Advanced Molecularly Imprinting Materials E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Serie: Advance Materials Series
• Sprache: Englisch

Seitenzahl: 1181

Veröffentlichungsjahr: 2016

Beschreibung

Molecularly imprinted polymers (MIPs) are an important functional material because of their potential implications in diverse research fields. The materials have been developed for a range of uses including separation, environmental, biomedical and sensor applications. In this book, the chapters are clustered into two main sections: Strategies to be employed when using the affinity materials, and rational design of MIPs for advanced applications. In the first part, the book covers the recent advances in producing MIPs for sample design, preparation and characterizations. In the second part, the chapters demonstrate the importance and novelty of creation of recognition imprinted on the materials and surfaces for a range of microbial detection sensors in the biomedical, environmental and food safety fields as well as sensing human odor and virus monitoring systems.         

Part 1: Strategies of affinity materials

• Molecularly imprinted polymers
• MIP nanomaterials
• Micro- and nanotraps for solid phase extraction
• Carbonaceous affinity nanomaterials
• Fluorescent MIPs
• MIP-based fiber optic sensors

Part 2: Rational design of MIP for advanced applications

• MIP-based biomedical and environmental sensors
• Affinity adsorbents for environmental biotechnology
• MIP in food safety
• MIP-based virus monitoring
• MIP-based drug delivery and controlled release
• Biorecognition imprints on the biosensor surfaces
• MIP-based sensing of volatile organic compounds in human body odour
• MIP-based microcantilever sensor system

Leseprobe

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 Introduction

1.2 Molecularly Imprinted Solid-phase Extraction

1.3 Molecularly Imprinted Solid-phase Microextraction

1.4 Molecularly Imprinted Stir Bar Sorptive Extraction

1.5 Other Formats

1.6 Conclusions

References

Chapter 2: A Genuine Combination of Solvent-free Sample Preparation Technique and Molecularly Imprinted Nanomaterials

2.1 Introduction

2.2 Molecularly Imprinted Polymer Modified Fiber for Solid-phase Microextraction

2.3 In-tube Solid-phase Microextraction Technique

2.4 Monolithic Fiber

2.5 Micro-solid-phase Extraction

2.6 Stir-bar Sorptive Extraction

2.7 Conclusion and Future Scope

Acknowledgments

Abbreviations

References

Chapter 3: Fluorescent Molecularly Imprinted Polymers

3.1 Introduction

3.2 Classes of Emitters to Endow MIPs with Fluorescence

3.3 Fluorescent Molecularly Imprinted Silica

3.4 Post-imprinting of MIPs

3.5 fMIPs as Labels

3.6 Formats for fMIPs

3.7 Conclusion

References

Chapter 4: Molecularly Imprinted Polymer-based Micro- and Nanotraps for Solid-phase Extraction

4.1 Introduction

4.2 MIPs as SPE Materials

4.3 Conclusions

References

Chapter 5: Imprinted Carbonaceous Nanomaterials: A Tiny Looking Big Thing in the Field of Selective and Specific Analysis

5.1 Introduction

5.2 Graphene-modified Imprinted Polymer

5.3 Carbon Nanotubes-modified Imprinted Polymer

5.4 Combination of Graphene, CNTs, and MIPs

5.5 Graphene Quantum Dots and/or Carbon Dots

5.6 Fullerene

5.7 Activated Carbon

5.8 Conclusions

Acknowledgments

List of Abbreviations

References

Chapter 6: Molecularly Imprinted Materials for Fiber-optic Sensor Platforms

6.1 Introduction

6.2 Material Aspect: Morphology and Physical Forms of MIPs in FO Sensors

6.3 Molecularly Imprinting Technology for Fiber-optic Sensors

6.4 State-of-the-art Fiber-optic Sensors Applications Using Molecularly Imprinted Materials

6.5 Conclusion

References

Part 2: Rational Design of MIP for Advanced Applications

Chapter 7: Molecularly Imprinted Polymer-based Sensors for Biomedical and Environmental Applications

7.1 Introduction

7.2 Molecularly Imprinted Polymers for Analytes of Biomedical Interest

7.3 Molecularly Imprinted Polymers for Analytes of Environmental Interest

7.4 Conclusion

Acknowledgments

References

Chapter 8: Molecularly Imprinted Polymers: The Affinity Adsorbents for Environmental Biotechnology

8.1 Introduction

8.2 Molecularly Imprinted Polymers

8.3 Cryogels

8.4 Process Technology

8.5 Applications

8.6 Elution of Captured Material

8.7 Concluding Remarks

8.8 Outlook

References

Chapter 9: Molecular Imprinting Technology for Sensing and Separation in Food Safety

9.1 Food Safety

9.2 Food Analysis

9.3 Current Separation Methods Used for Food Safety Purposes

9.4 What Is MIP?

9.5 MIP Applications Used for Food Safety Purposes

References

Chapter 10: Advanced Imprinted Materials for Virus Monitoring

10.1 Introduction

10.2 Virus Imprinting

10.3 Artificial MIP Receptors for Viruses

10.4 Virus Monitoring and Detection Using Biomimetic Sensors

10.5 Virus Imprinting for Separation Technologies

10.6 Conclusions

References

Chapter 11: Design and Evaluation of Molecularly Imprinted Polymers as Drug Delivery Systems

11.1 Introduction

11.2 Synthesis and Characterization of MIPs Intended for Drug Release Using Non-covalent Approaches

11.3 Design and Evaluation of Drug Delivery Systems Based on MIPs

11.4 Conclusions

References

Chapter 12: Molecularly Imprinted Materials for Controlled Release Systems

12.1 Introduction

12.2 Selectivity, Release Mechanism and Functionality of MIPs-based CR Systems

12.3 Molecularly Imprinted Polymers Production for Controlled Release

12.4 Controlled Release Applications Using Molecularly Imprinted Materials-based Controlled Release

12.5 Conclusion

References

Chapter 13: Molecular Imprinting: The Creation of Biorecognition Imprints on Biosensor Surfaces

13.1 Introduction

13.2 Molecular Imprinting

13.3 Microcontact Imprinting

13.4 Capacitive Biosensors

13.5 Surface Plasmon Resonance Biosensors

13.6 Concluding Remarks

References

Chapter 14: Molecular Imprinted Polymers for Sensing of Volatile Organic Compounds in Human Body Odor

14.1 Introduction

14.2 MIP-QCM Sensor Array Preparation

14.3 Chemical Vapor Sensing

14.4 Analysis Outcomes

14.5 Conclusion

Acknowledgments

References

Chapter 15: Development of Molecularly Imprinted Polymer-based Microcantilever Sensor System

15.1 Introduction to Mass Sensors

15.2 Principles of Mass Sensors

15.3 Mechanical Biosensors and Their Fields of Use

15.4 Molecularly Imprinted Polymer Technology

15.5 Molecularly Imprinted Polymer-based QCM Sensors

15.6 Ongoing Studies on Molecularly Imprinted Polymers-based Microcantilevers

Acknowledgments

References

Index

End User License Agreement

Guide

Cover

Copyright

Contents

Begin Reading

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 NH

4

HF

2

(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

−1

standard 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 Pb

2+

and Hg

2+

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 Eu

3+

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 Nd

3

+ imprinted polymers. (Reproduced with permission from [42].)

Figure 4.3: Schematic depiction of the prepared magnetic traps for Pb

2

+. (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 Fe

2

O

4

@DOX-MIP under magnetic field, (b) cumulative DOX release in percent versus time of Fe

2

O

4

@DOX-MIP, and (c) cumulative DOX release in percent versus time of Fe

2

O

4

@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.

Pages

ii

iii

iv

xvii

xviii

xix

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146

147

148

149

150

151

152

153

154

155

156

157

158

159

160

161

162

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

180

181

182

183

184

185

186

187

188

189

190

191

192

193

194

195

196

197

198

199

200

201

202

203

204

205

206

207

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

224

225

226

227

228

229

230

231

232

233

234

235

236

237

238

239

240

241

242

243

244

245

246

247

248

249

250

251

252

253

254

255

256

257

258

259

260

261

262

263

264

265

266

267

268

269

270

271

272

273

274

275

276

277

278

279

280

281

282

283

284

285

286

287

288

289

290

291

292

293

294

295

296

297

298

299

300

301

302

303

304

305

306

307

308

309

310

311

312

313

314

315

316

317

318

319

320

321

322

323

324

325

326

327

328

329

330

331

332

333

334

335

336

337

338

339

340

341

342

343

344

345

346

347

348

349

350

351

352

353

354

355

356

357

358

359

360

361

362

363

364

365

366

367

368

369

370

371

372

373

374

375

376

377

378

379

380

381

382

383

384

385

386

387

388

389

390

391

392

393

394

395

396

397

398

399

400

401

402

403

404

405

406

407

408

409

410

411

412

413

414

415

416

417

418

419

420

421

422

423

424

425

426

427

428

429

430

431

432

433

434

435

436

437

438

439

440

441

442

443

444

445

446

447

448

449

450

451

452

453

454

455

456

457

458

459

460

461

462

463

464

465

466

467

468

469

470

471

472

473

474

475

476

477

478

479

480

481

482

483

484

485

486

487

488

489

490

491

492

493

494

495

496

497

498

499

500

501

502

503

504

505

506

507

508

509

510

511

512

513

514

515

516

517

518

519

520

521

522

523

524

525

526

527

528

529

530

531

532

533

534

535

536

537

538

539

540

541

542

543

544

545

546

547

548

549

550

551

552

553

554

555

556

557

558

559

560

561

562

563

564

565

566

567

568

569

570

571

572

573

574

575

576

577

578

579

580

581

582

583

584

585

586

587

588

589

590

591

592

593

594

595

596

597

598

599

600

601

602

603

604

605

606

607

608

609

610

611

612

613

614

615

616

617

618

619

620

621

622

623

624

625

626

627

628

629

630

631

632

633

634

635

636

637

638

639

640

641

642

643

644

645

646

647

648

_649

650

651

652

653

654

655

656

657

658

659

660

661

662

663

664

665

666

667

668

669

670

671

672

673

674

675

676

677

678

679

680

681

682

683

684

685

686

687

688

689

690

691

692

693

694

695

Scrivener Publishing 100 Cummings Center, Suite 541J Beverly, MA 01915-6106

Advanced Materials Series The Advanced Materials Series provides recent advancements of the fascinating field of advanced materials science and technology, particularly in the area of structure, synthesis and processing, characterization, advanced-state properties, and applications. The volumes will cover theoretical and experimental approaches of molecular device materials, biomimetic materials, hybrid-type composite materials, functionalized polymers, supramolecular systems, information- and energy-transfer materials, biobased and biodegradable or environmental friendly materials. Each volume will be devoted to one broad subject and the multidisciplinary aspects will be drawn out in full.

Series Editor: Ashutosh Tiwari Biosensors and Bioelectronics Centre Linköping University SE-581 83 Linköping Sweden E-mail: [email protected]

Managing Editors: Sachin Mishra and Sophie Thompson

Publishers at Scrivener Martin Scrivener ([email protected]) Phillip Carmical ([email protected])

Advanced Molecularly Imprinting Materials

Edited by

Ashutosh Tiwari

Lokman Uzun

Copyright © 2017 by Scrivener Publishing LLC. All rights reserved.

Co-published by John Wiley & Sons, Inc. Hoboken, New Jersey, and Scrivener Publishing LLC, Beverly, Massachusetts. Published simultaneously in Canada.

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, [phone], fax [phone], or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, [phone], fax [phone], or online at http://www.wiley.com/go/permission.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at [phone], outside the United States at [phone] or fax [phone].

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com.

For more information about Scrivener products please visit www.scrivenerpublishing.com.

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

Preface

Molecularly imprinted polymers (MIPs) are a thoughtful, functional material due to their potential implications in diverse research fields. A range of affinity materials has been developed for separation, environmental, biomedical and sensor applications. In this book, the chapters are divided into two main sections: strategies for affinity materials and rational design of MIPs for advanced applications. In accordance with the main practice of MIPs, recent advances in producing MIPs for sample design, preparation and characterizations are covered in the first part of the book. In the second part, distinguished authors have summarized the importance and novelty of the creation of recognition imprinted on the materials and surfaces of sensors in biomedical, environmental and food safety applications; for example, microbial detection, drug delivery, cantilever sensor systems, chemical vapor sensing in human odor and virus monitoring.

In terms of advanced materials, molecularly imprinted polymers are a kind of applied material due to their potential uses. Therefore, the number of research and review articles, along with related books, has dramatically increased over the last decades. These materials are considered artificial recognition elements and are comprehensively evaluated as advanced smart materials for separation, environmental and biomedical sciences, and biosensor applications. Therefore, we could not ignore these materials when preparing the Advanced Materials Series and the editors are very proud to share this book with you. Included herein are milestone applications of affinity adsorbent for environmental biotechnology and solid-phase extraction, followed by a summary of two different perspectives on controlled drug release applications; enhancing the material properties and adjusting release kinetics.

As previously mentioned, the chapters of this book are divided into two main sections: MIPs as adsorbent and MIPs as recognition element. In accordance with the main practice with MIPs, recent advances in producing MIPs for sample preparation are presented in the first part of the book. Then, a smooth transition is made from separation science to the application of MIP sensors for food safety. In the second part of the book, the importance and novelty of creation of biorecognition imprinted on biosensor surfaces are summarized. Furthermore, MIP-based sensors for biomedical and environmental applications, fluorescent sensors, and fiber optic sensing platforms have also been compiled. Finally, the book ends with three interesting chapters on advanced imprinted materials for cantilever sensor systems, chemical vapor sensing in human odor, and virus monitoring.

The author of chapter 1 summarizes recent advances in molecularly imprinted materials for the purpose of sample preparation. In conjunction with this chapter, in chapter 2 compiles a genuine combination of solvent-free sample preparation techniques and molecularly imprinted nanomaterials. Recent progress in fluorescent molecularly imprinted materials is summarized in chapter 3; and chapter 4 includes some novel applications of imprinted materials as micro- and nanotraps for the purpose of solid phase extraction. A summary of carbonaceous imprinted materials with attractive applications for selective and specific analysis is presented in chapter 5. Chapter 6, which concludes the first part of the book, summarizes the use of imprinted materials as fiber optic sensor platform.

The second part of the book encompasses the rational design of imprinted materials for advanced applications. In chapter 7, the biomedical and environmental applications of imprinted materials-based sensors have been compiled. Moreover, chapter 8 summarizes the environmental biotechnology applications of imprinted materials. Molecular imprinting technology for sensing and separation in food safety is summarized in chapter 9. Advanced imprinted materials for virus monitoring are compiled in the pioneering work in chapter 10 which is the first comprehensive review of its kind in the related literature. In chapters 11 and 12, the authors summarize drug delivery and controlled release applications of imprinted materials while focusing on release kinetics and materials development strategies, respectively. Chapter 13 includes novel creation strategies for biorecognition imprints on biosensor surfaces. In chapter 14, the authors have figured out the recent application of imprinted materials for sensing of volatile organic compounds in human body odor. Finally, chapter 15 is a compilation of attractive applications of imprinted materials as recognition elements on the microcantilever sensor system.

This volume of the Advanced Materials Series includes 15 chapters in all showcasing the excellent efforts of prominent researchers from eleven different countries having more than twenty different academic and industrial affiliations. It is intended for a wide readership including university students and researchers from diverse backgrounds such as physics, chemistry and chemical engineering, materials science and nanotechnology engineering, electrical and computer engineering, biomedical engineering, environmental sciences, food sciences, life sciences, pharmacy, veterinary medicine, medicine, military science, and biotechnology. It can be used not only as a textbook for undergraduate and graduate students but also as a review and reference book for researchers in the materials science, bioengineering, medical, physics, forensics, agriculture, biotechnology, food safety, and nanotechnology arenas. We hope that the chapters of this book will provide the reader with valuable insight into molecularly imprinted polymers as advanced smart materials with respect to the different prominent features in novel designs and future applications.

Editors Ashutosh Tiwari, PhD, DSc Lokman Uzun, Doç. Dr. September 2016, Linköping

Part 1STRATEGIES OF AFFINITY MATERIALS

Chapter 1Recent Molecularly Imprinted Polymer-based Methods for Sample Preparation

Antonio Martín-Esteban

Departamento de Medio Ambiente, INIA, Madrid, Spain

Corresponding author: [email protected]

Abstract

In spite of the huge development in analytical instrumentation, sample preparation is still considered the bottleneck of the whole analytical process. Nowadays, several sample preparation techniques are available; however, all of them suffer from lack of selectivity making difficult in most cases the final determination of target analytes at the low concentration levels required. In this regard, molecularly imprinted polymers (MIPs) are considered excellent materials able to perform selective extractions. The incorporation of MIPs as sorbent in solid-phase extraction, so-called “molecularly imprinted solid-phase extraction” (MISPE), is already accepted in analytical laboratories, and some MIPs are commercially available. Besides, MIP incorporation to other sample preparation techniques, such as solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE), or matrix solid-phase dispersion (MSPD), has been recently proposed and successfully applied to the extraction of different analytes from complex samples. Thus, the objective of this chapter is providing the reader an overview of the uses of MIPs in sample preparation including the most recent developments in this field.

Keywords: Molecularly imprinted polymers, sample preparation, solid-phase extraction, solid-phase microextraction, stir bar sorptive extraction

1.1 Introduction

The development of analytical instrumentation has been huge during past decades allowing eventually the determination of any compound in environmental, food, and biological samples. Typically, target analytes are determined by chromatographic techniques coupled to common detectors (UV, fluorescence) or, more recently, mass spectrometry (MS), or tandem MS. However, direct injections of crude sample extracts are not recommended even when the selective detection provided by MS is used since matrix components can inhibit or enhance the analyte ionization, hampering accurate quantification. Poorly treated sample may invalidate the whole analysis, and thus, a clean sample is generally convenient to improve separation and detection. Therefore, sample preparation is a key step of the whole analytical process, being critical for unequivocal identification, confirmation, and quantification of analytes.

The main objectives of sample preparation are the removal of potential interferents, analyte preconcentration (especially in environmental water samples), converting (if needed) the analyte into a more suitable form for detection or separation, and providing a robust and reproducible method independent of variations in the sample matrix. More recently, new objectives have been set such as using smaller initial sample sizes, improvement of selectivity in extraction, facilitating the automation, and minimizing the amount of glassware and organic solvents to be used [1]. Traditional liquid–liquid extraction does not fulfill current requirements, and it has been displaced from laboratories by new extraction techniques such as solid-phase extraction (SPE), solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE), and more recently by matrix solid-phase dispersion (MSPD), micro solid-phase extraction (MSPE), or liquid-phase microextraction (LPME), among others. All the mentioned techniques suffer from lack of selectivity making necessary an extensive optimization of the typical steps involved. However, even after careful optimization, some matrix components are co-eluted with target analytes making difficult to reach detection limits according to the nowadays stringent regulations. Some years ago, antibodies immobilized on an adequate support, called immunosorbents, were proposed as an alternative for use in SPE applications [2, 3] in order to overcome the aforementioned drawbacks associated with typical nonspecific sorbents. Different immunosorbents have been employed for the determination of pesticides, drugs, and polyaromatic hydrocarbons, among others, showing an excellent degree of cleanup owing to the inherent selectivity of the antibodies used. However, the obtainment of antibodies is difficult, time-consuming, and expensive, and in addition, it is difficult to guarantee its success. Also, it is important to point out that after the antibodies have been obtained they have to be immobilized on an adequate support, which may result in poor antibody orientation or even complete denaturation.

Molecularly imprinted polymers (MIPs) are synthetic materials able to specifically rebind a target molecule in preference to other closely related compounds. These materials are obtained by polymerizing functional and cross-linking monomers around a template molecule, leading to a highly cross-linked three-dimensional network polymer. The monomers are chosen considering their ability to interact with the functional groups of the template molecule. Once polymerization has taken place, template molecule is extracted and binding sites with shape, size, and functionalities complementary to the target analyte are established. The resulting imprinted polymers are stable, robust, and resistant to a wide range of pH, solvents, and temperature. Therefore, MIPs emulate natural receptors but without the associated stability limitations. In addition, MIPs synthesis is also relatively cheap and easy, making them a clear alternative to the use of natural receptors.