no slide title - wayne state...
TRANSCRIPT
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Presented by
Ashis MukhopadhyayWayne State University
Soft MatterResearch challenges and opportunities
Everyday examples
Definition
Research areas
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Everyday examples
Think yourself at the airport screening
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Pierre-Gilles de Gennes:
“All physiochemical systems that have large response functions.”
Example: Rubber of the Amazon Indians (Nobel Lecture, 1991)
Liquid
Rubber
What is soft matter?
Dramatic change of mechanical properties from a mild chemical reaction
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Richard A. L. Jones, in Soft Condensed Matter:
“Materials in states of matter that are neither simple
liquids nor crystalline solids..;”
Radial distribution function
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Helmut Möhwald:
“Materials that are held together by non-covalent interactions.”
euro-cosmetics.com
Shear-thinning
• These are examples of non-Newtonian fluids
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Let’s watch Sheldon Cooper of Big Bang theory
https://www.youtube.com/watch?v=2CJJ6FrfuGU&t=45s
https://sites.google.com/view/mccready-williams-research/home
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Interactions• H-bonding
• Screened Coulomb
• van der Waals
• Hydrophobic
• depletion
• capillary
Associated energy kBT 0.03 eV 4 pN nm
Building blocks: Colloids, liquid crystals, surfactants, polymers, proteins, etc.
Structural phase transitions, glass transitions, pattern formation,
self-assembly, etc.
Log (length scale) nm
Amphiphile Bilayer Unilamellar vesicle Layered stacks Multilamellar vesicle
1 10 100 1000
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Questions we are trying to answer:
Polymers: How nanoparticle move through a polymer network
Colloids: What is the nature of crystals and defects on a curved surface?
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C CH
H
H
R
C CH
H
H
RN
N ~ 102 - 105
Degree of
Polymerization,
Polymers
Molecular weight: 103 g/mol to 107 g/mol
Polymer architecture
linearring star
H-branched
comb
ladderdendrimer
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Heteropolymers
…A-B-A-B-A-B-A-B-A-B-A-B… …A-A-B-A-B-B-A-B-B-A-A-B-B-B…
…A-A-A-A-A-A-B-B-B-B-B-B-B…
alternating random
block
As surfactants
Micro-phase separation
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Everyday examples: plastic cup, bottle, toy, tire, pillow, sofa, shirt, shoe,
bulletproof vest, newspaper, book, photograph, pen, eyeglass lens,
toothbrush, diaper, paint, CD or DVD, flexible circuit board, etc.
Medical examples: medical instruments to materials for endoscopic,
catheterization, and angioplastic procedures, to infection-control barriers,
intravenous tubes, dressings, and sutures, to pills, drug-delivery vehicles,
transdermal patches, and targeted antitumor agents, to implants anywhere
in the body, tissue engineering, intraocular lenses, dental restorative
materials, etc.
The universe of polymers
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Molecular dynamics of polymer chain
Length scale: 0.1 nm - 100 nm
Time scale: 10-12 s - few milliseconds
A smarter choice
Polymer dynamics
Brownian motion of a particle in the matrix
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Manifestation of statistical fluctuation
Brownian motion of 1 µm particles in water
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r2= 6Dt D=Diffusion coefficient
How the friction coefficient depends upon the length scale & time scale
in polymers and in other complex fluids?
Einstein’s fluctuation-dissipation theorem: D= kBT/
= friction coefficient
Important caveat: Many orders of magnitude difference in time scales
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Some results
1 10
1
10
100
1000
DGLE
+DhopD
GLE
D/D
SE
2Ro/d
t
0.10.1 0.2 0.3 0.4
0.01
0.1
1
10
-4.07
-2.28
-1.45
2.5 nm, 5k
2.5 nm, 35k
5 nm, 35k
10 nm, 35k
Power Law Fit
Hydrodynamic Fit
D (
m
2/s
)
Power law scaling
instead of exponential
• Hydrodynamics
• Obstruction & depletion effects
• Segmental motion
• Entanglement dynamics
• Caging & hopping
• Anomalous subdiffusion
Einstein theory
Generalized Langevin theory
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More recent theories and simulations
Advanced scaling theory
Rubinstein et. al.
Importance of hopping motion
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Schweizer et. al.
Statistical dynamical theory
Prediction of D/DSE vs. 2R0/a
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MD simulation by Kumar, Grest, Schweizer
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MD simulation near a nanoscale notch
Balazs, et. al Science (2006)
Polymer with spherical nanoparticles
Self-healing Polymer NanocompositesResearch project:
Role of depletion interaction?
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Research project: Effects of crowding in biology and soft matter
A day in Calcutta, India
Effect of obstruction
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Examples of Crowding in biology
Interior of a cell
Molecular motor
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Nanoparticle dynamics through mucus
Not something to talk about at
the dinner table!
Diseases: Asthma, bronchitis, cystic fibrosis, inflammatory bowel disease
An important biomaterial: shield against pathogens, maintain wet environment,
exchange gas, nutrients, etc.
Mucin molecule, a glycoprotein
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Nanoparticle dynamics through mucus
SEM image
b
dt 2Ro Lp
Rg
An entangled network /
viscous biogel
• Heterogeneity
• Adhesivity
• “Stealth” particles
• Particle of anisotropic shape
• Role of microscopic friction
• Active and passive transport in other
crowded system.
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Gold nanoparticles of variable sizes for nano-dynamics
Nature 2013
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Ultrafast laser spectroscopy
• An ensemble of very few molecules
• A large number fluctuations about a thermodynamic average
Thermal fluctuation~ kBT
V ~ 1 fL
<N> ~ 1
Objective
Pulsed Laser
Statistical physics of the system:
Fluctuations caught in the act
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Reconfigurable Colloidal Assembly
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Research Project:
Colloidal interaction and self-assembly by temperature
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Gecko feet
Spider silk
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Our Lego blocks: Colloidal discs and ellipsoids
Elongational strain
Uniaxial compression
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We can make helices and rings using colloidal discs
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Larger ones settle at the bottom
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2 m
10 m
Colloidal Rings
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We can make colloidal domes
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‘z’ scan of one dome
Confocal microscopy image
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Side view
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Packing of marbles on a flat surface
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Spherical Crystallography
How particles pack on a curved surface
Soccer ball
20 hexagons + 12 pentagons
Mathematician L. Euler
Topological charge
Pentagons= +1
Heptagons= -1
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5-7 defects in carbon nanotubes
5 m
5-7 defects in colloidal domes Fourier transform
Also C60
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5 m
5 m
25 µm (a) (c)
(b) (d)
5 m
5-7 defects in colloidal domes
Delaunay triangulation
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Melting
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Voronoi construction and Delaunay triangulation
Melting
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Bond orientational order parameter
𝑔6 𝑟 = < 𝜓6∗ 0 𝜓6( Ԧ𝑟) >
𝜓6 𝑟𝑖 =1
𝑛
𝑗=1
𝑛
exp [𝑖6Ѳ 𝑟𝑖𝑗 ]
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0 2 4 6 8 100
3
6
9
12
15
g(r
)
r (m)
Radial distribution function during melting
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Particle dynamics during melting
1 10
0.01
0.1
1
(s
)
q (m-1)
-2
Liquid phase
Crystalline phase
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Soft matter
-polymers, biopolymers, colloids, hybrid materials,
self-assembled structures
The scope is larger than physics
-with some fluid physics, chemistry, statistical mechanics,
image processing, computer simulation, etc.
Experimental methods: Ultrafast laser spectroscopy,
confocal microscopy, ellipsometry, Langmuir-Blodgett techniques,
AFM, image & large data analysis, surface chemistry, nano particle
synthesis, functionalization, and characterization, etc.
Concluding remarks:
Future job market: academia, industry, medical schools,
national labs, etc..