Table Of ContentADVANCED TOPICS
IN SCIENCE AND TECHNOLOGY IN CHINA
ADVANCED TOPICS
IN SCIENCE AND TECHNOLOGY IN CHINA
Zhejiang University is one of the leading universities in China. In Advanced
Topics in Science and Technology in China, Zhejiang University Press and
Springer jointly publish monographs by Chinese scholars and professors, as
well as invited authors and editors from abroad who are outstanding experts
and scholars in their fields. This series will be of interest to researchers, lec-
turers, and graduate students alike.
Advanced Topics in Science and Technology in China aims to present the
latest and most cutting-edge theories, techniques, and methodologies in var-
ious research areas in China. It covers all disciplines in the fields of natural
scienceandtechnology,includingbutnotlimitedto,computerscience,mate-
rials science, life sciences, engineering, environmental sciences, mathematics,
and physics.
Zhikang Xu
Xiaojun Huang
Lingshu Wan
Surface Engineering of
Polymer Membranes
With 184 figures
AUTHORS:
Prof. Zhikang Xu Dr. Xiaojun Huang
InstituteofPolymerScience, InstituteofPolymerScience,
ZhejiangUniversity, ZhejiangUniversity,
Hangzhou310027,China Hangzhou310027,China
Email:[email protected] Email:[email protected]
Dr. Lingshu Wan
InstituteofPolymerScience,
ZhejiangUniversity,
Hangzhou310027,China
Email:[email protected]
ISBN 978-7-308-06169-8 Zhejiang University Press, Hangzhou
ISBN 978-3-540-88412-5 Springer Berlin Heidelberg New York
e-ISBN 978-3-540-88413-2 Springer Berlin Heidelberg New York
Series ISSN 1995-6819 Advanced topics in science and technology in China
Series e-ISSN 1995-6827 Advanced topics in science and technology in China
Library of Congress Control Number: 2008936137
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Preface
Surface Engineering of Polymer Membranes embraces those processes which
modifymembranesurfacestoimprovetheirin-serviceperformance.Itmeans
‘modifyingthesurface’ofamembranetoconfersurfacepropertieswhich are
different from its bulk properties. The purpose may be to minimize fouling,
modulate hydrophilicity/hydrophobicity, enhance biocompatibility, act as a
diffusion barrier, provide bio- or chemical functionalities, mimic a biomem-
brane, fabricate nanostructures or simply improve the aesthetic appearance
of the membrane surface. The book begins with the basics of the surface
engineering of polymer membranes, including surface modification, biomim-
icking, enzyme immobilization, molecular imprinting and the various meth-
ods of the spectroscopic and structural study of membrane surfaces. These
are followed by descriptive treatments of topics such as surface modification
bygraftpolymerizationandmacromoleculeimmobilization,theconstruction
of biomimetic surfaces and their functionalities, enzyme immobilization and
bioactivity, molecular recognition and nanostructured surfaces. This book
provides a unique synthesis of our knowledge of the role of surface chemistry
and physics in membrane science and technology. I sincerely hope and antic-
ipate that this book, which contains plentiful information on the many and
varied aspects of membrane surfaces, will be useful to anyone interested or
involved in this fascinating and technologically important research area.
Since 2001 I have been devoted to the study of surface modification and
enzymeimmobilizationonpolymericmembranes.Itisunimaginablethatthe
work could have been carried out, year-by-year, without financial support.
Therefore I gratefully acknowledge the National Natural Science Foundation
of China (Grant nos. 20074033, 50273032, 20474054 and 20774080), the Na-
tional Natural Science Foundation of China for Distinguished Young Scholar
(Grant nos. 50625309), the High-Tech Research and Development Program
of China (Grant no. 2002AA601230 and 2007AA10Z301), and the Zhejiang
Provincial Natural Science Foundation of China (Grant no. Z406260) for the
financial support.
VI Preface
Itisindeedagreatpleasuretoextendmy“thankyou”toallmycolleagues
andstudentsfortheirdedicationtoourresearchprojects.Especially,Chapter
3 profits from the work of Bei-Bei Ke, Chapter 4 is part of the thesis by
Meng-Xin Hu, Chapters 5 and 7 are based on the parts of theses by Qian
Yang and Zheng-Wei Dai respectively, Chapter 8 profits from the work by
Ai-Fu Che and Yun-Feng Yang, and Chapters 9 and 10 are benefit from
the thesis by Zhen-Gang Wang. Their efforts are deeply appreciated and
acknowledged. Finally, I would like to thank the editorial staff of Springer
Verlag and Zhejiang University Press for their assistance.
Zhi-Kang Xu
Hangzhou
December 2007
Contents
1 Surface Engineering of Polymer Membranes: An
Introduction.............................................. 1
2 Techniques for Membrane Surface Characterization....... 5
2.1 General Principles ...................................... 5
2.1.1 Sample Preparation............................... 5
2.1.2 Where is the Surface?............................. 6
2.1.3 Is it Really the Surface?........................... 7
2.1.4 Invasive or Non-invasive........................... 8
2.2 Chemical Composition of Membrane Surfaces .............. 8
2.2.1 Attenuated Total Reflectance Fourier Transform
Infrared (ATR-FTIR) Spectroscopy ................ 9
2.2.2 X-ray Photoelectron Spectroscopy (XPS)............ 11
2.2.3 Static Secondary Ion Mass Spectrometry (SSIMS) .... 16
2.2.4 Energy Dispersive X-ray Spectroscopy (EDS) ........ 18
2.3 Morphologies and Microstructures of Membrane Surfaces .... 21
2.3.1 Surface Morphology of Membrane .................. 21
2.3.2 Introduction to Microscopy ........................ 21
2.3.3 Basic Conceptions in Microscopy ................... 22
2.3.4 Optical Microscopy ............................... 24
2.3.5 Laser Confocal Scanning Microscopy (LCSM) ........ 26
2.3.6 Scanning Electron Microscope...................... 30
2.3.7 Environmental Scanning Electron Microscopy ........ 35
2.3.8 Atomic Force Microscopy.......................... 39
2.4 Wettability of Membrane Surfaces ........................ 44
2.4.1 Wettability and Surface Properties of Membrane ..... 44
2.4.2 Principle of Contact Angle ........................ 45
2.4.3 Methods for Contact Angle Measurement............ 48
2.4.4 Contact Angle Hysteresis.......................... 50
VIII Contents
2.4.5 Factors Influencing the Contact Angle on Membrane
Surfaces......................................... 51
2.5 Characterization of Biocompatibility of Membrane Surfaces .. 53
2.5.1 Non-specific Adsorption of Proteins................. 53
2.5.2 Interactions between Blood and Membrane .......... 57
2.5.3 Interactions Between Cells and Membrane ........... 60
References ................................................. 61
3 Functionalization Methods for Membrane Surfaces ....... 64
3.1 Introduction ........................................... 64
3.2 Functionalization of Polymeric Membranes by Surface
Modification ........................................... 65
3.2.1 Coating ......................................... 65
3.2.2 Self-assembly .................................... 65
3.2.3 Chemical Treatment .............................. 67
3.2.4 Plasma Treatment................................ 67
3.2.5 Graft Polymerization ............................. 69
3.3 Functionalization of Polymeric Membrane by Molecular
Imprinting............................................. 71
3.3.1 Formation of Imprinting Sites by Surface Photografting 72
3.3.2 Formation of Imprinting Sites by Surface Deposition .. 72
3.3.3 Formation of Imprinting Sites by Emulsion
Polymerization on the Surface ..................... 73
3.4 Functionalization of Polymeric Membrane by Enzyme
Immobilization......................................... 74
3.4.1 Enzyme Immobilization by Physical Absorption ...... 74
3.4.2 Enzyme Immobilization by Chemical Binding ........ 74
3.4.3 Enzyme Immobilization by Entrapment ............. 75
3.4.4 Other Methods for Enzyme Immobilization .......... 76
3.5 Conclusion ............................................ 77
References ................................................. 77
4 Surface Modification by Graft Polymerization ............ 80
4.1 Introduction ........................................... 80
4.2 Graft Polymerization on Membranes ...................... 81
4.2.1 Surface Modification by Chemical Graft Polymerization 81
4.2.2 Surface Modification by Plasma-induced Graft
Polymerization................................... 86
4.2.3 Surface Modification by UV-induced Graft
Polymerization................................... 94
4.2.4 Surface Modification by High-energy Radiation-
initiated Graft ................................... 103
4.2.5 Other Methods................................... 108
4.3 Applications of Surface Modified Membranes............... 109
4.3.1 Environmental Stimuli-responsive Gating Membranes . 109
Contents IX
4.3.2 Antifouling Membranes ........................... 116
4.3.3 Adsorption Membranes ........................... 118
4.3.4 Pervaporation and Reverse Osmosis................. 122
4.3.5 Membranes for Energy Conversion Applications ...... 125
4.3.6 Nanofiltration Membrane Preparation............... 131
4.3.7 Gas Separation................................... 132
4.3.8 Biomedical and Biological Applications.............. 132
4.4 Conclusion ............................................ 133
References ................................................. 133
5 Surface Modification by Macromolecule Immobilization... 150
5.1 Introduction ........................................... 150
5.2 Immobilization with Synthetic Polymers................... 151
5.2.1 Polyethylene Glycol (PEG) ........................ 151
5.2.2 Poly(N-vinyl-2-pyrrolidone) (PNVP) ............... 155
5.2.3 Other Synthetic Polymers ......................... 158
5.3 Biomacromolecules ..................................... 161
5.3.1 Non-immune Proteins............................. 161
5.3.2 Antibodies (IgGs) ................................ 162
5.3.3 DNAs........................................... 164
5.4 Conclusion ............................................ 166
References ................................................. 167
6 Membranes with Phospholipid Analogous Surfaces ....... 170
6.1 Introduction ........................................... 170
6.2 Structure and Function of Biomembranes.................. 171
6.3 Biocompatibility of the Phospholipid...................... 171
6.4 Synthesis of Phospholipid Analogous Polymers ............. 173
6.4.1 Side Chain Type of Phospholipid Analogous Polymers 173
6.4.2 Backbone Chain Types of Phospholipid Analogous
Polymers........................................ 179
6.4.3 Other Phospholipid Analogous Polymers ............ 181
6.5 Surface Modification of Polymeric Membrane with
Phospholipid........................................... 181
6.5.1 Surface Adsorption and Coating.................... 182
6.5.2 Physical Blending ................................ 184
6.5.3 Surface Grafting Polymerization.................... 185
6.5.4 In-situ Polymerization............................ 190
6.5.5 Surface Chemical Treatment ....................... 192
6.6 Conclusion ............................................ 197
References ................................................. 197
X Contents
7 Membranes with Glycosylated Surface.................... 202
7.1 Introduction ........................................... 202
7.2 Surface Modification with Natural Polysaccharides.......... 204
7.2.1 Heparin ......................................... 204
7.2.2 Chitosan ........................................ 207
7.3 Surface Modification with Synthetic Glycopolymers......... 208
7.3.1 Glycosylation by UV-induced polymerization ........ 208
7.3.2 Glycosylation by Polymer Analogous Reactions ...... 216
7.3.3 Glycosylation by Surface Initiated Living
Polymerization................................... 218
7.4 Conclusion ............................................ 221
References ................................................. 222
8 Molecularly Imprinted Membranes ....................... 225
8.1 Introduction ........................................... 225
8.1.1 Development of Molecular Imprinting Technology .... 226
8.1.2 Basic Theory of Molecular Imprinting Technology .... 227
8.2 Preparation Methods and Morphologies of Molecularly
Imprinted Membran.e.s.................................... 231
8.2.1 Bulk Polymerization .............................. 232
8.2.2 Physical Mixing ................................. 234
8.2.3 Surface Imprinting ............................... 242
8.3 Separation Mechanism of Molecularly Imprinted Membranes . 247
8.3.1 Facilitated and Retarded Permeation ............... 248
8.3.2 Gate Effect ...................................... 250
8.4 Potential Applications of Molecularly Imprinted Membranes . 251
8.4.1 Separation Technology ............................ 252
8.4.2 Sensor and Controlled Release ..................... 254
8.5 Conclusion and Outlook................................. 254
References ................................................. 255
9 Membrane with Biocatalytic Surface...................... 263
9.1 Introduction ........................................... 263
9.2 Enzyme Immobilization ................................. 265
9.2.1 Natural Polymer-based Membranes ................. 265
9.2.2 Synthetic Polymer-based Membranes................ 273
9.3 Applications .......................................... 291
9.3.1 Membrane Bioreactor ............................. 291
9.3.2 Biosensor........................................ 295
9.4 Conclusion and Outlook ................................ 297
References ................................................. 297
