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Contents

Cover

Title page

Copyright page

Preface

Part 1: Strategies of Affinity Materials

Chapter 1: Recent Molecularly Imprinted Polymer-based Methods for Sample Preparation
1. 1.1 Introduction
2. 1.2 Molecularly Imprinted Solid-phase Extraction
3. 1.3 Molecularly Imprinted Solid-phase Microextraction
4. 1.4 Molecularly Imprinted Stir Bar Sorptive Extraction
5. 1.5 Other Formats
6. 1.6 Conclusions
7. References
Chapter 2: A Genuine Combination of Solvent-free Sample Preparation Technique and Molecularly Imprinted Nanomaterials
1. 2.1 Introduction
2. 2.2 Molecularly Imprinted Polymer Modified Fiber for Solid-phase Microextraction
3. 2.3 In-tube Solid-phase Microextraction Technique
4. 2.4 Monolithic Fiber
5. 2.5 Micro-solid-phase Extraction
6. 2.6 Stir-bar Sorptive Extraction
7. 2.7 Conclusion and Future Scope
8. Acknowledgments
9. Abbreviations
10. References
Chapter 3: Fluorescent Molecularly Imprinted Polymers
1. 3.1 Introduction
2. 3.2 Classes of Emitters to Endow MIPs with Fluorescence
3. 3.3 Fluorescent Molecularly Imprinted Silica
4. 3.4 Post-imprinting of MIPs
5. 3.5 fMIPs as Labels
6. 3.6 Formats for fMIPs
7. 3.7 Conclusion
8. References
Chapter 4: Molecularly Imprinted Polymer-based Micro- and Nanotraps for Solid-phase Extraction
1. 4.1 Introduction
2. 4.2 MIPs as SPE Materials
3. 4.3 Conclusions
4. References
Chapter 5: Imprinted Carbonaceous Nanomaterials: A Tiny Looking Big Thing in the Field of Selective and Specific Analysis
1. 5.1 Introduction
2. 5.2 Graphene-modified Imprinted Polymer
3. 5.3 Carbon Nanotubes-modified Imprinted Polymer
4. 5.4 Combination of Graphene, CNTs, and MIPs
5. 5.5 Graphene Quantum Dots and/or Carbon Dots
6. 5.6 Fullerene
7. 5.7 Activated Carbon
8. 5.8 Conclusions
9. Acknowledgments
10. List of Abbreviations
11. References
Chapter 6: Molecularly Imprinted Materials for Fiber-optic Sensor Platforms
1. 6.1 Introduction
2. 6.2 Material Aspect: Morphology and Physical Forms of MIPs in FO Sensors
3. 6.3 Molecularly Imprinting Technology for Fiber-optic Sensors
4. 6.4 State-of-the-art Fiber-optic Sensors Applications Using Molecularly Imprinted Materials
5. 6.5 Conclusion
6. References

Part 2: Rational Design of MIP for Advanced Applications

Chapter 7: Molecularly Imprinted Polymer-based Sensors for Biomedical and Environmental Applications
1. 7.1 Introduction
2. 7.2 Molecularly Imprinted Polymers for Analytes of Biomedical Interest
3. 7.3 Molecularly Imprinted Polymers for Analytes of Environmental Interest
4. 7.4 Conclusion
5. Acknowledgments
6. References
Chapter 8: Molecularly Imprinted Polymers: The Affinity Adsorbents for Environmental Biotechnology
1. 8.1 Introduction
2. 8.2 Molecularly Imprinted Polymers
3. 8.3 Cryogels
4. 8.4 Process Technology
5. 8.5 Applications
6. 8.6 Elution of Captured Material
7. 8.7 Concluding Remarks
8. 8.8 Outlook
9. References
Chapter 9: Molecular Imprinting Technology for Sensing and Separation in Food Safety
1. 9.1 Food Safety
2. 9.2 Food Analysis
3. 9.3 Current Separation Methods Used for Food Safety Purposes
4. 9.4 What Is MIP?
5. 9.5 MIP Applications Used for Food Safety Purposes
6. References
Chapter 10: Advanced Imprinted Materials for Virus Monitoring
1. 10.1 Introduction
2. 10.2 Virus Imprinting
3. 10.3 Artificial MIP Receptors for Viruses
4. 10.4 Virus Monitoring and Detection Using Biomimetic Sensors
5. 10.5 Virus Imprinting for Separation Technologies
6. 10.6 Conclusions
7. References
Chapter 11: Design and Evaluation of Molecularly Imprinted Polymers as Drug Delivery Systems
1. 11.1 Introduction
2. 11.2 Synthesis and Characterization of MIPs Intended for Drug Release Using Non-covalent Approaches
3. 11.3 Design and Evaluation of Drug Delivery Systems Based on MIPs
4. 11.4 Conclusions
5. References
Chapter 12: Molecularly Imprinted Materials for Controlled Release Systems
1. 12.1 Introduction
2. 12.2 Selectivity, Release Mechanism and Functionality of MIPs-based CR Systems
3. 12.3 Molecularly Imprinted Polymers Production for Controlled Release
4. 12.4 Controlled Release Applications Using Molecularly Imprinted Materials-based Controlled Release
5. 12.5 Conclusion
6. References
Chapter 13: Molecular Imprinting: The Creation of Biorecognition Imprints on Biosensor Surfaces
1. 13.1 Introduction
2. 13.2 Molecular Imprinting
3. 13.3 Microcontact Imprinting
4. 13.4 Capacitive Biosensors
5. 13.5 Surface Plasmon Resonance Biosensors
6. 13.6 Concluding Remarks
7. References
Chapter 14: Molecular Imprinted Polymers for Sensing of Volatile Organic Compounds in Human Body Odor
1. 14.1 Introduction
2. 14.2 MIP-QCM Sensor Array Preparation
3. 14.3 Chemical Vapor Sensing
4. 14.4 Analysis Outcomes
5. 14.5 Conclusion
6. Acknowledgments
7. References
Chapter 15: Development of Molecularly Imprinted Polymer-based Microcantilever Sensor System
1. 15.1 Introduction to Mass Sensors
2. 15.2 Principles of Mass Sensors
3. 15.3 Mechanical Biosensors and Their Fields of Use
4. 15.4 Molecularly Imprinted Polymer Technology
5. 15.5 Molecularly Imprinted Polymer-based QCM Sensors
6. 15.6 Ongoing Studies on Molecularly Imprinted Polymers-based Microcantilevers
7. Acknowledgments
8. References

Index

End User License Agreement

List of Tables

Chapter 2

Table 2.1: Silica-based MIP-SPME fibers.
Table 2.2: Metal-based MIP-SPME fibers.
Table 2.3: Monolithic MIP-SPME/μ-SPE fibers.

Chapter 4

Table 4.1: Some commercially available MIP-based SPE products.
Table 4.2: Some of the most recent applications of MIP-based SPE to environmental samples.
Table 4.3: Some of the most recent applications of MIP-based SPE to biological samples.
Table 4.4: Some of the most recent applications of MIP-based SPE to food and beverage samples.

Chapter 5

Table 5.1: A comparative study of various properties of carbon allotropes.

Chapter 7

Table 7.1: Approaches employed for molecular imprinting.
Table 7.2: MIP-based sensors for the detection of environment contaminants.

Chapter 8

Table 8.1: MIPs directed against HMs.
Table 8.2: Applications of MIPs for sensors of environmental interest.
Table 8.3: Examples of molecular imprinting based sensors against low molecular weight compounds.

Chapter 10

Table 10.1: Biomimetic sensors developed for virus detection.

Chapter 11

Table 11.1: Some interesting studies using MIPs as DDS.

Chapter 13

Table 13.1: Macromolecular imprinting techniques.
Table 13.2: Analytical results from sensors based on microcontact MIPs and other imprinting methods.
Table 13.3: Comparison of analytical performances of different techniques used for PSA detection.

Chapter 14

Table 14.1: Organic acids identified in GC–MS spectra from body odor [96].
Table 14.2: Aldehydes identified in GC–MS spectra from body odor [97, 98].
Table 14.3: SVM classification results for binary mixtures of acid odors by response analysis of MIP-1-QCM sensor array.
Table 14.4: SVM classification results for binary and tertiary mixtures of aldehyde odors by response analysis of MIP-1-QCM sensor array.
Table 14.5: SVM classification results for binary and tertiary mixtures of aldehyde odors by response analysis of MIP-2-QCM sensor array.

List of Illustrations

Chapter 1

Figure 1.1: Preparation of MIPs.
Figure 1.2: Scheme of the preparation of MIP microspheres with a silica mold and SEM images of the intermediate composite material (a) and the same beads after treatment with 3 M aqueous NH₄HF₂ (b). Reprinted from [23] with permission from Elsevier.
Figure 1.3: SEM micrographs of MIP composite membranes prepared with different polymerization solvents: (a) caprylonitrile/paraffin oil, (b) toluene/paraffin oil, (c) trihexyl(tetradecyl)phosphoniumtris(pentafluoroethyl) trifluorophosphate (PH3 T FAP), (d) 1-butyl-3-methylimidazolium tetrafluoroborate, (e) cross-sectional view of a PH3 T FAP MIP, and (f) unmodified glass microfiber membrane. Reprinted from [28] {Renkecz, 2013, Molecularly Imprinted Polymer Microspheres Containing Photoswitchable Spiropyran-Based Binding Sites} with permission from John Wiley & Sons.
Figure 1.4: Schematic of preparation of molecularly imprinted microSPE device. Reprinted from [55] with permission from Elsevier.
Figure 1.5: Scanning electron micrographs of a tetracycline MIP-coated fiber at ×300 (a) and ×10,000 (b) magnification. Preparation conditions of MIP-coated fiber: solvent: acetone; monomer: acrylamide; cross-linker: trimethylolpropanetrimethacrylate; initiator: azo(bis)-isobutyronitrile; polymerization time: 6 h; coating times: 10. Reprinted from [59] with permission from Elsevier.
Figure 1.6: LC–UV chromatograms obtained at 220 nm for (A) a soil sample extract directly injected without any previous cleanup, (B) a soil sample extract enriched with triazines at 0.1 mg.L⁻¹ concentration level after MI-SPME, (C) a 0.1 mg.L⁻¹standard solution of triazines after MI-SPME, and (D) a nonspiked soil sample extract after MI-SPME. Peak numbers: (1) desisopropylatrazine, (2) desethylatrazine, (3) simazine, (4) cyanazine, (5) atrazine, (6) propazine, and (7) yerbutylazine. Reprinted from [64] with permission of American Chemical Society.
Figure 1.7: Chromatograms of 10 mg L⁻¹ spiked water samples. (a) Directly injection of the spiked sample. (b) Spiked sample with NIP-coated SBSE. (c) Spiked sample with MIP-coated SBSE. (d) 1 mg L⁻¹ estrogens mixed standard solution. Peak numbers: (1) bisphenol A, (2) estradiol, (3) bisphenol B, (4) estrone, and (5) diethylstilbestrol. Reprinted from [71] with permission from Elsevier.
Figure 1.8: HPLC chromatograms obtained in the analysis of lake water sample (150 mL) enriched at the 0.5 ng mL⁻¹ concentration level extracted onto C18 cartridge (a) and using the LLSME technique (b). Peak numbers: (1) simazine, (2) cianizyne, (3) atrazine, (4) propazine, and (5) tercbutylazine. Reprinted from [78] with permission from Elsevier.

Chapter 2

Figure 2.1: (a) Graphical representation to understand the sample preparation technique. (b) Headspace (HS) and direct immersion (DI) solid-phase microextraction (SPME) technique. (c) Graphical representation for the preparation of molecularly imprinted polymers (MIPs). [Reproduced with permission from Ref. 28.]
Figure 2.2: Schematic representation of SPME technique: (a) binding with analyte and (b) extraction of analyte in a particular extraction solvent. [Reproduced with permission from Ref. 51.]
Figure 2.3: Commercial SPME syringe from Supelco (a and b) and (c) its individual components.
Figure 2.4: (a) Schematic representation of Sudan I MIP-coated fiber preparation via silynation steps. [Reproduced with permission from Ref. 47.] (b) Fabrication of MIP-SPME fiber selective for aspartic acid. [Reproduced with permission from Ref. 39.]
Figure 2.5: (a) Schematic diagram of the on-line DL-LSME-HPLC system. [Reproduced with permission from Ref. 43.] (b) Schematic representation of imprinting of endosulfan in poly(methacrylamide functionalized magnetic composites-co-N,N-methylene-bis-acrylamide). [Reproduced with permission from Ref. 55.]
Figure 2.6: Schematic diagram for electrospinning (a) and on-line MIP-SPME tool coupled with HPLC (b). [Reproduced with permission from Ref. 54.]
Figure 2.7: Schematic representation of automated MIP-coated SPME. [Reproduced with permission from Ref. 56.]
Figure 2.8: (a) In-tube extraction device. [Reproduced with permission from Ref. 71.] (b) Schematic diagram for preparing the MIP-coated SPME fibers. [Reproduced with permission from Ref. 82.]
Figure 2.9: (a) Schematic illustration of MIP monolith preparation and recognition procedure for enkephalin by epitope imprinting technique. [Reproduced with permission from Ref. 84.] (b) Scheme of the procedure for the preparation of MIP monoliths for SPME. [Reproduced with permission from Ref. 88.]
Figure 2.10: (a) Schematic diagram of microwave-assisted preparation of monolithic MIP fibers. [Reproduced with permission from Ref. 92.] (b) Preparation of molecularly imprinted fibers and etching with HF. [Reproduced with permission from Ref. 22].
Figure 2.11: (a) The preparation and extraction procedure of the electrode array. [Reproduced with permission from Ref. 128.] (b) Schematic representation of the stir-bar fabrication and analyte binding in MIP cavities. [Reproduced with permission from Ref. 129.]

Chapter 3

Scheme 3.1: Principle of MIP synthesis process.
Figure 3.1: Structures of putative and assumed M1 as well as cyhalothrin (a) and response of the fMIP (left) and fNIP (right) microspheres to cyhalothrin in the concentration range from 0 to 1.0 nM from [33] (b).
Figure 3.2: Structures of M2 and cocaine (a), M3 and BPA (b), and M4 and atrazine (c).
Figure 3.3: Structures of M5 and cyclobarbital (a) and M6 and (Z)-N’-cyclododecylidene picolinohydrazonamide (b).
Figure 3.4: Structure of M7 and schematic representation of the imprinting process from [42] (a) and structures of M8, diquat and paraquat (b).
Figure 3.5: Structure of M9 and schematic representation of the coordination of Pb²⁺ and Hg²⁺ from [44, 45] (a and b), structure of M10 (c), and structure of M11 (d).
Figure 3.6: Structure of M12 (a) and schematic drawing of the detection of Z-L-Phe including the structure of M13 (b) from [9].
Figure 3.7: Schematic representation of the energy transfer from the antenna ligand to the lanthanide ion from [28]; typical wavelengths for a Eu³⁺ system are exemplarily indicated.
Figure 3.8: Schematic drawing of the detection of an analyte using MIP-QDs from [63].
Figure 3.9: Illustration of the preparation of MIP CDs from [30].
Figure 3.10: Schematic illustrations of the fluorescence quenching of PFOS, the charge transfer and the structure of M14 from [79] (a), the structure of M15 (b), and schematic representation of fMISs synthesized with M16 from [81] (c).
Figure 3.11: Schematic illustration of the different post-imprinting strategies.
Figure 3.12: Schematic illustration of the cell imaging principle based on fMIPs from [90] (a) and principle of using fMIPs as tools for imaging of SA-terminated glycan motifs from [91] (b).
Figure 3.13: Schematic illustration of the different MIP formats.

Chapter 4

Figure 4.1: Principle of SPE.
Figure 4.2: Schematic representation of the prepared Nd³+ imprinted polymers. (Reproduced with permission from [42].)
Figure 4.3: Schematic depiction of the prepared magnetic traps for Pb²+. (Reproduced with permission from [44].)
Figure 4.4: Schematic illustration of the prepared MIP-based MWNT for BPA. (Reproduced with permission from [45].)
Figure 4.5: FPLC chromatogram of HA provided from (a) Fluka, (b) fish eye, and (c) S. equi culture. (Reproduced with permission from [74].)
Figure 4.6: SEM images of albumin-imprinted beads with 4000 times (a) and 25 000 times magnification (b), MIP composite cryogels (c and e), and NIP composite cryogels (d and f). (Reproduced with permission from [75].)
Figure 4.7: Schematic depiction of the prepared magnetic MIP toward biotin. (Reproduced with permission from [107].)

Chapter 5

Figure 5.1: Different forms of carbon allotropes.
Scheme 5.1: Various chemical routes for modification of graphene.
Scheme 5.2: Different chemical routes to modify the surface of the CNT.
Figure 5.2: (a) General scheme of molecularly imprinting technique and (b) schematic representation showing working principle of chemiluminescence (CL) system. (Reproduced with permission from Ref. [97]).
Figure 5.3: (a) Schematic diagram, showing synthesis of sunset yellow (SY)-imprinted polymer. (Reproduced with permission from Ref. [72].) (b) Schematic representation of simultaneous electrochemical immunoassay: (i) the preparative procedure of signal tags and (ii) the synthesis process of creating the capture probes and electrochemical detection. (Reproduced with permission from Ref. [85].)
Figure 5.4: (a) Schematic diagram showing fabrication of E. coli-imprinted polymer-modified surfaces. (Reproduced with permission from Ref. [92].) (b) Schematic diagram of CdTe QDs@luminol-chitosan/GM–MIP–CL sensor (i); the preparing process of CdTe QDs@luminol which was used to amplify the CL signal (ii); and Cs/GM–MIP (iii), which was used to recognize chrysoidine selectivity. (Reproduced with permission from Ref. [98].)
Figure 5.5: (a) Outline of l-Cys micro-contact imprinting. (Reproduced with permission from Ref[114].). (b) Design of the CNTs-imprinted polymer in step-wise modification with Microcystin–LR (MC–LR), monomers (vinyl benzyl) trimethylammonium chloride (VBTMA), 4-vinylbenzenesulfonate (VBSate), and vinyl benzoate (VBate), radical initiator (benzoyl peroxide, BPO), polymerization monomer, i.e. vinylbenzene (VB), and the cross-linker, i.e. divinylbenzene (DVB). (Reproduced with permission from Ref [118].)
Figure 5.6: (a) The reaction pathway for the preparation of MIP by iniferter polymerization technique. (Reproduced with permission from Ref. [122].) (b) Schematic illustration of the glucose-imprinted poly(NIPAM–AAm–VPBA)–CDs hybrid microgels based on the one-step free radical precipitation polymerization in water. (Reproduced with permission from Ref. [129].)
Figure 5.7: (a) Truth Table for determination of AFP. (Reproduced with permission from Ref. [133].) (b) The proposed simplified structural formula of the pre-polymerization complex of 1 with functional monomers 2, 3, and 4 as well as with the Pd(ac)₂ cross-linker. (Reproduced with permission from Ref. [139].)

Chapter 6

Figure 6.1: General principles of molecular imprinting process. (Left) Self-assembling approach and (right) preorganized approach [20].
Figure 6.2: Procedure of MIPs/NIPs-based FO array fabrication for detection of ENRO adopted from the work by Carrasco et al. [49].
Figure 6.3: SEM images of the 2,4-D MIPs-coated fibers. The scale bars are (a) 200 μm and (b) 2 μm. Adopted from the work by Xuan-Anh Ton et al. [52].
Figure 6.4: Simple scheme of an optical fiber [66].
Figure 6.5: Basic block diagram for a FO sensor system [68].
Figure 6.6: (a) Extrinsic sensor and (b) intrinsic sensor schematic illustration [71].
Figure 6.7: Optical fiber monitors the pressure and temperature to optimize the fuel-recovery process [124]. (Courtesy of LIOS Technology GmbH.)
Figure 6.8: Schematic representation of (up) end-tip (distal cuvette) and (down) etched-type FO sensor [70].
Figure 6.9: Reflection and refraction representation [125].
Figure 6.10: Representation of evanescent field [78].
Figure 6.11: Schematic representation of an evanescent-wave FO sensor (adopted from [79]).
Figure 6.12: (left) Experimental setup of system with showing end-tip fluorescence-based FO sensor and (right) performance of the work is shown with trying different materials [80].
Figure 6.13: Presentation of a U-shaped FO sensor [84].
Figure 6.14: A U-shaped absorption-based FO sensor experiment for sensing a FITC solution as an analyte model [89].
Figure 6.15: Operation of an FBG optical sensor [66].
Figure 6.16: (a) Tilted FBG used in MIPs system and (b) procedure in the sensing mechanism [56].
Figure 6.17: Simple representation of a Fabry–Perot interferometer (FPI) [66].
Figure 6.18: Output light response signal as a function of cavity distances [126].
Figure 6.19: (a) Mach–Zehnder and (b) Michelson interferometer configuration [91].
Figure 6.20: A typical SPR-based FO sensor configuration [94].
Figure 6.21: (a) Excitation of surface plasmon by EW and (b) normalized reflectance intensity vs. incident angle [94].
Figure 6.22: SPR spectrums for two different refractive indices [94].
Figure 6.23: Processes of molecular imprinting. 1: functional monomers, 2: cross-linker, 3: template, a: complex formation, b: polymerization, c: extraction [18].
Figure 6.24: Experimental setup of MIPs-based FO sensors to sense (a) Z-L-Phe [33] and (b) red9 dye [81].
Figure 6.25: Square-grating reflection-based sensor using MIPs [98].
Figure 6.26: Experimental setup of the SPR-based FO using MIPs to sense melamine [59].
Figure 6.27: Common functional monomers in MIPs [40].
Figure 6.28: Common cross-linkers used in molecular imprinting [40].
Figure 6.29: Typical morphology formation models in an MIPs [110].
Figure 6.30: SEM image of a polymer. Left side is macropores. Right side is mesopores [18].
Figure 6.31: A simple illustration of homogeneous and heterogeneous binding sites in MIPs [111].
Figure 6.32: Batch rebinding experimental setup [111].
Figure 6.33: Scatchard plot for ethyl adenine-9-acetate polymer [111].
Figure 6.34: Discrete (a and b) and continuous (c and d) models distributions [111].
Figure 6.35: The optical fiber sensing and the template binding in [80].

Chapter 7

Figure 7.1: Scheme of molecular imprinting by (a) non-covalent, (b) covalent, (c) semicovalent, and (d) electrostatic interactions.
Figure 7.2: Papers based on MIPs published in the last 6 years.
Figure 7.3: The scheme for the MIP fabrication and the catalytic mechanism for the analysis of metronidazole [66].
Figure 7.4: Fabrication and performance of a MIP-based sensor for TNT detection based on polythioaniline/AuNPs [47].

Chapter 8

Figure 8.1: (a–b) Picture of the plastic carriers of different types present an inert supporting medium for the formation of soft and highly elastic hydrophilic materials inside (c) macroporous gels bearing different functionalities formed inside the carriers. (Reproduced with permission from [37].)
Figure 8.2: (a) Appearance of an empty Kaldnes carrier and a MIP/PVA–MGs formed inside the plastic carrier (called MGPs). The SEM image represents the MIP/PVA–MGs formed inside the Kaldnes plastic carrier. (b) Schematic representation of a packed MGPs reactor (left) and a moving MGPs reactor (right). b1: Schematic representation of one layer of MGPs in packed MGPs reactor. The arrows show the water flow routes in the column. b2: Schematic representation of one layer of MGPs in moving MGPs reactor. The arrows show the perpetual motion of the MGPs in the column. (Reproduced with permission from [40].)
Figure 8.3: Capacitive response (nF) plotted toward time (min), each measurement was obtained with a 1-min interval. The capacitance values of a (○) MIP- and (•) NIP-functionalized electrode, and (□) the difference between both, were normalized for the baseline values (set equal to 0 nF) of each curve. The maximum difference in capacitance (ΔC) between the MIP and NIP electrode is indicated by the arrow. (Reproduced with permission from [69].)

Chapter 9

Figure 9.1: Several chemical entities involved in MIP preparation.
Figure 9.2: Schematic representation of molecular imprinting polymer.
Figure 9.3: Schematic representation of running process of MIPs-TLC-SERS biosensor. A and B: before and after improving of plate, respectively, C: plate surface after Au colloid covering; spot 1: 0 ppm Sudan I spike paprika extract, spot 2: 100 ppm Sudan I standard solution, spot 3: 100 ppm Sudan I spiked paprika extract. Reprinted from Ref. [59] with permission of Elsevier.
Figure 9.4: SERS spectra of Sudan I scanned in wave length between 703 and 1262 cm⁻¹. Reprinted from Ref. [59] with permission of Elsevier.
Figure 9.5: Schematic illustration of fabricating MIP–ir–AuNPs. Reprinted from Ref. [83] with permission of Elsevier.
Figure 9.6: The preparation procedure of the CS–NR–Mag–MIP. Reprinted from Ref. [122] with permission of Elsevier.
Figure 9.7: Illustration of the synthesis of Mag–MIP for detection of biotin proposed by Uzuriaga-Sanchez et al. Reprinted from Ref. [129] with permission of Elsevier.

Chapter 10

Figure 10.1: Schematic illustration of glass bead preparation with template for solid-phase MIP synthesis. Reproduced with permission from [18].
Figure 10.2: Principles of the high-affinity MIP production using a novel solid-phase synthesis method. Reproduced with permission from [19].
Figure 10.3: Schematic diagram showing the mode of operation of the automated solid-phase MIP nanoparticle synthesizer. Reproduced with permission from [73].
Figure 10.4: A diverse range of biosensors based on transduction modes for viruses monitoring and detection.
Figure 10.5: Affinity-based sensor assays for virus detection. Reproduced with permission from [19].

Chapter 11

Figure 11.1: Chemical structure of some monomeric species used in the synthesis of MIPs intended for drug release.
Figure 11.2: MIP monolith synthesized by bulk polymerization (a); and imprinted microparticles suspended in the porogenic solvent synthesized by precipitation polymerization (b). (Images obtained by the authors.)
Figure 11.3: SEM images of MIPs synthesized by bulk polymerization using nicotine as template in two different fields. (Results obtained by the authors.)
Figure 11.4: SEM (a) and AFM (b) images of imprinted nanoparticles synthesized by precipitation polymerization using nicotine as template. (Results obtained by the authors.)
Figure 11.5: Characterization of copolymers synthesized using methacrylic acid, 2-hydroxyethyl methacrylate, and ethylene glycol dimethacrylate by ATR–FTIR. The arrow (1620 cm⁻¹) indicates the stretching related to vinyl moieties (C=C) of residual monomers at spectrum of the unwashed polymer. (Results obtained by the authors.)
Figure 11.6: Characterization of copolymer synthesized using methacrylic acid, 2-hydroxyethyl methacrylate, and ethylene glycol dimethacrylate by TGA. (Results obtained by the authors.)
Figure 11.7: Hydrodynamic diameter of MIP particles. (Results obtained by the authors.)
Figure 11.8: Chemical structure of the surfactants.
Figure 11.9: Experimental apparatuses I (basket) and II (paddle).
Figure 11.10: Vertical diffusion cell used to evaluate transdermal and topical formulations.
Figure 11.11: Drug release profiles following the Higuchi model (grey) and zero-order model (black).

Chapter 12

Figure 12.1: Diagram of the synthesis of MIPs and the preparation of MIPs-based drug delivery and re-loading steps after the drug release. The distorted drug receptors are also depicted after the effect of stimuli.
Figure 12.2: The three major approaches to control the release from DDS.
Figure 12.3: MIPs toward enantiomers and enantioselective-controlled delivery of racemic drugs.
Figure 12.4: Theophylline release profiles from imprinted polymer (theophylline:EGDMA:MAA in chloroform) loaded with various quantities of drug in phosphate buffer pH 7 [21].
Figure 12.5: Propranolol release of discs synthesized with non-imprinted (NIP) or imprinted (MIP) polymers (EGDMA:MAA in chloroform) embedded in a non-polar transdermal adhesive [9].
Figure 12.6: The release rate of the R and S enantiomers of ibuprofen from granules including S-ibuprofen-imprinted polystyrene particles and racemic drug under different drug/polymer ratios [56].
Figure 12.7: Time course of relative ratio of R-propranolol and S-propranolol enantiomers released from tablets constituted by a low-swelling imprinted polymer shell and a racemic propranolol core (MAA:EGDMA: template 12 mmol:310 mmol:3 mmol in chloroform) [66].
Figure 12.8: Illustration for imprinting process of a peptide [58].
Figure 12.9: Timolol release profiles from re-loaded imprinted hydrogels at 37 °C in artificial lachrymal fluid [76].
Figure 12.10: Mechanism of action of stimuli-sensitive polymers.
Figure 12.11: Testosterone release rate in the presence of hydrocortisone or without hydrocortisone [86].
Figure 12.12: External stimulus such as change in electric field, temperature, or pH result in volume phase transition of the hydrogel [94].
Figure 12.13: Overall affinity with respect to cross-linker (methylenebis-(acrylamide)) for calcium ions of non-imprinted and imprinted NIPAAms (6 M) gels in water in shrunken state [97].
Figure 12.14: Re-absorption and release of DPA in water as a function of temperature with imprinted NIPAAm (6 M) gels synthesized with various concentrations of Imprinter-Q [100].
Figure 12.15: Glucose sensors obtained with a carbohydrate template and [(4-(N-vinylbenzyl)diethylenetriamine) copper(II)] diformate at alkaline pH [111].
Figure 12.16: Rebinding ability of non-imprinted and glucose-imprinted polymers in water for mannose, glucose, and galactose [111].
Figure 12.17: Reversible covalent binding of glucose to phenylboronic acid in alkaline medium [117].
Figure 12.18: Schematics of common MIP synthesis methods: (a) bulk polymerization, (b) suspension polymeri;zation, (c) precipitation polymerization, and (d) emulsion polymerization.
Figure 12.19: Structure of the most common anticancer therapeutic drugs used for molecular imprinting until now.
Figure 12.20: (a) Schematic representation of the release of DOX from Fe₂O₄@DOX-MIP under magnetic field, (b) cumulative DOX release in percent versus time of Fe₂O₄@DOX-MIP, and (c) cumulative DOX release in percent versus time of Fe₂O₄@DOX-NIP at 37 °C without magnetic field and under AMF. (Reproduced with permission from N. Griffete, J. Fresnais, A. Espinosa, C. Wilhelm, A. Bée, C. Ménager, Nanoscale, 2015, 7, 18891, Royal Society of Chemistry) [167].
Figure 12.21: (a) SEM images magnetic nanoparticles and magnetic nanoparticles coated by of 5-FU-imprinted polymer; (b) Concentration of 5-FU in tumor, liver, and kidney tissues of tumor-bearing mice with different treatments. 5-FU: 5-fluorouracil; 5-FU-IP: 5-fluorouracil-imprinted polymer; 5-FU-IPM: 5-fluorouracil-imprinted polymer with magnetic field*: Indicates significant difference compared with other groups. (Reproduced with permission from H. Hashemi-Moghaddam, S. Kazemi-Bagsangani, M. Jamili, S. Zavareh, International Journal of Pharmaceutics, 2016, 497, 228. ©2016, Elsevier) [170].
Figure 12.22: Schematic illustration of the fabrication of propranolol-imprinted nanotubes in a porous AAO membrane. (Reproduced with permission from J. Yin, Y Cui, G. Yang, H Wang, Chem. Commun., 2010, 46, 7688, Royal Society of Chemistry) [177].
Figure 12.23: (a) Human skin structure with possible routes for drug permeation indicated: (1) across the continuous skin, and via (2) the hair follicles, and (3) the sweat ducts; (b) Simplified structure of the stratum corneum. (Reproduced with permission from K. Higaki, C. Amnuaikit, T. Kimura, American Journal of Drug Delivery, 2003, 1, 187, Springer Link) [182].

Chapter 13

Figure 13.1: Schematic representation of microcontact imprinting technique. (a) Preparation of the glass cover slips (protein stamps), (b) preparation of the capacitive gold electrodes, (c) microcontact imprinting of BSA onto the gold electrode surface via UV polymerization and (d) removal of template protein (BSA) from the electrode surface. (Reproduced from [49] with permission.)
Figure 13.2: Assaying principle of capacitive biosensors. Actual capacitive sensorgrams showing real-time binding signal (1.0 × 10⁻¹⁴ M) with a total assay time of 37 min (22 min regeneration and baseline stabilization and 15 min sample binding reaction). Numbered phases represent: (1) stable baseline, (2) injection, (3) binding and (4) regeneration and each point represents a pulse. Inset: sensor response to the different concentrations of MC–LR. (Reproduced from [42] with permission.)
Figure 13.3: (a) Reproducibility of the PSA–MIP capacitive biosensor (PSA concentration 1.0 ng mL⁻¹; flow rate 100 μL min⁻¹; sample volume 250 μL; running buffer 10 mM phosphate, pH 7.4; regeneration buffer 25 mM glycine–HCl, pH 2.5; T 25 °C) and (b) reproducibility of the anti-PSA capacitive biosensor (PSA concentration 1.0 ng mL⁻¹; flow rate 100 μL min⁻¹; sample volume 250 μL; running buffer 10 mM phosphate, pH 7.4; regeneration buffer 25 mM glycine-HCl, pH 2.5; T 25 °C). (Reproduced from [44] with permission.)
Figure 13.4: Automated flow injection system used for current pulse capacitive immunosensor. (Reproduced from [87] with permission.)
Figure 13.5: Assaying principle of SPR. SPR detects changes in the refractive index in the immediate vicinity of the surface layer of a sensor chip. SPR is observed as a sharp shadow in the reflected light from the surface at an angle that is dependent on the mass of material at the surface. The SPR angle shifts (from I to II in the lower left-hand diagram) when biomolecules bind to the surface and change the mass of the surface layer. This change in resonant angle can be monitored non-invasively in real time as a plot of resonance signal (proportional to mass change) versus time. (Reproduced from [89] with permission.)
Figure 13.6: Schematic representation of microcontact imprinting of PSA onto the SPR biosensor and surface modification of glass cover slips: (a) preparation of glass cover slips (protein stamps), (b) preparation of SPR chips, (c) microcontact imprinting of PSA via UV polymerization, (d) surface modification of glass cover slips with APTES, (e) activation of amino groups on glass cover slips with glutaraldehyde and (f) PSA immobilization onto the glass cover slips. (Reproduced from [8] with permission.)
Figure 13.7: (a) Real-time response of SPR biosensor against several PCT solutions in phosphate buffer at different concentrations. (b) Concentration dependency of PCT-imprinted SPR biosensor showing the high linearity of the sensor response in the studied concentration range. (Reproduced from [143] with permission.)
Figure 13.8: Selectivity of SPR and QCM sensors for E. coli against Bacillus and Staphylococcus. (Reproduced from [9] with permission.)

Chapter 14

Figure 14.1: Schematic representation of MIP formation.
Figure 14.2: Graphic representation of four elements MIP-QCM sensor array system [96–98].
Figure 14.3: MIP-QCM sensor array system used in sensing of acids and aldehydes odors [96–98].
Figure 14.4: GC–MS spectra of human body odor in (a) female left axilla, (b) male right axilla, and (c) female right axilla [96–98].
Figure 14.5: Response of MIPs-1-QCM sensor (propenoic acid -PAA MIP based) to (a) propenoic acid (5 μl), and (b) mixture of propenoic acid (5 μl) and hexanoic acid (5 μl).
Figure 14.6: MIPs-1-QCM sensor array response to single acids odors for (a) 5 μL, and (b) 10 μL, (c) 5 μL, and (d) 10 μL, (e) 5 μL, (f) 10 μL, and to binary mixtures of acids for (g) 5 +5 μL, and (h) 5+10 μL, (i) 5 +5 μL, and (j) 5+10 μL, (k) 5 +5 μL, and (l) 5+10 μL.
Figure 14.7: Structure of (a) PAA, (b) propenoic acid, (c) hexanoic acid, (d) octanoic acid, (e) hexanal, (f) heptanal, (g) nonanal and the probable H-bonding of PAA, (h) propenoic acid, (i) hexanoic acid, (j) octanoic acid odors, (k) hexanal, (l) heptanal, and (m) nonanal.
Figure 14.8: MIPs-1-QCM sensor array response to nonanal (5 μL) odor.
Figure 14.9: MIPs-1-QCM sensor array response to the binary mixture of hexanal (5 μL) and nonanal (5 μL) odor.
Figure 14.10: MIPs-1-QCM sensor array response to the tertiary mixture of hexanal (5 μL), heptanal (5 μL) and nonanal (5 μL) odor.
Figure 14.11: Response of MIPs-1-QCMsensor-2 to (a) heptanal (5 μl), (b) binary mixture of hexanal (5 μl), and heptanal (5 μl), (c) binary mixture of heptanal (5 μl), and nonanal (5 μl), and (d) tertiary mixture of hexanal (5 μl), heptanal (5 μl), and nonanal (5 μl).
Figure 14.12: MIPs-2-QCM sensor array response to (a) water (5 μl), (b) hexanal (5 μl), (c) heptanal (5 μl), and (d) nonanal (5 μl).
Figure 14.13: MIPs-2-QCM sensor array response to binary mixture of (a) hexanal (5 μl) and heptanal (5 μl), (b) heptanal (5 μl) and nonanal (5 μl), (c) hexanal (5 µl) and nonanal (5 μl), and (d) tertiary mixture of hexanal (5 μl), heptanal (5 μl), and nonanal (5 μl).
Figure 14.14: Response representation of MIPs-2-QCM sensor array to (a) hexanal (5 μl) (b) heptanal (5 μl), (c) nonanal (5 μl), and (d) water (5 μl), and to binary mixture of aldehydes (e) hexanal (5 μl)+heptanal (5 μl), (f) heptanal (5 μl)+nonanal (5 μl), (g) hexanal (5 μl)+nonanal (5 μl), and (h) tertiary mixture of hexanal (5 μl)+heptanal (5 μl)+nonanal (5 μl).
Figure 14.15: MIP-QCM sensor array response analysis flow chart.
Figure 14.16: Representation of single acids odors in PC space by response analysis of MIPs-1-QCM sensor array in measurement cycle (a) 1, (b) 2, (c) 3, and (d) 4.
Figure 14.17: Acid odor representation in PC space by response analysis of MIPs-1-QCM sensor array to binary mixtures of acids in (a) measurement cycle 1, (b) measurement cycle 2, and to both single and binary mixtures of acids in measurement cycle 1.
Figure 14.18: Single aldehyde odors representation in PC space with response analysis of MIPs-1-QCM sensor array by (a) excluding the response of the non-MIP-QCM sensor, and (b) including the response of the non-MIP-QCM sensor.
Figure 14.19: Representation of binary mixture of aldehydes in PC space with response analysis of MIPs-1-QCM sensor array by (a) excluding the response of the non-MIP-QCM sensor, and (b) including the response of the non-MIP-QCM sensor.
Figure 14.20: Representation of tertiary mixture of aldehydes in PC space with response analysis of MIPs-1-QCM sensor array by (a) excluding the response of the non-MIP-QCM sensor and (b) including the response of the non-MIP-QCM sensor.
Figure 14.21: Representation of single, binary, and tertiary mixture of aldehydes together in PC space with response analysis of MIPs-1-QCM sensor array by excluding the response of the non-MIP-QCM sensor and assuming (a) single class (b) three separate classes for all the binary mixtures of aldehydes; by including the response of the non-MIP-QCM sensor and assuming (c) single class (d) three separate classes for all the binary mixtures of aldehydes.
Figure 14.22: Single aldehyde odors representation in PC space with response analysis of MIPs-2-QCM sensor array by (a) excluding the response of the non-MIP-QCM sensor and (b) including the response of the non-MIP-QCM sensor.
Figure 14.23: Representation of binary mixtures of aldehydes odor in PC space with response analysis of MIPs-2-QCM sensor array by (a) excluding the response of the non-MIP-QCM sensor and (b) including the response of the non-MIP-QCM sensor.
Figure 14.24: Representation of tertiary mixtures of aldehydes odors in PC space with response analysis of MIPs-2-QCM sensor array by (a) excluding the response of the non-MIP-QCM sensor and (b) including the response of the non-MIP-QCM sensor.
Figure 14.25: Representation of single, binary, and tertiary mixture of aldehydes together in PC space with response analysis of MIPs-2-QCM sensor array by excluding the response of the non-MIP-QCM sensor and assuming (a) single class (b) three separate classes for all the binary mixtures of aldehydes; by including the response of the non-MIP-QCM sensor and assuming (c) single class and (d) three separate classes for all the binary mixtures of aldehydes.

Chapter 15

Figure 15.1: Schematic representation of quartz crystals with electrodes on both sides (left) and frequency response for binding of analytes on receptors (right).
Figure 15.2: Schematic representation of static and dynamic modes of microcantilever.
Figure 15.3: Ragweed pollen positions along the transversal coordinate on a rectangular commercial microcantilever. Reproduced with permission of IOP Publishing from Xie, H.; Vitard, J.; Haliyo, S.; Régnier, S. Enhanced sensitivity of mass detection using the first torsional mode of microcantilevers. Measurement Science and Technology 2008, 19, 055207.
Figure 15.4: Illustration of mass measurement modes of microfluific channels embedded on a cantilever and filled with fluid by Burg et al. [75].
Figure 15.5: Schematic representation of MIP technology.
Figure 15.6: Process of immobilization of core–shell MIP nanoparticles with amino groups on the shell using a SAM of (3-glycidoxypropyl)trimethoxysilane as binding layer [130].
Figure 15.7: Chemical structures of EDC and NHS and the mechanism of EDC/NHS activation reaction to form a stable amide bond between aminated surface and free carboxyl end of MIP nanoparticles.
Figure 15.8: (a) Real-time MIP immobilization on a QCM crystal with EDCH/NHS activation method. (b) An online binding experiment performed with a MIP-covered QCM crystal.
Figure 15.9: Chemical structures of molecules: (a) 17EE, (b) β-estradiol, and (c) estriol.
Figure 15.10: A diagram of desiccator and the chemical structure of 3-aminopropyl-triethoxysilane (APTES) and triethyleneamine (TEA) molecule (left). The schematic representation of an aminated surface of a cantilever and MIP nanoparticles immobilized on it (right).
Figure 15.11: The real-time MIP immobilization on a cantilever surface with EDCH/NHS activation method. Smooth curve fitting was applied to the data series.
Figure 15.12: (a) Frequency changes (AF) after APTES coating and MIP immobilization of an AFM cantilever. (b) Nominal, APTES-coated, and MIP-immobilized resonance frequencies (F) of an AFM cantilever.
Figure 15.13: SEM images of 17EE-IPN. (a) Single particle coverage with EDC/NHS activation with 1:10 dilution. (b) Monolayer coverage with EDC/NHS activation without any dilution. (c) Accumulation of polymeric nanoparticles immobilized with UV exposure without any dilution.
Figure 15.14: (a) The calibration graph; frequency change (ΔF) versus concentration (c) and (b) frequency change (ΔF) versus mass change (Δm).
Figure 15.15: (a) The competing agents study: comparison of frequency changes due to treatment of 17EE-IPN with 0.5 ppm 17EE, β-estradiol, and estriol. (b) The non-imprinted polymer study: comparison of frequency changes due to treatment of 17EE-IPN and NIP with 0.5 ppm 17EE molecule.

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Library of Congress Cataloging-in-Publication Data:
Names: Tiwari, Ashutosh, 1978- editor. | Uzun, Lokman, editor.
Title: Advanced molecularly imprinting materials / edited by Ashutosh Tiwari and Lokman Uzun.
Other titles: Advanced materials series (Scrivener Publishing).
Description: Hoboken, New Jersey : John Wiley & Sons, Inc. ; Beverly, Massachusetts : Scrivener Publishing LLC, [2017] | Series: Advanced material series | Includes index.
Identifiers: LCCN 2016039439 (print) | LCCN 2016039851 (ebook) | ISBN 9781119336297 (hardback) | ISBN 9781119336310 (pdf) | ISBN 9781119336167 (epub)
Subjects: | MESH: Molecular Imprinting | Polymers–chemistry | Polymerization | Biotechnology
Classification: LCC TP156.P6 (print) | LCC TP156.P6 (ebook) | NLM QT 37.5.P7 | DDC 668.9/2–dc23
LC record available at https://lccn.loc.gov/2016039439

ISBN 978-1-119-33629-7