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Molecular Imprinting and Functional Polymers for all Transducers and Applications
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Molecular Imprinting and Functional Polymers for all Transducers and Applications

A special issue of Sensors (ISSN 1424-8220). This special issue belongs to the section "Chemical Sensors".

Deadline for manuscript submissions: closed (1 May 2017) | Viewed by 67411

Special Issue Editor

Prof. Dr. Franz L. Dickert

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Guest Editor
Chemical Sensors and Optical Molecular Spectroscopy, Institute of Analytical Chemistry, University of Vienna, 1090 Vienna, Austria
Interests: physicochemical basis of sensors; chemical sensors; physical sensors; metrology; supramolecular chemistry; molecular recognition; molecular imprinting; anisotropic phases
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The main challenge in developing a chemical sensor is the synthesis of recognition coatings, which are very sensitive and selective to analytes of interest. Molecular imprinting has proven to be the most innovative strategy for this purpose, to design functional polymers in the last few decades. Furthermore, the introduction of functional groups will open new applications for all available transducers.

Sensitivity and selectivity features of sensor coatings can be tuned by this approach. The strategy produces molecular cavities and interaction sites in sensor coatings. The synthesis of these tailored recognition materials is performed in an outstanding manner, which saves time and high costs of chemicals. Furthermore, intermolecular interactions between the analyte and chemical layers will generate sites, which are complementary to the analyte.

This procedure can easily be done, directly on a transducer surface, which includes engulfing the analyte by a prepolymer followed by crosslinking of polymeric material. These imprinted polymers form a robust recognition layer on the transducer surface, which cannot be peeled off and withstand against very harsh conditions, both in gaseous and liquid media. These recognition materials are very suitable, for small molecules even up to large bioparticles.


Prof. Dr. Franz L. Dickert
Guest Editor

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Keywords

  • Volatile organic compounds (VOCs)
  • Humidity
  • Ions
  • Polycyclic aromatic hydrocarbons (PAHs)
  • Pesticides and insecticides
  • Hazardous compounds
  • Complex mixtures
  • Proteins
  • Viruses, bacteria and cells
  • Process control
  • Healthcare
  • Optical sensors
  • Mass-sensitive sensors
  • Electrochemical transducer

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Published Papers (8 papers)

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Editorial

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5 pages, 173 KiB  
Editorial
Molecular Imprinting and Functional Polymers for All Transducers and Applications
by Franz L. Dickert
Sensors 2018, 18(2), 327; https://doi.org/10.3390/s18020327 - 24 Jan 2018
Cited by 13 | Viewed by 3349
Abstract
The main challenge in developing a chemical sensor is the synthesis of recognition coatings, which are very sensitive and selective to analytes of interest. Molecular imprinting has proven to be the most innovative strategy for this purpose in functional polymer design in the [...] Read more.
The main challenge in developing a chemical sensor is the synthesis of recognition coatings, which are very sensitive and selective to analytes of interest. Molecular imprinting has proven to be the most innovative strategy for this purpose in functional polymer design in the last few decades. Moreover, the introduction of functional groups brings about new applications for all available transducers. Sensitivity and selectivity features of sensor coatings can be tuned by this approach. The strategy produces molecular cavities and interaction sites in sensor coatings. The synthesis of these tailored recognition materials is performed in an outstanding manner, saving time and the high costs of chemicals. Furthermore, intermolecular interactions between the analyte and chemical layers will generate sites that are complementary to the analyte. This procedure can easily be done, directly on a transducer surface, which entails engulfing the analyte by a prepolymer and crosslinking the polymeric material. These imprinted polymers form a robust recognition layer on the transducer surface, which cannot be peeled off and can withstand very harsh conditions, both in gaseous and liquid media. These recognition materials are very suitable, for small molecules and even large bioparticles. Full article
(This article belongs to the Special Issue Molecular Imprinting and Functional Polymers for all Transducers and Applications)

Research

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9320 KiB  
Article
A Formaldehyde Sensor Based on Molecularly-Imprinted Polymer on a TiO2 Nanotube Array
by Xiaohui Tang, Jean-Pierre Raskin, Driss Lahem, Arnaud Krumpmann, André Decroly and Marc Debliquy
Sensors 2017, 17(4), 675; https://doi.org/10.3390/s17040675 - 24 Mar 2017
Cited by 62 | Viewed by 8561
Abstract
Today, significant attention has been brought to the development of sensitive, specific, cheap, and reliable sensors for real-time monitoring. Molecular imprinting technology is a versatile and promising technology for practical applications in many areas, particularly chemical sensors. Here, we present a chemical sensor [...] Read more.
Today, significant attention has been brought to the development of sensitive, specific, cheap, and reliable sensors for real-time monitoring. Molecular imprinting technology is a versatile and promising technology for practical applications in many areas, particularly chemical sensors. Here, we present a chemical sensor for detecting formaldehyde, a toxic common indoor pollutant gas. Polypyrrole-based molecularly-imprinted polymer (PPy-based MIP) is employed as the sensing recognition layer and synthesized on a titanium dioxide nanotube array (TiO2-NTA) for increasing its surface-to-volume ratio, thereby improving the sensor performance. Our sensor selectively detects formaldehyde in the parts per million (ppm) range at room temperature. It also shows a long-term stability and small fluctuation to humidity variations. These are attributed to the thin fishnet-like structure of the PPy-based MIP on the highly-ordered and vertically-aligned TiO2-NTA. Full article
(This article belongs to the Special Issue Molecular Imprinting and Functional Polymers for all Transducers and Applications)
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3408 KiB  
Article
Molecularly Imprinted Sol-Gel-Based QCM Sensor Arrays for the Detection and Recognition of Volatile Aldehydes
by Chuanjun Liu, Bartosz Wyszynski, Rui Yatabe, Kenshi Hayashi and Kiyoshi Toko
Sensors 2017, 17(2), 382; https://doi.org/10.3390/s17020382 - 16 Feb 2017
Cited by 40 | Viewed by 6905
Abstract
The detection and recognition of metabolically derived aldehydes, which have been identified as important products of oxidative stress and biomarkers of cancers; are considered as an effective approach for early cancer detection as well as health status monitoring. Quartz crystal microbalance (QCM) sensor [...] Read more.
The detection and recognition of metabolically derived aldehydes, which have been identified as important products of oxidative stress and biomarkers of cancers; are considered as an effective approach for early cancer detection as well as health status monitoring. Quartz crystal microbalance (QCM) sensor arrays based on molecularly imprinted sol-gel (MISG) materials were developed in this work for highly sensitive detection and highly selective recognition of typical aldehyde vapors including hexanal (HAL); nonanal (NAL) and bezaldehyde (BAL). The MISGs were prepared by a sol-gel procedure using two matrix precursors: tetraethyl orthosilicate (TEOS) and tetrabutoxytitanium (TBOT). Aminopropyltriethoxysilane (APT); diethylaminopropyltrimethoxysilane (EAP) and trimethoxy-phenylsilane (TMP) were added as functional monomers to adjust the imprinting effect of the matrix. Hexanoic acid (HA); nonanoic acid (NA) and benzoic acid (BA) were used as psuedotemplates in view of their analogous structure to the target molecules as well as the strong hydrogen-bonding interaction with the matrix. Totally 13 types of MISGs with different components were prepared and coated on QCM electrodes by spin coating. Their sensing characters towards the three aldehyde vapors with different concentrations were investigated qualitatively. The results demonstrated that the response of individual sensors to each target strongly depended on the matrix precursors; functional monomers and template molecules. An optimization of the 13 MISG materials was carried out based on statistical analysis such as principle component analysis (PCA); multivariate analysis of covariance (MANCOVA) and hierarchical cluster analysis (HCA). The optimized sensor array consisting of five channels showed a high discrimination ability on the aldehyde vapors; which was confirmed by quantitative comparison with a randomly selected array. It was suggested that both the molecularly imprinting (MIP) effect and the matrix effect contributed to the sensitivity and selectivity of the optimized sensor array. The developed MISGs were expected to be promising materials for the detection and recognition of volatile aldehydes contained in exhaled breath or human body odor. Full article
(This article belongs to the Special Issue Molecular Imprinting and Functional Polymers for all Transducers and Applications)
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2762 KiB  
Article
Selectivity Enhancement in Molecularly Imprinted Polymers for Binding of Bisphenol A
by Noof A. Alenazi, Jeffrey M. Manthorpe and Edward P. C. Lai
Sensors 2016, 16(10), 1697; https://doi.org/10.3390/s16101697 - 14 Oct 2016
Cited by 18 | Viewed by 5650
Abstract
Bisphenol A (BPA) is an estrogen-mimicking chemical that can be selectively detected in water using a chemical sensor based on molecularly imprinted polymers (MIPs). However, the utility of BPA-MIPs in sensor applications is limited by the presence of non-specific binding sites. This study [...] Read more.
Bisphenol A (BPA) is an estrogen-mimicking chemical that can be selectively detected in water using a chemical sensor based on molecularly imprinted polymers (MIPs). However, the utility of BPA-MIPs in sensor applications is limited by the presence of non-specific binding sites. This study explored a dual approach to eliminating these sites: optimizing the molar ratio of the template (bisphenol A) to functional monomer (methacrylic acid) to cross-linker (ethylene glycol dimethacrylate), and esterifying the carboxylic acid residues outside of specific binding sites by treatment with diazomethane. The binding selectivity of treated MIPs and non-treated MIPs for BPA and several potential interferents was compared by capillary electrophoresis with ultraviolet detection. Baclofen, diclofenac and metformin were demonstrated to be good model interferents to test all MIPs for selective binding of BPA. Treated MIPs demonstrated a significant decrease in binding of the interferents while offering high selectivity toward BPA. These results demonstrate that conventional optimization of the molar ratio, together with advanced esterification of non-specific binding sites, effectively minimizes the residual binding of interferents with MIPs to facilitate BPA sensing. Full article
(This article belongs to the Special Issue Molecular Imprinting and Functional Polymers for all Transducers and Applications)
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1897 KiB  
Article
One Binder to Bind Them All
by Oliver Hayden
Sensors 2016, 16(10), 1665; https://doi.org/10.3390/s16101665 - 10 Oct 2016
Cited by 7 | Viewed by 5214
Abstract
High quality binders, such as antibodies, are of critical importance for chemical sensing applications. With synthetic alternatives, such as molecularly imprinted polymers (MIPs), less sensor development time and higher stability of the binder can be achieved. In this feature paper, I will discuss [...] Read more.
High quality binders, such as antibodies, are of critical importance for chemical sensing applications. With synthetic alternatives, such as molecularly imprinted polymers (MIPs), less sensor development time and higher stability of the binder can be achieved. In this feature paper, I will discuss the impact of synthetic binders from an industrial perspective and I will challenge the molecular imprinting community on the next step to leapfrog the current status quo of MIPs for (bio)sensing. Equally important, but often neglected as an effective chemical sensor, is a good match of transducer and MIP coating for a respective application. To demonstrate an application-driven development, a biosensing use case with surface-imprinted layers on piezoacoustic sensors is reported. Depending on the electrode pattern for the transducer, the strong mechanical coupling of the analyte with the MIP layer coated device allows the adoption of the sensitivity from cell mass to cell viability with complete reversibility. Full article
(This article belongs to the Special Issue Molecular Imprinting and Functional Polymers for all Transducers and Applications)
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1945 KiB  
Article
Molecularly Imprinted Polymer Nanoparticles for Formaldehyde Sensing with QCM
by Munawar Hussain, Kira Kotova and Peter A. Lieberzeit
Sensors 2016, 16(7), 1011; https://doi.org/10.3390/s16071011 - 30 Jun 2016
Cited by 64 | Viewed by 9361
Abstract
Herein, we report on molecularly imprinted polymers (MIPs) for detecting formaldehyde vapors in air streams. A copolymer thin film consisting of styrene, methacrylic acid, and ethylene glycol dimethacrylate on quartz crystal microbalance (QCM) yielded a detection limit of 500 ppb formaldehyde in dry [...] Read more.
Herein, we report on molecularly imprinted polymers (MIPs) for detecting formaldehyde vapors in air streams. A copolymer thin film consisting of styrene, methacrylic acid, and ethylene glycol dimethacrylate on quartz crystal microbalance (QCM) yielded a detection limit of 500 ppb formaldehyde in dry air. Surprisingly, these MIPs showed specific behavior when tested against a range of volatile organic compounds (VOCs), such as acetaldehyde, methanol, formic acid, and dichloromethane. Despite thus being a suitable receptor in principle, the MIPs were not useful for measurements at 50% humidity due to surface saturation by water. This was overcome by introducing primary amino groups into the polymer via allyl amine and by changing the coating morphology from thin film to nanoparticles. This led to the same limit of detection (500 ppb) and selectivity as before, but at the real-life conditions of 50% relative humidity. Full article
(This article belongs to the Special Issue Molecular Imprinting and Functional Polymers for all Transducers and Applications)
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860 KiB  
Article
Molecularly Imprinted Electropolymer for a Hexameric Heme Protein with Direct Electron Transfer and Peroxide Electrocatalysis
by Lei Peng, Aysu Yarman, Katharina J. Jetzschmann, Jae-Hun Jeoung, Daniel Schad, Holger Dobbek, Ulla Wollenberger and Frieder W. Scheller
Sensors 2016, 16(3), 272; https://doi.org/10.3390/s16030272 - 23 Feb 2016
Cited by 37 | Viewed by 7737
Abstract
For the first time a molecularly imprinted polymer (MIP) with direct electron transfer (DET) and bioelectrocatalytic activity of the target protein is presented. Thin films of MIPs for the recognition of a hexameric tyrosine-coordinated heme protein (HTHP) have been prepared by electropolymerization of [...] Read more.
For the first time a molecularly imprinted polymer (MIP) with direct electron transfer (DET) and bioelectrocatalytic activity of the target protein is presented. Thin films of MIPs for the recognition of a hexameric tyrosine-coordinated heme protein (HTHP) have been prepared by electropolymerization of scopoletin after oriented assembly of HTHP on a self-assembled monolayer (SAM) of mercaptoundecanoic acid (MUA) on gold electrodes. Cavities which should resemble the shape and size of HTHP were formed by template removal. Rebinding of the target protein sums up the recognition by non-covalent interactions between the protein and the MIP with the electrostatic attraction of the protein by the SAM. HTHP bound to the MIP exhibits quasi-reversible DET which is reflected by a pair of well pronounced redox peaks in the cyclic voltammograms (CVs) with a formal potential of −184.4 ± 13.7 mV vs. Ag/AgCl (1 M KCl) at pH 8.0 and it was able to catalyze the cathodic reduction of peroxide. At saturation the MIP films show a 12-fold higher electroactive surface concentration of HTHP than the non-imprinted polymer (NIP). Full article
(This article belongs to the Special Issue Molecular Imprinting and Functional Polymers for all Transducers and Applications)
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Review

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1575 KiB  
Review
Blood Group Typing: From Classical Strategies to the Application of Synthetic Antibodies Generated by Molecular Imprinting
by Adnan Mujahid and Franz L. Dickert
Sensors 2016, 16(1), 51; https://doi.org/10.3390/s16010051 - 31 Dec 2015
Cited by 61 | Viewed by 19613
Abstract
Blood transfusion requires a mandatory cross-match test to examine the compatibility between donor and recipient blood groups. Generally, in all cross-match tests, a specific chemical reaction of antibodies with erythrocyte antigens is carried out to monitor agglutination. Since the visual inspection is no [...] Read more.
Blood transfusion requires a mandatory cross-match test to examine the compatibility between donor and recipient blood groups. Generally, in all cross-match tests, a specific chemical reaction of antibodies with erythrocyte antigens is carried out to monitor agglutination. Since the visual inspection is no longer useful for obtaining precise quantitative information, therefore there is a wide variety of different technologies reported in the literature to recognize the agglutination reactions. Despite the classical methods, modern biosensors and molecular blood typing strategies have also been considered for straightforward, accurate and precise analysis. The interfacial part of a typical sensor device could range from natural antibodies to synthetic receptor materials, as designed by molecular imprinting and which is suitably integrated with the transducer surface. Herein, we present a comprehensive overview of some selected strategies extending from traditional practices to modern procedures in blood group typing, thus to highlight the most promising approach among emerging technologies. Full article
(This article belongs to the Special Issue Molecular Imprinting and Functional Polymers for all Transducers and Applications)
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