Molecularly Imprinted Polymers: Man-made Mimics of Antibodies and their Aplications in Analytical Chemistry

583 Pages·2000·30.28 MB·English

by  Börje Sellergren (Eds.)

TECHNIQUES AND INSTRUMENTATION IN ANALYTICAL CHEMISTRY-V OLUME 23
MOLECULARLY IMPRINTED POLYMERS
Man-made mimics of antibodies and their applications in
analytical chemistry
TECHNIQUES AND INSTRUMENTATION IN ANALYTICAL CHEMISTRY
Volume 1 Evaluation and Optimization of Laboratory Methods and Analytical
Procedures. A Survey of Statistical and Mathematical Techniques
by D.L. Massart, A. Dijkstra and L. Kaufman
Volume 2 Handbook of Laboratory Distillation
by E. Krell
Volume 3 Pyrolysis Mass Spectrometry of Recent and Fossil Biomaterials.
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Part A. Analysis of Biogenic Amines
edited by G.B. Baker and R.T. Coutts
Part B. Hazardous Metals in HumanToxicology
edited byA. Vercruysse
Part C. Determination of Beta-Blockers in Biological Material
edited byV. Marko
Volume 5 Atomic Absorption Spectrometry
edited by J.E. Cantle
Volume 6 Analysis of Neuropeptides by Liquid Chromatography and Mass
Spectrometry
by D.M. Desiderio
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Media and in Automated Chemical Control
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Volume 22 Interlaboratory Studies and Certified Reference Materials for
Environmental Analysis: the BCR approach
by Ph. Quevauviller and E.A. Maier
Volume 23 Molecularly Imprinted Polymers
Man-made mimics of antibodies and their applications in analytical
chemistry
edited by B. Sellergren
TECHNIQUES AND INSTRUMENTATION IN ANALYTICAL CHEMISTRY VOLUME 23
MOLECULARLY
IMPRINTED POLYMERS
Man-made mimics of antibodies and
their applications in analytical
chemistry
Edited by B6rje Sellergren
Department of Inorganic Chemistry and Analytical Chemistry
Johannes Gutenberg University Mainz
Duesbergweg 10-14
D-55099 Mainz, Germany
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Printed inThe Netherlands.
Contents
Preface ................................................................................................... xvii
List of Contributors ................................................................................. xix
Abbreviations .......................................................................................... xxii
CHAPTER 1. A HISTORICAL PERSPECTIVE OF THE DEVELOPMENT
OF MOLECULAR IMPRINTING
1.1 Introduction ................................................................................. 1
1.2 Polyakov invents molecular imprinting ............................................ 1
1.3 The contributions of Pauling and Dickey ........................................ 3
1.3.1 Theories of antibody formation ............................................ 3
1.3.2 Bio-imprinting in the 1940s .................................................. 5
1.3.3 Dickey invents molecular imprinting ..................................... 6
1.4 Methods for preparing molecularly imprinted silicas ........................ 6
1.5 The mechanism(s) of selectivity ...................................................... 7
1.5.1 More studies on Dickey's system--molecular footprints? ....... 9
1.5.2 An association mechanism? .................................................. 9
1.5.3 Objections to the association mechanism ............................... 10
1.6 Applications of molecularly imprinted silicas ................................... 11
1.6.1 Separation .......................................................................... 11
1.6.1.1 Column chromatography ....................................... 11
1.6.1.2 Thin layer chromatography ................................... 12
1.6.2 Structure elucidation ............................................................ 13
1.6.3 Catalysis .............................................................................. 13
1.6.4 Other applications ............................................................... 14
1.6.5 Making money using molecular imprinting? .......................... 15
1.7 The decline of imprinted silica research ........................................... 15
1.8 Molecular imprinting in organic polymers ....................................... 15
1.9 Conclusions .................................................................................. 17
Acknowledgements .................................................................................. 17
References .............................................................................................. 17
CHAPTER 2. FUNDAMENTAL ASPECTS ON THE SYNTHESIS AND
CHARACTERISATION OF IMPRINTED NETWORK
POLYMERS
2.1 Introduction ................................................................................. 21
vi Contents
2.2 Free radical polymerisation ........................................................... 23
2.2.1 Initiation ............................................................................ 23
2.2.2 Propagation ....................................................................... 25
2.2.3 Termination ....................................................................... 25
2.2.4 Steady state ........................................................................ 26
2.2.5 Chain transfer .................................................................... 26
2.2.6 Inhibition ........................................................................... 27
2.2.7 Copolymerisation ............................................................... 27
2.2.8 Tacticity ............................................................................ 28
2.3 Copolymers of divinyl monomers and monovinyl monomers ............ 29
2.3.1 Pre-gel regime and kinetics .................................................. 29
2.3.1.1 The EDMA-MMA system ................................... 29
2.3.1.2 The EDMA-MAA molecularly imprinted polymer
(MIP) system: primary structure ............................ 32
2.3.1.3 The EDMA-MAA MIP system: secondary structure 32
2.3.2 Build-up of the porous structure: the tertiary structure .......... 33
2.4 Site stability, integrity and accessibility ........................................... 35
2.5 Polymer porosity and swelling ....................................................... 37
2.6 Thermochemically versus photochemically initiated polymerisations. 39
2.7 The cross-linking monomer ........................................................... 41
2.8 Extraction of template .................................................................. 43
2.9 Functional group titrations ............................................................ 44
2.10 Binding site location ..................................................................... 46
2.11 Characterisation techniques for cross-linked vinyl polymers and MIPS 47
2.11.1 Elemental analysis .............................................................. 48
2.11.2 Gravimetric analysis ........................................................... 48
2.11.3 Nuclear magnetic resonance spectroscopy ............................. 49
2.11.4 Infrared spectroscopy .......................................................... 49
2.11.5 Fluorescence probes of network solvation ............................. 49
2.11.6 Pore structure in the dry state .............................................. 50
2.11.6.1 Gas sorption measurements .................................. 51
2.11.6.2 Mercury penetration ............................................. 52
2.11.6.3 Surface areas ....................................................... 53
2.11.6.4 Pore volume ........................................................ 53
2.11.6.5 Pore size distribution ............................................ 53
2.11.7 Pore structure in the swollen state ........................................ 54
2.11.8 Thermal analysis ................................................................. 55
References ............................................................................................. 55
CHAPTER 3. THERMODYNAMIC PRINCIPLES UNDERLYING
MOLECULARLY IMPRINTED POLYMER FORMULATION
AND LIGAND RECOGNITION
3.1 Introduction ................................................................................. 59
3.2 Physical principles underlying MIP preparation .............................. 59
3.3 Physical principles underlying MIP-ligand recognition .................... 64
Contents vii
3.4 Conclusions .................................................................................. 68
Acknowledgements .................................................................................. 68
References .............................................................................................. 68
CHAPTER 4. MOLECULAR IMPRINTING WITH COVALENT OR
STOICHIOMETRIC NON-COVALENT INTERACTIONS
4.1 Introduction ................................................................................. 71
4.2 The concept of imprinting .............................................................. 72
4.3 The optimisation of the polymer structure ....................................... 74
4.4 The role of the binding-site interactions .......................................... 81
4.5 Examples of covalent interactions in molecular imprinting ................ 82
4.5.1 Boronic acid-containing binding sites .............................................. 82
4.5.2 Other types of covalent binding ...................................................... 85
4.5.3 Covalent binding during imprinting and non-covalent binding
during equilibration ....................................................................... 95
4.6 Molecular recognition and catalysis with stoichiometric
non-covalent interactions ............................................................... 97
Acknowledgements .................................................................................. 107
References .............................................................................................. 107
CHAPTER 5. THE NON-COVALENT APPROACH TO MOLECULAR
IMPRINTING
5.1 Introduction ................................................................................. 113
5.2 Structure-binding relationships ....................................................... 118
5.2.1 Examples of imprinted chiral stationary phases (CSPs) ........... 118
5.2.1.1 High enantioselectivity, high substrate selectivity ..... 118
5.2.1.2 High enantioselectivity, low substrate selectivity ...... 121
5.2.2 Antibody-like recognition ..................................................... 121
5.3 Adsorption isotherms and site distribution ...................................... 126
5.3.1 Batch rebinding experiments ................................................ 127
5.3.2 Results from frontal analysis ................................................ 129
5.4 Adsorption-desorption kinetics and chromatographic band
broadening ................................................................................... 132
5.4.1 Adsorption-desorption kinetics in batch rebinding
experiments ................................................................................... 132
5.4.2 Peak dispersion and asymmetry in chromatography using
MIP-phases ......................................................................... 133
5.5 Factors influencing the recognition properties of MIPs ..................... 138
5.5.1 Choice of the functional monomer ........................................ 138
5.5.2 Influence of the number of template interaction sites .............. 146
5.5.3 Thermodynamic considerations ............................................ 147
5.5.3.1 Concentration of functional monomer and template 149
5.5.3.2 Polymerisation temperature ................................... 149
5.5.3.3 Polymerisation pressure ......................................... 151
viii Contents
5.5.3.4 Polymerisation diluent .......................................... 153
5.5.4 Influence of the template shape ............................................ 154
5.5.5 Influence of the monomer-template rigidity .......................... 156
5.5.6 Studies of the monomer-template solution structures ............. 156
5.6 Post-treatments affecting affinity, selectivity and mass transfer
properties ..................................................................................... 161
5.6.1 Thermal annealing or curing ................................................ 161
5.6.2 Esterification ...................................................................... 164
5.6.3 Hydrolysis .......................................................................... 165
5.7 Medium dependence in the rebinding to MIPs ................................ 165
5.7.1 Effect of swelling and porosity in different media .................. 165
5.7.2 Chromatographic retention modes ....................................... 167
5.7.2.1 Electrostatic interactions- Organic mobile phases .. 167
5.7.2.2 Ion exchange retention mode ................................ 173
5.7.2.3 Hydrophobic interactions- Aqueous mobile phases 176
5.7.3 Mobile phase optimisation .................................................. 179
5.8 Conclusions ................................................................................. 180
References ............................................................................................. 180
CHAPTER 6. METAL-ION COORDINATION IN DESIGNING
MOLECULARLY IMPRINTED POLYMERIC RECEPTORS
6.1 Introduction ................................................................................. 185
6.2 Binding site interactions in molecularly imprinted polymers ............. 186
6.3 Advantages of metal-coordination interactions in molecular
recognition ................................................................................... 186
6.4 Design of molecularly imprinted polymers based on
metal-coordination interaction ....................................................... 187
6.4.1 Bulk polymerised metal-coordinating polymeric receptors ...... 187
6.4.2 Surface modified metal-coordinating imprinted polymers ....... 191
6.5 Applications of metal-coordinated imprinted polymers .................... 192
6.5.1 Sorbents for separation media ............................................. 193
6.5.2 Recognition and binding of proteins .................................... 195
6.5.3 Catalysis ............................................................................ 197
6.5.4 Sensors .............................................................................. 197
6.6 Conclusions and outlook ............................................................... 199
References ............................................................................................. 201
CHAPTER 7. COVALENT IMPRINTING USING SACRIFICIAL
SPACERS
7.1 Introduction ................................................................................. 203
7.2 Sacrificial spacer method ............................................................... 204
7.3 Combination of non-covalent and sacrificial spacer methodologies ... 206
7.4 Amino acid sequence specific polymers ........................................... 208
7.5 Conclusions ................................................................................. 211
Contents ix
Acknowledgements .................................................................................. 211
References .............................................................................................. 211
CHAPTER 8. MOLECULAR IMPRINTING APPROACHES USING
INORGANIC MATRICES
8.1 Introduction ................................................................................. 213
8.1.1 Sol-gel chemistry ................................................................. 214
8.2 Two-dimensional matrices .............................................................. 217
8.3 Three-dimensional matrices ............................................................ 221
8.3.1 Thin films ........................................................................... 221
8.3.2 Bulk structures .................................................................... 222
8.3.3 Separations ......................................................................... 233
8.3.4 Catalysis ............................................................................. 235
8.4 Zeolites and supramolecular imprinting ........................................... 239
8.5 Conclusion ................................................................................... 241
Acknowledgements .................................................................................. 241
References .............................................................................................. 242
CHAPTER 9. IMPRINTING POLYMERISATION FOR RECOGNITION
AND SEPARATION OF METAL IONS
9.1 Introduction ................................................................................. 245
9.2 Survey of preparation methods of metal ion-imprinted resins ............ 245
9.3 Early studies on metal ion-imprinting ............................................. 247
9.3.1 Method 1 in Scheme 9.1 ...................................................... 247
9.3.2 Method 2 in Scheme 9.1 ...................................................... 248
9.4 Metal ion-imprinted microspheres prepared by reorganisation of
coordinating groups on a surface .................................................... 250
9.4.1 The concept of surface imprinting by the use of seed emulsion
polymerisation .................................................................... 250
9.4.2 Preparation and physicochemical characterisation of the
microspheres ....................................................................... 251
9.4.3 Metal adsorption behaviour of the microspheres .................... 252
9.4.4 FT-IR and ESR studies on Cu(II)-loaded microspheres .......... 253
9.5 Metal ion-imprinted resins prepared by o/w emulsion polymerisation 255
9.5.1 Surface imprinting by use of O/W emulsion .......................... 255
9.5.2 Potassium oleate and dioleyl hydrogen phosphate as
functional monomers .......... ................................................. 256
9.5.3 Metal ion-imprinted resins by O/W emulsion polymerisation .. 256
9.6 Metal ion-imprinted resins prepared by W/O emulsion
polymerisation .............................................................................. 260
9.6.1 Imprinting polymerisation in W/O emulsion .......................... 260
9.6.2 Dioleyl phosphate (DOLPA) as functional monomer with
y-ray irradiation .................................................................. 263
9.7 Applications of metal ion-imprinted resins and future aspects ........... 264