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 Molecularly Imprinted
Catalysts
Principles, Syntheses, and Applications
Edited by

Songjun Li
School of Materials Science & Engineering,
Jiangsu University, Zhenjiang, Jiangsu, China

Shunsheng Cao
Associate Professor, Jiangsu University, China
Secretary-General, the Chinese Advanced Materials Society
Marie Curie Fellow, European Commission

Sergey A. Piletsky
Department of Chemistry, University of Leicester, Leicester, UK

Anthony P.F. Turner

Biosensors & Bioelectronics Centre, IFM, Linköping University, Linköping, Sweden

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

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Elsevier
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 Contributors
Zhiyong Chen School of Chemistry and Chemical Engineering, Jinan University,
Jinan, Shandong, China

Francis D’Souza Department of Chemistry, University of North Texas, Denton,

TX, USA

Decha Dechtrirat Department of Materials Science, Faculty of Science, Kasetsart

University, Bangkok, Thailand

Adil Denizli Chemistry Department, Faculty of Science, Hacettepe University, Ankara,

Turkey

Franz L. Dickert Department of Analytical Chemistry, University of Vienna, Vienna,

Austria

Christos Didaskalou School of Chemical Engineering and Analytical Science,

The University of Manchester, Manchester, UK

Pierre Dramou Department of Analysis, Drug R&D Center, Hangzhou HEZE

Pharmaceutical Technology, Hangzhou, Zhejiang Province, China

K. Eersels Institute for Materials Research, Hasselt University, Diepenbeek, Belgium

Arzu Ersöz Chemistry Department, Faculty of Science, Anadolu University, Eskişehir,

Turkey

Cong Fu College of Chemistry and Biological Engineering, Guilin University of

Technology, Guilin, China

Clovia I. Holdsworth Discipline of Chemistry, School of Environmental and Life

Sciences, University of Newcastle, Callaghan, NSW, Australia

Shan Huang College of Chemistry and Molecular Engineering, Peking University,

Beijing, China

T. Junkers Institute for Materials Research, Hasselt University, Diepenbeek, Belgium;

IMEC vzw, Division IMOMEC, Diepenbeek, Belgium

xi
xii CONTRIBUTORS

Rüstem Keçili Plant, Drug and Scientific Research Center, Anadolu University,
Eskişehir, Turkey

Wlodzimierz Kutner Department of Physical Chemistry of Supramolecular

Complexes, Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland;
Faculty of Mathematics and Natural Sciences, School of Science, Cardinal Stefan
Wyszynski University in Warsaw, Warsaw, Poland

Kristian Lettau Drägerwerk AG & Co. KGaA, Lübeck, Germany

Jianping Li College of Chemistry and Biological Engineering, Guilin University of

Technology, Guilin, China

Songjun Li School of Materials Science & Engineering, Jiangsu University,

Zhenjiang, Jiangsu, China

K. Fremielle Lim Discipline of Chemistry, School of Environmental and Life Sciences,

University of Newcastle, Callaghan, NSW, Australia

Klaus Mosbach Department of Pure and Applied Biochemistry, Lund University,

Lund, Sweden

Adnan Mujahid Department of Analytical Chemistry, University of Vienna, Vienna,

Austria; Institute of Chemistry, University of the Punjab, Quaid-i-Azam Campus,
Lahore, Pakistan

M. Peeters Institute for Materials Research, Hasselt University, Diepenbeek, Belgium;

School of Biological and Chemical Sciences, Queen Mary University of London,
London, UK

Lei Peng Institute for Biochemistry and Biology, University of Potsdam, Potsdam,
Germany

Sergey A. Piletsky Department of Chemistry, University of Leicester, Leicester, UK

Edwin Romano Chemistry Department, Negros Oriental State University, Kagawasan

Avenue, Dumaguete City, Negros Oriental, Philippines

Rıdvan Say Chemistry Department, Faculty of Science, Anadolu University, Eskişehir,

Turkey
 CONTRIBUTORS xiii

Frieder W. Scheller Institute for Biochemistry and Biology, University of Potsdam,

Potsdam, Germany; Fraunhofer Institute for Cell Therapy and Immunology IZI-BB,
Potsdam, Germany

Piyush Sindhu Sharma Department of Physical Chemistry of Supramolecular

Complexes, Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland

Xiantao Shen State Key Laboratory of Environment Health (Incubation), Key

Laboratory of Environment and Health, Ministry of Education; Key Laboratory of
Environment and Health (Wuhan), Ministry of Environmental Protection; School of
Public Health, Tongji Medical College, Huazhong University of Science and Technology,
Wuhan, Hubei, China

Gyorgy Szekely School of Chemical Engineering and Analytical Science,

The University of Manchester, Manchester, UK

Nazia Tarannum Department of Chemistry, Indian Institute of Technology, Bombay,

India

Anthony P.F. Turner Biosensors & Bioelectronics Centre, IFM, Linköping University,
Linköping, Sweden

P. Wagner Institute for Materials Research, Hasselt University, Diepenbeek, Belgium;

IMEC vzw, Division IMOMEC, Diepenbeek, Belgium

Erica J. Wanless Discipline of Chemistry, School of Environmental and Life Sciences,

University of Newcastle, Callaghan, NSW, Australia

Michael J. Whitcombe Department of Chemistry, University of Leicester, Leicester,

UK

Agnieszka Wojnarowicz Department of Physical Chemistry of Supramolecular

Complexes, Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland

Ulla Wollenberger Institute for Biochemistry and Biology, University of Potsdam,

Potsdam, Germany

Aysu Yarman Institute for Biochemistry and Biology, University of Potsdam,

Potsdam, Germany; Fraunhofer Institute for Cell Therapy and Immunology IZI-BB,
Potsdam, Germany

Yasuo Yoshimi Department of Applied Chemistry, Shibaura Institute of Technology,

Koto-ku, Tokyo, Japan
xiv CONTRIBUTORS

Lianming Zhang College of Chemistry and Biological Engineering, Guilin University

of Technology, Guilin, China

Meiping Zhao College of Chemistry and Molecular Engineering, Peking University,

Beijing, China

Maiyong Zhu School of Materials Science & Engineering, Jiangsu University,

Zhenjiang, Jiangsu, China

Azrinawati Mohd Zin Discipline of Chemistry, School of Environmental and Life

Sciences, University of Newcastle, Callaghan, NSW, Australia
Editors’ Biographies

Professor Songjun Li is a distinguished professor at

Jiangsu University and currently president of the Chinese
Advanced Materials Society. He was also behind the
launch of the International Congress on Advanced
Materials (AM2011). As a postdoctoral associate, he
joined the University of Wisconsin–Milwaukee (USA) in
2008, followed by the Marie Curie Fellowship in Cranfield
University (UK) from 2009 to 2011. He joined Jiangsu
University as a distinguished professor in 2012. There,
he leads the research group of Polymers and Functional
Materials in the School of Materials Science and
Engineering. He was further awarded Jiangsu distin-
guished professor by Jiangsu Province in 2012 owing to his outstanding contribution
to polymer research. He currently holds editorship of the Journal of the Chinese
Advanced Materials Society (Taylor & Francis), the International Journal of Physical
Science, The Open Electrochemistry Journal, and Advancement in Scientific and
Engineering Research. He is also on the editorial boards of the Journal of Inorganic
and Organometallic Polymers and Materials (Springer) and the American Journal
of Environmental Sciences.

Professor Sergey A. Piletsky is a professor of bio-

analytical chemistry at the University of Leicester, UK.
He joined Cranfield University in 1998 and became a
full professor of bioorganic and polymer chemistry
and head of the Cranfield Biotechnology Center in
2002. His major interests include molecularly imprinted
polymers, conjugated polymers, sensor and membrane
technology, and the chemistry of dormant radicals.
Professor Piletsky has received a number of awards
including JSPS, DFG, and Leverhulme Fellowships, the
award of the President of Ukraine, and the Royal Society
Wolfson Research Merit Award. Professor Piletsky moved to the University
of Leicester in 2012 and was selected as secretary-general of the International Union
of Advanced Materials in 2013.

xv
xvi EDITORS’ BIOGRAPHIES

Professor Shunsheng Cao received his doctoral degree

in 2006 at the Chengdu Institute of Organic Chemistry,
Chinese Academy of Sciences. Subsequently, he joined
Jiangsu University as a lecturer in April 2009. Currently,
he is an associate professor at Jiangsu University. In the
past few years, as the primary investigator, he has
published more than 30 articles in peer-reviewed jour-
nals and several chapters in books by prestigious pub-
lishers including Wiley-VCH and Elsevier. He has been
invited on numerous occasions to be the reviewer for
grants and international journals. His recent interest
focuses primarily on designing and constructing func-
tional materials for biomedical applications, particularly
those with novel core–shell and porous structure.

Professor Turner’s name is synonymous with the field of

biosensors. In 2010, he joined IFM-Linköping to create a
new Center for Biosensors and Bioelectronics. His pre-
vious 35-year academic career in the United Kingdom
(UK) culminated in the positions of principal of
Cranfield University at Silsoe and distinguished profes-
sor of biotechnology. He was elected a fellow of
the Royal Society of Chemistry in 1996 and invited to a
fellowship of the Institute of Biology in 1999 and the
Institute of Physics in 2006. He was awarded a higher
doctorate (DSc) for his exceptional contribution to
biosensors by the University of Kent in 2001 and an
honorary DSc by the University of Bedfordshire in 2008,
where he served as a governor for 6 years. He was admitted to the United States
National Academy of Engineering in 2006 for his work on glucose sensors, environ-
mental monitors, and synthetic recognition molecules. He won the Royal Society
of Chemistry (UK) Theophilus Redwood Medal for Analytical Science (http://www.
rsc.org/ScienceAndTechnology/Awards/TheophilusRedwoodAward/PreviousWinners.
asp) in 2011 and was elected to the Royal Swedish Academy of Engineering Science
(IVA, http://www.iva.se/) in 2013.
Foreword

I welcome the timely publication of this volume entitled Molecularly Imprinted Catalysts:
Principles, Syntheses, and Applications. For many, molecular imprinting is associated with
traditional areas of application such as selective adsorbents, separations, and solid-phase
extraction. Indeed, the latter has achieved some commercial success, with a number of
products available in the marketplace. The next wave of products based on molecularly
imprinted polymers (MIPs) is likely to come from technological developments in the areas of
sensors, diagnostic assays, and biomedicine. A significant challenge currently facing the
chemical industries is the development of selective catalytic systems. Catalysts both reduce
the temperature at which specific chemical transformations take place and steer reactions in
favor of the desired product over undesirable byproducts, reducing energy demand and
lowering waste in the process. This clearly has economic, environmental, and societal ben-
efits resulting from a “green chemistry” approach and has spurred the development of new
catalysts. Scientists working on MIPs have not been slow to take up the challenge. Catalytic
MIPs can make a unique contribution to this field because they can combine design elements
from nature in the form of biomimetic catalysis or from manmade transition metal catalyst
design, combined with elements of smart polymer synthesis. These sophisticated approaches
may pave the way for a new generation of switchable MIP catalysts offering exquisite regio-
and stereoselectivity in chemical transformations. In parallel, new MIP-based catalysts may
compete with enzymes in areas such as sensors and assays and may find new applications in
environments (such as extremes in temperature or pH) in which enzymes would be rapidly
degraded. This volume describes key advances made to date in the field of MIP-based
catalysis.
This book is composed of 13 chapters describing the field of molecularly imprinted
catalysis and catalyst design. In the first chapter, Li et al. critically review some of the key
issues involved in the design, synthesis, and application of catalytic MIPs. Similarities and
differences between synthetic approaches to conventional MIPs and imprinted polymers
designed to show catalytic properties are highlighted. The future outlook for catalytic MIPs is
also discussed. The chapter by Scheller et al. focuses on catalytically active MIP architectures.
This is a developing field that combines enzyme-like catalysis with a biomimetic design to
achieve selective catalytic function. Progress made in esterolytic MIPs, MIPs using metal
complexes and prosthetic groups, new MIP–enzyme architectures, and protein-based MIPs is
presented. One of the most frequently applied methods used in the preparation of catalyti-
cally active MIPs is the imprinting of a transition state analogue of the target reaction, which
is intended to lower the activation barrier for a reaction to take place within the MIP. Another
approach is to incorporate transition metals such as Fe(III), Cu(II), Co(II), Zn(II), or mimics of
the catalytic center of enzymes.
In Chapter 3, Dramou et al. describe different approaches to the design of MIPs for
biomimetic catalysis, including progress made in the area intended to enhance the effect. It is
a challenge for chemists to mimic the catalytic machinery of nature through synthetic
methods. This requires a proper understanding of the nature of enzymatic catalysis, which
would help when designing tailor-made catalysts. Molecularly imprinted polymers represent

xvii
xviii FOREWORD

one of the most efficient techniques by which the selectivity and specificity of enzymes can be
mimicked using a comparable range of geometric constraints analogous to natural catalysts.
The chapter by Holdsworth et al. summarizes the design and synthesis of molecularly
imprinted microspheres. Major strategies in polymer design and synthesis applicable to
molecularly imprinted nano- and microparticulates are reviewed, including alternative
initiation processes, “greener” porogens, alternative cross-linkers, and custom-designed
monomers. The difficulty in assessing the binding performance of MIP microspheres asso-
ciated with changes in particle size owing to template effects is briefly discussed.
Core–cross-linked star polymers, accessible via modern polymer synthetic routes, are intro-
duced as a way forward for applications that require processable or soluble MIP materials. In
Chapter 5, Dickert and Mujahid discuss the development of molecularly imprinted catalysts
by citing examples prepared using different binding interactions such as covalent, non-
covalent, stoichiometric noncovalent, and metal-coordination approaches. Challenges in
using imprinted polymers as synthetic catalysts and possible solutions to these problems are
highlighted. In addition, some emerging trends in the design of imprinted catalysts, i.e., the
developments of microgels and nanogels are described along with a description of their
contribution to the field.
Most chemical and biochemical reactions subject to enzymatic catalysis occur with a
high degree of specificity and with rapid reaction rates under very mild conditions. Therefore,
the creation of artificial catalysts that can reproduce the catalytic performance of natural
enzymes has been an aspiration of scientists. In Chapter 6, Say et al. describe how to design
MIPs as artificial catalysts as enzyme mimics. In the following two chapters, Szekely et al.
present the synthesis and applications of mimics of metalloenzymes obtained via imprinting,
and Li et al. describe the mechanism of recognition and selectivity of molecularly imprinting
membranes. It is evident that imprinted metal-containing catalysts can be designed to
control reactions that are not catalyzed by natural enzymes, such as the degradation of
contaminants present in soil or water contaminants, and for hydrogen production. Rational
design methodologies and statistical methods such as the design of experiments are expected
to assist in the screening of matrices for their catalytic performance and consequently
accelerate further developments in the field. Methods of improving the recognition
performance of the molecular imprinting technique include changing the environment
of aggregation and testing; modifying the imprinting unit; employing the effect of metal
ion-coordination; applying dendrimers, monolayers, and multilayer self-assembly-based
molecularly imprinted techniques; and using combinatorial methods in synthesis and of
chemometric forecasting methods to design MIPs with the desired specific recognition
properties. Kutner and D’Souza et al. review MIPs as synthetic catalysts in Chapter 9, and
Shen describes molecularly imprinted photocatalysts in Chapter 10. Zhao et al. introduce the
use of MIPs as biomimetic catalysts in Chapter 11. Significant progress in improvement of the
morphology, solubility, and monodispersity of MIP catalysts and some successful applica-
tions in eliminating contaminants from polluted water or soil samples are summarized.
Yoshimi reviews MIPs applicable for biomimetic catalysts in sensors in Chapter 12. Wagner
et al. describe the use of MIPs as synthetic receptors in diagnostic medical devices in Chapter
13. It appears possible that a straightforward sensor platform compatible with electro-
chemical impedance spectroscopy and featuring a novel readout technique can be developed
by incorporating MIPs into sensing devices.
Several volumes, each consisting of many chapters, are probably insufficient to cover all
of the new developments made in molecularly imprinted catalysts. Therefore, this book can
provide only an overview to highlight some of the most important recent research. The
editors are to be congratulated in having assembled a volume that includes the most
 FOREWORD xix

extensively studied areas, and which I am sure will be of interest to a broad range of in-
vestigators and researchers in this and related fields. I would also like to thank both Elsevier
and the leading editor, Dr Songjun Li, for inviting me to write this Foreword, and I
congratulate all of the contributors for making this interesting book possible.

Dr. Michael J. Whitcombe

President of the Society for Molecular Imprinting
Department of Chemistry
University of Leicester
Leicester LE1 7RH, UK
Preface

Catalysis is currently the subject of intense research because of its importance in a broad
range of implications, from industry to agriculture, aerospace to aviation, environment to
ecology, military to civilian purposes, and inanimate objects to living bodies. The emerging
challenge associated with the tantalizing demand for selective catalytic ability has fueled an
essential need for novel catalytic technology and materials. Progress is slowly being made in
this field by the adoption of multifunctional supports and emerging technology, including
molecular sieve catalysts, nanoparticle catalysts, and organic topologic inclusions, which often
have properties that can control the access of substrate to the encapsulated metal nano-
particles and/or active frameworks. It appears possible that selective catalysts may be ach-
ieved by carefully controlling the size of metal particles, metal–support interaction, and/or
tuned active frameworks. Nonetheless, it remains a challenge to achieve a generic protocol
suitable for the development of selective catalytic ability, based on currently reported findings.
One important reason associated with the phenomena may be the low structural complexity
and simplicity of these conventional supported or nanometer catalysts, in contrast to the
elaborate architectures in active biomacromolecules. It is difficult and even impossible to
straightforwardly develop a well-tuned relationship between the structures of conventional
catalysts and their functions, which was often held by active biomacromolecules. Novel
technology and methods are clearly required.
Known as “key-to-lock” technology, the latest development in molecular imprinting
has led to a promising solution to the struggling field of selective catalysis. The technology is
able to create binding sites with desired templates that are comparable to natural antibodies.
To fabricate molecular imprinting, the template and functional monomers are first allowed
to form a self-assembled architecture, in which the functional monomers are regularly
positioned around the template. Polymerization is then performed to fix the self-organized
architecture in place, followed by removal of the imprinted template from the polymeric
networks, which then leaves behind binding sites stereochemically complementary to the
imprinted template. The binding sites left behind constitute an induced molecular memory of
the template, which then endows the resulting polymers (i.e., molecular imprinted polymers
[MIPs]) with molecular recognition ability.
For use in catalysis, the prepared MIPs are expected to have the ability to stabilize the
transition state of reactants, decreasing the activation energy of the ongoing reactions. As
such, the use of a template analogous to the transition state of the reactants (also known as
the TSA template) should allow the objective to be achieved. The other way to achieve
selective catalytic ability is to use MIPs as the carrier of active metals. The imprinted
networks will provide regulated access to the imprinted substrate, which allows only the
specified substrate to gain access and denies access to analogues. Compared with biogenic
antibodies, MIPs are highly cross-linked and have the advantages of easy preparation,
reusability, and robustness under chemical and physical stresses. Hence, MIPs can be
used under harsh conditions to resist elevated temperature and pressure and to resist
acids, bases, metal ions, organic solvents, etc. Arguably, molecular imprinting technology is
furnishing a revolutionary transition to the conventional recognition of catalysts, pro-
foundly changing our understanding of the basic concept of catalysis.
xxi
xxii PREFACE

As a rapidly developing field, a body of knowledge for molecularly imprinted catalysts is

already available. Nonetheless, the major achievement made in this field has not yet been
summarized into a single book or edited collection. Thus, as the first endeavor, it is difficult
for us to fulfill the task of achieving an entire and comprehensive summary. Fortunately,
because of their expertise, all of the contributors have done their best when preparing their
chapters. Because of the multidisciplinary nature of this subject, a large number of experts
with different backgrounds have been invited to contribute their research. Without doubt,
if such a diverse group of experts had not participated, we would not have been able to
accomplish our goal of developing a complete book on the field of molecularly imprinted
catalysts.
We want to express our deepest thanks to Elsevier for generous support of the endeavor.
We would also like to acknowledge all of our colleagues, who enthusiastically contributed to
the success and in fact to the publication of this book. Thanks also should be expressed to the
National Science Foundation of China (No. 51473070). The essence of scientific research is to
learn from nature and to solve complicated problems in society. Thus, we hope that the book
will help bring out more secrets of nature and vigorously promote the development of
selective catalysis.

Edited by
Prof. Songjun Li, PhD
Distinguished Professor, Jiangsu University, China (Lsjchem@ujs.edu.cn)
Jiangsu Distinguished Professor, Jiangsu Province
President, Chinese Advanced Materials Society
Marie Curie Fellow, European Commission
Prof. Shunsheng Cao, PhD
Associate Professor, Jiangsu University, China (sscao@ujs.edu.cn)
Secretary-General, the Chinese Advanced Materials Society
Marie Curie Fellow, European Commission
Prof. Sergey A. Piletsky, PhD
Professor, University of Leicester, UK (sp523@le.ac.uk)
Secretary-General, the International Union of Advanced Materials
Prof. Anthony P.F. Turner, PhD, DSC, FRSC
Professor, Linköping University, Sweden (anthony.turner@liu.se)
Foreign Associate, USA National Academy of Engineering
Fellow, the Royal Swedish Academy of Engineering Science
Fellow, the Royal Society of Chemistry
 1
Molecularly Imprinted Polymers for
Enzyme-like Catalysis: Principle,
Design, and Applications

Songjun Li1, Maiyong Zhu1, Michael J. Whitcombe2,

Sergey A. Piletsky2, Anthony P.F. Turner3
1
SCHOOL OF MATERI ALS SCIENCE & ENGINEERING, JIANGSU UNIVERSITY,
ZHENJIANG, JIANGSU, CHI NA; 2 D EPA R TM EN T O F CH E MI S T R Y,
UNIVERSITY OF LEICESTER, LEICESTER, UK; 3 BIOSENSORS & B IOELEC TR ONICS C ENTRE,
IFM, LINKÖPING UNIVERS ITY, LINKÖPING, SWEDEN

1. Introduction
Catalysis has been at the forefront of intense research owing to its importance in a broad
range of applications ranging from industry to agriculture, aerospace to aviation, envi-
ronment to ecology, military to civilian purposes, and inanimate objects to living bodies
(1–3). Emerging challenges associated with increasing demands for selective catalysis
have fueled an essential need for novel catalytic materials. Over the past few years,
impressive progress has been made in this field by adopting new design methods and
polymer supports. It appears possible that selective catalysts can be prepared with
careful control of active specimens, catalytic binding sites, or polymer supports (4, 5).
Nonetheless, it remains a significant challenge to acquire a generic protocol suitable for
the development of selective catalytic materials. One reason may be the lower structural
complexity and simplicity of these reported catalysts compared with the elaborate
structures in enzyme or other active biomacromolecules. In fact, it is almost impossible
to build a well-tuned relationship between the structures of these conventional catalysts
and their selective catalytic ability in a straightforward manner, based on these reported
findings (6). As such, a natural approach to achieve selective catalysis would be to
translate the principle of enzyme catalysis for the design of new catalytic materials
(known also as artificial enzyme analogues). These new catalytic materials might be
synthesized to possess high catalytic activity and selectivity comparable to enzymes.
They might also be better accessible and more stable, and catalyze a larger variety of
reactions. The most prominent is the so-called “molecularly imprinted polymers”
(MIPs), which are capable of creating active binding sites and selectivity comparable to

Molecularly Imprinted Catalysts. http://dx.doi.org/10.1016/B978-0-12-801301-4.00001-3 1

Copyright © 2016 Elsevier Inc. All rights reserved.
2 MOLECULARLY IMPRINTED CATALYSTS

enzymes (7, 8). To some extent, the use of MIPs as catalysts offers an opportunity for the
characteristics of enzyme catalysis to be studied in a greater detail by systematically
varying functional groups in active sites. This can help us gain a better understanding of
the selective essence of catalytic processes.
The term “molecular imprinting” has been used for some time (at least since the
late 1960s) to describe the induced molecular recognition by stamping the impression
of molecules into a polymeric network, recording a chemical and stereochemical
negative image of the template molecule in the process (9–11). A more complete
definition of molecular imprinting can be described as the template-induced forma-
tion of specific recognition sites in a material in which the template directs the
positioning and orientation of the material’s structural components by a self-assembly
mechanism. The material itself could be oligomeric, polymeric, or a two-dimensional
surface assembly. To be useful in a technological sense, the imprints should be fixed
by a polymerization, cross-linking, precipitation, or condensation process that ce-
ments the relative positions of the structural components before separation or removal
of the template species. The imprinting process is thus recognized as a tool to produce
a range of materials with biomimetic recognition properties (12–15). Compared with
biogenic molecular recognition systems such as antibody–antigen, enzyme–substrate,
and deoxyribonucleic acid (DNA)–complementary DNA, MIPs are highly cross-linked
polymers and usually have the merits of easy preparation, reusability, and robust-
ness to chemical and physical stresses. Thus, as a promising substitute of bio-
molecules, MIPs can be used under harsh conditions to resist elevated temperature
and pressure and resist acids, bases, metal ions, organic solvents, etc. For these rea-
sons, MIPs have shown much use as in separation, adsorption, sensing, and drug
delivery (16–18).
For catalytic applications, MIPs are normally expected to show an ability to stabilize
the transition state of chemical reactions, decreasing the activation energy of the
ongoing reaction. Thus, the use of a template analogous to the transition state of the
reaction would allow this objective to be achieved (19, 20). Nonetheless, it has been
also discovered that straight use of the reactant or product as the template can achieve
the same selective catalytic objective in some cases (21). One more way to achieve
selective catalytic ability could be the use of MIPs as the support for active metal
nanoparticles (22, 23). The imprinted networks will provide access to the imprinted
substrate, but restrict and/or block the analogues. Despite some different conditions
in a range of cases, the paradigm of MIP–substrate interactions is similar to the
binding interactions between enzyme and substrate, which consist of electrostatic
interactions, hydrogen bonds, hydrophobic interactions, or a combination of these
interactions. Thus, one key issue in preparing MIP catalysts would be to ensure the
particular arrangement of functional groups and the suitable MIPs–substrate interac-
tion. The arrangement of binding sites and the shape of the active specimens should
be complementary to the structure of the intended substrate. As such, the substrate
can be bound and catalyzed in a selective way. Such binding of the substrate would
 Chapter 1 • Molecularly Imprinted Polymers for Enzyme-like Catalysis 3

produce an appreciable change in the three-dimensional conformation of the sub-

strate and thereby causes selective catalysis.
Regarding the imprinted polymer catalysts, some reviews and research articles have
been available over the past few years (24–26). Readers of this chapter can refer to these
reviews and articles for detailed information. Nonetheless, as an emerging field, current
knowledge in MIP catalysts largely depends on our understanding of enzyme and
enzyme-like catalysis. Some important issues such as the inherent mechanism and se-
lective catalytic essence remain a significant challenge. In this chapter, we focus on some
key issues involved in the use of imprinted polymers as catalysts. Other aspects relating
to the principle, design methods, and future outlook of MIP catalysts are also discussed.
To address these issues, we should consider a number of aspects of the subject. These
are: (1) How does molecular imprinting happen? (2) How can the molecular imprinting
cause catalytic reactivity and selectivity? And (3) what are the similarities and differences
between preparing conventional MIPs and MIP catalysts? With these questions in mind,
we focus on discussing active MIPs for catalytic applications.

2. Generic Profile of Molecular Imprinting

Molecular imprinting is usually dubbed a “key-to-lock” technology that is capable
of forming polymer networks with the ability to recognize the imprinted species (i.e., the
template). In general terms, the prepolymerized complex that is supposed to lead to
the final imprint is first formed via the molecular self-assembly between templates and
functional monomers. During the self-assembling process, the functional monomers
are regularly positioned around the template molecules owing to different interac-
tions (Figure 1) (27, 28). The self-assembled complex is subsequently fixed using

FIGURE 1 Schematic presentation of the

principle for molecular imprinting ((a)
molecular self-assembly, (b)
polymerization, (c) remove/rebinding
template). Reprinted from Ref. (28) with
permission.
4 MOLECULARLY IMPRINTED CATALYSTS

polymerization in the presence of a cross-linker. Once the imprinted template is

removed from the polymeric matrix, the binding sites with stereochemical correspon-
dence to the template are left behind. The position and arrangement of these binding
sites constitutes an induced molecular memory, enabling the resulted polymers
(i.e., MIPs) to recognize the imprinted species molecularly. Thus, during the rebinding
process the host–guest interaction within the molecular imprinting system is similar
to some natural biosystems such as receptor–ligand, antibody–antigen, and enzyme–
substrate (29, 30). As such, MIPs are suitable to be used as separation materials in
separation, adsorption, sensing, drug delivery, etc.
There are two major methods to achieve molecular imprinting: one depends on
reversible covalent bonds pioneered by Wulff (31) and the other relies on noncovalent
interactions suggested by Mosbach (32). In covalent molecular imprinting, the templates
are bound to monomers with covalent bonds, such as phenyl-a-D-mannopyranoside and
4-vinylbenzeneboronic acid (Figure 2). Two molecules of 4-vinylbenzeneboronic acid
(monomer) are bound with covalent linkages to the template phenyl-a-D-mannopyr-
anoside. After fixing the oligomer using polymerization, the covalent linkage is cleaved

FIGURE 2 Covalent molecular imprinting proposed by Wulff. Where the template phenyl-a-D-mannopyranoside
was be removed from (a) with water or methanol to give (b). Solvation of the functional groups leads to swelling
of the cavity (c). When the template binds again, the original shape is restored. Adapted from Ref. ( 31).
16 MOLECULARLY IMPRINTED CATALYSTS

26. Wulff, G. Enzyme-Like Catalysis by MIPs. Chem. Rev. 2002, 102, 1–27.
27. Zheng, M.; Li, S.; Luo, X. Rationally Designing MIP toward a High Specific Adsorbent by Using Metal
as Assembled Pivot. J. Macromol. Sci. Part A Pure Appl. Chem. 2007, 44, 1187–1194.
28. Ge, Y.; Turner, A. P. F. Too Large to Fit? Recent Developments in Macromolecular Imprinting. Trends
Biotechnol. 2008, 26 (4), 218–224.
29. Andersson, L. I. Molecular Imprinting for Drug Bioanalysis - A Review on the Application of Imprinted
Polymers to Solid-phase Extraction and Binding Assay. J. Chromatogr. B 2000, 739, 163–173.
30. Chen, X.; Zhang, Z. H.; Yang, X.; Liu, Y. N.; Li, J. X.; Peng, M. J.; Yao, S. Z. Novel MIPs Based on
Multiwalled Carbon Nanotubes with Bifunctional Monomers for Solid-Phase Extraction of Rhein
from the Root of Kiwi Fruit. J. Sept. Sci. 2012, 35, 2414–2421.
31. Wulff, G.; Sarhan, A. The Use of Polymers with Enzyme-Analogous Structures for the Resolution of
Racemates. Angew. Chem. Int. Ed. 1972, 11, 341.
32. Arshady, R.; Mosbach, K. Synthesis of Substrate-Selective Polymers by Host-Guest Polymerization.
Macromol. Chem. Phys. 1981, 182, 687–692.
33. Sellergren, B.; Lepistö, M.; Mosbach, K. Highly Enantioselective and Substrate-Selective Polymers
Obtained by Molecular Imprinting Utilizing Noncovalent Interactions - NMR and Chromatographic
Studies on the Nature of Recognition. J. Am. Chem. Soc. 1988, 110, 5853–5860.
34. Osmani, Q.; Hughes, H.; Flavin, K.; Hedin-Dahlstrom, J.; Allender, C.; Frisby, J.; McLoughlin, P. The
Use of FTIR and NMR Spectroscopies to Study Prepolymerization Interactions in Nitrogen
Heterocycles. Anal. Bioanal. Chem. 2008, 391, 1229–1236.
35. Dhal, P. K.; Arnold, F. H. Substrate Selectivity of MIPs Incorporating a Rigid Chelating Monomer, bis-
Methacrylato (4-Methyl, 40 -Vinyl) 2,20 -Bipyridine Cu(II). New. J. Chem. 1996, 20, 695–698.
36. Svenson, J.; Andersson, H. S.; Piletsky, S. A.; Nicholls, I. A. Spectroscopic Studies of the Molecular
Imprinting Self-assembly Process. J. Mol. Recognit. 1998, 11, 83–86.
37. Subrahmanyam, S.; Karim, K.; Piletsky, S. A. Computational Approaches in the Design of Synthetic
Receptors. In Designing Receptors for the Next Generation of Biosensors; Piletsky, S. A.,
Whitcombe, M. J., Eds.; Springer Series on Chemical Sensors and Biosensors; Springer: Berlin,
Heidelberg, 2013, Vol. 12; pp 131–165.
38. Chianella, I.; Lotierzo, M.; Piletsky, S. A.; Tothill, I. E.; Chen, B. N.; Karim, K.; Turner, A. P. F. Rational
Design of a Polymer Specific for Microcystin-LR Using a Computational Approach. Anal. Chem.
2002, 74, 1288–1293.
39. Karlsson, B. C. G.; O’Mahony, J.; Karlsson, J. G.; Bengtsson, H.; Eriksson, L. A.; Nicholls, I. A. Structure
and Dynamics of Monomer-Template Complexation: An Explanation for MIP Recognition Site
Heterogeneity. J. Am. Chem. Soc. 2009, 131, 13297–13304.
40. Wangchareansak, T.; Sangma, C.; Choowongkomon, K.; Dickert, F.; Lieberzeit, P. Surface Molecular
Imprints of WGA Lectin as Artificial Receptors for Mass-Sensitive Binding Studies. Anal. Bioanal.
Chem. 2011, 400, 2499–2506.
41. Nicholls, I. A.; Andersson, H. S. Thermodynamic Principles Underlying MIP Formulation and Ligand
Recognition. In MIPs: Man-made Mimics of Antibodies and Their Applications in Analytical
Chemistry; Sellergren, B., Ed.; Techniques and Instrumentation in Analytical Chemistry; Elsevier:
Amsterdam, 2001, Vol. 23; pp 60–70.
42. Salian, V. D.; Vaughan, A. D.; Byrne, M. E. The Role of Living/Controlled Radical Polymerization in
the Formation of Improved Imprinted Polymers. J. Mol. Recognit. 2012, 25, 361–369.
43. Wulff, G.; Gross, T.; Schonfeld, R. Enzyme Models Based on Molecurlarly Imprinted Polymers with
Strong Esterase Activity. Angew. Chem. Int. Ed. 1997, 36, 1961–1964.
44. Sellergren, B.; Shea, K. J. Enantioselective Ester Hydrolysis Catalyzed by Imprinted Polymers.
Tetrahedron: Asymmetry 1994, 5, 1403–1406.
Another random document with
no related content on Scribd:
 which I published at the time.
9
Contemporary Review, October, 1911, p. 569.
10
Contemporary Review, January, 1912, p. 111.
11
Contemporary Review, January, 1912, p. 114.
12
Contemporary Review, April, 1912, p. 566.
13
Contemporary Review, April, 1914, p. 571–2.
14
One of my last articles on this subject appeared in the July
issue of the Contemporary Review.
15
The general strike, accompanied in places by riots, a few
months ago.
16
Contemporary Review, July, 1914, p. 122–128.
17
Daily Telegraph, July 25th, 1914.
18
Cf. Sir M. de Bunsen’s Despatch, July 29th, to Sir Edward
Grey, with White Paper.
19
Ibidem.
20
Cf. White Paper. Sir M. de Bunsen’s Despatch, July 30th.
21
White Paper. Sir M. de Bunsen’s Despatch, July 30th.
22
See White Paper. Despatch sent by Sir G. Buchanan, July
30th.
23
White Paper. Despatch sent by the British Ambassador in St.
Petersburg, dated July 27th.
24
Sir Edward Grey’s Despatch, July 29th.
25
Cf. Sir M. de Bunsen’s Despatch dated London, Sept 1st.
26
The Kaiser was then addressing his soldiers.
27
Monday, August 3rd.
28
Friday, July 31st, 1914.
29
White Paper. Despatch of British Ambassador in Berlin, dated
July 29th.
30
White Paper. Sir G. Buchanan’s Despatch, July 30th.
31
July 29th.
32
White Paper. Sir Edward Goschen’s Despatch, July 29th.
33
Literally “danger of war.”
34
July 31st.
35
July 31st.
36
August 1st.
37
Daily Telegraph.
38
Le Soir, August 9th; La Metropole, August 8th, 1914.
39
Westminster Gazette, September 22nd.
40
Westminster Gazette, September 18th.
41
Ibidem.
 Transcriber’s Notes
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when a predominant preference was found in the original book;
otherwise they were not changed.
Simple typographical errors were corrected; unbalanced
quotation marks were remedied when the change was obvious,
and otherwise left unbalanced.
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