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Keith Johnston Research Group Nanomaterials Chemistry/Colloid and Interface Science/Polymer Science
Advanced Functional Nanomaterials (metals and metal oxides/polymers) Control of particle morphology/crystallinity via nucleation and growth in solution
Colloidal stability and functional properties (ligands and polymers on the surface)
Optical, magnetic and catalytic properties = f (morphology)
Nanoparticle Interactions with Liquid and Solid Interfaces Oil/water and gas/water interfaces (emulsions and foams)
Solid surfaces (adsorption and transport in porous media)
Metals and metal oxides on conductive supports for electrocatalysis
Nanocluster Self Assembly Platform for Enhanced Properties
Protein nanoclusters (new composition of matter)
Metals: Au photonic NIR nanoclusters (biodegradable)
Metal oxides for subsurface imaging and electrocatalysis
50 nm
Φ(h)
h
vdW, depletion attr.
elect. rep. steric
h
Tools Nano subsurface sci. Foams and Emulsions Oil spills, EOR CO2 sequestration Green Fracturing
Nano Subsurface Electromag Imaging
Electrochem Energy Storage (KS)
Protein Stability/ Delivery
Au Nanoclusters for Biomedical Imaging/Therapy
Materials Chemsistry: Nucleation, growth, passivation(aq., org.)
Colloid interactions/stability (colloid sci./polymer science)
Colloidal assembly nanocluster platform
Nps/surfactants /polymers interfacial phen.
Nps at solid interfaces/transport in porous media
Target morphology to advanced functional properties
Optical properties
Magnetic properties
Catalytic properties
Scientific building blocks to create and advance applications in energy, materials and pharmaceutical/biomedical fields
100 nm
Nanoclusters composed on nanoparticles by tuning colloidal forces
Magnetic nanoclusters for subsurface imaging (high suscept.) – Xue, Foster, Tarkington, Kong
Protein Nanocluster Dispersions(400 mg in 1 mL) – Stable protein and low viscosity for sub Q injection – Borwankar, Dear, Hung, Zhang, Labor
Biodegradable gold nanoclusters for imaging/therapy - Weakly adsorbed polymers to drive cluster formation
Murthy, Stover
Sub-5 nm gold particles
Clustering of gold nanoparticles
mediated by weakly adsorbing polymer
PLA-b-PEG-b-PLA
Gold nanoparticle bound together by
polymerSub-5 nm gold particles
Clustering of gold nanoparticles
mediated by weakly adsorbing polymer
PLA-b-PEG-b-PLA
Gold nanoparticle bound together by
polymer
Capsid of dsRNA virus Junhua Pan et al. PNAS, 106 (09) Hundreds crystallographic X-rays 5 nm protein building blocks
100 nm 50 nm
Φ(h)
h
vdW, depletion attr.
elect. rep.
steric
Subsurface Foams, Emulsions and Colloid Science/Nanotech: (Sequestration, EOR, fracturing, oil spills: energy, water, environmental in massive qtys)
CO2
q q water
CO2
CO2
water
CO2
water
Oil or CO2
Design nps/surf. for low ift and high stability
Np adsorption at interface vs. surface structure
Foam stability: lamellae thickness, disjoining pressure, hole nucleation
Low adsorption on rock: DLVO theory
Oil jets dispersed w/ 1:100 clay
W W CO2
We propose self-healing holes
Deepwater Horizon spill
Magnetic Imaging Agents for Energy Applications
• Electromagnetic imaging – porous media in reservoirs – oil drops coated with adsorbed magnetic np
contrast agents • Magnetic resonance imaging of oil spills
• Synthesize magnetic nanoparticles with
high magnetic susceptibility – Coated with amphiphilic polymers for stability
and transport – Control transport and interfacial activity
• Hz = f(eikr) where k = f(m) mag.
permeability
Bagaria, KPJ et al. ACS Appl. Mat. Interfaces, 2013
High mag. susceptibility magnetic Nps with grafted polymers: transport and interfacial properties(contrast agents oil reservoirs, spills, fracturing, cancer)
6
Superparamag. IO clusters with amine coated surfaces
50 nm
• Dense clusters for high magnetic susceptibility • Charged copolymers for electrosteric stab. in brine • Low adsorption on sandstone:
Graft density, MW, copolymer composition
-
-
- -
-
-
Amide Bonds PAMPS-PAA grafts
-150
-100
-50
0
50
100
150
-40 -20 0 20 40
Mag
ne
tiza
tio
n [
em
u/g
Fe
]
Field [kOe]
NP 8NP 7NP 5NP 15
0
0.5
1
0 2 4 6C
/C0
Pore Volume Bagaria, KPJ et al. ACS Appl. Mat. Interfaces, 2013
Synergistic efficient dispersants: nps and surfactants
Carbon Black with Corexit-9500 or DTAB
Scale bar = 1 µm
Colloidal silica (30 nm bare) Caprylamidopropyl betaine
• Stable oil/seawater emulsion with only 0.5 wt.% • Surfactant lowers ift • Irreversibly adsorbed nps prevent coalesc.
• High synergy rules: control each amphiphile partitioning into various interfaces • Silica, C, clays, iron oxide with all types of surf.
Bose, John Johnston, Truskett, Bryant, Bielawski, John
Worthen, KPJ et al. Langmuir, 2014
50 mm
Phase Inversion of Emulsions Stabilized with Natural Clay Microparticles and only 10 ppm Ethoxylated Amine Surfactant
natural clay MMT (Montmorillonite)
low HLB, oil soluble
cost effective
• Little surfactant needed for modification of low surf. area 10 micron clay • Phase inversion: attempt to mimic McCormick/Larson/Walker/Anna et al. mechanisms
ethoxylated (2) oleylamine E-O/12 (Ethomeen O/12)
1 10 100 10000
20
40
60
80
100
re
lativ
e v
ol%
size (mm )
t=0
t=1 h
t=24 h
o/w emulsion stable to
coalescence
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.90.15
0.20
0.25
0.30
0.35
0.40
o/w
0 20 50 100 200 300 400 600
w
[E-O
/12
]/[M
MT
]
w/o
initial droplet size (μm)
E-O
/12 (
wt%
)
MMT ( wt % )
0 1 5 10 15 20 30 40 50
10.50.250.1
0.01
0.001
0.1
creaming stability (min)
1% MMT + 0.001% E-O/12
Self-limiting nanocluster size: attraction balances electrostatic repulsion = f (q)
• Minimization wrt nc
• Bjerrum length λ = e2/4πЄrЄ0kBT
9
Groenewold and Kegel, J.P.C. B, (01) Johnston et al., ACS Nano (13) Borwanker, KPJ et al., Soft Matter (13)
q+
q+ q+
q+
q+
q+
q+ q+
q+ q+
q+ q+ q+
q+ q+
q+ q+
q+
q+
q+
q+
q+
2R 2Rc
2R
Energy gain due to neighbors
Interfacial free energy penalty (γ = ε/surface area)
Coulombic repulsion as q2 grows
Free energy per protein
50 nm Entropy of counterions
Tunable protein nanoclusters: drug delivery and protein stabilization
1. Advance colloid theory, structural characterization: SANS, DLS, SEM
2. Low viscosity at high concentration 3. Protein stabilization in crowded state 4. Extend to new proteins/peptides/crowders 5. Revolutionize health care: cancer, infections
disease, immune disorders 6. Discussions/res with major pharma. companies Johnston et al., ACS Nano (13)
Borwankar, KPJ et al., Soft Matter (13)
11 nm 55 nm
Roadmap for design of protein nanoclusters
• Lyophilization dilution (LD) and conc. filtration produce similar sizes • Clusters dissociate upon dilution of protein/crowder in buffer • Excellent qualitative agreement between theory and experiment
Borwankar et al., Soft Matter, 2013
C 250:100
11
Hierarchy of Intracluster vs Intercluster Interactions near pI
• Separation between particles order of radius (φ ~0.2)
• Monomer to monomer attraction (depletion) dominant with low charge
• Intracluster: (monomer to cluster) attraction balances elect. rep.
• Intercluster electrostatic repulsion dominant
• colloidal stability • low intrinsic viscosity • buried attraction
12
Solution of Monomer Spec. short range dom Dispersion of 200 nm
Nanoclusters
5 nm
55 nm
11 nm 55 nm
q~ 1 (near pI) * 1000 proteins in cluster
q~ 1 near pI
Borwankar et al., Soft Matter, 2013
Protein
concentration
(c, mg/ml)
Trehalose
concentration
(cE, mg/ml)
Viscosity
(η, cP)
𝜙eff Intrinsic
viscosity ([η])
Hydrodynamic
diameter
275 (IgG) 275 63 0.34 7.4 88.0
260 (IgG soln) 0 57 0.19 18 9.66
Control Size and Morphology of Quenched Equilibrium Gold Nanoclusters
• Form “quenched equilibrium” nanoclusters with weakly adsorbed polymer – Tunable size by from 20 to 40 nm varying Au concentration and polymer/Au ratio – Nanoclusters quenched at equilibrium size by polymer adsorption – Semi-quantitatively predict nanocluster size with free energy equil. model
• balance short ranged depletion and vdW attractions with electrostatic repulsion
– Close spacings of primary gold particles produces intense NIR extinction
• Demonstrate reversibility of biodegradable nanoclusters – pH 5 HCl: degrades PLA groups on polymer, removes polymer quenching – Primary particle surface charge sufficient for dissociation to monomer
small enough for potential kidney clearance
Tam, Sokolov, Johnston, Murthy et al., ACS Nano (10) Langmuir (10) Murthy, Johnston, Sokolov, Truskett, Stover ACS Nano (13), JACS (13)
13
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
400 500 600 700 800 900
Wavelength (nm)
Ab
so
rba
nc
e |
Before evaporation50% evaporation60% evaporation80% evaporation95% evaporation100% evaporationCitrate/lysine-capped colloidal Au
14
50 nm
100%
50 nm
60%
50 nm 50 nm
0% 50%
100%
50 nm
Cluster Size Increases with Evaporation ()
Polymer shell • 3 mg/ml Au, 50 mg/ml PLA-b-PEG-b-PLA 1K-10K-1K, lysine/citrate ligands on surface
• Greater evaporation higher particle and polymer concentration • greater polymer induced depletion attraction and VDW attraction
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
400 500 600 700 800 900
Wavelength (nm)
Ab
so
rba
nc
e |
Before evaporation50% evaporation60% evaporation80% evaporation95% evaporation100% evaporationCitrate/lysine-capped colloidal Au
Tam, KPJ et al. ACS Nano 2010; Langmuir 2010
Nanocluster Size Can Be Predicted Semi-Quantitatively with Free Energy Model
- Size increases with gold concentration (counterion entropy) and polymer concentration (depletion attraction)
- Polymer “quenching” nanoclusters size retained upon dilution - Model is predictive given charge from zeta potential and assumed - Murthy, Stover et al (2013) ACS Nano - e 15
50 nm
20-4.0
Reversibility: Nanoclusters Dissociate Upon Polymer Degradation (polymer: Au = 20)
16
- Incubated in pH 5 HCl (mimic cancer cell pH) - DLS and UV-Vis-NIR spectra indicate monomer - Polymer degradation: charged Au nps dissociate
Mixed Charge Monolayers: “Buried” Charges Result in Reduced Protein Adsorption Even on Charged Nanospheres
Lysine/citrate monolayer Cysteine/citrate monolayer
17
Murthy, Stover, KPJ et al., JACS 2013
-16 mV -22 mV
[1]Lee, IrO2 and RuO2 OER, JPCL 2011 [2]Suntivich, Perovskite OER, Science 2011 [3]Liang, Co3O4 Graphene Catalyst, Nature Mat. 2011 [4]Hardin, Johnston, K.P. et al. ; Highly Active LaNiO3, J. Phys. Chem. Let. 2013
LaNiO3 generates 3 times more current per mass than the leading precious metal oxide catalyst IrO2 by utilizing lattice oxygen
Oxygen Evolution Reaction (OER)
OH- → OHads + e- OHads + OH- → Oads + H2O + e-
Oads + OH- → OOHads + e-
OOHads + OH- → H2O + e- + O2
LaNiO 3
/AB
NC
Co 3
O 4/N
GO
IrO2
LaNiO 3
/NC
0
20
40
60
80
100
1.56 V RHE
Mass A
ctivity [m
A/m
go
xid
e]
Nanostructured Perovskite Oxides for Electrocatalysis
recharg. Zn-air batteries, supercapacitors, water splitting
Colloidal dispersion of mixed metal hydroxides → thin film freezing → lyophilization → calcination
Phase pure nanostructured perovskites: reverse phase arrested growth precipitation avoids phase segregation
OER
Experimental tools • Scattering: DLS, SLS, SAXS, SANS, XRD
• Spectroscopy: UV-vis/NIR, FTIR, CD, FTIR-ATR,
Flame AAS, XPS, NMR, GCMS, Ind. Coupled Plasma
MS, Energy dispersive x-ray spectroscopy (EDS)
• Microscopy: optical, TEM, SEM, High-resolution
aberration corrected transmission electron, high-
angle annular dark-field imaging
• Electrophoretic mobility/zeta potential
• Chromatography: HPLC, SEC, GC, GPC
• Separations (other): Tangential flow filtration,
Centrifugation, Membrane centrifugation
• Viscometry: capillary viscometer, cone and plate
viscometer, flow through porous media
• Tensiometry: pendant drop, captive bubble,
contact angle
• Ellipsometry
• Magnetic properties: SQUID, Vibrating sample
magnetometry (VSM) susceptometry
• Electrochemistry: CV, Coulometry, Rotating disk
• Thermogravimetric analysis (TGA)
• BET nitrogen sorption (specific surface area)
• Differential scanning calorimetry (DSC)
• Elemental analysis
• Dynamic mechanical analysis (DMA)
• High T and P: foam generation, rheology, stability
measurements, phase behavior
• Homogenization (pore and rotary), Probe
sonication, Lyophilization, thin film freezing
• Hyperspectral imaging and photoacoustic imaging
(BME)
• Mouse studies: in vivo injection/dissection
Johnston group
Bart Dear (Proteins) CPE 5.430, [email protected]
Andrew Worthen (Subsurface energy, CO2 EOR, Oil dispersants) CPE 5.428, [email protected]
Will Hardin (Electrochem.) CPE 5.426, [email protected]
Bobby Stover (Biomedical imaging Au) CPE 5.432, [email protected] Faculty Collaborators: Jennifer Maynard, Tom Truskett, Kostia Sokolov, Chris Bielawski and Keith Stevenson(Chemistry), Steve Bryant, George Hirasaki, and Quoc Nguyen (PGE)
Bart Andrew Will
Bobby
Destination of Recent PhD Students
• Gupta Auburn
• Balbuena Texas A + M
• Meredith Ga. Tech.
• Yates U. Rochester
• Da Rocha Wayne State U.
• Lee U. S. California
• Ziegler U. Florida
• Lu Nat. Univ. Singapore
• Shah Pfizer • Pham Sematech • Chen Abbott • Dickson Exxon-Mobil • Smith Exxon-Mobil • Overhoff Schering-Plough • Engstrom Bristol-Meyers-Squibb • Matteucci Dow • Gupta Exxon-Mobil • Tam Bristol-Meyers-Squibb • Patel Lam Research • Ma Dupont • Miller Medimmune • Slanac Dupont • Murthy Roche
Selected References • Worthen, A. J.; Bagaria, H. G.; Chen, Y. S.; Bryant, S. L.; Huh, C.; Johnston, K. P., Nanoparticle-stabilized carbon dioxide-in-water foams with fine
texture. Journal of Colloid and Interface Science 2013, 391, 142-151.
• Murthy, A. K.; Stover, R. J.; Hardin, W. G.; Schramm, R.; Nie, G. D.; Gourisankar, S.; Truskett, T. M.; Sokolov, K. V.; Johnston, K. P., Charged Gold Nanoparticles with Essentially Zero Serum Protein Adsorption in Undiluted Fetal Bovine Serum. J. Am. Chem. Soc. 2013, 135, (21), 7799-7802.
• Murthy, A. K.; Stover, R. J.; Borwankar, A. U.; Nie, G. D.; Gourisankar, S.; Truskett, T. M.; Sokolov, K. V.; Johnston, K. P., Equilibrium Gold Nanoclusters Quenched with Biodegradable Polymers. ACS Nano 2013, 7, (1), 239-251.
• Hardin, W. G.; Slanac, D. A.; Wang, X.; Dai, S.; Johnston, K. P.; Stevenson, K. J., Highly active, nonprecious metal perovskite electrocatalysts for bifunctional metal-air battery electrodes. J. Phys. Chem. Lett. 2013, 4, 1254-1259.
• Borwankar, A. U.; Dinin, A. K.; Laber, J. R.; Twu, A.; Wilson, B. K.; Maynard, J. A.; Truskett, T. M.; Johnston, K. P., Tunable equilibrium nanocluster dispersions at high protein concentrations. Soft Matter 2013, 9, (6), 1766-1771.
• Bagaria, H. G.; Xue, Z.; Neilson, B. M.; Worthen, A. J.; Yoon, K. Y.; Nayak, S.; Cheng, V.; Lee, J. H.; Bielawski, C. W.; Johnston, K. P., Iron Oxide Nanoparticles Grafted with Sulfonated Copolymers are Stable in Concentrated Brine at Elevated Temperatures and Weakly Adsorb on Silica. ACS Appl. Mater. Interfaces 2013, 5, (8), 3329-3339.
• Yoon, K. Y.; Li, Z.; Neilson, B. M.; Lee, W.; Huh, C.; Bryant, S. L.; Bielawski, C. W.; Johnston, K. P., Effect of Adsorbed Amphiphilic Copolymers on the Interfacial Activity of Superparamagnetic Nanoclusters and the Emulsification of Oil in Water. Macromolecules (Washington, DC, U. S.) 2012, 45, 5157-5166.
• Slanac, D. A.; Hardin, W. G.; Johnston, K. P.; Stevenson, K. J., Atomic Ensemble and Electronic Effects in Ag-Rich AgPd Nanoalloy Catalysts for Oxygen Reduction in Alkaline Media. J. Am. Chem. Soc. 2012, 134, 9812-9819.
• Johnston, K. P.; Maynard, J. A.; Truskett, T. M.; Borwankar, A. U.; Miller, M. A.; Wilson, B. K.; Dinin, A. K.; Khan, T. A.; Kaczorowski, K. J., Concentrated Dispersions of Equilibrium Protein Nanoclusters That Reversibly Dissociate into Active Monomers. Acs Nano 2012, 6, (2), 1357-1369.
• Yoon, K. Y.; Kotsmar, C.; Ingram, D. R.; Huh, C.; Bryant, S. L.; Milner, T. E.; Johnston, K. P., Stabilization of Superparamagnetic Iron Oxide Nanoclusters in Concentrated Brine with Cross-Linked Polymer Shells. Langmuir 2011, 27, (17), 10962-10969.
• Ma, L. L.; Tam, J. O.; Willsey, B. W.; Rigdon, D.; Ramesh, R.; Sokolov, K.; Johnston, K. P., Selective Targeting of Antibody Conjugated Multifunctional Nanoclusters (Nanoroses) to Epidermal Growth Factor Receptors in Cancer Cells. Langmuir 2011, 27, (12), 7681-7690.
• Adkins, S. S.; Chen, X.; Chan, I.; Torino, E.; Nguyen, Q. P.; Sanders, A. W.; Johnston, K. P., Morphology and Stability of CO2-in-Water Foams with Nonionic Hydrocarbon Surfactants. Langmuir 2010, 26, (8), 5335-5348.
• Johnston, K. P.; da Rocha, S. R. P., Colloids in supercritical fluids over the last 20 years and future directions. Journal of Supercritical Fluids 2009, 47, (3), 523-530.
• Holmes, J. D.; Johnston, K. P.; Doty, R. C.; Korgel, B. A., Control of Thickness and Orientation of Solution-Grown Silicon Nanowires. Science 2000, 287, (5457), 1471-1473.
• Johnston, K. P.; Harrison, K. L.; Clarke, M. J.; Howdle, S. M.; Heitz, M. P.; Bright, F. V.; Carlier, C.; Randolph, T. W., Water-in-Carbon Dioxide Microemulsions: A New Environment for Hydrophiles Including Proteins. Science 1996, 271, 624.
