PowerPoint 簡報 - ac.nctu.edu.tw · “Nano-atoms”refer to shape-persistent molecular nanoparticles (MNPs) such as fullerenes, polyhedral oligomeric silsesquioxanes, polyoxometalates,

2018Program Book

Multi-Length-Scale Engineering

of Advanced Materials 2018

June 17-19, 2018,

Hsinchu

Multi-Length-Scale Engineering of

Advanced Materials 2018

Government Sponsorship

Program of the Workshop for

“Multi-Length-Scale Engineering of

Advanced Materials”

June 17-19, 2018, Hsinchu

Funding source: Ministry of Education,

Taiwan

106B604-106年度國際共同人才培育計畫—擴大推動學術合作交流計畫

Venue:

National Chiao Tung University,

Department of Applied Chemistry,

SBII 210

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Venue:National Chiao Tung University,

Department of Applied Chemistry, SBII 210

Map

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National Chiao Tung University

Location of

Landis Inn Chuhu

SBII 210





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Map



Detailed Program



Tuesday, June 19, 2018

Morning9:00-9:10 Prof. Chain-Shu Hsu “Opening remark”

• Section I: Unique Structures and Functions of Advanced Materials

9:10-9:50 Prof. Stephen Z. D. Cheng

TOPIC: Topological Engineering of Giant Molecules toward Unconventional

Structures and Functions

9:50-10:30 Prof. Kilwon Cho

TOPIC: Surface-Directed Molecular Assembly in Organic Electronics

10:30- 11:10 Prof. L. James Lee

TOPIC: Silicon Carbide Catalyzed Fast Graphene Network Synthesis and

Applications in Electronics and Thermal Management

11:10-13:00 Photo & Lunch

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Detailed Program

Tuesday, June 19, 2018

Afternoon

• Section II: Manipulation of Nanomaterials

13:00-13:30 Prof. Zhu Lei

TOPIC: Dielectric Phenomena in Polymers and Multilayered Dielectric Films

13:30-14:00 Prof. Christopher Y. Li

TOPIC: Designed Polymer Crystallization for Functional Nanomaterials

14:00-14:30 Prof. Jiun-Tai Chen

TOPIC: Polymer Nanostructures by Wetting Nanopores in Anodic Aluminum

Oxide Templatese

14:30-15:00 Coffee Break

• Section III: Self-Assembly of Nanomaterials

15:00-15:30 Prof. Tianbo Liu

TOPIC: Hydrophilic Macroions – What Happens When Soluble Ions Reach the

Nanometer Scale, and How Can We Improve Them as Functional materials?

15:30-16:00 Prof. Rong-Ming Ho

TOPIC: Universal Behaviors for Chirality Effect on Self-Assembly of Block

Copolymers

16:00-16:30 Prof. Chien-Lung Wang

TOPIC: Nano-Reactors and Artificial Water Channels Made by Amphiphilic

POSS Molecular Nanoparticles

16:30 Close Remark

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Prof. Stephen Z. D Cheng

Department of Polymer Science

College of Polymer Science and Polymer Engineering

University of Akron

U.S.A.

Topic: Topological Engineering of Giant Molecules toward Unconventional

Structures and Functions

Session Ⅰ: Unique Structures and Functions of Advanced Materials

Date: Tuesday, June 19 Time: 9:10-9:50

Inverse design and inverse thinking are critical steps in the materials genome approach.

When we design materials with specific functional properties, we often start with

independent building blocks which possess well-defined molecular functions and precise

chemical structures. Using “Lego” type of modules, we can then assemble such elemental

building blocks together in preferred secondary structures (or packing schemes) to

construct materials possessing topologically mandated hierarchical structures with desired

functions. In this talk, a unique approach along this design and thinking path will be

presented. Various “giant molecules” based on “nano-atoms” are designed and synthesized.

“Nano-atoms” refer to shape-persistent molecular nanoparticles (MNPs) such as fullerenes,

polyhedral oligomeric silsesquioxanes, polyoxometalates, and folded globular proteins.

These “nano-atoms” possess precisely-defined chemical structures, surface functionalities

and molecular shapes, serving as elemental units for the precision synthesis of “giant

molecules” by methods such as click chemistry and other efficient chemical

transformations. These “giant molecules” include, but are not limited to, giant surfactants,

giant shape amphiphiles, and giant polyhedra. These “giant molecules” can assemble into

diverse higher order building blocks to further construct the thermodynamically stable and

metastable hierarchical structures in the bulk, thin-film, and solution. Unconventional

nanostructures can be obtained in various environments via sequence/topology mandated

assemblies to exhibit specifically desired properties. This approach has provided a

versatile platform for engineering nanostructures that are not only scientifically intriguing,

but also technologically relevant.

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Prof. Kilwon Cho

Department of Chemical Engineering

Pohang University of Science and Technology

Korea

E-mail: [email protected]

Topic: Surface-Directed Molecular Assembly in Organic Electronics



Microstructure in organic semiconductor thin films has been regarded as the key factor

determining the performance of the organic electronic devices. In the case of organic field

effect transistors (OFETs) and organic photovoltaics (OPVs), the control of the surface

characteristics of underlying substrates can govern the mesoscale and/or nanoscale

ordering of the semiconductor assembled on them. Here, we present the effects of

molecular orientation on the performance of OFETs and OPVs in various aspects. The

correlation between molecular orientation of organic semiconductor thin film and the

charge carrier mobility as well as the bias stress stability of an OFET is presented. Also,

the orientation-dependence of photovoltaic properties is discussed in OPVs.

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Prof. L. James Lee

Department of Chemical and Biomolecular Engineering

College of Polymer Science and Polymer Engineering

Ohio State University

U.S.A.

Topic: Silicon Carbide Catalyzed Fast Graphene Network Synthesis and Appli-

cations in Electronics and Thermal Management



Graphenes have recently received a great deal of attention because of their extraordinary

mechanical, electrical and thermal properties. They can be achieved by the “bottom up” approach

through epitaxial growth on the substrates via chemical vapor deposition or the “top down”

approach from graphite by overcoming the van der Waals or π-orbital interactions between

graphene nanosheets in graphite through liquid exfoliation, thermal shock, or chemically reduced

pathways. The resulting graphene building blocks can then be assembled into functional thin

films, coatings or other structures by the same van der Waals or π-orbital interactions. The weak

non-covalent bonding among graphene nanosheets and between the graphene and the substrate,

however, limits their industrial applications. Despite of one-decade research in this area, the

construction of atomically bonded graphene networks, which are bridged at the edges of graphene

nanosheets or linked via the graphene basal planes, remains a formidable challenge. We have

recently discovered a simple and yet versatile method to atomically bind graphene nanosheets on

a variety of solid substrates with unprecedented properties. This one-step approach can achieve

high-strength carbide-catalyzed graphene networks on both non-metallic and metallic substrates

through low-cost Chemical Vapor Deposition (CVD) followed by thermal deposition of graphene

sheets onto the substrate surfaces at elevated temperatures with the aid of silicone oxide radicals.

The thickness of graphene coating ranging from nanometers to microns can be finely tuned by

adjusting the loading content of carbon and silicone sources. We demonstrated the applicability of

this new material and technology from transparent conducting, semiconducting, to enhanced

thermal management for high power electronics and precision molding.

Reference

1. W. Huang, X. Ouyang and L.J. Lee, “High-Performance Nanopapers Based on Benzenesul-

fonic Functionalized Graphenes”,ACS Nano, 6(11), 10178 (2012).

2. W. Huang, J. Yu, K.J. Kwak, D. Gallego-Perez, W.C. Liao, L. Li, H. Yang., X. Ouyang, W. Lu,

G. Lafyatis and L.J. Lee, “Atomic Carbide Bonding Leads to Superior Graphene Networks”,

Advanced Materials, 25, 4668-4672 (2013).

3. L. Li, L.J. Lee and A. Yi, “Graphene Coated Si Mold for Precision Glass Optics Molding”,

Optics Letters, 38(14), 2625-2628 (2013).

4. E.D. Cabrera, P. Zhang, W-C Liao, Y-C Yen, J. Yu, J. Castro and L.J. Lee, “ Graphene Coating

Assisted Injection Molding of Ultra-Thin Thermoplastics”, Polymer Engineering and Science, 6,

1374-1381 (2015)

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Prof. Zhu Lei

Department of Macromolecular Science and Engineering

Case Western Reserve University

United States


Topic: Dielectric Phenomena in Polymers and Multilayered Dielectric Films

Section II: Manipulation of Nanomaterials


High dielectric constant and low dielectric loss are desirable electrical properties for next

generation polymer dielectrics that show promise for applications in pulsed power, power

electronics, and printable electronics. Unfortunately, the dielectric constant of polymers is

often limited to 2-5, much lower than that of inorganic dielectrics, because of the nature of

hydrocarbon covalent bonds for electronic and atomic polarizations. It is essential to

understand the fundamental physics of different types of polarization and the associated

loss mechanisms in polymers. In this presentation, we discuss the characteristics of each

polarization and explain how to enhance the polarization using rational molecular designs

without causing significant dielectric losses. Among various approaches for high dielectric

constant and low loss polymers, the multilayer film technology is of particular interest

because a multilayer film is a unique one-dimensional system with tailored material

choices, layer thicknesses, and interfaces. By minimizing the disadvantageous

polarizations and enhancing the advantageous polarizations, multilayer films hold promise

as advanced dielectrics for future polymer film capacitors

Reference

1. Baer, E.; Zhu, L., Dielectric phenomena in polymers and multilayered dielectric films.

Macromolecules 2017, 50, 2239-2256 (perspective).

2. Zhu, L. Exploring strategies for high dielectric constant and low loss polymer dielectrics. J.

Phys. Chem. Lett. 2014, 5, 3677-3687 (Perspective).

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Prof. Christopher Y. Li

Department of Materials Science and Engineering

Drexel University

U.S.A


Topic: Hierarchical Nanostructures from Functional Reactive Mesogens



Crystallization is ubiquitous in nature and semicrystalline polymers are of crucial

importance in our daily life. Compared with small molecules, polymers crystallize via a

more complex pathway because of their long chain nature and numerous metastable states

associated with polymer crystals. In this talk, we will show that the complex

conformational change of polymer chains upon crystallization can be utilized to design

and fabricate a variety of functional nanomaterials. Three examples will be discussed. First,

ordered hybrid nanomaterials were formed by controlling the interaction between low-

dimensional nanoparticles and polymer single crystals with tailor-designed fold surfaces.

These ordered hybrids can find applications ranging from polymer nanocomposites,

artificial nanomotors to Janus nanoparticle synthesis and assembly. Second, single-

crystal-like hollow capsules named “crystalsomes” were grown at nanoscale curved

liquid/liquid interface. Because the curved interface is incommensurate with classical

translation symmetry, chain packing is frustrated, and defects are asymmetrically

distributed into the crystalsome, leading to significantly enhanced mechanical properties

of the assembly, a topic that will be discussed in the context of recently reported spherical

crystallography. Third, by using end-functionalized crystalline polymers and controlling

chain folding during crystallization, super dense, loop, and gradient polymer brushes with

precise chain anchoring points were synthesized. We envisage that not only can the

designed polymer crystallization help better understand the crystallization mechanisms of

long chain polymers, it is also a powerful tool to synthesize novel functional nanomaterials.

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Prof. Jiun-Tai Chen

Department of Applied Chemistry


Hsinchu


Topic: Polymer Nanostructures by Wetting Nanopores in Anodic Aluminum

Oxide Templatese



We study the fabrication and characterization of different polymer-related nanomaterials by

wetting porous templates.[1-5] The templates we choose are anodic aluminum oxide (AAO)

templates because of the regular pore distribution, high pore density, and high aspect ratio of the

pores. Different nanomaterials such as amorphous carbon nanotubes, amphiphilic block

copolymer nanotubes, and porous inorganic materials are fabricated by using these templates. We

also investigate the morphology transitions of polystyrene-block-polydimethylsiloxane (PS-b-

PDMS) nanorods confined in the nanopores of AAO templates. The nanorods are formed by

solvent-assisted template wetting, and the morphologies are compared to those in the bulk state.

By blending PS-b-PDMS with homopolystyrene (hPS), the morphologies of the nanorods can be

controlled because of the changes of the effective volume fractions. PS-b-PDMS micelle

solutions are also used to prepare micelle nanostructures, and the critical parameters affecting the

morphologies are determined. Micelle nanorods, micelle nanospheres, and multi-components

nanopeapods can be prepared by wetting AAO templates with the micelle solutions. Rayleigh-

instability-driven transformation is discovered to play an important role in controlling the

morphologies of the micelle nanostructures. Zwitterionic polymer-grafted AAO templates are

also prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) and the

geometric effect on the polymer chain growth in the confined nanopores are investigated.

Reference

1. C. W. Chu, Y. Higaki, C. H. Cheng, M. H.

Cheng, C. W. Chang, J. T. Chen,* and A Takahara,*

Polym. Chem., 2017, 8, 2309.

2. H. W. Ko, T. Higuchi, C. W. Chang, M. H. Cheng,

K. Isono, M. H. Chi, H. Jinnai,* and J. T. Chen,*

Soft Matter, 2017, 13, 5428.

3. C.W. Chang, M. H. Chi, H. W. Ko, C. W. Chu, Z. X. Fang, Y. H. Tu and J. T. Chen,*

Polym. Chem., 2017, 8, 3399.

4. H. W. Ko, M. H. Chi, C. W. Chang, C. W. Chu, K. H. Luo, and J. T. Chen,*, ACS Macro

Lett., 2015, 4, 717.

5. M. H. Chi, C. W. Chang, H. W. Ko, C. H. Su, C. W. Lee, C. H. Peng, and J. T. Chen,*

Macromolecules, 2015, 48, 6241.

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Prof. Tianbo Liu

Department of Polymer Science

University of Akron

U.S.A.


Topic: Hydrophilic Macroions - What Happens When Soluble Ions Reach the

Nanometer Scale, and How Can We Improve Them as Functional materials?

Section III: Self-Assembly of Nanomaterials


Between traditional simple ions and large colloidal particles, we found that there exists a

transitional stage – macroionic solutions. In this regime the charged solutes have solution

behavior fundamentally different from the above two categories. The best model

macroions are structurally well-defined molecular clusters with accurately tunable charge.

Such macroions tend to strongly attract with each other although they carry the like

charges, and demonstrate unique self-assembly behaviors involving counter-ion-mediated

attraction. In dilute solutions, they tend to reversibly self-assemble into single-layered,

hollow, spherical “blackberry” structures while the blackberry structure size can be

accurately controlled by solvent content, macroionic charge density or pH. The blackberry

structure represents a universal, free-energy favored state of soluble macroions with

moderate charge, and mimics some biological processes, such as the virus capsid shell

formation. The macroions can also be used as simple models to understand some

fundamental biological behaviors such as the self-recognition and chiral selection of

biological assemblies. The inorganic macroions with can achieve the level of self-

recognition similar to biomolecules in dilute solution, even among highly similar

macroions (identical in size, shape or change) or enantiomers.

By covalently linking organic components to the molecular clusters, the new hybrid

materials combine the advantages of both inorganic and organic materials and behave like

novel surfactants with giant polar head groups. The functionalized clusters show much

improved compatibility to organic media therefore can expand the application of the

catalytic clusters. By designing suitable functional groups on the organic groups, the

hybrids demonstrate reversible self-assembly processes in response to the external stimuli,

such as metal ions, UV radiation or sunlight. Additional new features can be achieved by

properly designing such hybrids with proper organic ligands, including pH-controlled

fluorescence, emulsion catalysts and catalytically active 1-D nanobelts and nanotubes.

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Prof. Rong-Ming Ho

Department of Chemical Engineering

National Tsing Hua University

Hsinchu


Topic: Universal Behaviors for Chirality Effect on Self-Assembly of Block Co-

polymers



Here, we aim to investigate the universal behaviors of the chirality effect on the self-

assembly of chiral block copolymers (BCPs*). Poly(cyclohexylglycolide) (PCG)-

containing BCPs* (i.e., poly(benzyl methacrylate)-b-poly(D-cyclohexylglycolide)

(PBnMA-PDCG) and PBnMA-b-poly(L-cyclohexyl glycolide) (PBnMA-PLCG)) have

been synthesized for self-assembly to give systematic comparisons with polylactide

(PLA)-containing BCPs* with respect to the chirality effect on BCP self-assembly.

Opposite handedness of PCG helical chains in the enantiomeric BCPs* were identified by

the vibrational circular dichroism (VCD) results of carbonyl group (C=O) stretching due to

intramolecular chiral interactions of constituted chiral entities. By taking advantage of

intermolecular chiral interactions as evidenced by the VCD results of C-O-C vibration, the

self-assembly of the PCG-containing BCP* gave the formation of helical phases (H*) with

preferential handedness of helical microdomains (i.e., right- and left-handed H* (H*R and

H*L)) recognized by electron microscopy tomography (EMT), suggesting the chirality

effect on BCP self-assembly and the homochiral evolution from molecular to hierarchical

chirality. Moreover, on the basis of calculated results of rotational strength by electronic

circular dichroism (ECD), the rotational strength (i.e., twisting power) of chiral PCGs is

larger than that of chiral polylactide by increase of substituent size. These observations

and self-consistent field theory predictions for chiral diblocks with stronger intermolecular

chirality, that is a tighter inter-segment pitch, stabilizes the formation of H* of over achiral

domain morphologies suggest a scenario where inter-molecular chiral interactions in PCG-

containing BCPs* are relatively stronger than in PLA-containing BCPs*, accounting for

the observation of enhanced thermodynamic stability of H* in former case. Taken together

with the appearance of VCD signals of the C-O-C vibration for chiral PCG diblocks, this

supports a hypothesis that inter-molecular chirality leads to “chiral mesogon-like”

segmental interactions, which in turn drive chirality transfer to the mesodomain shape.

Reference

1. T. Wen, H.-F. Wang, M.-C. Li, R.-M. Ho* “Homochiral Evolution in Self-Assembled Chiral

Polymers and Block Copolymers” Acc. Chem. Res. 50, 1011-1021 (2017).

13



Prof. Chien-Lung Wang

Department of Applied Chemistry


Hsinchu


Topic: Nano-Reactors and Artificial Water Channels Made by an Amphiphilic

POSS Molecular Nanoparticle



Molecular nanoparticles (MNPs) such as POSS and C60 are well-defined nano-objects that

are widely used as the building blocks of topologically complex giant molecules and

functional materials.1-3 In this presentation, the synthesis and self-assembly behavior of a

low-generation POSS amphiphilic dendrimer (POSS-AD) will be discussed. Small angle

X-ray scattering (SAXS) shows that although the POSS-AD lacks the ability to maintain a

specific shape in solution, it co-assembles with monomers in solution to form well-defined

nano-reactors. The nano-reactors are robust enough to maintain its shape through the

polymerization process to afford the formation of polymer nano-particles with dimensions

less than 10 nm.4

In addition to the fascinating solution behavior, co-assemble of the POSS-AD and water

in condensed phase also results in a hexagonal columnar phase with lattice parameters of a

= b = 3.7 nm, α = β = 90o, and γ = 120o. Polarized light optical microscope (POM)

micrograph shows that the POSS-AD/water co-assembles can form highly oriented

ordered domains that contain numerous aligned water channels (diameter ~ 3 nm) in the

thin film. The unique solution-phase and condensed-phase behaviors of the POSS-AD

thus prove it as a novel and useful nano-building block for nano-reactors and artificial

water channels.

Reference

1. W.-B. Zhang, X. Yu, C.-L. Wang, H.-J. Sun, I. F. Hsieh, Y. Li, X.-H. Dong, K. Yue, R.

Van Horn, S. Z. D. Cheng, "Molecular Nanoparticles Are Unique Elements for

Macromolecular Science: From “Nanoatoms” to Giant Molecules", Macromolecules

2014, 47, 1221.

2. Nierengarten and coworkers, Chem. Rec. 2015, 15, 31; Angew. Chem. Int. Ed. 2011,

50, 2364; J. Am. Chem. Soc. 2012, 134, 988-998.

3. S.-L. Wu, C.-Y. Hong, K.-Y. Wu, S.-T. Lan, C.-T. Hsieh, H.-L. Chen, C.-L. Wang

“Conformational Preferences and the Phase Stability of Fullerene Hexa-adducts” Chem.

Asian J. 2016, 11, 2011.

4. J.-T. Weng, T.-F. Yeh, A. Z. Samuel, Y.-F. Huang, J.-H. Sie, K.-Y. Wu, C.-H. Peng, H.

Hamaguchi, C.-L. Wang “Cylindrical micelles of a POSS amphiphilic dendrimer as

nano-reactors for polymerization” Nanoscale, 2018, 10, 3509.

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Prof. Kwang-Un Jeong

Department of Polymer-Nano Science and Technology

Chonbuk National University

South Korea

Topic: Hierarchical Nanostructures from Functional Reactive Mesogens

Anisotroptic liquid crystal (LC) networks prepared from reactive mesogens (RM) have

numerous advantages in optoelectronic devices especially because of the excellent

processability. To fabricate the robust LC thin films with excellent thermal, chemical and

mechanical stabilities, the photo-polymerization of anisotropically pre-oriented RMs

should be conducted on the optimized conditions. Since the final physical properties of

anisotroptic LC networks depend on chemical functions and physical intermolecular

interactions, the hierarchical superstructures of the programmed RMs with specific

chemical functions should be controlled on the different length and time scales before

polymerization. The presentation describes the fundamental characteristics and recent

research interests of anisotropic LC networks, elastomers and gels fabricated using various

programmed RMs.

Reference

1. Asymmetric Fullerene Nanosurfactant: Interface Engineering for Automatic Molecular

Alignments, Kim, D.-Y.; Lee, S.-A.; Kim, S.; Nah, C.; Jeong, K.-U.; Lee, S.,Small, 2018,14,

1702439.

2. Interfacial Engineering for the Synergistic Enhancement of Thermal Conductivity of

Discotic Liquid Crystal Composites, Kang, D.-G.; Kim, N.; Park, M.; Nah, C.; Kim, J.-S.; Lee,

C.-R.; Kim, Y.; Kim, C.-B.; Goh, M.; Jeong, K.-U., ACS Appl. Mater. Interfaces, 2018, 10,

3155-3159.

3. From Smart Denpols to Remote-Controllable Actuators: Hierarchical Superstructures of

Azobenzene-Based Polynorbornenes, Kim, D.-Y.; Shin, S.; Yoon, W.-J.; Choi, Y.-J.; Hwang, J.-

K.; Kim, J.-S.; Lee, C.-R.; Choi, T.-L.; Jeong, K.-U., Advanced Functional Materials, 2017,

27, 1606294

4. Free-Standing and Circular-Polarizing Chirophotonic Crystal Reflectors:

Photopolymerization of Helical Nanostructures, Kim, D.-Y.; Nah, C.; Kang, S.-W.; Lee, S.-H.;

Lee, K.-M.; White, T.; Jeong, K.-U., ACS Nano, 2016, 10, 9570-9576.

5. Flexible and Patterned Thin Film Polarizer: Photopolymerization of Perylene-Based

Lyotropic Chromonic Reactive Mesogens, Im, P.; Kang, D.-G.; Kim, D.-Y.; Choi, Y.-J.; Yoon,

W.-J.; Lee, M.-H.; Lee, I.-H.; Lee, C.-R.; Jeong, K.-U., ACS Applied Materials & Interfaces,

2016, 8, 762-771.

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Documents

PowerPoint 簡報 - ac.nctu.edu.tw · “Nano-atoms”refer to shape-persistent molecular nanoparticles (MNPs) such as fullerenes, polyhedral oligomeric silsesquioxanes, polyoxometalates,