable property in a pH-responsive manner, directed toward a molecular design of
functional surface of biomaterials.
References
[1] Hiroyasu Takemoto, et al. Angew. Chem. Int. Ed. 57, 5057 (2018).
Figure 1: Illustration of the developed polymer.
ICBZM 2019 - Contributed lecture
64
Bioactive Zwitterionic Surfaces for Biosensing
Jacob Baggerman1,2
1Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6708 WE, Wageningen, The
Netherlands; 2Aquamarijn Micro Filtration BV, IJsselkade 7, NL-7201 HB Zutphen, The Netherlands
Bioactive layers are the core of many biosensing devices. The bioactive layers should be
antifouling to prevent non-specific interactions for interfering species. Zwitterionic materials
offer great potential for this purpose. Different strategies have been developed to attach
recognition elements to zwitterionic polymers. Optimal antifouling and specific capture of
analytes requires to balance the loading capacity of biorecognition elements with the
presence of antifouling functionality. Hierarchical antifouling brushes offer new
opportunities for this. By creating diblock polymer brushes with a antifouling base layer and
a biofunctionalizable top layer the antifouling performance and biofunctionalization can be
decoupled allowing for antifouling brushes with a improved loading of biorecognition
elements.
ICBZM 2019 - Poster – P1
65
Influence of ion structures of zwitterions
on the cellulose dissolution ability and toxicity to microorganisms
Ai Ito1, Kosuke Kuroda1, Satria Heri2, Kazuaki Ninomiya3, Kenji Takahashi1
1Graduate school of Natural science and Technology, Kanazawa University,
2Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Lampung, 3Institute for Frontier Science Initiative, Kanazawa University
Scheme 1. Scheme of ethanol from biomass by using ionic liquid
It is known that some ionic liquids can dissolve cellulose and increase the efficiency of the
hydrolysis of cellulose to glucose (Figure 1). However, when the resulting glucose is
successively fermented in the same solution, the ionic liquids prevent the fermentation
because they are highly toxic to microorganisms. The mechanism of the toxicity of ionic
liquids has been reported as follow: insertion of the alkyl chain of the cation into the
hydrophobic part of lipid bilayer membrane of microorganisms [1]. To solve this problem,
we have developed lower toxic liquid zwitterions[2][3]. Especially, a carboxylate-type
zwitterion satisfies cellulose dissolution ability and low toxicity to fermentative
microorganisms and enables ethanol production from biomass in one-pot.
In this submission, we will discuss the different mechanism of the toxicity of between
ionic liquids and zwitterions. For one-pot ethanol production, we synthesized the novel
zwitterions of carboxylate-type and investigated their cellulose dissolution ability and
toxicity to microorganisms. As a result, these were correlated with their structures.
Zwitterions which have long alkyl side chain did not dissolve cellulose and showed high
toxicity to fermentative microorganisms, but those which have oligoether side chain
dissolved cellulose and showed low toxicity. In addition, zwitterions which have long spacer
showed higher toxicity than those which have a short one, when side chain is middle length
(around four carbons). From this result, the carboxylate-type zwitterions which have
oligoether side chain were suitable for cellulose dissolution, and the carboxylate-type
zwitterions which have short alkyl or oligoether side chain and short spacer were suitable
for fermentation with microorganisms.
References
[1] G. S. Lim, J. Zidar, D. W. Cheong, S. Jaenicke, and M. Klahn, J. Phys. Chem. B 118, 10444 (2014).
[2] K. Kuroda, H. Satoria, K. Miyamura, Y. Tsuge, K. Ninomiya and K. Tokahashi, J. Am. Chem. Soc. 139,
16502 (2017).
[3] H. Satoria, K. Kuroda, Y. Tsuge, K. Ninomiya and K. Tokahashi, New J. Chem. 42, 13225(2018).
ICBZM 2019 - Poster – P2
66
Synthesis of a pH-Responsive Polyampholytic Maleic Acid-alt-
Methyldiallylamine Copolymer and its Application as Antiscalant
H. A. Al-Muallem, I. Y. Yaagoob, S. A. Ali, and M. A. J. Mazumder
Chemistry Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
E-mail: [email protected]
Copolymerization of methyldiallylamine (1) with maleic acid (2) has been carried out using
ammonium persulfate (APS) initiator or UV light at a of 365 nm. The polyampholyte
copolymer (PA) 4 has been synthesized in excellent yield with an anticipation that it could
be a potential antiscalant. Under pH-induced changes, the stimuli-responsive PA 4 was
transformed to cationic 5, polampholyte-anionic 6, and dianionic polyelectrolyte 7 to
examine their viscosity. The viscosity values of 4 in the presence of salt NaCl confirmed its
antipolyelectrolyte behaviour. PA 4 was evaluated as an antiscalant for potential application
in reverse osmosis (RO) plants. At concentrations of 5 and 20 ppm, it demonstrated
remarkable efficiency of ≈100% for CaSO4 scale inhibition from its supersaturated solution
for 50 and 500 min, respectively, at 40 °C. Since an antiscalant should be effective for the
duration of brine’s residence time (≈30 min) in the osmosis chamber, the synthesis of PA 4
in excellent yields from cheap starting materials and its very impressive performance may
accord it a prestigious place among many an environment-friendly phosphate-free
antiscalant. Note that polyphosphate additives used for controlling scale formation, when
discharged in the sea have deleterious influence over the marine biota picture. [1]
Scheme 1: Synthesis of alternate copolymers
from 1 and 2 and pH induced changes in the
charge types in the backbone of 4-7.
Table 1: Percent scale inhibition in the presence of PA 4
in 3 CBa supersaturated CaSO4 solution at 40 °C.
Entry Sample
(ppm) Percent inhibition at times (min) of
50 100 200 300 400 500 700
1 5 100 92 71 24 22 17 17
2 10 100 100 88 81 76 71 63
3 15 100 99 96 91 88 83 75
4 20 100 100 100 100 100 100 98
aThree times the concentration of Ca2+ and SO42- found
in the concentrated brine of an RO plant.
References
[1] - A. M. Shams El Din, Sh. Aziz and B. Makkawi, Desalination, 97, 373 (1994).
ICBZM 2019 - Poster – P3
67
Antifouling Activity of Graft-to Poly(carboxybetaine) Pre and Post Flow
K A Amoako, K Cook1, S. Jiang2
Affiliation: Biomedical Eng., University of New Haven, Biomedical Eng., Carnegie Mellon1 Chemical Eng.,
University of Washington 2, [email protected]
This study evaluates the effect of surface coatings on anti-fouling activity under different
flows for the analyses of coating stability. This was done by exposing DOPA-PCB-
300/dopamine coated polydimethylsiloxane (PDMS) to physiological shear stresses using a
recirculation system. The effect of shear stress induced by phosphate buffered saline flow
on coating stability was characterized with differences in fibrinogen adsorption between
control (coated PDMS not loaded with shear stress) and coated samples loaded with
various shear stresses. Fibrinogen adsorption data (Figure 1) showed that relative
adsorption on coated PDMS that weren’t exposed to shear (5.73% ± 1.97%) was
significantly lower than uncoated PDMS (100%, p < 0.001). Furthermore, this fouling
level, although lower, was not significantly different from coated PDMS membranes that
were exposed to 1 dynes/cm2 (9.55% ± 0.09%, p = 0.23), 6 dynes/cm2 (15.92% ± 10.88%, p
= 0.14), and 10 dynes/cm2 (21.62% ± 13.68%, p = 0.08). Our results show that DOPA-
PCB-300/dopamine coating are stable, with minimal erosion, under shear stresses tested.
The techniques from this fundamental study may be used to determine the limits of
stability of coatings in long-term experiments.
Figure 1: Fibrinogen fouling levels on pCB-grafted polydimethylsiloxane polymer after shear stress
application.
References
[1] – A Belanger, A Decarmine, S Jiang, K Cook, and K Amoako, Langmuir 35, 5, 1984 (2019). [2] – S Jiang and Z Cao Adv Mater. 22, 9, 920 (2010).
[3] – J B. Schlenoff, Langmuir. 30, 32, 9625 (2014).
[4] Z. Zhang, M. Zhang, S. F. Chen, T. A. Horbetta, B. D. Ratner, S. Y. Jiang, Biomaterials 29, 4285 (2008)
ICBZM 2019 - Poster – P4
68
Parallelized microfluidic accumulation assay to test zwitterionic fouling
release coatings for marine applications
C. D. Beyer, K.A. Nolte, J. Schwarze, O. Özcan, Julian Koc, Eric Schönemann, Andre
Laschewsky and A. Rosenhahn
Analytical Chemistry–Biointerfaces, Ruhr-University Bochum, Universitätsstraße 150, 44801 Bochum
Germany, [email protected]
Due to the unwanted adhesion of marine organisms on synthetic surfaces, the marine
industry has high annual maintenance costs and has to cope with an increased fuel
consumption of ships.[1] Non-toxic fouling release coatings based on silicones are an
environmentally friendly solution as they rely on reducing attachment instead of using
biocides. Hydrophilic components like ethylene glycols are important additives for fouling-
release formulations, which enhance the efficiency of the coatings.[2,3] Due to the
susceptibility of polyethers against oxidative degradation, it is desirable to develop more
stable and more effective additives.[4,5] For a rapid test of the efficiency of new polymer
coatings, a parallelized microfluidic testing platform has been developed. This experiment
allows to study the performance of different chemistries against settlement of marine
organisms in a highly parallelized fashion.[6] The spectrum of tested samples ranges from
model chemistries to technical coatings. The method has successfully been applied to a range
of zwitterionic coating chemistries for a detailed structure-activity correlation.[7]
References
[1] M. P. Schultz, J. A. Bendick, E. R. Holm, W. M. Hertel, Biofouling 2011, 27, 87–98.
[2] R. Wanka, J. A. Finlay, K. A. Nolte, J. Koc, V. Jakobi, C. Anderson, A. S. Clare, H. Gardner, K. Z.
Hunsucker, G. W. Swain, et al., ACS Appl. Mater. Interfaces 2018, 10, 34965–34973.
[3] A. Rosenhahn, S. Schilp, H. J. Kreuzer, M. Grunze, Phys. Chem. Chem. Phys. 2010, 12, 4275.
[4] Y. L. Jeyachandran, T. Weber, A. Terfort, M. Zharnikov, J. Phys. Chem. C 2013, 117, 5824–5830.
[5] S. Sharma, R. W. Johnson, T. A. Desai, Langmuir 2004, 20, 348–356.
[6] K. A. Nolte, J. Schwarze, C. D. Beyer, O. Özcan, A. Rosenhahn, Biointerphases 2018, 13, 41007.
[7] J. Koc, E. Schönemann, A. Amuthalingam, J. Clarke, J. A. Finlay, A. S. Clare, A. Laschewsky, A.
Rosenhahn, Langmuir 2019, 35, 1552–1562.
ICBZM 2019 - Poster – P5
69
Zwitterionic self-assembled nanoparticles for drug delivery
P. Cabanach, S.Borrós
Grup d’Enginyeria de Materials, Institut Químic de Sarrià, Universitat Ramon Llull, Barcelona, Spain.
Zwitterionic polymers have emerged in the recent years as a promising option for the design
of drug delivery systems due to their super-hydrophilic surface that confer them unique
properties [1]. They have been proposed as substitute of PEG for the design of “stealth” nanoparticles [2] as they avoid
immunogenic reactions improving the blood circulation lifetime [3-4]. Moreover this super-hydrophilicity also
make them interesting in the design of oral drug delivery systems [5].
Trying to take advantage of these unique properties of zwitterionic polymers, our work has
been focused on the development of amphiphilic nanoparticles consisting in zwitterionic
block copolymers. Reversible Addition-Fragmentation chain-Transfer polymerization
(RAFT) has been used to produce different amphiphilic block copolymers with a controlled
structure, and their self-assembly in water has been studied.
It has been proved how the zwitterionic block type has an important contribution on the self-
assembly of the amphiphilic polymers, observing big differences between polymers having
an UCST and polymers without this thermoresponsivity.
The capability of drug loading of the nanoparticles produced has been studied, proving that
the micelle self-assembled zwitterionic nanoparticles have a high potential for encapsulation
hydrophobic drugs such as Curcumin or Paclitaxel. And their performance in vitro has been
studied in different human cell lines.
Figure 1: Scheme of the zwitterionic self-assembled nanoparticles
References
[1] Q. Jin, Y. Chen, Y. Wang, and J. Ji, Colloids Surfaces B Biointerfaces, 124 (2014).
[2] L. Zheng, H. S. Sundaram, Z. Wei, C. Li, and Z. Yuan, React. Funct. Polym., 118 (2017).
[3] B. Li, J. Xie, Z. Yuan, P. Jain, X. Lin, K. Wu, and S. Jiang, Angew. Chemie - Int. Ed. 57, 17 (2018).
[4] B. Li, Z. Yuan, H.-C. Hung, J. Ma, P. Jain, C. Tsao, J. Xie, P. Zhang, X. Lin, K. Wu, and S. Jiang,
Angew. Chemie Int. Ed. (2018).
[5] W. Shan, X. Zhu, W. Tao, Y. Cui, M. Liu, L. Wu, L. Li, Y. Zheng, and Y. Huang, ACS Appl. Mater.
Interface, 8,38 (2016).
Superhydrophilic
Surface:• Ultra-antifoulingsurface
• AvoidsProteinCorona
• IncreasetheTargetingCapacity
• DecreasetheImmuneResponse
• LongBloodCirculation
+
-
HighversatilityProducedbyRAFTpolymerization:
• Controloverpolymerstructure
• Eachmonomeroffersdifferentcharacteristics
• Multipleoptionsofmodification
ICBZM 2019 - Poster – P6
70
One-step surface zwitterionization by bio-inspired polyphenolic coating
B. Cheng1, K. Ishihara1, 2, H. Ejima1
Affiliation: 1Department of Materials Engineering and 2Department of Bioengineering, School of
Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku 113-8656, Japan.
*Author: e-mail:[email protected], [email protected]
Mussel-inspired polydopamine (PDA) coating has been studied for two decades because of
its unique, material-independent, and convenient coating process [1]. The combination of
PDA coating and zwitterionic polymer poly(2-methacryloyloxyethyl phosphorylcholine)
(PMPC) has proved to be very effective for preparing nonfouling surface even on
polytetrafluoroethylene (PTFE) substrate [2]. Recently, a series of phenolic molecules has
attracted a lot of research interests for their environmentally friendly concept and coating
ability [3] that similar to PDA. Among these phenolics, the gallol-functionalized polymer
showed incredible adhesive property [4].
Inspired by its strong adhesive property, we hereby report a synthetic gallol-functionalized
polymer comprising zwitterionic phosphorylcholine (PC) group. Through the simple dipping
into the solution of this copolymer, the surface became hydrophilic and nonfouling. The
formation of coating layer on polystyrene and polyethylene surface was characterized by X-
ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy and static water
contact angle measurement. Once coated onto surfaces, the coated polymer layer exhibited
exceptional stability and not being detached by the rinsing with various solvents. Protein
adsorption was substantially reduced, confirmed by a gold colloid-labeled immunoassay
method.
Figure 1: Basic structure of polymer using in this study
The copolymer reported in this study provides a simple and effective process for preparing
nonfouling surface and thus, the applications in multiple fields including biomedical, energy,
and environmental engineering are expected.
References
[1] H. Lee, M. S. Dellatore, M. W. Miller, P. B. Messersimth, Science 2007, 318, 426.
[2] B. Cheng, Y. Inoue, K. Ishihara, Colloids Surf. B, Biointerface 2019, 173, 77.
[3] T. S. Sileika, D.G. Barrett, R. Zhang, K. H. A. Lau, P. B. Messersmith, Angew. Chem. Int. Ed. 2013, 52,
10766.
[4] K. Zhan, C. Kim, K. Sung, H. Ejima, N. Yoshie, Biomacromolecules, 2017, 18, 2959.
ICBZM 2019 - Poster – P7
71
Designing Corneal Implants with Zwitterionic and Supramolecular Materials
A.J. Feliciano, F.A.A. Ruiter, T.Bosman1, S. Giselbrecht, L. Moroni, P.Y.W. Dankers2, C. van
Blitterswijk, M.B. Baker.
MERLN Institute for Technology-Inspired Regenerative Medicine, Maastricht University, Maastricht, NL. 1SupraPolix, Eindhoven, NL. 2Department of Biomedical Engineering, Eindhoven University of Technology,
Eindhoven, NL.
Implantable stromal devices, or stromal equivalents for tissue regeneration, necessitate specific
requirements in order to maintain the native tissue of the cornea especially in terms of
biocompatibility. Normally quiescent, corneal keratocytes can differentiate into fibroblasts and
ultimately myofibroblasts as a response to changes in ECM matrix components, chemokines,
stress, or stiffness. So, whether as a result from a wound healing or foreign body response, these
activated cells will no longer secrete collagen in the lamellar and orthogonal structure that the
cornea relies on for optical transparency. We are interested in designing implants that are
rendered invisible to the body by utilizing combinatorial zwitterionic and supramolecular
monomers. We propose a poly(zwitterionic-co-UPy) polymer for use in corneal tissue products
such as presbyopic inlays and stromal constructs in order to achieve an optimal quiescent state for
healthy corneal ECM production.
ICBZM 2019 - Poster – P8
72
Biocompatibility of Polyampholyte Polymers for Tissue Engineering
Applications
S.L. Haag,1 and M.T. Bernards1
1Department of Chemical and Materials Engineering, University of Idaho, Moscow, ID
There has been increasing interest in the use of polyampholyte polymers as a platform for
tissue engineering. Polyampholytes are a subgroup of zwitterionic materials that are created
from monomers with oppositely charged groups. They have been shown to be resistant to
non-specific protein adsorption, that limits the foreign body response, while also capable of
covalently attaching biomolecules [1]. In addition, these hydrogels have tunable mechanical
properties through the selection of cross-linker density and underlying monomers [2]. Prior
studies have investigated short term adhesion of MC3T3-E1 osteoblast-like cells onto gels
with conjugated protein. A more encompassing biocompatibility study is needed prior to
utilizing polyampholytes to aid in the regeneration of tissue defects in vivo.
In this work, we further investigate the biocompatibility of polyampholyte polymers
composed of positively charged [2-(acryloyloxy) ethyl] trimethyl ammonium chloride
(TMA) and negatively charged 2-carboxyethyl acrylate (CAA) crosslinked with triethylene
glycol dimethacrylate (TEGDMA). The hydrogel solution was studied before and after free-
radical polymerization occurred, and the buffer formulation was refined to improve the long
term biocompatibility. Following refinement, the non-fouling and biomolecule conjugation
capabilities were validated. Biocompatibility was assessed following both short-term (2
hour) adhesion of MC3T3-E1 cells and long-term (24 hour and 7 day) proliferation utilizing
light and fluorescent microscopy. A discussion of the results and their correlation to the
underlying electrostatic and counter ion interactions will be included.
References
[1] – M. Schroeder, K. Zurick, D. McGrath, and M.T. Bernards, Biomacromolecules. 14, 3112 (2013).
[2] – S. Cao, M. Barcellona, F. Pfeiffer, and M.T. Bernards, J. Appl. Polym. Sci. 133, 13985 (2016).
ICBZM 2019 - Poster – P9
73
Zwitterionic Supplement in Poly(ethylene glycol) Hydrogel Dressings
Accelerating Wound Healing by Anti-inflammation and Enhanced Cell
Proliferation, Angiogenesis and Collagen Deposition
H. He1,2, Z. Xiao2, S. Li1, Y. Yang1, Y. Chen1, J. Chen1, J. Wu1,2
1College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325035, China; 2School
of Pharmaceutical Sciences, Wenzhou Medical University, Wenzhou, 325035, China. [email protected]
Due to its excellent biocompatibility, poly(ethylene glycol) (PEG) based hydrogels have
been extensively investigated as wound dressings for skin regeneration. However, these
hydrogels fail to improve the skin recovery because they usually have high stiffness which
are not compatible with soft skin tissues. Herein, by supplementing PEG hydrogels with
zwitterionic poly(sulfobetaine methacrylate) (pSBMA), a skin compatible hydrogel
composite (named as PEG-SBMA) was fabricated and its potent in accelerating skin wound
generation was fully evaluated. In vitro result found that PEG-SBMA was much softer than
PEG hydrogel, and its highly porous structure endowed it with an increased oxygen
permeability compared to PEG hydrogel. In vivo data demonstrated that PEG-SBMA could
effectively promote skin regeneration via efficiently inducing granulation formation,
collagen deposition, cells proliferation and vascularization in the mouse full-thickness
cutaneous wounds model. Further histological results revealed that PEG-SBMA enhanced
skin recovery by up-regulating the secretion of transforming growth factor-β (TGF-β) and
reducing inflammation through down-regulating inflammatory factor (TNF-α). All these
data suggested that the PEG-SBMA hydrogel would be a promising wound dressing
candidate for the treatment of skin injury.
Figure 1: The SBMA-PEG composite hydrogel enhanced skin wound regeneration over PEG hydrogel.
References
[1] - H. He, Z. Xiao, Y. Zhou, A. Chen, X. Xuan, J. Zheng, J. Xiao, J. Wu, J. Mater. Chem. B 7, 1697 (2019)
[2] - J. Wu, Z. Xiao, A. Chen, H. He, C. He, X. Shuai, et al., Acta Biomater. 71, 293 (2018)
ICBZM 2019 - Poster – P10
74
Achieving Antifouling under Air Condition via Controlled Radical
Polymerization of Carboxybetaine
Daewha Hong*, Hyeongeun Kang, Wonwoo Jeong
Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University,
Busan 46241, South Korea. *E-mail: [email protected]
In this study, we achieved antifouling on gold surfaces by controlled radical polymerization
of carboxybetaine (CB) under air condition.1 In contrast to air-tight, atom transfer radical
polymerization (SI-ATRP), we used air-tolerant, activator regenerated by electron transfer
(ARGET) ATRP for grafting poly(CB) brush on surfaces.2 Therefore, the polymerization
process did not require any cumbersome degassing step or complicated equipment. The
surface coated with poly(CB) brush showed high fidelity of antifouling performance against
fibrinogen adsorption, indicating that extremely low-fouling can be achieved with ease.3
This method was still valid toward real-life, large surface area including daily-life plastic,
glass, or polydimethylsiloxane (PDMS) for their potential applications in diagnostic
platform, biosensors, and medical devices.
Figure 1: SI-ARGET ATRP of CB in the presence of air.
References
[1] - S. Jiang et al., ACS Appl. Mater. Interfaces 9, 9255 (2017)
[2] - K. Matyjaszewski et al., Angew. Chem., Int. Ed. 57, 933 (2018)
[3] - S. Jiang et al., Langmuir 25, 11911 (2009)
ICBZM 2019 - Poster – P11
75
Zwitterionic supramolecular prodrug micelles for photodynamic cancer
therapy
Qiao Jin, Yongyan Deng, Jian Ji
MOE Key Laboratory of Macromolecule Synthesis and Functionalization of Ministry of Education,
Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, Zhejiang
Province, PR China. E-mail: [email protected]
As an emerging strategy, photodynamic therapy (PDT) has drawn increasing attention in
cancer treatment due to its minimal invasion, low side effects, and few drug resistance[1].
Unfortunately, the hypoxic environment of cancer tissues may decrease the concentration of
available oxygen and restrict ROS production in PDT. Meanwhile, high level intracellular
glutathione (GSH) acts as natural scavenger of oxidants, protecting cancer cells from the
toxicity of ROS. In order to solve these problems, zwitterionic supramolecular prodrug
micelles were fabricated for the co-delivery of photosensitizer chlorin e6 (Ce6) and nitric
oxide (NO) via LEGO-like host-guest interaction. The supramolecular nanocarriers could
not only deplete intracellular GSH, but also relieve hypoxia at tumor sites through NO
mediated blood vessel relaxation. Furthermore, reactive nitrogen species (RNS) with
enhanced biocidal activity could be produced by the reaction between NO and reactive
oxygen species (ROS), generated from α-cyclodextrin (α-CD) conjugated S-nitrosothiol and
light-activated chlorin e6 (Ce6) respectively. Due to multiple combined effects between NO
and PDT, the NO acts as the loaded gunpowder inside a ‘grenade’, ‘explosively’ amplifying
the therapeutic effects that the light responsive ‘fuse’ Ce6 could exert. The present work may
well serve as an inspiration for future creative approaches of photodynamic cancer therapy [2].
Figure 1: Multiple synergistic effects between NO and PDT generated from the supramolecular nanocarrierss
to improve therapeutic efficacy.
References
[1] – M. Ethirajan, Y. Chen, P. Joshi and R. K. Pandey, Chem. Soc. Rev. 40, 340 (2011)
[2] – Y. Deng, F. Jia, S. Chen, Z. Shen, Q. Jin, G. Fu and J. Ji. Biomaterials 187, 55 (2018)
ICBZM 2019 - Poster – P12
76
Photoinduced Amphiphilic Zwitterionic Carboxybetaine Polymer Coatings
with Marine Antifouling Properties
F. Koschitzki1, A. Rosenhahn1
Affiliation: 1Analytical Chemistry – Biointerfaces, Ruhr University Bochum, [email protected],
Due to ecological and economic consequences, the prevention of undesirable settlement of
biomass on surfaces in the marine environment is of key interest. Thus, research on effective
surface-modification and application of antifouling coatings is demanded. Zwitterion
containing hydrogels with stable hydration have shown promising results for ultra-low fouling
materials. The spectrum of application ranges from protein and plasma resistance [1], studies
of bacterial adhesion [2], biomedical purposes [3] to settlement experiments with marine
biofoulers. [4] Although understanding the influence of anionic and cationic groups, charge
distribution and charge neutrality can be discussed using self-assembled monolayers [5]
(SAM), zwitterionic moieties must eventually be applied in the form of polymer coatings for
technical purposes. To combine mechanical and antifouling properties of several materials,
amphiphilic polymers are increasingly being explored. [6] To demonstrate the advantage of
random copolymers over homopolymers regarding antifouling performance [7], polymer
coatings with varying hydrophilicity were prepared. Therefore, a carboxybetaine methacrylate
was incorporated into a hydrophobic matrix via «grafting to» photoinduced radical
polymerisation. Monomer solutions were applied on glass substrates, functionalized by 3-
trimethoxysilyl propyl methacrylate. The samples were characterized by atomic force
microscopy (AFM), contact-angle measurements, infrared spectroscopy (IR) and scanning
electron microscope (SEM). For further investigations concerning the antifouling properties,
microfluidic experiments with the diatom genus Navicula perminuta were carried out. The
results display severe enhancement of fouling prevention at small zwitterionic content of only
(5 wt%).
References
[1] – W. Yang, H. Xue, W. Li, J. Zhang and S. Jiang, Langmuir 25, 11911-11916 (2009).
[2] – G. Cheng, G. Z. Li, H. Xue, S. F. Chen, J. D. Bryers and S. Y. Jiang, Biomaterials 30, 5234-5240 (2009).
[3] – L. Zhang, Z. Cao, T. Bai, L. Carr, J.-R. Ella-Menye, C. Irvin, B. D. Ratner and S. Jiang, Nat. Biotech. 31,
553-556 (2013).
[4] – S. Y. Jiang and Z. Cao, Adv. Mater. 21, 1-13 (2009).
[5] – S. Bauer, J.A. Finlay, I. Thome, K. Nolte, S. C. Franco, E. Ralston, G. E. Swain, A. S. Clare, and A.
Rosenhahn, Langmuir 32, 5663 (2016).
[6] – C. Ventura, A. J. Guerin, O. El-Zubir, A. J. Ruiz-Sanchez, L. I. Dixon, K. J. Reynolds, M. L. Dale, J.
Ferguson, A. Houlton, B. R. Horrocks, A. S. Clare and D. A. Fulton, Biofouling 33, 892-903 (2017).
[7] – A. L. Hook, C.-Y. Chang, J. Yang, J. Luckett, A. Cockayne, S. Atkinson, Y. Mei, R. Bayston, D. J. Irvine,
and R. Langer et al., Nat. Biotechnol. 30, 868 (2012).
ICBZM 2019 - Poster – P13
77
Diblock antifouling-bioactive polymer brushes for the next generation of
biosensors
Andriy R. Kuzmyn1,2, Ai T. Nguyen1, Han Zuilhof2.3 and Jacob Baggerman 1,2
1Aquamarijn Micro Filtration BV, IJsselkade 7, NL-7201 HB Zutphen, The Netherlands; 2Laboratory of
Organic Chemistry, Wageningen University, Stippeneng 4, 6708 WE, Wageningen, The Netherlands; 3School of Pharmaceutical Science and Technology, Tianjin Univeristy, Tianjin, P.R. China.
Non-specific interactions between biological media and artificial biointerfaces typically
result in reduced performance of e.g. biomaterials, biosensors, and drug-delivery systems.
The best performing coatings that can eliminate those interaction are polymer brushes
synthetized by living radical polymerization (LRP), based on hydrogels of
acrylates/acrylamides with oligo(ethylene glycol), hydroxy alkyl and/or zwitterionic
functionalities. Progress in robust LRP techniques enables the design of advanced
hierarchical brush architectures. Here, we present a method to create hierarchical antifouling
brush architectures for advanced biosensors.
Figure 1: (a) Optical image of poly(HPMA) surface patterned with poly(CBMA) (b) AFM profile of
patterned surfaces.
Hierarchical bioactive surfaces were created with visible light-induced surface-initiated LRP
with tris[2-phenylpyridinato-C2,N]iridium(III) as a photocatalyst. Micro-patterned, block
copolymer structures (Fig. 1) could be grown using antifouling block copolymers consisting
of N (2 hydroxypropyl)methacrylamide (HPMA, 1st block) and carboxybetaine
methacrylate (CBMA, 2nd block). The chemical structure of the synthetized brushes was
confirmed by XPS and IRRAS measurements. The living nature of the polymerization was
shown via the linear increase in layer thickness over time (as measured by AFM), and
possibility of reinitiation of the polymerization for creating a patterned second block of
copolymer. Furthermore, the 2nd block could be biofunctionalized with fluorescent bovine
serum albumin. The antifouling properties of synthetized brushes were investigated by
exposing them to fluorescently labeled protein solutions. We anticipate utilization of this
technique in biosensors.
This project has received funding from the European Union’s Horizon 2020 research and
innovation programme under the Marie Sklodowska-Curie grant agreement No 720325’
ICBZM 2019 - Poster – P14
78
“Schizophrenic” Micellar Self-organization
of Twofold Switchable Zwitterionic Block Copolymers
A. Laschewsky1,2, V. Hildebrand1, L. Kreuzer,3 P. Müller-Buschbaum3,
Noverra M. Nizardo,1 C. M. Papadakis3, N. Vishnevetskaya3
1 University of Potsdam, Inst. Chemistry, 14476 Potsdam-Golm, Germany; [email protected]
2 Fraunhofer Institute of Applied Polymer Research IAP, 14476 Potsdam-Golm, Germany 3 Technische Universität Munich/ Physics Department, 85748 Garching, Germany
We have designed dual thermoresponsive, doubly switchable diblock copolymers. Featuring
lower and upper critical solution temperature behavior (LCST, UCST), their thermo-
responsive self-assembly may serve for nanocarriers in advanced delivery purposes. We
present diblock copolymers having a non-ionic LCST-block (of PNIPAM or PNIPMAM)
and a zwitterionic, biocompatible UCST block (of a polysulfobetaine) (Figure 1), which is
additionally sensitive to ionic strength [1]. In aqueous solution, these diblock copolymers
are expected to form core-shell micelles with the UCST block building the core and the
LCST block forming the shell (IIa), or vice versa (IIb), i.e. so-called schizophrenic behavior
[2]. Depending on the values of the respective cloud points, the switching between these
states may proceed via a molecularly dissolved state (I) or via precipitation (III). Using
turbidimetry and small-angle neutron scattering, we investigate the phase behavior and the
micellar structures in dependence on the chemical structure of the two blocks and on the
block copolymer composition [3-6].
Figure 1: block copolymers studied (R = H, CH3), and their schematic aqueous phase diagram.
References
[1] M. Arotçaréna, B. Heise, S. Ishaya and A. Laschewsky, J. Am. Chem. Soc., 2002, 124, 3787-3793.
[2] V. Bütün, S. Liu, J. V. M. Weaver, X. Bories-Azeau, Y. Cai and S. P. Armes, React. Funct. Polym., 2006,
66, 157-165
[3] V. Hildebrand, M. Heydenreich, A. Laschewsky, H. M. Möller, P. Müller-Buschbaum, C. M. Papadakis,
D. Schanzenbach and E. Wischerhoff, Polymer, 2017, 122, 347-357
[4] N. S. Vishnevetskaya, V. Hildebrand, B.-J. Niebuur, I. Grillo, S. K. Filippov, A. Laschewsky, P. Müller-
Buschbaum and C. M. Papadakis, Macromolecules, 2017, 50, 3985-3999.
[5] N. S. Vishnevetskaya, V. Hildebrand, M. A. Dyakonova, B.-J. Niebuur, K. Kyriakos, K. N. Raftopoulos,
Z. Di, P. Müller-Buschbaum, A. Laschewsky and C. M. Papadakis, Macromolecules, 2018, 51, 2604-2614.
[6] N. S. Vishnevetskaya, V. Hildebrand, N. M. Nizardo, C.-H. Ko, Z. Di, A. Radulescu, L. C. Barnsley, P.
Müller-Buschbaum, A. Laschewsky and C. M. Papadakis, Langmuir, 2019, 35, submitted.
ICBZM 2019 - Poster – P15
79
Long-Term Stability of Zwitterionic Polymers against Hydrolysis
A. Martínez Guajardo1, E. Schönemann1, A. Laschewsky1,2 , A. Rosenhahn3
1 University of Potsdam, Inst. Chemistry, 14476 Potsdam-Golm, Germany; [email protected]
2 Fraunhofer Institute of Applied Polymer Research IAP, 14476 Potsdam-Golm, Germany 3 Ruhr-Universität Bochum, Institute of Analytical Chemistry, 44801 Bochum, Germany
Polymers that are applied in aqueous environments, e.g., for coatings with anti-fouling
properties, must resist hydrolysis. Yet, although most polymers employed contain a priori
hydrolytically labile groups, long-term exposure studies have been virtually missing.
Therefore, we prepared and evaluated a large set of polymers that have been proposed for
use in low-fouling coatings [1,2], comprising - within others - the well-established non-ionic
PEG-analogue poly(oligoethylene glycol methylether methacrylate) (P-OEGMA), and
zwitterionic poly(sulfobetaine)s [3], such as poly(3-(N-2-methacryloylethyl-N,N-dimethyl)
ammoniopropanesulfonate) (“sulfobetaine methacrylate”, P-SPE), and poly(3-(N-3-meth-
acrylamidopropyl-N,N-dimethyl)ammoniopropanesulfonate) (“sulfobetaine methacryl-
amide”, P-SPP). We further included in our study selected polysulfabetaines, a new family
of polyzwitterions that were suggested as particularly hydrolysis-stable, but have been rarely
studied up to now [4,5].
Figure 1: Selection of the polymers studied.
Hydrolysis resistance upon extended storage in aqueous solution at ambient temperature is
followed by 1H NMR over the pH range 0-14, also deducing possible degradation
mechanisms from decomposition products. Whereas monomers suffer slow (in PBS) to very
fast hydrolysis (in 1 M NaOH), polymers proved to be much more stable. No degradation
not only of the styrenic but also of the carboxyl ester or amide is observed after 1 year in
PBS, 1 M HCl, or sodium carbonate buffer of pH 10. This demonstrates the basic suitability
of such polymers for long-term uses in water. Remarkably, poly(sulfobetaine
methacrylamide) shows no signs of degradation over the 1 year period even in 1 M NaOH,
while polystyrene derivatives do. Regarding the zwitterionic moieties, the sulfobetaine
moiety remains completely inert. In contrast, the hemisulfate group of the polysulfabetaines
is partially labile, the stability depending sensitively on the detailed betaine structure.
Consequences for the design of "inert" polymers are discussed, as well as the particular
stability of the various carbonyl groups attached to the polymer backbone.
References
[1] E. Schönemann, A. Laschewsky and A. Rosenhahn, Polymers, 2018, 10, [639] 631-623.
[2] A. Laschewsky and A. Rosenhahn, Langmuir, 2019, 35, 1056-1071.
[3] A. Laschewsky, Polymers, 2014, 6, 1544-1601.
[4] V. A. Vasantha, S. Jana, A. Parthiban and J. G. Vancso, RSC Adv., 2014, 4, 22596-22600.
[5] Q. Shao and S. Jiang, Adv. Mater., 2015, 27, 15-26.
ICBZM 2019 - Poster – P16
80
Title: Alternating Charge Peptides Confers Stability to Proteins
Authors: Patrick J. McMullen1, Erik Liu1, Shaoyi Jiang1
Affiliations: 1University of Washington Department of Chemical Engineering, [email protected]
Protein drug stability is a major issue for its production and storage as well as for its in vivo
efficacy. Polymer conjugation is the most common strategy to ameliorate these issues.
Recently, conjugation to the zwitterionic polymer polycarboxybetaine (PCB) has demonstrated
promise in improving the stability and efficacy of protein drugs. In addition, PCB even
performs better than polyethylene glycol (PEG), the current gold standard, due to its superior
hydration compared to PEG [1], [2].
To produce a uniform and biodegradable polymer, we look to nature which is able to
consistently produce polymerized amino acids that are a uniform molecular weight and
enzymatically biodegradable. Using genetic engineering, we design a DNA sequence encoding
a zwitterionic peptide composed of amino acids of alternating charge. We select glutamic acid
(E) and lysine (K) as the negatively and positively charged residues for their superior non-
fouling performance compared to other charged amino acids [3]. Then, this DNA construct is
delivered to E. coli, which synthesizes the EK peptide using its own protein production
machinery. Furthermore, the zwitterionic EK DNA sequence is inserted adjacent to the
therapeutic protein of interest so that the protein drug and EK peptide are linked by a peptide
bond, thus abrogating the need for chemical conjugation.
Figure 1: Strategy used to produce EK fused to protein drugs with genetic engineering in E. coli. [4]
To assess the stabilizing effects of EK peptides, we expressed and purified EK fused to β-
lactamase, organophosphate hydrolase, and other proteins from E. coli and subsequently tested
their activity in response to environmental stressors that inactivate these proteins by
denaturation. EK peptides conferred protection against high salt concentrations and thermal
stress indicating that EK preserves activity of proteins similar to PCB and other zwitterionic
polymers [4].
References: [1] A. J. Keefe and S. Jiang, Nat. Chem. 4, 1, 2012.
[2] P. Zhang et al., Proc. Natl. Acad. Sci. 112, 39, 2015.
[3] A. D. White, A. K. Nowinski, W. Huang, A. J. Keefe, F. Sun, and S. Jiang, Chem. Sci. 3, 12, 2012.
[4] E. J. Liu et al., Biomacromolecules 16, 10, 2015.
ICBZM 2019 - Poster – P17
81
Swelling of pseudo-zwitterionic co-polymer hydrogels
Bela Nagy1, Mario Campana2, Thomas Ederth1
1 IFM, Linköping University, SE-581 83 Linköping, Sweden
2 Rutherford Appleton Laboratory, Didcot, OX11 0QX, United Kingdom
Author’s email: [email protected]
The accumulation of undesired biomaterials onto surfaces is a problem in both industry and
healthcare. [1] Currently, there are three main paths in marine anti-fouling, that is, measures
countering fouling. [2] First, there are biocide-releasing and foulant-degrading coatings,
which are being phased out due to environmental concerns. Second, there are fouling-release
coatings, which counter fouling by releasing foulants through a self-cleaning effect. The
third strategy involves hydrophilic materials that bind water strongly and make it harder for
the foulant to attach, since the water must be removed first. The latter strategy aligns well
with the requirements for biomedical, as well as several food and pharmaceutical
applications, were the first two approaches are not applicable. Thus, exploration of this
strategy is of broad and general interest in antifouling research.
Zwitterionic polymers are prime candidates for anti-fouling coatings since they interact with
water strongly through polar interactions, but their zero net charge means they do not
participate in Coulomb interactions. To bypass the difficulties arising from the synthesis of
zwitterionic monomers, co-polymers of oppositely charged monomers, also referred to as
pseudo-zwitterionic co-polymers, are explored and used as model systems.
Studies performed on cationic poly(2-aminoethyl methacrylate) and anionic poly(2-
carboxyethyl acrylate) grafted sequentially with the top layer as a thickness gradient, show
that optimal fouling resistance exist in a well defined region along the gradient, and that the
position of the optimum depends on the pH [3]. This is explained by a model that correlates
the optimum to a highly condensed, charge-balanced region of the gradient.
In this work we use neutron reflectometry and spectroscopic ellipsometry to investigate the
mixing and swelling of poly(2-methylacrylic acid-co-2-aminoethyl methacrylate) copolymer
hydrogels. Utilizing the difference in neutron contrast for deuterium and hydrogen, we use
a deuterated methacrylic acid monomer to determine the depth profile of the concentration
of the deuterated monomer, in an attempt to correlate the composition to the swelling
properties.
References
[1] Callow, M. E. and Callow, J. A. Biologist, 49(1), 1-5, (2002).
[2] Banerjee, I. et al., Adv. Mater., 23, 690–718,(2011)
[3] Tai, F. I. et al., Soft matter, 10(32), 5955-5964, (2014).
ICBZM 2019 - Poster – P18
82
Synthesis and characterisation of zwitterionic siloxanes as marine
antifouling coatings
Patricia Palitza1, John Finlay2, Robin Wanka1, Anthony S. Clare2, Axel Rosenhahn1
1Analytical Chemistry - Biointerfaces, Ruhr-University Bochum, Bochum, Germany 2School of Marine Science and Technology, Newcastle University, Newcastle, United Kingdom,
The ideal marine protective coating is a universal, green, environmentally neutral and non-toxic
coating comprising antifouling (AF) as well as fouling release (FR) properties1. Therefore,
established FR coatings based on polydimethylsiloxane (PDMS) were combined with
zwitterionic sulfopropylbetaines (SPB). The amphiphilic system merges the advantages of both
components in one single system2–4. The hydrophobic PDMS offers a low modulus and low
surface energy, while the modification with the zwitterionic SPB yields higher hydrophilicity
and therefore enhances the resistant properties of the silicone coating. PDMS films
incorporating the SPB zwitterion were prepared and characterised by contact angle goniometry
and AFM. AF performance was tested in a laminar flow against N. perminuta using a
microfluidic setup5. The results suggest that the incorporation of the zwitterionic SPB into
PDMS based films enhances the AF properties significantly. Furthermore, a major difference
in AF potential between linear and branched zwitterionic subunits has been observed.
References:
1. Magin CM, Cooper SP, Brennan AB. Non-toxic antifouling strategies. Mater Today.
2010;13(4):36-44. doi:10.1016/S1369-7021(10)70058-4.
2. Hibbs MR, Hernandez-Sanchez BA, Daniels J, Stafslien SJ. Polysulfone and polyacrylate-
based zwitterionic coatings for the prevention and easy removal of marine biofouling.
Biofouling. 2015. doi:10.1080/08927014.2015.1081179.
3. Dundua A, Franzka S, Ulbricht M. Improved Antifouling Properties of Polydimethylsiloxane
Films via Formation of Polysiloxane/Polyzwitterion Interpenetrating Networks. Macromol
Rapid Commun. 2016;37(24):2030-2036. doi:10.1002/marc.201600473.
4. Shivapooja P, Yu Q, Orihuela B, et al. Modification of Silicone Elastomer Surfaces with
Zwitterionic Polymers: Short-Term Fouling Resistance and Triggered Biofouling Release. ACS
Appl Mater Interfaces. 2015. doi:10.1021/acsami.5b09199.
5. Nolte KA, Schwarze J, Beyer CD, Özcan O, Rosenhahn A. Parallelized microfluidic diatom
accumulation assay to test fouling-release coatings. Biointerphases. 2018;13(4):041007.
doi:10.1116/1.5034090.
ICBZM 2019 - Poster – P19
83
A Simultaneously Protein-repellent and Antimicrobially Active
Zwitterionic Polymer Network
S. Paschke1, E. K. Riga1, F. Marx1, K. Lienkamp1
1Institute for Microsystems Engineering and Freiburg Center for Interactive Materials and Bioinspired
Technologies, University of Freiburg, Georges-Koehler-Allee 105, 79110 Freiburg i. Br., Germany,
So far, simultaneously protein-repellent and antimicrobially active surfaces could only be
achieved by bringing together multiple components with the desired properties. [1] These
materials often leach the antimicrobial component, which may be undesirable, or suffer from
stability issues. Therefore, a single long-term stable material with the two desired properties
would be useful for many applications for example in medical sciences.
Surface-attached zwitterionic polymers are well known for their protein-repellency yet were
so far not deemed antimicrobial. We recently reported two polyzwitterions with intrinsically
antimicrobial activity (Fig. 1a & b). [1,2] Both carry carboxylate groups combined with
either primary or quaternary ammonium groups. To understand the molecular features that
cause the antimicrobial properties, our aim is to synthesise a library of structurally similar
polyzwitterions.
To that end, various zwitterionic polymers were synthesised by copolymerising a (protected)
cationic precursor-monomer with a suitable UV-crosslinker-monomer via
ring-opening metathesis polymerization (Fig. 1c & d). These were surface-immobilized,
cross-linked and the cationic precursor was hydrolysed to yield the zwitterionic surface. IR
measurement confirmed the complete conversion and the stability of the functional groups.
Figure 1: Structures of the zwitterionic polymers. They all carry carboxylate groups as anions. The cationic
groups are a) primary ammonium group, b) quarternary ammonium group in betaine structure, c) quaternary
ammonium group and d) guanidinium group. c) and d) also show the used crosslinker comonomer.
These surfaces were then tested for protein-repellency, antimicrobial activity and
cell-compatibility, and the results were correlated to the molecular structure. The data
indicates that, besides the ionic functional groups, the overall polymer hydrophilicity is
crucial to obtain the desired properties pattern.
References
[1] - Siedenbiedel, F.; Tiller, J. C. Polymers 4, 46 (2012).
[2] - Kurowska, M.; Eickenscheidt, A.; Guevara-Solarte, D.-L.; Widyaya, V. T.; Marx, F.; Al-Ahmad, A.;
Lienkamp, K. Biomacromolecules 18, 1373 (2017).
[3] - Kurowska, M.; Eickenscheidt, A.; Al-Ahmad, A.; Lienkamp, K. ACS Applied Bio Materials 1, 613
(2018).
ICBZM 2019 - Poster – P20
84
Stimuli-responsive polyzwitterionic microgels by RAFT precipitation
polymerization
Pabitra Saha,1 Michael Kather,1,2 Sovan L. Banerjee,3 Nikhil K. Singha,3 Andrij Pich1,2,*
1 DWI – Leibniz-Institute for Interactive Materials, Germany, 2 Institute of Technical and Macromolecular
Chemistry, RWTH Aachen University, Germany, 3 Rubber Technology Centre, Indian Institute of
Technology Kharagpur, India, *E-mail: [email protected]
Abstract: Microgel, a smart class of material with size between 0.1 and 100 µm has drawn
attention in a past few decades due to its response to external stimuli like temperature, pH
and ionic strength of the solution1. Among them one type of polymer becomes soluble and
the other becomes insoluble in water upon heating displaying upper critical solution
temperature (UCST) (e.g. polysulfobetaine, PSB) and lower critical solution temperature
(LCST) (e.g. poly(N-vinylcaprolactam, PVCL)) respectively. Polyzwitterions, electrically
neutral polymers are biocompatible, biodegradable and non-cytotoxic in nature and presence
of zwitterionic pendant group in the main backbone makes them stable against temperature
and pH variations and strong hydration capability in salt solution promotes them to be used
as interfacial bio-adhesion resistance material2. Majority of zwitterionic microgels have been
synthesized in mini- emulsion technique using free radical polymerization approach.3 Here,
a new route to synthesize stimuli-responsive PVCL microgels decorated with zwitterionic
PSB chains was developed by a purely water-based surfactant-free reversible addition–
fragmentation chain transfer (RAFT) precipitation polymerization. PSB macro-RAFTs
having different molecular weights were synthesized and utilized for surface-grafting with
PVCL microgels varying the macro-RAFT and N,N′-Methylenebis(acrylamide) (BIS) cross-
linker concentration. Increasing the PSB and BIS concentration in the PVCL microgels
resulted in a linear increase in the electrophoretic mobility (µe) and the volume phase
transition temperature (VPTT). However, increasing the molecular chain length of the
zwitterionic macro-RAFT resulted in shifting of VPTT towards lower temperatures.
Figure 1: Proposed microgel formation mechanism during zwitterionic macro-RAFT initiated precipitation
polymerization of VCL at 80 °C. (a) nucleation on addition of VCL and BIS to macro-RAFT (b) particle growth
followed by crosslinking (c) formation of microgel decorated with polyzwitterionic chains.
References
[1] Plamper, F. A.; Richtering, W. Functional Microgels and Microgel Systems. Acc. Chem. Res. 2017,
50 (2), 131–140.
[2] S. Kudaibergenov, W. Jaeger, A. Laschewsky, Supramolecular Polymers Polymeric Betains
Oligomers, 2006, Polymeric Betaines: Synthesis, Characterization, and Application, pp. 157–224,
Springer, Heidelberg, Berlin. [3] Schroeder, R.; Richtering, W.; Potemkin, I. I.; Pich, A. Stimuli-Responsive Zwitterionic Microgels
with Covalent and Ionic Cross-Links. Macromolecules 2018, 51, 6707−6716.
ICBZM 2019 - Poster – P21
85
Molecular Simulations of Zwitterionic Electrolytes for Lithium Ion
Batteries
Q. Shao, M. T. Nguyen
Department of Chemical and Materials Engineering, University of Kentucky Lexington KY USA
email: [email protected]
We report a simulation-based effort that aims to understand mechanisms for zwitterionic
electrolyte to conduct lithium ion. A zwitterionic motif contains both cationic and anionic
groups. Such unique molecular structure provides opportunities for energy applications. One
of the promising applications for zwitterionic materials is to serve as electrolytes for lithium
ion batteries. However, little is known about the underlying mechanisms and interactions
that govern the ability of zwitterionic materials to conduct lithium ions and their relationship
with the molecular structure of zwitterionic molecules. To shed light on this issue, we
investigate structural and dynamic properties of systems composed of five zwitterionic
molecules and five types of Li salts using molecular dynamics simulations. The five
zwitterionic molecules possess the same cationic groups (imidazolium), different anionic
groups (carboxylic, sulfonate and phosphate) and the distances between the charged groups
range from one, two to three methylene groups. The five Li salts possess different counter-
anions: BF4-, ClO4
-, bis(perfluoroethylsulfonyl) imide (BETI), trifluoromethanesulfonate
(TFO), and bis(trifluoromethylsulfonyl) imide (TFSI). The analysis of these simulation
results helps identify the key structural features of zwitterionic molecules for their ionic
conductivity and provide molecular basis for designing zwitterionic materials for energy
applications.
ICBZM 2019 - Poster – P22
86
Thermal Analysis of Bound Water Restrained by
Poly(2-methacryloyloxyethyl inverse-phosphorylcholine)
Shohei Shiomoto1, Kazuo Yamaguchi2, Hiroki Uehara3, Masaru Tanaka3
and Motoyasu Kobayashi2
1Grad. Sch. of Eng. and 2Sch. of Adv. Eng., Kogakuin Univ., 2665-1 Nakano-machi, Hachioji, Tokyo 192-
0015, Japan, 3Inst. Mater. Chem. Eng., Kyusyu Univ., 744 Motooka, Nishi-ku Fukuoka 819-0395, Japan, 2E-mail: [email protected]
Poly(2-methacryloyloxyethyl phosphorylcholine) (poly(MPC)) is a widely known as a biocompatible polyzwitterion due to low adhesive interaction with cells and proteins. Ishihara et al. and Hatakeyama et al. measured the melting temperature and the melting enthalpy of the hydrated water in poly(MPC) by differential scanning calorimetry (DSC) to investigate the hydration structures[1],[2]. In this study, we synthesized polyzwitterion containing cholinephosphate (CP) group having the reversed orientation of quaternary amine and phosphate[3] in contrast to phosphorylcholine (PC) (Figure 1), and characterized its hydration states by DSC.
The methacrylate monomer bearing CP (MCP) was synthesized by two-step reactions from 2-chloro-2-oxo-1,3,2-dioxaphospholane. Atom transfer radical polymerization of MCP gave the poly(MCP) with Mn = 52,000 and Mw/Mn = 1.5. Aqueous solution of the poly(MCP) was hermetically sealed in an DSC pan. The sample was cooled from 50 C to −100 C at the rate of 5 C/min, held at −100 C for 10 min, and then heated to 50 C at the rate of 5 C/min.
When water content Wc (= the mass of water/the mass of dry polymer) of the hydrated poly(MCP) was 0.73 g g−1, a heat capacity change due to glass transition was observed at Tg = −86 C during the heating process, as shown in Figure 2. The cold crystallization was observed as a exothermic peak at Tcc = −44 C, indicating that freezing-bond water (intermediate water) was contained in the hydrated poly(MCP). The endothermic peak was observed at Tm = −14 C due to the melting of the freezing-bond water. According to the enthalpy changes of the cold crystallization and melting, the amounts of non-freezing water and freezing-bound water calculated to be 0.56 g g−1 and 0.17 g g−1 (the mass per the mass of dry polymer), respectively. Interestingly, it is revealed that the hydrated poly(MCP) contains the freezing-bound water with similar behaviour as poly(MPC). References [1] K. Ishihara; H. Nomura, T. Mihara, K. Kurita, Y. Iwasaki, N. Nakabayashi, J. Biomed. Mater. Res. 39, 323 (1998). [2] T. Hatakeyama, M. Tanaka, H. Hatakeyama, Acta Biomater., 6, 2077 (2010). [3] S. Mihara, K. Yamaguchi, M. Kobayashi, Langmuir, 35, 1172 (2019).
Figure 1. Chemical
structures of
poly(MPC) and
poly(MCP).
-100 -80 -60 -40 -20 0 20
Temperature, C
Endoth
erm
ic
Tg
Tcc
Tm
Figure 2. DSC
heating curve of
hydrated
poly(MCP) at
water content Wc =
0.73 g g−1. Heating
rate = 5 C/min.
CH2 C
CH3
CO2(CH2)2 O P (CH2)2
O
O
N CH3
CH3
CH3
n
Poly(MPC)
CH2 C
CH3
CO2(CH2)2 N
CH3
(CH2)2O
CH3
P
O
O
O
n
CH
CH3
CH3
Poly(MCP)
ICBZM 2019 - Poster – P23
87
Efficient Initiator for Grafting Polymer Brushes Based on
Carboxybetaine (Meth)acrylamide
Frantisek Surman1, 2, Andres de los Santos Pereira1, Ognen Pop-Georgievski1
1Institute of Macromolecular Chemistry, Czech Academy of Sciences, Heyrovsky sq. 2, 162 06 Prague,
Czech Republic, [email protected] 2Tissue Engineering + Biofabrication Laboratory, Institute for Biomechanics, ETH Zürich,
Otto-Stern-Weg 7, 8093 Zürich, Switzerland, [email protected]
Polymer brushes based on poly(carboxybetaines), poly(CB), have been proven to be the
most efficient in preventing nonspecific protein adsorption from complex and medically
relevant fluids such as undiluted human blood plasma and serum. Poly(CB) type brushes are
extensively prepared by surface-initiated copper-mediated radical polymerizations (SI-
CRP), such as ATRP, SET-LRP, photo-induced, of respective CB (meth)acrylates or
(meth)acrylamides.[1] Importantly, (meth)acrylamide type brushes possess better
nonbiofouling properties that their (meth)acrylate counterparts.[2] Unfortunately, SI-CRP of
(meth)acrylamide monomers is associated with loss of bromine end groups, which
contributes to poor control of the polymerization. While the most commonly applied
initiators for SI-CRP are those containing 2-bromoisobutyrate groups (BiBB), recently, it
was found that appropriate combination of initiator and ligand can satisfactorily improve the
solution polymerization of methacrylamide monomers.[3] Inspired by these results, we
introduce a novel initiator bearing 2-chloropropionate group (MCP) for SI-ATRP of
carboxybetaine (meth)acrylamides (CBAA) and (CBMAA) onto gold-coated substrates
(Figure 1). Herein, we report the grafting of thick poly(CB) brushes from the self-assembled
monolayer of MCP initiator by SI-ATRP. The evolution of polymer thickness was measured
by ellipsometry and increased linearly. The control of the process was established by
carrying out the reinitiation polymerization of the same monomer. The resistance of these
brushes to fouling from blood plasma was demonstrated by surface plasmon resonance.
Therefore, we anticipate that the new initiator will allow access to a wide variety of surface-
tethered hierarchical CB polymer architectures to achieve desired functions, e.g., in the field
of label-free affinity biosensors.
Figure 1: Schematic representation of initiator modified gold substrate, the structure of monomers, and data
of time evolution of polymer brush thickness measured by ellipsometry.
References
[1] - Zoppe, J. O.; Ataman, N. C.; Mocny, P.; Wang, J.; Moraes, J.; Klok, H. A., Chem Rev 2017, 117 (3),
1105-1318.
[2] - Rodriguez-Emmenegger, C.; Brynda, E.; Riedel, T.; Houska, M.; Subr, V.; Alles, A. B.; Hasan, E.;
Gautrot, J. E.; Huck, W. T., Macromolecular rapid communications 2011, 32 (13), 952-7.
[3] - Raus, V.; Kostka, L., Polym Chem-Uk 2019, 10 (5), 564-568.
ICBZM 2019 - Poster – P24
88
Zwitterionic-based Platforms for Biopharmaceutics
C. Tsao1, P. Zhang, B. Li, S. Jiang
1Department of Chemical Engineering, University of Washington, Seattle, [email protected]
Biopharmaceutics offer significant advantages over small molecule therapeutics owing to
their specific bioactivity and high potency. More than two hundred biotech products were
marketed during the last three decades, with hundreds of new products currently in the
pipeline. Despite the huge success achieved by their uniqueness, these structurally complex
biomacromolecules often face great challenges regarding their instability, inadequate
circulation half-life, and immunogenicity. Short half-life limits their therapeutic efficacy and
requires a frequent administration regimen; Immune responses against many biological
drugs not only result in accelerated blood clearance during chronic use but also potentially
endanger the patients with undesired effects including anaphylaxis and infusion reactions.
The most common strategy thus far to overcome these shortcomings is the conjugation of
polyethylene glycol (PEG) to these biomacromolecules, a process known as PEGylation.
PEG was considered as a biologically inert material with no immunogenicity and
antigenicity in early studies. However, animal studies in the ensuing decades have started to
discover anti-PEG antibodies after immunization of PEGylated proteins. Until recently, with
more PEGylated products entering the clinic, several reports correlated the generation of
anti-PEG antibodies with loss of therapeutic efficacy and there has been an increase of
reported adverse effects after repeated administrations. In addition to PEGylated proteins,
PEG-modified nanoparticles, e.g. liposomes and micelles, have also been reported to
stimulate anti-PEG antibodies generation in different animal models. Altogether, these
findings raise alarming concerns regarding the safety and efficacy of PEGylated drugs. An
alternative to this ‘gold standard’ strategy is urgently desired to supplement or replace
PEGylation.
Our group has dedicated our studies in developing next-generation polymeric-based
platforms for improving the therapeutic efficacies of numerous biopharmaceutics.
Poly(carboxybetaine) (PCB) is a zwitterionic, ultra-hydrophilic polymer designed based on
a natural osmolyte, glycine betaine. PCB’s “water-loving” nature makes it highly compatible
in biological environment. Various PCB-based drug delivery systems have demonstrated to
enhance biopharmaceutics’ stabilities, increase circulation half-lives, and provide effective
protection against the immune system of the host. This presentation will focus on PCB-based
platforms for the delivery of proteins (e.g., uricase and organophosphorus hydrolase) using
nanogel and chemical conjugation method) for their therapeutic and protective applications.
ICBZM 2019 - Poster – P25
89
Fabrication and characterization of biomimetic texture for antifouling
applications
E. Védie1, V. Senez2, H. Brisset1, J.F.Briand1, C. Bressy1
Affiliation: 1MAPIEM EA 4323, Université de Toulon, La Garde, France, 2IEMN, UMR CNRS 8520, Cité
Scientifique, Villeneuve d’ascq, France with [email protected]
Every surface submersed in seawater is subjected to colonization by thousands of micro-
organisms. This phenomenon, named biofouling, inflicts deteriorations of all immersed
structures and leads to high maintenance costs. [1] In nowadays ecological needs, developing
non-toxic marine antifouling coatings which cause no harm to the environment and the
marine species is currently an important matter. Microtopographical surfaces have been
studied as a non-toxic strategy limiting the percentage of adhesion of marine species based
on the attachment point theory. [2] The wetting properties of the microtopographical surface
and its elastic modulus are two main parameters affecting the adhesion of the fouling and its
release. The effect of each parameter has been previously studied. [3,4] But no investigation
tried to study the combined effects of those two parameters on fouling.
We present here the development of a mold with a biomimetic textured surface known as
Sharklet™, inspired by the shark skin, using photolithography technique. From this mold,
different Sharklet™-textured surfaces have been produced using materials with various
wetting and mechanical properties. The surfaces obtained have been characterized by SEM
and contact angle measurements. Results acquired will be presented and discussed.
Figure 1: SEM images of the Sharklet™ molds made of silicone thanks to photolithography and dry etching
techniques with the dimensions: 40SK20×20 (heightSKwidth×spacing in μm).
References
[1] –M. Lejars, A. Margaillan, C. Bressy, Chem. Rev., 112, 4347 (2012).
[2] –F. W. Y. Myan, J. Walker, O. Paramor, Biointerphases, 8, 30 (2013).
[3] – A. M. Brzozowska, S. Maassen, R. Goh Zhi Rong, P. I. Benke, C.-S. Lim, E. M. Marzinelli, D.
Jańczewski, S. L.-M. Teo, G. J. Vancso, ACS Appl. Mater. Interfaces, 9, 17508 (2017).
[4] J. Genzer, K. Efimenko, Biofouling, 22, 339 (2006).
ICBZM 2019 - Poster – P26
90
Multifarious Zwitterions applications: from low fouling membrane
coatings to excellent surfactants for enhanced oil recovery
E.Virga1,2, W. M. de Vos1
1University of Twente, 2Wetsus, [email protected]
Zwitterionic materials stand out in many various fields due to their versatility and peculiar
physical-chemical nature. In particular, zwitterions possess all main properties for low
fouling applications [1]: they are neutral and well hydrated.
In Produced Water (PW) treatment, where fouling constitutes the major problem when
membranes are applied [2], zwitterions are especially interesting. Zwitterions can
functionalize a membrane surface towards a low fouling tendency, but they can also be used
as surfactants for easier chemical cleaning and enhanced oil recovery.
In this work, we show how zwitterionic based materials represent a promising alternative for
the treatment of challenging waste-stream, such as PW. First, we show that our
polyzwitterion based membranes highly reduce fouling by synthetic PW, made of oil-in-
water emulsions stabilized by surfactants. Later, we investigate how zwitterionic surfactants
are ideally suited for marine or high salinity applications, such as PW treatment. Zwitterionic
surfactants showed excellent performances in enhanced oil recovery due to their hydration
layer, with almost no flux decline for ceramic and polymeric membrane at high ionic
strengths.
References
[1] – J. B. Schlenoff, Langmuir, 30, 9625-9636 (2014);
[2] – J. M. Dickhout et al., J. Colloid Interface Sci. 487, 523-534 (2017).
ICBZM 2019 - Poster – P27
91
Spectroscopic Ellipsometry of Zwitterionic and Nonionic Polymer
Coatings in Liquid Environment
I. Víšová1, M. Vrabcová1, D. Chvostová1, H. Vaisocherová-Lísalová1, A.
Dejneka1
1Institute of Physics CAS, Na Slovance 2, 182 21 Prague, Czech Republic, [email protected]
In order to address increasing public-health threats, an intensive research has been pursued
worldwide to development of surface-sensitive molecular-based bioanalytical and diagnostic
bio-chip technologies for complex real-world samples analysis. These technologies rely on
dual-functional surface coatings combining i) high resistance to nonspecific biofouling, and
ii) high biorecognition element loading capacities. Nowadays, one of the best performing
ultra-low fouling functionalizable coatings are carboxy-functional zwitterionic polymer
brushes. To optimize both critical features of dual-functional polymer brushes, it is necessary
to characterize precisely the swelling properties of the coating structure and thus to measure
both dried and wet thicknesses. Here we report on the advanced method of spectroscopic
ellipsometry of ultra-low fouling state-of-art zwitterionic and non-ionic polymer brushes in
dried and wet state. A set of optical cuvettes enabling ellipsomentric analysis of a single
coatings was designed for our ellipsometry experiments. Four types of state-of-art ultra-low
fouling polymer brushes were measured: zwitterionic poly(carboxybetaine acrylamide),
poly(CBAA); poly(carboxybetaine methacrylamide), poly(CBMAA); non-ionic poly(N-(2-
hydroxypropyl) methacrylamide), (pHPMA); and random copolymer poly(HPMA-ran-
CBMAA). The optical constants of the gold substrates were studied separately to increase
the reliability of calculations. The dielectric functions of the wet polymer brushes were
extracted using a least squares regression analysis and an unweighted error function to fit the
experimental ellipsometric spectra to an optical model consisting of semi-infinite BK7
substrate / Ti layer/ gold layer/ polymer coating layer / water. The obtained results were
compared with those obtained using SPR and AFM methods. The results demonstrate wet
spectroscopic ellipsometry as a powerful tool to characterize optical properties of thin
polymer layers in liquid environments.
Figure 1: Scheme of polymer brush coating on gold layer used for bio-chips development
Spectroscopic Ellipsometry of Polymer Brushes in Liquid Environment for
Ultra-Low Fouling Functionalizable Biosensors
Ivana Víšová1, Markéta Vrabcová1, Dagmar Chvostová1, Hana Lísalová1, Alexandr Dejneka1
1 Institute of Physics CAS, Na Slovance 1999/2, 182 21 Prague 8, Czech Republic
As a reaction to increasing public-health threats, an intensive research has been pursued worldwide to development of
surface-sensitive molecular-based bioanalytical and diagnostic bio-chip technologies for complex real-world samples
analysis. These technologies rely on dual-functional surface coatings combining i) high resistance to nonspecific
biofouling and ii) high biorecognition element loading capacities. Nowadays, one of the best performing ultra-low
fouling functionalizable coatings are carboxy-functional zwitterionic polymer brushes. To optimize both critical
features of dual-functional polymer brushes, it is necessary to characterize precisely the thickness and the swelling
properties of the coating structure. Moreover, to enhance the performance of many important potential applications
(i.e. optical biosensors) it is desired to determine optical constants of hydrated polymer layers. Here we report the
ellipsometric study of polymer brushes in air and in liquid environment providing dry as well as wet thicknesses of
brush layers. These values together with optical constants provide a precise swelling characteristics. For ellipsometric
measurements a special sample holder and a set of 60° and 70° cuvettes was designed. Four types of state-of-art ultra-
low fouling polymer brushes were measured – zwitterionic poly(carboxybetaine acrylamide), poly(CBAA),
poly(carboxybetaine methacrylamide), poly(CBMAA), non-ionic poly(N-(2-hydroxypropyl) methacrylamide),
pHPMA and random copolymer poly(HPMA-ran-CBMAA).
The obtained spectra were analyzed using a WVASE32 software package. The optical constants of the gold substrates
were studied separately to increase the reliability of calculations. The dielectric functions of the wet polymer brushes
were extracted using a least squares regression analysis and an unweighted error function to fit the experimental
ellipsometric spectra to an optical model consisting of semi-infinite BK7 substrate / Ti layer/ gold layer/ polymer
coating layer / water. The obtained results show a great advance of ellipsometry technique for ultra-low fouling
functionalizable polymer brushes research.
Gold layer
Polymer brush coating in water
Ti layer
BK7
Fig. 1 Scheme of polymer brush coating on gold layer used for bio-chips development
ICBZM 2019 - Poster – P28
92
Zwitterionic Poly(sulfobetaine methacrylate) Grafted Cellulose
Acetoacetate via Enzyme-Mediated Polymerization
Ruochun Wang1,2, Xiaofeng Sui1,2*
1Key Lab of Science & Technology of Eco-textile, Ministry of Education, College of Chemistry, Chemical
Engineering and Biotechnology, Donghua University, Shanghai 201620, People’s Republic of China 2Innovation Center for Textile Science and Technology of DHU, Donghua University, Shanghai, 201620,
People’s Republic of China
E-mail: [email protected] (Ruochun Wang), [email protected] (Xiaofeng Sui)
Here, a novel approach was developed to prepare cellulose graft poly(sulfobetaine
methacrylate) via horseradish peroxidase (HRP)-mediated polymerization. Cellulose
acetoacetate (CAA) as a macroinitiator was first gained by transesterification between tert-
butyl acetoacetate (t-BAA) and cellulose in ionic liquid. The cellulose graft
poly(sulfobetaine methacrylate) (CAA-g-PSBMA) was synthesized by using a ternary
initiate system consisted of CAA, HRP and hydrogen peroxide (H2O2). The products were
characterized by FT-IR, NMR, TG and element analysis. The results confirmed that
poly(sulfobetaine methacrylate) chains were successfully grafted onto cellulose backbones.
The HRP-mediated graft polymerization provides a mild, simple, efficient and green strategy
for synthesizing functional cellulose graft copolymers. This enzymatic strategy has the
potential to be widely employed in grafted polymer brush modifications for biomedical and
other applications.
References
[1] - Haruka Fukushima, Michinari Kohri, Takashi Kojima, Tatsuo Taniguchi, Kyoichi Saito, and Takayuki
Nakahira, Polym. Chem. 3, 1123 (2012).
[2] – Yung Chang, Wan-Ju Chang, Yu-Ju Shih, Ta-Chin Wei, and Ging-Ho Hsiue, ACS Appl. Mater.
Interfaces 3, 1228 (2011).
ICBZM 2019 - Poster – P29
93
Soft Tissue Mimicking Zwitterionic Hydrogels through Reversible
Strain-Induced Anisotropic Polar Filament Bundles to Achieve
Hyperelasticity for Healthy Implantation Jiang Wu1, Ying An1, Huacheng He1,2, Xiaokun Li1, Jian Xiao1, Jie Zheng1,2, Shengfu
Chen1,2
1 Molecular Pharmacology Research Center, School of Pharmacy, Wenzhou Medical University, Wenzhou,
Zhejiang, 325035 China. [email protected]
2 College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325027, China
Soft tissue mimicking materials requires both special mechanical property and bio-
compatibility in clinic biomedical applications.[1][2] Herein, we developed a hyperelastic
hydrogel based on super antifouling zwitterionic sulfobetaine methacrylate (SBMA) through
reduced chemical crosslinker covalent bonding replaced by dynamic reversible strain-
induced dipole pairings noncovalent association. The newly made SBMA hydrogel
demonstrates unique strain-induced nonlinear mechanical property from very soft at low
compression to stiff at high compression, as well as incompressibility (compressive stress
up to 5.78±0.79 Mpa at strain 95% without broken). Such super deformation could quickly
recovered back to initial state without any time interval caused by inter-chain lubrication at
low compression by hydration water molecules around the polymers and pairwise interlocks
through the unique zwitterionic SB dipole-dipole side chain at high compression. Further
strain-induced anisotropic polar filament bundles were observed by stretching using
polarized microscopy. Moreover, soft zwitterionic SBMA hydrogels also exhibited excellent
in vitro antifouling property to resist protein adsorption and cell adhesion, as well as in vivo
implants in mice to resist the foreign-body reaction. SBMA hydrogel existed long-term
structural stability and early to progressive host integration with no immune response,
suggesting their future potential for bio-applications. Thus, we concluded that this new
concept of SBMA hydrogel systems holds prospective potential for biocompatible
substitutions for soft tissues replacement requiring both mechanical and antifouling
properties.
Figure 1: Soft tissue mimicking zwitterionic SBMA hydrogel responds to strength from hyper-elasticity
through the interlocking of sulfobetaine groups.
References
[1] Cianchetti M, Laschi C, Menciassi A, et al. Biomedical applications of soft robotics[J]. Nature Reviews
Materials, 2018, 3(6): 143-153.
[2] Du, X.; Zhou, J.; Shi, J.; Xu, B., Supramolecular Hydrogelators and Hydrogels: From Soft Matter to
Molecular Biomaterials. Chemical Reviews 2015, 115 (24), 13165-13307.
ICBZM 2019 - Poster – P30
94
Vapor-Deposited Zwitterionic Coatings for Seawater Desalination
Rong Yang
Cornell University
Biofouling, the undesirable settlement and growth of organisms, occurs immediately when
a clean surface is immersed in natural seawater. It is a universal problem and the bottleneck
for seawater desalination, which reduces both the yield and the quality of desalted water.
Mitigation of fouling in a desalination operation is an on-going challenge due to the delicate
nature of desalination membranes, the vast diversity of fouling organisms, and the additional
cross-membrane transport resistance exerted by an extra layer of coating.
Recent advances in benign interface engineering methods and ultra-thin zwitterionic coating
synthesis have bridged this gap in surface modification strategies. The direct application of
ultra-thin coatings on commercial membranes is enabled by a room-temperature vapor
treatment called initiated Chemical Vapor Deposition (iCVD), leaving membrane
permeability unchanged. Diffusion-limited reaction conditions significantly improves the
surface concentration of the antifouling zwitterionic moieties, improving the fouling
resistance of modified membranes. The ultra-thin coating is cross-linked and tethered to the
desalination membrane via covalent bonds to improve the durability of coated membranes.
The durability of the antifouling coating is manifested by its resistance to oxidative reagents
commonly used for disinfection. The dual effect of the coating and disinfectants leads to an
unprecedented synergistic effect that improved long-term fouling resistance. That synergistic
effect also provides unique insight into the adhesion mechanisms of microbial foulant.
The outcomes of this report promise to lower the price of freshwater in water-scarce
countries, where desalination may serve as the only viable means to provide the water supply
necessary to sustain agriculture, support personal consumption, and promote economic
development.
Figure 1: Setup and mechanism of initiated Chemical Vapor Deposition (iCVD)
ICBZM 2019 - Poster – P31
95
Polyelectrolyte Multilayers reinforced by Zwitterionic Silanes as Marine
Protective Coatings
W.Yu, P. Palitza,Y. Wang, A.Rosenhahn
1Analytical Chemistry-Biointerfaces, Ruhr University Bochum, Bochum, Germany
Polyelectrolyte multilayers (PEMs) consisting of naturally occurring polysaccharides such
as hyaluronic acid (HA) and chitosan (CH) have been proven to be effective in deterring
protein adsorption [1] and bacteria adhesion [2] in literature studies. Our own previous work
showed that these multilayers have marine antifouling properties if chemically crosslinked
[3]. The chemical stabilization after assembly is important since the presence of ions in sea
water challenge the stability of the multilayers and frequently lead to disassembly. In this
study we tested silanes as cross-linking agents to form siloxane bonds with the
polysaccharide. The cross-linked multilayers showed good stability during 7 days immersion
in salt water. This methodology gives us the possibility to incorporate further functional
groups into the silane crosslinking unit. Besides a standard triethoxylmethylsilane (TEMS),
the zwitterionic 3-(4-(2-(triethoxysilyl)ethyl)pyridine-1-ium-1-yl)propane-1-sulfonate
(ISTES) was synthesized and used as crosslinker. Multilayers stabilized by both silanes were
constructed and tested in terms of stability and hydrophilicity during immersion in salt water.
Their surface morphology was characterized with atomic force microscopy (AFM).
Antifouling of the multilayer coatings was evaluated against the species Navicula perminuta
in a microfluidic setup. The results showed that the zwitterionic silane crosslinkers enhanced
the antifouling performance of the polyelectrolyte multilayers. The work on the
polyelectrolyte multilayer model systems reveals the unique properties of HA, CH and
zwitterionic crosslinkers and suggests their use in future ultra low-fouling polymer
formulations.
References
[1] – Bongaerts, J.H.H.; Cooper-White, J.J.; Stokes, J.R. Biomacromolecules 2009, 10, 1287-1294
[2] – Richert, L.; Lavalle, P.; Payan, E.; Shu, X.Z.; Prestwich, G.D.; Stoltz, J.F.; Schaaf, P.; Voegel, J.-C.;
Picaart, C. Langmuir 2004, 20, 448-458
[3] – Yu, W.; Koc, J.; Finlay.J.A.; Clarke, J.; Clare, A.S.; Rosenhahn,A. submitted manuscript
ICBZM 2019 - Poster – P32
96
Tailoring Zwitterionic, Antifouling Polymer Brushes
L.W. Teunissen1 , M.M.J. Smulders1 , H. Zuilhof1,2
Laboratory of Organic Chemistry, Wageningen University, The Netherlands; e-mail: [email protected]
1Laboratory of Organic Chemistry, Wageningen University, The Netherlands
2School of Pharmaceutical Science and Technology, Tianjin University, Nankai District, Tianjin, P. R. China
Introduction
Surface fouling is a significant problem in various applications, such as membranes,
biomedical devices and marine structures. Antifouling coatings prevent such undesired
deposition and have been studied extensively in the past years. Thin films of polymers
covalently linked to a surface, universally known as polymer brushes (Figure 1), can be
employed to induce antifouling properties in materials.[1]
During the past two decades, zwitterionic polymer brushes have been studied extensively and
have been found to possess excellent antifouling properties.[2] Specifically, polymer brushes
synthesized from carboxybetaine and sulfobetaine monomers (Figure 2) have proven to be
highly effective against different fouling material and organisms.[3]
Project Aim
In this project, the potential of antifouling zwitterionic polymer brushes is further explored.
Zwitterionic brushes are synthesized using surface-initiated atom transfer radical
polymerization (SI-ATRP) on a diverse set of surfaces, varying parameters including grafting
density, brush thickness and type of zwitterionic monomer. The synthesized polymer brushes
are analyzed thoroughly using XPS, AFM, ellipsometry and contact angle measurements.
Additionally, they are screened for potential responsiveness and self-healing ability.
References
1. J. O. Zoppe, N. C. Ataman, P. Mocny, J. Wang, J. Moraes, and H. A. Klok, Chem. Rev. 117, 1105 (2017).
2. Y. Higaki, M. Kobayashi, D. Murakami, and A. Takahara, Polym. J. 48, 325 (2016).
3. E. Van Andel, I. De Bus, E. J. Tijhaar, M. M. J. Smulders, H. F. J. Savelkoul, and H. Zuilhof, ACS Appl.
Mater. Interfaces 9, 38211 (2017).
Figure 1: Sulfobetaine polymer brush as an antifouling coating.
Figure 2: Monomers used in the synthesis of antifouling zwitterionic polymer brushes: sulfobetaine
methacrylate and carboxybetaine methacrylate.
ICBZM 2019 - Poster – P33
97
Dynamic Microporous Coating for On-demand Encapsulation of
Functional Agents
Ke-Feng Ren, Xia-Chao Chen, Wei-Pin Huang, Jian Ji MOE Key Laboratory of Macromolecule Synthesis and Functionalization, Department of Polymer Science
and Engineering, Zhejiang University, Hangzhou, P.R. China, [email protected]
The medical coating containing functional agents shows huge promise not only to improve
medical device longevity, but also provide improved and new therapeutic function.
However, through traditional coating methods, the drugs or biomacromolecules have mostly
been pre-immobilized within the coating with fixed species and quantities, providing
physicians solely an “one-size-fits-all-approach”. In addition, the traditional coating
methods are not suitable for encapsulating biomacromolecules since the organic solvents,
industrial sterilization, and storage would significantly destroy their bioactivities.
Here, we present a dynamic spongy coating for encapsulating diversified molecules and to
realize the “load-and-play” coating strategy. Polyelectrolytes [1-2] and amphiphilic
copolymer [3] were successfully used to prepare this dynamic spongy coating. We show that
the spongy microporous structure facilitates simple and fast loading of any kind of molecules
(e.g. small molecular drugs and biomacromolecules) into the coating because of the
mechanism of capillary force. The loading densities of molecules can be precisely controlled.
More importantly, the microporous structure can “self-heal” back to its original thin solid
structure, by which the loaded molecules were immobilized. Our coating strategy present a
“precision medical coating” that can aid physicians to decide a specific coating with
controlled species and quantities of active agents during the treatment.
Figure 1: Schematic illustration the comparison between our “load-and-play” strategy with conventional
coating strategy.
References
[1] – XC.Chen, KF.Ren, J.Ji, et al., Adv. Funct. Mater. 25, 7470 (2015).
[2] – XC.Chen, KF.Ren, J.Ji, et al., Small 15(9), 1804867 (2019).
[3] – W.Jing, KF.Ren, J.Ji, et al., Biomaterials 192, 15 (2019).
ICBZM 2019 - Poster – P34
98
Design, Synthesis and Characterization of
Fully Zwitterionic, Functionalized Dendrimers
E. Roeven,1,2 L. Scheres,2 M.M.J. Smulders,1 H. Zuilhof 1
1 Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6708 WE Wageningen, The
Netherlands.
2 Surfix BV, Bronland 12 B-1, 6708 WH Wageningen, The Netherlands.
Dendrimers are interesting candidates for various applications due to the high level of control
over their architecture, the presence of internal cavities and the possibility for multivalent
interactions have made dendrimers interesting candidates for various applications [1]. More
specifically, zwitterionic dendrimers modified with an equal number of oppositely charged
groups have found use in in vivo biomedical applications. However, the design and control
over the synthesis of these dendrimers remains challenging, in particular with respect to
achieving full modification of the dendrimer.
In this work we show the design and subsequent synthesis of dendrimers that are highly
charged whilst having zero net charge, i.e. zwitterionic dendrimers that are potential
candidates for biomedical applications [2]. First we designed and fully optimized the
synthesis of charge-neutral carboxybetaine and sulfobetaine zwitterionic dendrimers.
Following their synthesis, the various zwitterionic dendrimers were extensively
characterized. In this study we also report for the first time the use of X-ray photoelectron
spectroscopy (XPS) as an easy-to-use and quantitative tool for the compositional analysis of
this type of macromolecules that can complement e.g. NMR and GPC. Finally, we designed
and synthesized zwitterionic dendrimers that contain a variable number of alkyne and azide
groups that allow straightforward (bio)functionalization via click chemistry.
Figure 1: Schematic representation of fully zwitterionic, functionalized zwitterionic dendrimers.
[1] – C.C. Lee, J.A. MacKay, J.M.J. Fréchet, F.C. Szoka; Nat. Biotechnol. 23, 12 (2005)
[2] – E. Roeven, L. Scheres, M.M.J. Smulders, H. Zuilhof; ACS Omega. 4, 2 (2019)
Author Index
99
A Ahmad, A. Al........................................ 31
Aldred, N. ............................................. 38
Ali, S. A. ............................................... 66
Al-Muallem, H. A. ................................ 66
An, Ying ............................................... 93
Appelhans, Dietmar .............................. 27
B Baggerman, Jacob ........................... 64, 77
Banerjee, Sovan L. ................................ 84
Benetti, Edmondo M............................. 24
Bernards, M.T. ................................ 49, 72
Beyer, C. D. .......................................... 68
Biehl, P. ................................................ 29
Blittersw, C. van ................................... 71
Bosman, T. ............................................ 71
Brug, B. ten ........................................... 58
C Cabanach, P. ......................................... 69
Campana, Mario ................................... 81
Cao, Zhiqiang ....................................... 50
Chen, Shengfu ...................................... 93
Chen, Shin-Ya ...................................... 60
Chen, Xia-Chao .................................... 97
Cheng, B. .............................................. 70
Chr, Chung Yuan .................................. 51
Chvostová, D. ....................................... 91
Clare, A.S. ............................................ 38
Clare, Anthony S. ................................. 82
D Dankers, P.Y.W. ................................... 71
de, S. ..................................................... 58
Dejneka, A. ..................................... 33, 91
Deng, Yongyan ..................................... 75
Dutz, S. ................................................. 29
E E. Roeven.............................................. 98
Eck, G. Ritsema van ............................. 58
Ederth, T. .............................................. 32
Ederth, Thomas ..................................... 81
Ejima, H. ............................................... 70
F Feliciano, A.J. ....................................... 71
Finlay, J.A....................................... 38, 76
Finlay, John .......................................... 82
G Giselbrecht, S........................................ 71
Gleason, K.K. ....................................... 47
Guajardo, A. Martínez .......................... 79
H Haag, S.L. ....................................... 49, 72
Hao, Lingxia ......................................... 62
He, Huacheng ....................................... 93
Heri, Satria ........................................... 65
Hildebrand, V. ...................................... 78
Hong*, Daewha .................................... 74
Houska, M. ........................................... 33
Huang, Chun-Jen .................................. 34
Huang, Kang-Ting ................................ 34
Huang, Wei-Pin .................................... 97
I Ishihara, K. ......................... 16, 51, 70, 86
Ishihara, Kazuhiko ......................... 16, 34
Ito, Ai ................................................... 65
Iwasaki, Y. ................................ 45, 46, 86
J Jain, Priyesh ......................................... 60
Jeong, Wonwoo .................................... 74
Ji, Jian ....................................... 28, 75, 97
Jiang, Lei .............................................. 56
Jiang, S. 31, 38, 42, 67, 69, 74, 76, 79, 80,
88
Jiang, Shaoyi ............................ 17, 50, 80
Jin, Qiao ............................................... 75
K Kang, E. ................................................ 36
Kang, Hyeongeun ................................. 74
Kather, Michael .................................... 84
Kawasaki, H. .................................. 45, 46
Kheirabad, Atefeh Khorsand ................ 19
Kim, T-H .............................................. 36
Kobayashi, and Motoyasu .................... 86
Koc, J. ....................................... 38, 42, 68
Koc, Julian ............................................ 68
Kreuzer, L. ............................................ 78
Kuroda, Kosuke .................................... 65
Kurowska, M. ....................................... 31
Kuzmyn, Andriy R. .............................. 77
L Laschewsky, A. 31, 38, 42, 68, 78, 79, 84
Laschewsky, Andre .............................. 68
Leonida, M.D. ...................................... 36
Li, Huan ................................................ 28
Li, Xiaokun ........................................... 93
Li, Xu ................................................... 28
Li, Yihan ............................................... 53
Author Index
100
Liedberg, B. .......................................... 32
Lienkamp, K. .................................. 31, 83
Lin, Weifeng ......................................... 53
Liu, Danqing ......................................... 22
Liu, Erik ................................................ 80
Liu, Mingjie .......................................... 35
Lühe, M. von der .................................. 29
Lunov, O. .............................................. 33
M Mariner, E. ............................................ 49
Mazumder, and M. A. J. ....................... 66
McMullen, Patrick J. ............................ 80
Mecwan, Marvin ................................... 40
Min, Wenfeng ....................................... 62
Moreno, Silvia ...................................... 27
Moroni, L. ............................................. 71
Müller-Buschbaum, P. .......................... 78
Münch, Alexander S. ............................ 37
N Nagy, B. ................................................ 32
Nagy, Bela ............................................ 81
Nguyen, Ai T. ....................................... 77
Nguyen, M. T........................................ 85
Nijkamp, J.-W....................................... 58
Ninomiya, Kazuaki ............................... 65
Nishiyama, Nobuhiro............................ 63
Nizardo, Noverra M. ............................. 78
Nolte, K.A............................................. 68
Noree, S. ............................................... 45
O Özcan, O. .............................................. 68
P Palitza, Patricia ..................................... 82
Papadakis, C. M. ................................... 78
Pereira, Andres de los Santos ............... 87
Pich, Andrij ........................................... 84
Pokholenko, O. ..................................... 20
Pop-Georgievski, Ognen ...................... 87
Q Qian, Haofeng ....................................... 53
R R, A. .................. 16, 38, 42, 68, 76, 78, 79
Ratner, Buddy ....................................... 40
Ren, Ke-Feng ........................................ 97
Roeven, E.............................................. 59
Rosenhahn, A................ 38, 42, 68, 76, 79
Rosenhahn, Axel ................................... 82
Ruiter, F.A.A. ....................................... 71
S Saha, Pabitra ......................................... 84
Sangsuwan, A. ...................................... 45
Schacher, F. H. ..................................... 29
Scheres, L. ............................................ 59
Schoenemann, E. .................................. 38
Schönemann, E. ........................ 42, 68, 79
Schönemann, Eric ................................. 68
Schwarze, J. .......................................... 68
Sharker, K. K. ....................................... 23
Shen, Y. ................................................ 61
Shen, Yi He* and ................................. 53
Shiomoto, Shohei ................................. 86
Singh, M. .............................................. 20
Singha, Nikhil K. .................................. 84
Skallberg, A. ......................................... 32
Smolková, B. ........................................ 33
Smulders, M.M.J. ........................... 59, 96
Steele, T.W.J. ....................................... 20
Sui, Xiaofeng ........................................ 92
Sun, Delin ............................................. 62
Sun, Jianke ........................................... 19
Surman, Frantisek ................................. 87
T Takahashi, Kenji ................................... 65
Takemoto, Hiroyasu ............................. 63
Tan, N. .................................................. 20
Tanaka, Masaru .................................... 86
Tao, J. ................................................... 61
Teunissen, L.W. ................................... 96
U Uehara, Hiroki ...................................... 86
Uhlmann, Petra ..................................... 37
Uvdal, K. .............................................. 32
Uzhytchak, M. ...................................... 33
V Vaisocherová-Lísalová, H. ............. 33, 91
Vancso, G. J. .................................. 58, 89
Velden, L. van der ................................ 58
Víšová, I. ........................................ 33, 91
Voit, Brigitte ......................................... 27
Vos, W. M. de ...................................... 90
Vos, Wiebe M. de ................................. 41
Vrabcová, M. .................................. 33, 91
Vries, I. de ............................................ 58
W Wang, longgang ................................... 53
Wang, Ruochun .................................... 92
Wang, Xueyi ......................................... 27
Author Index
101
Wang, Yapei ......................................... 48
Wanka, Robin ....................................... 82
Weidner, A. ........................................... 29
Wicaksono, G. ...................................... 20
Wu, Jiang .............................................. 93
Wu, Peiyi .............................................. 44
X Xiang, Ziyin .......................................... 53
Xiao, Jian .............................................. 93
Xie, Y.................................................... 61
Xu, Liangbo .......................................... 53
Xu, Nan ................................................. 53
Y Yaagoob, I. Y........................................ 66
Yamaguchi, Kazuo ............................... 86
Yandi, W. ............................................. 32
Yang, Rong ........................................... 94
Yu, Shukun Zhong and Qiuming ......... 60
Yuan, Jiayin .......................................... 19
Yusa, S. ................................................ 23
Z Zhang, Weiyi ........................................ 19
Zhao, Qiang .......................................... 19
Zheng, Erjin .......................................... 60
Zheng, Jie ....................................... 52, 93
Zuilhof, H. .......................... 21, 55, 59, 96
Zuilhof, Han ......................................... 77
4th International Conference on Bioinspired and Zwitterionic Materials
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