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Surface-Grafted Polymer Gradients: Formation, Characterization, and Applications

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Surface-Initiated Polymerization II

Part of the book series: Advances in Polymer Science ((POLYMER,volume 198))

Abstract

This review presents to-date progress in the formation of surface-tethered polymer assemblies with gradually varying physico-chemical properties. The typical characteristics of the grafted polymers that may change spatially along the specimen include molecular weight, grafting density on the substrate, and chemical composition. The concept of surface-anchored polymer assemblies is employed in several projects, including, study of the mushroom-to-brush transition in surface-tethered polymers, monitoring kinetics of controlled/“living” radical polymerization, synthesis of surface-anchored copolymers with tunable compositions, and analysis of macromolecular conformations in weakly charged grafted polyelectrolyte and polyampholyte systems. We also discuss the application of grafted polymer gradient systems in studying three-dimensional dispersions of nanosized guest objects. In the aforementioned examples, the use of gradient structures both enables methodical exploration of a system's behavior and facilitates expeditious data measurement and analysis. Furthermore, we outline methods leading to the formation of orthogonal gradients—structures in which two distinct gradients traverse in orthogonal directions. We illustrate the applicability of molecular weight/grafting density orthogonal gradients in organizing nanoparticles and controlling protein adsorption on polymer surfaces. Finally, we identify several areas of science and technology, which will benefit from further advances in the design and formation of gradient assemblies of surface-bound polymers.

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Abbreviations

3-D:

three-dimensional

ATRP:

atom transfer radical polymerization

BMPUS:

[11-(2-bromo-2-methyl)propionyloxy] undecyltrichlorosilane

CMPE:

1-trichlorosilyl-2-(m/p-chloromethylphenyl) ethane

DI:

deionized

[DS]:

degree of swelling

EGF:

epidermal growth factor

FTIR:

Fourier transform infrared spectroscopy

GPS:

3-glycidoxypropyl trimethoxysilane

h :

dry thickness of surface-anchored polymer

H :

wet thickness of surface-anchored polymer

[H +]:

proton concentration in bulk solution

H b :

height of a grafted polymer in a brush conformation

H DIW :

polymer wet thicknesses in “pure” water

H(IS):

polymer wet thicknesses evaluated at a given IS

H m :

height of a grafted polymer in a mushroom conformation

IEP:

isoelectric point

IS :

solution ionic strength

IS max :

solution ionic strength at the transition from OB to SB

K a :

equilibrium constant of the acid-base equilibrium

MMA:

methyl methacrylate

M n :

number average molecular weight of polymer

MW :

molecular weight

N :

degree of polymerization

N A :

Avogadro's number

NB:

neutral brush

NEXAFS:

near-edge X-ray absorption fine structure

OB:

osmotic brush

OTS:

n-octyltrichlorosilane

P2VP:

poly(2-vinyl pyridine)

PAA:

poly(acrylic acid)

PAAm:

poly(acryl amide)

PDMAEMA:

poly(dimethyl aminoethyl methacrylate)

PE:

polyethylene

PEG:

poly(ethylene glycol)

PEG-MA:

poly(ethylene glycol) methacrylate

PEO:

poly(ethylene oxide)

PEY:

partial electron yield

PGMA:

poly(glycidyl methacrylate)

PHEMA:

poly(2-hydroxylethyl methacrylate)

PMAA:

poly(methacrylic acid)

PMMA:

poly(methyl methacrylate)

PO:

paraffin oil

PS:

polystyrene

PtBA:

poly(tert-butyl acrylate)

R g :

radius of gyration of a polymer

R p :

rate of polymerization

SAM:

self-assembled monolayer

SB:

salted brush

SE:

spectroscopic ellipsometry

SFM:

scanning force microscopy

tBA:

tert-butyl acrylate

T g :

glass transition temperature of a polymer

XPS:

X-ray photoelectron spectroscopy

α:

degree of dissociation in bulk solution

αo :

“internal” degree of dissociation

Δ, Ψ:

ellipsometric angles related to the change of amplitude and phase shift

θDIW :

contact angle of deionized water

λ:

wavelength of light

v :

excluded volume parameter

v e :

electrostatic excluded volume parameter

ρ:

polymer density

ρs,∞ :

salt concentration in bulk solution

σ:

polymer grafting density

φ:

polymer volume fraction

χ:

Flory–Huggins interaction parameter

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Acknowledgments

The authors gratefully acknowledge financial support from the National Science Foundation (Grants CTS-0209403, CTS-0403535, and EEC-0403903) and The Camille & Henry Dreyfus Foundation. The NEXAFS experiments were carried out at the National Synchrotron Light Source, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy. The SE was purchased with funds awarded to JG through the NSF's Instrumentation for Materials Research Program (Grant No. DMR-9975780). The work reviewed here would not have been possible without numerous collaborative efforts with several researchers. We thank Dr. Kirill Efimenko (NCSU) and Dr. Daniel Fischer (NIST) for their assistance during the course of the NEXAFS experiments, Dr. Igal Szleifer and Mr. Peng Gong (Purdue University) for the theoretical work involving surface-tethered charged systems, Dr. Andrea Liebmann-Vinson, Mr. Bryce N. Chaney, and Mr. Harry W. Sugg (Becton Dickinson Technologies) for the XPS work and experiments involving protein adsorption on gradient polymer surfaces. Dr. Petr Vlček and Dr. Vladimír Šubr (Institute of Macromolecular Chemistry, Prague, Czech Republic) are thanked for their numerous contributions in characterizing polyelectrolyte macromolecules. We also thank Professor Michael Rubinstein (University of North Carolina at Chapel Hill) for many fruitful discussions about polyampholytes. We also thank Professor Gregory N. Parsons and Professor Stefan Franzen (NCSU) for allowing us to use their SFM and FTIR set-ups. The authors would like to thank Ms. Jan Singhass (NCSU glass shop) for her assistance in building the polymerization apparatus.

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Authors and Affiliations

  1. Department of Chemical & Biomolecular Engineering, North Carolina State University, 27695-7905, Raleigh, North Carolina, USA

    Rajendra R. Bhat, Michael R. Tomlinson, Tao Wu & Jan Genzer

  2. Polymers Division, National Institute for Standards and Technology, Gaithersburg, Maryland, USA

    Tao Wu

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  1. Rajendra R. Bhat
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  2. Michael R. Tomlinson
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  3. Tao Wu
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  4. Jan Genzer
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Correspondence to Jan Genzer .

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Rainer Jordan

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Bhat, R.R., Tomlinson, M.R., Wu, T., Genzer, J. Surface-Grafted Polymer Gradients: Formation, Characterization, and Applications. In: Jordan, R. (eds) Surface-Initiated Polymerization II. Advances in Polymer Science, vol 198. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_060

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