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Sala, Alexandre. "Synthèse et caractérisation de polymères à empreintes ionique du cuivre pour la conception d'électrodes modifiées." Electronic Thesis or Diss., Toulon, 2022. http://www.theses.fr/2022TOUL0010.
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L’utilisation du cuivre en tant qu’agent biocide dans les revêtements anti-salissures sur les bateaux a provoqué son accumulation dans les eaux portuaires. Le but de ces travaux de thèse est de développer des capteurs électrochimiques permettant sa détection dans des échantillons marins. Pour cela des polymères à empreintes du cuivre(II) ont été élaborés et utilisés pour la modification d’électrodes.Dans un premier temps, des particules de polymères à empreintes ont été synthétisées à l’aide d’un agent réticulant (le diméthacrylate d’éthylène glycol ou le N,N’-méthylène-bis-acrylamide) et d’un monomère fonctionnel, la méthacrylamido-L-histidine (MAH) qui permet la formation d’un complexe avec le cuivre(II). La caractérisation physico-chimique a permis de confirmer la bonne intégration de la MAH et d’évaluer les propriétés morphologiques des polymères.Les propriétés de rétention du cuivre(II) ont ensuite été étudiées et les particules présentant les meilleures performances ont été utilisées pour la fabrication d’électrodes à pâte de carbone. Ces électrodes, avec une limite de détection de 5,9 x 10-2 μM (ou 3,75 μg/L), ont permis la détermination de cuivre(II) dans des échantillons marins.Enfin, de nouvelles voies de modifications de surface ont été explorées pour la formation de film polymère in situ. Ainsi, des iniferters ont été greffés sur des électrodes en or par formation de mono-couches auto-assemblées mais aussi par électropolymérisation d’un polymère avec des fonctions iniferters pendantes. Cette dernière voie a permis de photopolymériser un film de polymère à empreintes du cuivre(II) sur une électrode de carboneThe use of copper as a biocide in anti-fouling coatings on ships has led to its accumulation in harbour waters. The aim of this work is to develop electrochemical sensors for its detection in marine samples. For this purpose, copper(II)-imprinted polymers were prepared and used for the modification of electrodes.Firstly, imprinted polymer particles were synthesised using a cross-linking agent (ethylene glycol dimethacrylate or N,N'-methylene-bis-acrylamide) and a functional monomer, methacrylamido-L-histidine (MAH), which can form a complex with copper(II). The physico-chemical characterization of the polymer particles confirmed the integration of MAH and allowed to evaluate the morphological properties of the polymers.The copper(II) binding properties were then evaluated and the particles with the best performance were used to make carbon paste electrodes. These electrodes, with a detection limit of 5.9 x 10-2 μM (or 3.75 μg/L), allowed the determination of copper(II) in marine samples.Finally, new approaches for surface modification were explored for in situ polymer film formation. Thus, iniferters were grafted onto gold electrodes by the formation of self-assembled monolayers but also by electropolymerisation of a polymer with pendant iniferter functions. The latter route allowed the photopolymerisation of a copper(II)-imprinted polymer film on a carbon electrode
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Mandadi, Deepika. "A Characterization of Caffeine Imprinted Polypyrrole Electrode." TopSCHOLAR®, 2009. http://digitalcommons.wku.edu/theses/130.
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Nanotechnology holds great potential for improving our lives by creating many new materials and devices in medical sciences, electronics and also in energy production. Molecularly imprinted polymers (MIPs) are highly stable synthetic polymers that possess molecular recognition properties due to cavities created in the polymer matrix that are complementary to an analyte both in shape and in positioning of functional groups. These MIPs have been widely employed for diverse applications (e.g., in chromatographic separation, drug screening, chemosensors, catalysis, immunoassays etc) due to their specificity towards the target molecules and high stability against physicochemical perturbations. Conductive polymers, (CPs) such as polypyrrole, can be likened to semiconductors because of small band gaps and low electronic mobility. CPs are exploited as an excellent tool for the preparation of nanocomposites with nano scaled biomolecules. Polypyrrole (Ppy) was the first of this key family of compounds to show high conductivity. So, electrically conducting polypyrrole (Ppy) has numerous applications.
In this study, caffeine imprinted electrodes (CIE) were prepared and characterized. This research project mainly focused on three important aspects: &#;To determine the thickness of the polymeric film. &#;To determine the Limit of detection (LOD) of the polymeric film at different conditions. &#;To determine the Analytical Sensitivity (γ) of the polymeric film at varied conditions.
In summary these are conclusions stated: •The thickness of the electrode increased with an increase in the number of pulses. The film thickness increased linearly up to an application of 30 pulses and after 30 pulses, an increase in slope occurred with again a linear correlation up to the maximum applied number of pulses, 42. This change in slope may indicate a different mechanism taking place.
•LOD is improved as the caffeine load is reduced from 10.0 to 3.0 mM and as the number of pulses is reduced from 36 to 24.
•γ increases the number of pulses increase from 24 to 36 and also increases as the caffeine load increases.
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O'Donnell, Elizabeth Anne. "Water-compatible molecularly imprinted polymers." Thesis, University of Strathclyde, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.438467.
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Robak, Andrew Joseph. "Development of coenzyme-imprinted molecularly imprinted polymers as catalysts /." view abstract or download file of text, 2007. http://proquest.umi.com/pqdweb?did=1276397881&sid=1&Fmt=2&clientId=11238&RQT=309&VName=PQD.
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Thesis (Ph. D.)--University of Oregon, 2007.Typescript. Includes vita and abstract. Includes bibliographical references (leaves 94-100). Also available for download via the World Wide Web; free to University of Oregon users.
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Tsai, Mei-Hsuan. "Boron containing molecular imprinted polymer (MIP) templates from symmetric and asymmetric diboration of olefins and other boron containing functional polymers." Thesis, University of Cambridge, 2013. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.608235.
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Bates, Ferdia. "Design and development of molecularly imprinted polymers and imprinted sensors." Doctoral thesis, Universitat Autònoma de Barcelona, 2016. http://hdl.handle.net/10803/399170.
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Esta tesis se ha hecho principalmente para estudiar e investigar polímeros impresos (MIPs) con la intención de usarlos como sensores de larga vida. La línea de investigación de esta tesis es la dirigida a conseguir la integración de estas formaciones impresas dentro de una lengua electrónica (ET), que es la rama de especialización en la que se ha desarrollado principalmente este proyecto. Después de hacer una revisión de la literatura, que inicialmente se centraba en la aplicación de MIPs a un equipo electroquímico, un sensor voltamétrico impreso y un procedimiento sensitivo complementario, el procedimiento se creó a través de una combinación de protocolos tomados de la literatura. Este sensor, descrito en el Artículo 1, presentaba una buena selectividad hacia el analito primario, teofilina, además de la especificidad requerida frente a sus análogos estructurales. Aunque el diseño del sensor permitía una mejor regeneración de la superficie respecto a otros sistemas parecidos encontrados en la literatura, el comportamiento de los polímeros usados en el MIP retardaba la tasa de transferencia de electrones en la superficie del sensor. Por culpa de este fenómeno, la sensibilidad del sensor se reducía.
Justo después de estos experimentos iniciales, se hizo una colaboración con el grupo del Profesor Sergey Piletskey en la Universidad de Leicester (UoL) de Reino Unido. Durante este período, se realizó un estudio intensivo del proceso de diseño de impresión molecular asistido por un sistema computacional de modelización molecular ‘inhouse’. Se puso énfasis en el diseño de un receptor impreso para la molécula de baja solubilidad melanina, que se toma como ‘template modelo’. El MIP resultante se caracterizó y usó para la detección de melanina en muestras de leche, tal y como se describe y detalla en el Artículo 2.
Más tarde, utilizando los conocimientos adquirido durante la estancia en Leicester, se desarrollaron nuevas técnicas de modelización computacional para la evaluación de los métodos utilizados en la modelización de MIPs, con el objetivo de obtener una técnica de evaluación virtual para el diseño de receptores impresos, optimizados para los requerimientos necesarios para su posterior aplicación en un sensor ET, tal como se detalla en el Artículo 3.
Tal y como se detalla en el capítulo final de esta tesis, la experiencia y conocimientos adquiridos durante la investigación, se usaron para diseñar un grupo de sensores que funcionan asociados a ET. Este desarrollo podría ampliarse profundizando en la selección computacional de polielectrolitos, que luego serían inmovilizados en la superficie de un electrodo voltamétrico mediante una tinta de grafito conductora, de elevada robustez y estabilidad.
En este sentido, también se proponen otras recomendaciones para lograr la mejora de la capacidad de regeneración de los MIPs utilizados, por ejemplo mediante la separación de MIP y electrodo. Finalmente, se presentan algunas sugerencias para colaboraciones institucionales, con el propósito de crear un sistema ET móvil, que permita recoger y analizar muestras en campo.This thesis was predominantly undertaken to study and investigate molecular imprinted polymers (MIPs) with a view to their use as high longevity sensing elements in sensor arrays. The research line of the thesis was intended to lead to the integration of these imprinted arrays into an Electronic Tongue (ET) sensing system which is the area of expertise of the research group in which this project was primarily executed. Having initially executed a review of the literature, focusing initially on the application of the MIPs to an electrochemical device, an imprinted voltammetric sensor and a complimentary sensing procedure was developed using a combination of protocols extracted from the literature. This sensor, described in Article 1, had good selectivity toward the primary analyte, theophylline, and specificity against structural analogues. Though the design of the sensor allowed for significantly improved regeneratibility of the sensor relative to similar systems in the literature, the insulating nature of the polymers used in the MIP reduced the electron transfer rate at the sensor surface and thus resulted in a reduction in sensitivity. Following this initial experimental study, a secondment was undertaken in the University of Leicester under the supervision of Professor Sergey Piletsky. During this period, an intensive study of the design process of molecular imprinting, aided by an in-house computational molecular modelling platform, was conducted focusing on the design of an imprinted receptor for the low solubility 'model template', melamine. This MIP was successfully synthesised, characterised and used in the detection of melamine in milk samples, as detailed in Article 2. Further development of computational modelling techniques for the evaluation of MIP modelling techniques was also achieved with a view to create a virtual evaluation technique for the design of imprinted receptor sites optimised for the requirements of their application to an ET sensor array using the skills acquired during the Leicester secondment as detailed in Article 3. As detailed in the final chapter of this thesis, the insight into the imprinting process which was acquired during the research has been used to design a sensor array system which meets the specifications of ET experimental runs. This takes the form of the introduction of the research topic computationally selected polyelectrolytes, immobilised onto a voltammetric electrode surface via highly robust conducting graphite ink. Additional recommendations are also made to further enhance the on-going MIP projects within the laboratory, such as the separation of the MIP and the electrode to increase MIP regeneratibility. Some final suggestions for some other inter-institutional collaboration are also presented which aim to creating portable ET system for in-field sample collection and analysis.
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Yvenou, Etienne. "Développement de modules thermoélectriques imprimés et flexibles pour des applications à température ambiante." Thesis, Université Grenoble Alpes (ComUE), 2017. http://www.theses.fr/2017GREAI071/document.
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L’effet thermoélectrique permet la conversion directe et réversible d’un flux de chaleur en courant électrique via l’utilisation de semi-conducteurs de type-p et de type n. Les polymères conjugués, comme le poly(3,4-éthylènedioxythiophène) (PEDOT) sont pressentis pour être des alternatives aux alliages de tellurure de bismuth (Bi2Te3) coûteux, toxiques et difficiles à synthétiser.Cette thèse se propose d’améliorer la conductivité électrique d’un PEDOT et de faciliter sa mise en œuvre par une technique d’impression grande surface comme le spray.La première partie porte sur l’amélioration de la synthèse par tournette du PEDOT : OTf dont le dopage est stabilisé par le contre-ion trifluorométhanesulfonate (OTf-). Plusieurs co-solvants sont testés comme la pyridine ou la NMP. Ces co-solvants permettent de ralentir la polymérisation et d’améliorer ainsi la structure du matériau. Des conductivités électriques de 3600 S.cm-1 avec un coefficient Seebeck aux environs de 20 µV.K-1 sont atteintes.La seconde partie étudie les avantages et les inconvénients d’une synthèse de ce PEDOT : OTf amélioré par spray ultrasonique. Cette technique permet de conserver la formulation développée pour le dépôt par tournette. Il est possible d’obtenir des films épais (~ 1 µm) avec une conductivité électrique supérieure à 1650 S.cm-1. Des études par diffraction des rayons X et de transports permettent de comparer les deux méthodes de dépôt et d’orienter les choix de formulation et de procédé.Finalement, avec ces améliorations apportées, des exemples de modules thermoélectriques imprimés sont présentés et évalués. Ainsi en imprimant plus de 300 thermocouples connectés en série puis roulés, un tel module thermoélectrique occupe une surface inférieure à une pièce de 50 centimes d’euro et peut générer 1 µW avec un gradient de température de 35 °C.Cette thèse souhaite pouvoir apporter des éléments de réponse sur la relation entre la mise en œuvre et les propriétés électriques des polymères conducteursThermoelectricity can convert directly and reversibly a heat flux into an electric current with p and n-type semiconductors. Conjugated polymers, such as poly(3,4-ethylenedioxithiophene) (PEDOT), offers an alternative to the best room temperature thermoelectric materials based on bismuth telluride alloys which used scarce, hazardous and hard to process raw materials.This PhD work aims to enhance the electrical conductivity of an in-situ polymerised PEDOT and make it easy to process with large scale printing techniques like spray-coating.The first part focus on the optimisation of this synthetized PEDOT through spin-coating. The doping of this PEDOT is stabilised with the counter-ion trifluoromethanesulfonate (OTf-). One way of enhancement is to add co-solvents like pyridine and NMP in order to slow down the polymerisation rate. Consequently, PEDOT:OTf get a better structure and reach an outstanding electrical conductivity of 3,600 S.cm-1 without decreased the Seebeck coefficient which remains around 20 µv.K-1.The second part studies pro and cons of the ultrasonic spray as a coating technic to this enhanced PEDOT:OTf. This technic allows to keep an ink formulation closed of the spin-coating one and can print thick films (~ 1 µm) with an electrical conductivity above 1650 S.cm-1. XRD and transport measurements are achieved in order to understand and compare both spray and spin-coating techniques. And therefore, to enlighten improvement on formulation and process.At last, several examples of spray-coated thermoelectric generators are shown and tested. Thus by printing more than 300 thermocouples connected in series and rolled into a cylinder, such devices could produce 1 µW with a gradient of temperature of 35 °C on a surface less than a 5 cm2 (size of a coin).This thesis work wishes to provide insight on the process-electrical relationship in conducting polymers
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Bonini, Francesca. "Molecularly imprinted polymers for protome analysis." Thesis, Cranfield University, 2008. http://dspace.lib.cranfield.ac.uk/handle/1826/2716.
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Fast and efficient methods for the detection of insurgence and progression of diseases are at the basis of modern diagnostics and medicine. In this concern, biomarkers represent a powerful diagnostic tool, as their expression profiles well correlate with the pathology progression. Thus, the pathological state could be diagnosed by measuring the altered presence of a biomarker. In this direction, conspicuous help has been given by proteomics, intended as the study of the protein pattern of a sample and most frequently performed by two-dimensional electrophoresis. Although the proteome approach is a powerful analytical method, its application to biological samples for the detection and quantification of putative biomarkers is hampered by technical problems, in fact, the wide diversity in concentrations exhibited by the proteins present in the biological samples, with a concentration range spanning over nine orders of magnitude, and the relative abundance of each protein, are responsible of masking the less abundant species and of their loss in traceability. The aim of my PhD project is to apply Molecularly Imprinted Technology to the specific removal of a high abundance protein (Human Serum Albumin, HSA) frequently affecting proteomic analysis, in order to increase the detection of potential biomarkers. This technology allows the creation of artificial recognition sites in synthetic polymers for a specific protein. These sites are tailor-made in situ by co-polymerisation of functional monomers and cross-linkers around the template molecules. Two different approaches have been assayed in order to remove HSA: • Immobilisation of protein template on a rigid silica support (bead) and creation of polymer around beads. • Polymerisation in bulk of a polymer with protein template and application of this polymer to multicompartment electrolyser. In both of the cases, the chemical and structural features of the polymers have been analysed, after that they have been applied to complex proteome pre-treatment, obtaining encouraging results.
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Mistry, Reena. "Niacinamide analysis using molecularly imprinted polymers." Thesis, University of British Columbia, 2002. http://hdl.handle.net/2429/43182.
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The objectives of this research were to use molecularly imprinted polymers (MIP) and microfluidic chips as an approach to a rapid and low cost analytical method for niacinamide analysis. Lab-on-a-chip (microfluidics) devices are becoming increasingly popular due to their relatively low cost, sensitivity, and speed. MIPs may be able to serve as solid-phase extraction packing material in microfluidic chips.
To reach the objectives, it was necessary to identify the mechanisms by which binding of analyte to polymer occur, determine the optimal functional monomer to cross-linker ratio, and gain an understanding of the polymeric structure and characteristic bonds. An MIP was created using niacinamide (NAM) as the template, methacrylic acid (MAA) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, azobisisobutyronitrile (AIBN) as the free-radical initiator, and chloroform as the porogen. It was hypothesized that rebinding occurs via hydrogen-bonding of the carbonyl and amide groups of NAM to the oxygen atoms in the carboxyl group of MAA.
Rebinding studies were conducted using compounds with similar functional groups to NAM to determine binding mechanism to the polymer. Both the pyridyl nitrogen and the amide group were found to be important in hydrogen bonding interactions with the polymer.
Polymers were optimized for rebinding by using different ratios of functional monomer:cross-linker (MAA:EGDMA) and determining imprint factor of NAM to each polymer. The 1:4 polymer yielded the highest imprinting factor, indicating that the polymer is most selective for NAM.
FTIR was conducted to determine the structure of polymers created and whether NAM detection and quantification was possible. There was a peak at 1725 cm⁻¹, which was a shift of the C=O stretching band from 1694 cm⁻¹ in MAA and 1717 cm⁻¹ in EGDMA, indicating a chemical interaction between the two compounds. The disappearance of a peak at 1633 cm⁻¹ showed a loss of conjugation in the carboxylic acid in the polymeric structure.
Through this research, knowledge was gained about the polymer optimization and structure. However, more studies need to be conducted to determine the feasibility of an MIP application for a lab-on-a-chip device.
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Wang, Jinfang. "Xanthine-imprinted polymers for decaffeination applications." Thesis, University of Strathclyde, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.431777.
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Abd, Bashar H. "Molecularly imprinted polymers for drug delivery." Thesis, University of Leicester, 2018. http://hdl.handle.net/2381/43042.
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Molecularly imprinted polymers (MIP) have received much attention and increased interest thanks to their excellent cost efficiency, robustness, high selectivity and simple short synthesis. The molecular imprinting process can be defined as creation of molecular recognition sites in a synthetic polymer. The template-derived sites thus created within the polymeric matrix allow MIP to selectively recognise and bind the target molecule. In light of these properties, MIP have been successfully applied in sensors, assays separation, and for drug delivery applications. Because of their small size, MIP nanoparticles (MIP NPs) can be used in biomedicine as specific drug delivery device, since the nanoscale format is potentially suitable for cellular or in vivo applications. This work has demonstrated that MIP NPs could be used as carriers for targeted drug delivery. For this purpose, the anti-inflammatory and anti-cancer agent curcumin was selected to develop a high throughput screening method which allows to optimise the controlled delivery of drugs using magnetic MIP NPs. Senescent cells which contribute to a number of pathophysiological conditions including fibrosis, diabetes, cancer, Alzheimer's and ageing, were selected as a model system to demonstrate the ability of specific MIP NPs to recognise them and deliver the cytotoxic drugs. Fluorescent MIP NPs specific for two epitopes of senescent cells B2M and DEP were prepared and characterised. In vitro tests based on two human cell lines have demonstrated the ability of the developed MIP NPs to recognise the senescent cells and confirmed that they were not toxic to the cells. In order to demonstrated the targeted drug delivery double-imprinted fluorescent MIP NPs with binding site specific for senescent cells and containing cytotoxic drugs Dasatnib and Gramicidin have been produced. In vitro tests with groups of old and young mice injected with MIP NPs demonstrated the targeted induction of cell death. It is possible to conclude that fluorescent MIP NPs could be effectively used as imaging tool for in vitro analysis as well as carriers for targeted delivery of the drugs in vivo. The protocols developed in this work are applicable for any other targets of clinical importance.
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Whetton, Stephen. "Novel imprinted polymers as artificial enzymes." Thesis, Aston University, 2001. http://publications.aston.ac.uk/9644/.
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Derivatives of L-histidine were investigated as suitable models for the Asp-His couple found in the catalytic triad of serine proteases. A combination of molecular dynamics and IH NMR spectroscopy suggested that the most populous conformations of N-acetyl-L-histidine and the N-acetyl-L-histidine anion were predominated by those in which the carboxylate group was gauche to the imidazole ring overcoming steric and electrostatic repulsion, suggesting there is an interaction between the carboxylate group and the imidazole ring. Kinetic studies, using imidazole, N-acetyl-L-histidine and the N-acetyl-L-histidine anion showed that in a DMSO/H20 9: 1 v/v solution, the N-acetyl-L-histidine anion catalysed the hydrolysis of p-nitrophenyl acetate at a greater rate than using either imidazole or N-acetyl-L-histidine as catalyst. This indicates that the carboxylate group affects the nucleophilicity of the unprotonated imidazole ring. 31P MAS NMR spectroscopy was investigated as a new technique for the study of the template molecule environment within the polymer networks. It was found that it was possible to distinguish between template associated with the polymer and that which was precipitated onto the surface, though it was not possible to distinguish between polymer within imprinted cavities and that which was not. Attempts to study the effect of the carboxylate group/imidazole ring interaction in the imprinted cavity of a molecularly imprinted polymer network were hindered by the method used to follow the reaction. It was found though that in a pH 8.0 buffered solution the presence of imprinted cavities increased the rate of reaction for those polymers derived from L-histidine. Some preliminary investigations into the design and synthesis of an MIP which would catalyse the oxy-Cope rearrangement were carried out but the results were inconclusive.
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Hu, Lucy Yue. "Binding studies on molecularly imprinted polymers." W&M ScholarWorks, 2004. https://scholarworks.wm.edu/etd/1539623453.
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Molecular imprinting is a rapidly developing technique for preparation of polymeric materials that are capable of molecular recognition for selective separation and chemical identification. to prepare molecularly imprinted polymers (MIPs), a functional monomer and a crosslinker are polymerized in the presence of a template molecule. Then the template is extracted leaving sites which are complementary in both shape and chemical functionality to those of the template. This resin then becomes capable of selectively absorbing the template species. Because of MIPs' stability, predesigned selectivity, and easy preparation, they have been used for separation, sensor, drug development and directed synthesis.;In this study, we focused on characterizing and understanding the mechanism underlying formation and recognition of MIPs. Three resins imprinted with 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and 6-methoxy-alpha-methyl-2-napthaleneacetic acid ((S)-naproxen) were prepared in a free radical polymerization. Hydrogen bonding between the template and functional monomer is the main interaction: it not only controls the template molecules in and out of the binding sites, but also contributes a high concentration of specific binding sites in the resulting polymer resin. After polymerization, the amount of template that can be effectively removed during each extraction was quantified in the naproxen imprinted system. For comparison, another resin was prepared under the same condition without the presence of the template, which was designated as NIP.;The binding experiments were performed for the affinity and selectivity tests. The MIP showed a special affinity for the template, but not for other analytes, which is consistent with the principle that an imprinted resin's recognition ability is dependent on the analyte's size, shape, and functionality. The NIP had similar affinities for the analytes and thus it could not differentiate among them. The binding behavior of the MIP is characterized by an association constant and the density of each kind of site using a simple two-binding-site model with one kind of sites special for the template and the others being more general with similar affinities as the NIP. The binding sites common to both the imprinted resin and the non-imprinted resin were found to have higher affinity but are less numerous than the sites unique to the imprinted resin.
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Tshikhudo, Tshinyadzo Robert. "Development of nickel-selective molecularly imprinted polymers." Thesis, Rhodes University, 2002. http://hdl.handle.net/10962/d1004449.
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A series of eight novel bidentate ligands, designed for use in the construction of nickel-selective molecularly imprinted polymers (MIP's), have been prepared. The synthetic pathway was established by retrosynthetic analysis of the target molecules to the readily available precursors, pyridine-2-carbaldehyde (or 6-methylpyridine-2-carbaldehyde) and ethyl bromoacetate. The ligands were designed to contain an allyl group for co-polymerisation and amine and pyridyl nitrogen donors, located to permit the formation of 5-membered nickel chelates. The eight novel ligands and their respective precursors were characterized by elemental (high-resolution MS) and spectroscopic (IR and ¹H and ¹³C NMR) analysis. High resolution electron-impact mass spectrometry has also been used, together with B/E linked scan data, to explore the fragmentation patterns of selected ligands. The various nickel(ll) complexes were analyzed using spectroscopic techniques and, in some cases, elemental analysis; computer modelling has also been used to explore conformational effects and complex stability. Numerous MIP's, containing nickel(II) complexes of the bidentate ligands, have been prepared, using ethylene glycol dimethylacrylate (EGDMA) as the cross-linker, azobis(isobutyronitrile) (AlBN) as the polymerization initiator and MeOH as the porogenic solvent. The template nickel(II) ions were leached out with conc. HCI, and the nickel(II) selectivity [in the presence of Fe(Ill)] of the nickel-imprinted polymers was examined by ICP-MS analysis. The ICP-MS data indicate that the MIP's examined exhibit extremely high selectivity for nickel over iron.KMBT_363
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Rick, John Frank. "Molecularly imprinted polymers as biological receptor analogues." Thesis, University of East Anglia, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.249781.
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Kearton, Brian L. "Controlled free radical cyclisations in imprinted polymers." Thesis, University of Nottingham, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367355.
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Li, Bin. "Molecularly imprinted polymers for applications in cosmetology." Thesis, Compiègne, 2013. http://www.theses.fr/2013COMP2083.
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Un polymère à empreintes moléculaires (MIP) est un récepteur synthétique supramoléculaire, un matériau possédant des cavités pouvant reconnaître spécifiquement une molécule cible. Il est synthétisé en mettant en contact la molécule cible, avec un mélange de monomères fonctionnels et réticulants qui permettent d'obtenir un réseau polymérique tridimensionnel rigide. L'élimination de la molécule empreinte laissera des sites vides complémentaires de cette dernière. Ces cavités sont maintenant capables de la recapturer spécifiquement. Ces polymères sont utilisés dans les domaines tels que l’extraction en phase solide, la chromatographie d’affinité, la catalyse enzymatique, les biocapteurs et la vectorisation des médicaments. Bien que le concept des MIPs a pour origine les travaux réalisés sur des matériaux sol-gel imprimés dans les années 1930, ces derniers sont restés dans l’ombre jusqu’à l'introduction de polymères organiques imprimés plus versatiles. Par rapport aux MIPs organiques, les MIPs sol-gel présentent quelques avantages comme une plus grande stabilité thermique, une meilleure compatibilité avec l'eau et une plus grande porosité. Dans cette thèse, nous avons développé des MIPs organiques et des MIPs sol-gel pour leur application en cosmétologie et pour la vectorisation de médicaments. Dans la première partie, nous présentons des MIPs pouvant adsorber d’une façon spécifique l’acide oléique (OA), un biomarqueur de l’état pelliculaire sur le cuir chevelu. Pour la préparation des MIPs organiques, nous avons employé plusieurs monomères basiques dont l’acryloylaminobenzamidine (AB), que nous avons tout spécialement synthétisé. Tous les MIPs pouvaient lier l’OA mais beaucoup d’interaction non-spécifique était observé. D’autre part, les MIPs sol-gel présentaient une bonne reconnaissance spécifique et une capacité élevée pour OA; par exemple, un MIP de composition OA:APTES:TEOS = 1:1.6:1.7 pouvait adsorber 625 μmol.g-1 de OA dans le sébum artificiel. Des tests pour capturer l’OA sur le stratum corneum et la peau reconstruite (Episkin) ont également été effectués. La pénétration de l’OA sur les deux types de peau était plus faible en présence de MIP que de NIP. Les MIPs comme matériaux désodorisants font l’objet de la deuxième partie de cette thèse. Des MIPs pouvant adsorber les précurseurs de molécules malodorantes comme les conjugués glutamine des acides (E)-3-méthyl-2-hexénoïque (3M2H) et 3-hydroxy-3-méthyl-hexanoïque (3H3MH) ont été préparés. Le N-hexanoyl glutamine et le N-hexanoyl glutamate ont été utilisés comme template. Nous observons que le MIP synthétisé avec AB comme monomère fonctionnel possède la plus grande capacité d'adsorption pour le N-hexanoyl glutamine, ainsi que pour les précurseurs glutamines des molécules malodorantes. Des résultats préliminaires et très prometteurs ont également été obtenus dans la sueur. La dernière partie de cette thèse concerne des MIPs pour la vectorisation de médicaments. L'acide salicylique (SA) est un médicament efficace utilisé dans le traitement de l’acné. Des MIPs organiques et sol-gel contre SA ont été synthétisés. Les MIPs sol-gel ont une plus grande capacité d’adsorption, 180 μmol.g-1, que les MIPs organiques et ils lient le SA sept fois plus que le NIP. Les tests de relargage du SA ont été effectués dans plusieurs milieux, avec la plus grande efficacité dans l’eau pure. En conclusion, les applications de MIPs en cosmétologie et en vectorisation de médicaments ont étés étudiés. Nos résultats montrent que les MIPs sol-gel sont les plus appropriés pour ce type de travailMolecularly imprinted polymers (MIPs) are tailor-made synthetic receptors possessing specific cavities for a given target molecule. They are produced by introducing, into the polymer precursors, guest molecules that act as templates at the molecular level. Interacting and cross-linking monomers are then copolymerized to form a cast-like shell. After removal of the template, cavities complementary to the template in size, shape and position of functional groups are revealed in the polymer, which can now specifically bind the template. Thanks to these specific molecular recognition properties, MIPs have found applications in areas like bio sensors, solid phase extraction, affinity chromatography, catalysis, and drug delivery. Although the MIP concept originated from imprinted silica in the 1930s, imprinted sol-gel materials received little attention afterwards due to the introduction of the more versatile organic polymers as imprinting matrix. However, compared to organic polymers, sol-gels possess higher thermal stability, better water compatibility and larger inner surface area. There have been many applications to biomolecules in aqueous conditions with sol-gel imprinting materials. In this thesis, we have developed organic and silica sol-gel MIPs for applications in cosmetics and drug delivery. MIPs able to adsorb the dandruff-inducing molecule oleic acid (OA) were produced via both the organic and inorganic routes. In the organic MIPs synthesis, different positively charged monomers were used, one of which, acryloyl aminobenzamidine, was specifically synthesized. Although some binding of oleic acid was obtained, specificity and capacity of these polymers were not satisfying. Sol-gel MIPs, on the other hand, exhibited good specific recognition and high binding capacity for OA. A MIP of the composition OA:APTES:TEOS= 1:1.6:1.7 yielded a capacity of 625 μmol.g-1 in artificial sebum. Furthermore, tests were carried out to capture OA on stratum corneum and reconstructed skin (Episkin). Less penetration of OA was observed in the presence of a MIP than with a non-imprinted control polymer. Deodorant materials are another topic of this thesis. MIPs that are able to adsorb certain precursors of odorant molecules, the glutamine conjugates of (E)-3-methyl-2-hexenoic acid (3M2H) and 3-hydroxy-3-methyl-hexanoic acid (3H3MH) were prepared. N-hexanoyl glutamine and N-hexanoyl glutamate were used as templates. After optimization of the MIP composition, we found that MIPs synthesized with acryloyl aminobenzamidine as functional monomer had the highest adsorption capacity for N-hexanoyl glutamine, and also recognised the glutamine targets of 3M2H and 3H3MH. Some preliminary promising binding results were obtained in artificial sweat. The third part of this work concerns a drug delivery MIP. Salicylic acid (SA) is a drug used to treat acne. SA-imprinted polymers were prepared via both organic imprinting and the sol-gel process.Compared to organic MIPs, sol-gel MIPs have a higher capacity, 180 μmol.g-1, and 7 times higher binding than to a non-imprinted control polymer was observed. Release tests were carried out in different aqueous media, the most efficient drug release was observed in pure water. In conclusion, applications of molecularly imprinted polymers for cosmetics and drug delivery have been investigated. Our results demonstrate the great potential of in particular sol-gel MIPs for these purposes
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Joshi, V. P. "Transport and reactions in molecularly imprinted polymers." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 1998. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/3397.
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Tomečková, Kristýna. "Využití syntetických protilátek v imunohistochemii." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2021. http://www.nusl.cz/ntk/nusl-449380.
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This diploma thesis deals with the optimization of the preparation of molecularly imprinted (MIP) nanoparticles doped with metal ions, selective for the selected protein. In this work, the model protein – chymotrypsinogen A was chosen as a template. The free radical polymerization method was used for the preparation of molecularly imprinted nanoparticles. Dopamine was used as a functional monomer because it is able to bind metal ions to each other. It also undergoes very rapid oxidative polymerization under alkaline conditions without the need for the addition of polymer reaction initiators. MIP optimization was performed by capillary electrophoresis with UV-Vis detection. The MIP thus prepared can serve as recognition elements in immunohistochemical analyzes that use LA-ICP-MS as a detection method. Their applicability for immunohistochemistry was studied using the dot block method.
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Vinjamuri, Anil Kiran Kumar. "A Selectivity Study on the Use of Caffeine and Theobromine Imprinted Polypyrrole Surface Electrodes." TopSCHOLAR®, 2008. http://digitalcommons.wku.edu/theses/5/.
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Fairhurst, Robert. "Designing molecularly imprinted polymeric phases for sensors, separations and high throughput extractions : spherical and thin-film polymers." Thesis, University of East Anglia, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.423395.
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Bourdillon, Céline. "Etude de cristaux photoniques et de polymères stimulables : réalisation d'un capteur de nanoparticules." Thesis, Paris 6, 2016. http://www.theses.fr/2016PA066659/document.
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L’essor des techniques d’analyse à l’échelle nanométrique a initié la synthèse et le développement de nombreuses nanostructures et nanoparticules. De par les propriétés spécifiques induites par leur taille, ces nanoparticules sont à présent omniprésentes dans la vie quotidienne et leur utilisation introduit de nouveaux enjeux environnementaux et toxicologiques. Il est donc important de pouvoir les capter et les détecter à l’état de trace en fonction de leur taille et de leur chimie de surface, deux facteurs dont dépend leur toxicité. Ce travail de thèse porte sur l’association des propriétés optiques d’un cristal photonique, l’opale, et des propriétés de reconnaissance d’un polymère stimulable, le polymère à empreintes de nanoparticules, afin de réaliser un capteur sensible, spécifique et sélectif (notamment en revêtement de surface) de nanoparticules. Les nanoparticules cibles que nous avons étudiées sont des nanocristaux fluorescents de CdSeTe/ZnS. Cette thèse se décompose en deux parties : dans la première, nous avons étudié le filtrage de l’émission des nanocristaux cibles par des hétérostructures à base d’opales directes. Dans la seconde partie, nous avons synthétisé, pour la première fois à notre connaissance, un polymère à empreintes de nanocristaux, en nous basant sur les travaux réalisés dans le cadre des polymères à empreintes moléculaires. Ce polymère a été utilisé pour réaliser une opale inverse permettant la détection de ces nanoparticules à partir de mesures de réflectivité. Ce capteur est généralisable à toute nanoparticule présentant une fonctionnalisation de surfaceSince the emergence of analysis techniques at the nanometer scale, many nanostructures and nanoparticles have been elaborated. Because of the specific properties induced by their size, nanoparticles are present in a lot of products used in the everyday life and can present a high toxicity. This toxicity depends, inter alia, on their size and surface chemistry. Therefore, it is really important to collect and detect them specifically when they are present as trace contaminants. This thesis deals with the combination of the optical properties of a photonic crystal, an opal, and the chemical properties of a stimulable polymer, a nanoparticles imprinted polymer, to realize a sensitive, specific and selective nanoparticles sensor. The nanoparticles that we used as targets are fluorescent CdSeTe/ZnS nanocrystals. In the first part of this thesis, we studied the filtering of the emission of the targets by heterostructures based on direct opals. In the second part, we synthetized, for the first time to our knowledge, a polymer presenting nanocrystals imprints. We used this polymer to realize an inverse opal allowing the sensing of these nanoparticles by specular reflection measurements. This sensor can be generalized to any functionalized nanoparticle
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Myint, Mo Aung, and n/a. "Investigation of molecular interactions with molecularly imprinted polymers." University of Otago. Department of Chemistry, 2009. http://adt.otago.ac.nz./public/adt-NZDU20090617.131516.
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Currently, very little information is available for an in-depth understanding of the molecular binding interactions with molecularly imprinted polymers (MIPs). To address this issue MIPs that have high binding affinities for their template compounds were made so that the nature of these interactions could be elucidated using spectroscopic techniques.
12 functional MIPs were prepared using a series of azobenzene and anthracenyl derivatives as the templates. Affinities of these MIPs for the corresponding templates and analogues were determined by performing batch and competitive binding tests. It was found that extensively conjugated compounds that contain at least two OH groups, an electron-withdrawing substituent and have limited conformational freedom were effective templates.
The most efficient MIP, M34, was prepared with 4-[(4-nitrophenyl)azo]-1,2-benzenediol (12). M34 exhibited high affinities for azobenzene derivatives of catechol, and bound those that did not contain non electron-withdrawing substituents more specifically. M34 did not lose affinity for 12 in the presence of analogues, and vice versa, in competitive binding tests. These observations suggested a distribution of different binding sites on M34.
M34 bound substrates rapidly, which was attributed to its highly porous polymer matrix giving ready access to binding sites. Formation of the porous matrix was facilitated by the use of DMF as the porogen in the preparation of M34. DMF is not a conventional choice of porogen because use of such highly polar H-bonding solvents is thought to disrupt complexation between template and polymer precursors, which is required for the formation of binding sites.
Significant changes in the wavenumbers and the intensities of absorption bands assigned to the catechol substructure of 12 were observed in the FT-Raman spectra of 12 bound to M34. These findings suggested that the catechol substructure was responsible for interactions of 12 with M34 that are critical to rebinding and imprinting.
In-situ analyses of dithranol (8) being removed from and bound to its MIP, M23, were performed using ATR-IR spectroscopy. Only one band, assigned to the aromatic substructure of 8, was not obstructed by solvent bands in the spectra of unwashed M23 and washed M23 that was treated with the rebinding solution. The wavenumbers of the corresponding bands in the two spectra were significantly different. This observation suggested that there were differences in the vibrational characteristics of 8 bound to M23 under the two conditions.
Evidence was found for H-bonding between OH groups of 8 and C=O group of methacrylic acid using transmission FT-IR spectroscopy. However, no evidence was found that showed significant interactions between 12 and 2-vinylpyridine. Methacrylic acid and 2-vinylpyridine were used as the functional monomers in the preparations of M23 and M34. The FT-IR spectra of mixtures of 12 and 4-vinylpyridine showed three new bands assigned to H-bonded OH stretches. These observations indicated that 4-vinylpyridine H-bonds with 12, and would be a more effective functional monomer than 2-vinylpyridine in the preparation of the MIPs for 12.
Titration of 12 with 2-vinylpyridine was analysed by �H NMR spectroscopy. Only small changes to the signals of the corresponding compounds were observed. This lack of change was attributed to the use of d₇DMF, which would compete against 2-vinylpyridine for H-bonding interactions.
The findings made using ATR-IR spectroscopy and FT-Raman were novel because previously reported data on bound templates obtained using the corresponding techniques did not show changes in the vibrational characteristics of templates as they bind to MIPs. This investigation has shown that rebinding and spectroscopic studies can provide information about the nature of the binding interactions in MIPs.
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Bowen, Jenna Louise. "Detection of lipopolysaccharide pyrogens by molecularly imprinted polymers." Thesis, Cardiff University, 2011. http://orca.cf.ac.uk/54444/.
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Lipopolysaccharide (LPS) is commonly implicated in the development and rapid progression of sepsis however no efficient diagnostic assay currently exists. The over-arching aim of this project was therefore to develop a novel biomimetic peptide-polymer hybrid system capable of recognising and binding LPS in a variety of biologically relevant environments. Target selective peptides (both commercially available and synthesised) have been used as high affinity 'functional monomers' in a molecular imprinting approach. To reduce the concept to practice, a bi-functionalised resin was prepared so as to allow the use of two independent surface attachment strategies. Controlled polymer growth was initiated from surface bound iniferter groups whilst the attachment of the peptide was achieved through amme-amine imidoester linkages or via azide-alkyne "click" chemistry. Polymyxin, a small, conformationally constrained cyclic peptide that possesses high affinity for lipopolysaccharide (LPS) was used to provide proof-of-principle. Polymyxin resins, produced via the immobilisation of alkyne derivitised polymyxin B on the surface of azidomethyl polystyrene via "click" chemistry, were able to efficiently bind LPS from aqueous solutions with an apparent Ka of 0.2 μM. Although the development of the peptide-polymer hybrid system using these resins appeared somewhat unsuccessful, whether the observed reduction in binding is due to changes in the Bmax or the Kd of the resin remains to be elucidated. The assay performed with the polymerisation samples produced using resin displaying polymyxin immobilised via a dimethyl adipimidate linker, suggest that the hypothesised approach is feasible but that optimisation of a number of variables is needed before definitive results can be obtained.
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Ritt, Cody. "Assessment of Molecularly Imprinted Polymers as Phosphate Sorbents." Thesis, North Dakota State University, 2017. https://hdl.handle.net/10365/28417.
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Wastewater effluents and agricultural runoff are major sources of phosphorus overloading in surface waters. Phosphorus overloading ignites eutrophication, which devastates aquatic ecosystems. On the other hand, phosphorus, which is currently produced from phosphate rock, is a critical component of fertilizer mixes. However, the world is predicted to face a shortage of phosphate supply beyond 2033 due to unsustainable mining. This research aims to develop a polymeric sorbent that recovers low-concentration phosphorus for eutrophication prevention and fertilizer reuse. Available polymer-based products have underwhelmed expectations by having poor selectivity or lacking appropriate biodegradation rates. This research identified molecularly imprinted polymers (MIPs) as possible sorbents for overcoming the deficiencies of reported technologies. Screening of several MIPs resulted in one potentially feasible MIP for phosphate sorption. Further studies showed a sorption capacity of ~28 mg PO43--P/g and partial phosphate-selectivity. Potential phosphate removal mechanisms were identified, providing foresight into MIPs? viability as phosphorus sorbents.North Dakota Department of Commerce (NDDoC Grant #: 14-11-J1-70); the National Institute of Food and Agriculture (NIFA-USDA Grant #: 2015-607022-22996); North Dakota Water Resources Research Institute (NDWRRI)
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Leibl, Nadja. "Development of molecularly imprinted polymers for chemical sensors." Thesis, Compiègne, 2018. http://www.theses.fr/2018COMP2446.
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Cette thèse propose une approche rationnelle pour le design de polymères à empreintes moléculaires (MIPs) pour la détection de nitro-explosifs. Les polymères à empreintes moléculaires qui miment la reconnaissance moléculaire biologique, ont l’avantage d’être stables dans des environnements sévères et peuvent adopter différentes formes physiques pour le couplage avec des transducteurs. Leur synthèse est basée sur la co-polymérisation de monomères fonctionnels et réticulants en présence de la molécule cible, ou comme dans cette thèse, d’un analogue ayant une structure proche de celle de la molécule cible. Cela conduit à la formation d’un réseau polymérique tridimensionnel rigide avec des sites de liaison complémentaires en taille, forme et position des groupes fonctionnels de la molécule cible ou de l’analogue. Pour identifier le meilleur monomère fonctionnel pour notre molécule cible, une approche rationnelle basée sur la modélisation moléculaire, la résonance magnétique nucléaire (RMN) et le titrage par calorimétrie isotherme (ITC) a été utilisée. Elle permet d’optimiser le mélange de pré-polymérisation pour identifier le monomère fonctionnel interagissant le plus fortement avec la molécule cible. Les résultats obtenus ont été confrontés à des études de liaison à partir de polymères synthétisés. La formulation polymérique ainsi conçue est intégrée aux surfaces du transducteur sous forme de nanoparticules, de films et de nanoparticules incorporés dans des films de polydopamine électropolymérisés. En plus des polymères traditionnels obtenus par polymérisation radicalaire classique sous forme de particules, des films de MIP à base de polydopamine électropolymérisés ont été étudiés en tant qu'approche alternative pour la détection électrochimique de nitro-explosifsThis thesis proposes a rational design approach towards molecularly imprinted polymers (MIPs) for sensing nitro-explosives. Molecularly imprinted polymers are mimicking biological molecular recognition. They have the advantage to be stable in harsh environments and can be tailored into different physical forms for interfacing with transducers. Their synthesis is based on the co-polymerization of functional and cross-linking monomers in the presence of the target analyte or, as in this thesis, with a structural analogue leading to a rigid three-dimensional polymer network with binding sites complementary to the template in size, shape and position of the functional groups. The choice of the functional monomer was carried out with a rational design approach combining molecular modelling, nuclear magnetic resonance (NMR) and isothermal calorimetry (ITC) studies. This allows to optimize the pre-polymerization mixture in order to get strong complexation between the functional monomer and the template. The obtained results were confronted with binding studies performed on synthesized polymers. The thus designed polymer formulation was interfaced with transducer surfaces in form of nanoparticles, films and nanoparticles embedded into electro-polymerized polydopamine films. In addition to the traditional MIPs by free radical polymerization, molecularly imprinted in-situ electro-polymerized polydopamine films were investigated as an alternative approach for sensing nitro-explosives electrochemically
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Jin, Weize. "Relative Alignment of CZA (Cold Zone Anneal) Polymer In Nano Imprinted Films." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1430229845.
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Shi, Huaiqiu Galen. "Protein recognition of template imprinted polymer surfaces /." Thesis, Connect to this title online; UW restricted, 1999. http://hdl.handle.net/1773/8075.
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Saadaoui, Asma. "Développement de nouveaux monomères biosourcés à base d’Isosorbide et applications à la synthèse de matériaux à applications spécifiques." Thesis, Lyon, 2017. http://www.theses.fr/2017LYSE1036.
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L'isosorbide et ses dérivés sont des diols chiraux issus de l'amidon de maïs. L'utilisation de ce dernier en tant que monomère pour l'élaboration de polymères s'est révélée efficace, ces derniers égalant les propriétés des polymères conventionnels. Dans le cadre de cette thèse, ces diols sont employés pour synthétiser de nouvelles plateformes des monomères biosourcés AA et AB à partir des 1,4 :3,6- dianhydrohexitols. La synthèse d'intermédiaires à base de dinitriles ou de mononitriles et leurs dérivés à partir des trois isomères ainsi que les résultats d'essais de polymérisation de l'un de ces monomères prometteurs ont été décrits. Le polymère obtenu a révélé semi-cristallin grâce à l'agencement stéréorégulier des monomères AB. Ce travail est aussi le premier à décrire l'utilisation des réticulants chiraux à base de 1,4 :3,6-dianhydrohexitols participant à la formation du réseau tridimensionnel pour l'élaboration de polymères à empreintes (MIP) biosourcés pour la détéction de la Méthyltestostérone (MT). Les polymères synthétisés par polymérisation par précipitation ont été caractérisés. Les propriétés de rétention ont été évaluées en mode batch par HPLC-MS/MS. Ces MIPs présentent de bonnes propriétés d'adsorption vis-à-vis la MT avec des facteurs d'empreinte supérieurs à 1 montrant l'efficacité de l'impression. Ces matériaux présentent une bonne capacité d'adsorption comparée à la littérature. Les polymères non imprimés (NIP) ont même montré des capacités d'adsorption supérieure aux MIP classiques. La capacité d'adsorption la plus élevée a été observée pour cMIP-Is à base d'isosorbide, pour les concentrations importantes (500 mg L-1). Les données expérimentales ont été étudiées selon les modèles d'adsorption de Langmuir et Freundlich pour interpréter les phénomènes d'adsorption. Ces cMIP développés ont été adaptés pour l'extraction de la méthyltestotérone sur phase solide (SPE). Une procédure d'extraction a été développée en menant au travers d'une optimisation complète finalisée par une application aux eaux uséesThe isosorbide and its derivatives are chiral diols obtained from cornstarch. The use of the latter as a monomer for the development of polymers has proved to be effective. The diols match the properties of conventional polymers. As part of this thesis, the diols are used to synthesize new platforms of bio based AA and AB from the 1,4: 3,6 - dianhydrohexitols monomers. The synthesis of intermediaries based on dinitriles or mononitrilies and their derivaties starting from the three isomers as well as the test results from one of these promising monomers polymerization which have been described. The resulting polymer revealed semi-cristallin through stereoregulier AB monomers layout. This work is also the first to describe the use of the reticulants chiral at base of 1.4: 3, 6-dianhydrohexitols participating in the formation of three-dimensional network for the development of polymers to footprints (MIP) Excelsior for detection of Methyltestosterone (MT). The polymers synthesized by polymerization have been characterized by precipitation. The properties of retention were evaluated in batch mode by HPLC-MS/MS. These MIPs present good properties of adsorption towards the MT with factors of footprint greater than 1 showing the effectiveness of printing. These materials have a good ability of adsorption compared to literature. Unprinted polymers (PIN) have shown even greater adsorption capacity than the conventional MIP. The high adsorption capacity was observed in cMIP-Is based on isosorbide for the concentrations (500 mg L-1). The experimental data have been studied according to Langmuir and Freundlich adsorption models to interpret the phenomena of adsorption these developed cMIP have been adapted for the methyltestoterone on the phase of extraction (SPE) solid. An extraction procedure has been developed leading through a full optimization finalized by an application in wastewater
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Eppler, Stefan [Verfasser]. "Advanced strategies for characterizing molecular imprinted polymers / Stefan Eppler." Ulm : Universität Ulm. Fakultät für Naturwissenschaften, 2014. http://d-nb.info/1052586007/34.
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Bolisay, Linden De Venecia. "Molecularly imprinted polymers for the recognition of tobacco viruses." College Park, Md. : University of Maryland, 2007. http://hdl.handle.net/1903/7277.
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Thesis (Ph. D.) -- University of Maryland, College Park, 2007.Thesis research directed by: Chemical Engineering. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
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Davies, Matthew Paul. "The use of molecularly imprinted polymers in pharmaceutical analysis." Thesis, Queen Mary, University of London, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.408545.
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Kirsch, Nicole. "Molecular recognition of poorly functionalised molecules with imprinted polymers." Thesis, University of Reading, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.325167.
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Le, Strat Loïc. "Imprinted polymers and templated cyclic peptides : a combinatorial approach." Thesis, University of Southampton, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.274468.
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Tamboli, Vibha. "Detection of prostate cancer biomarker using molecularly imprinted polymers." Thesis, Cardiff University, 2017. http://orca.cf.ac.uk/103518/.
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Successful treatment of prostate cancer (PCa) depends on early diagnosis and screening, which currently relies on the measurement of serum prostate specific antigen (PSA) levels. The overarching aim of the project was to generate molecularly imprinted polymers for PCa biomarkers, with subsequent integration with a sensing platform to allow for rapid, point of care detection and monitoring. The initial work involved the use of simple PSA epitopes for epitope imprinting using conventional imprinting techniques. A four amino acid sequence from the Cterminus of PSA was imprinted with MAA, Aam and Urea monomers to obtain bulk imprinted polymers. Apparent Kd of 102 μM, 154 μM, 194 μM was obtained for MAA, AAm, Urea based bulk mini-MIPs respectively. Epitope imprinting was further developed using a surface imprinting approach, via electropolymersiation of dopamine to detect an epitopic sequence from pro-PSA. An improvement in Kd from bulk-imprinted polymers, with an apparent Kd of 2.9 μM was obtained with the surface electrochemical MIP sensor. However, both epitope imprinting technique lacked sensitivity to measure clinical relevant concentrations of PSA (nM range). As a consequence, a more sophisticated technique called hybrid imprinting was developed to build an electrochemical MIP sensor. Hybrid MIP imprinting utilised an aptamer with established affinity towards PSA to trap the aptamer-PSA complex into a surface grown electropolymer (polydopamine). The resulting aptamer lined polymer pockets exhibited high selectivity and affinity towards PSA (apparent Kd 0.3 nM). The apta-MIP sensor was also able to discriminate from a homologous protein (human Kallikrein 2) and was resilient to fouling from serum proteins. The apta-MIP sensor was further translated to a MOSFET device whereby successful detection of PSA at clinically relevant concentration was obtained in human plasma. Although good sensitivity and selectivity was obtained with the hybrid-MIP sensors, further research is required to understand the binding mechanism of the template to the MIP.
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Silva, Mara Lília Soares da. "Development of molecularly imprinted polymers using supercritical fluid technology." Doctoral thesis, Faculdade de Ciências e Tecnologia, 2011. http://hdl.handle.net/10362/6697.
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Dissertação para obtenção do Grau de Doutor em
Química SustentávelWithin the last decade, the interest in molecularly imprinted polymers (MIPs) has strongly increased because of their promising applications in separation processes, drug delivery, biomimetic sensing and catalysis. This thesis reports the development of MIPs using supercritical fluid technology as a viable and greener alternative to the synthesis and processing of these molecular recognition polymers. The affinity to the target molecule was introduced by means of non-covalent and semicovalent molecular imprinting and the performance of the materials was evaluated in specific applications of drug delivery, chiral chromatography and adsorption of environmental pollutants. The influence of experimental parameters, such as crosslinking degree, functional monomer nature and template: monomer ratio, on molecular recognition was investigated. The results show that it is possible to tune the affinity of the polymers by optimizing the imprinting reactional mixture. MIPs show higher loading capacities and affinity constants to the template molecule, both in supercritical and aqueous environments. Hybrid membranes were prepared by a scCO2-assisted phase inversion method, showing that imprinted particles can be immobilized into porous structures introducing affinity to the materials. Further, HPLC experiments attested that the synthesized MIPs have high selectivity towards the template, as an enantiomeric differentiation was achieved when the racemic mixture was loaded into the imprinted polymeric stationary phase. The work developed in this thesis contributes to the consolidation of scCO2 as alternative solvent and demonstrates the feasibility of synthesizing clean, easy-to-make and ready-to-use molecular recognition polymers using sustainable technologies.
Fundação Ciência e Tecnologia - grant SFRH/BD/31085/2006 and projects PTDC/QUI/66086/2006 and PTDC/QUI-QUI/102460/2008
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Janiak, Daniel S. "Molecularly imprinted polymers for the selective recognition of proteins." College Park, Md.: University of Maryland, 2009. http://hdl.handle.net/1903/9157.
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Thesis (Ph. D.) -- University of Maryland, College Park, 2009.Thesis research directed by: Dept. of Material Science and Engineering. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
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TOMMASINI, MARTINA. "Fluorescent Molecularly Imprinted Polymers as sensors for anticancer drugs." Doctoral thesis, Università degli Studi di Trieste, 2019. http://hdl.handle.net/11368/2952847.
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Chemotherapy is a medical treatment mainly aimed at damaging solid and haematological tumors, by the administration of specific drugs able to target cancer cells. These drugs, however, often show many secondary effects and present variable inter-individual pharmacokinetics. Hence, the ideal optimization of the therapy would consist of continuously monitoring, in each patient, drug absorption in blood circulation, in order to adjust the daily dose regimen, decreasing therefore its side effects and improving the whole treatment. This methodology is known as Therapeutic Drug Monitoring (TDM) and requires the determination of drug concentration in various biological matrix, as blood, plasma, urine or saliva, and evaluation of these concentrations in terms of relevant clinical parameters. The main goal of TDM consists of individualization of therapeutic treatment of the patient.
However, TDM application usually involves the support of specific instrumentations, as HPLC-MS or LC-MS/MS, that allow to perform an accurate and precise analysis of the samples, but they result time consuming, expensive and require trained personnel. Thanks to the recent technological developments, it is possible to miniaturize all of this, towards the design of specific Point-of-Care (POC) devices, able to perform a rapid quantification of the sample, without requirement of clinical support. The main advantages of using POC devices are portability, inexpensiveness and easiness to handle, hence to be used directly from patients themselves.
This work is part of the project “Application of Advanced Nanotechnology in the development of innovative cancer diagnostic tools”, funded by Associazione Italiana Ricerca Cancro (AIRC) and coordinated by Centro di Riferimento Oncologico di Aviano (CRO); one of its aims consists of the development of Point-of-Care devices to be used for the Therapeutic Drug Monitoring of several anticancer drugs, included irinotecan and imatinib. This thesis project is focused, in particular, on the development of artificial receptors, named Molecularly Imprinted Polymers (MIPs), that can act as sensors for antitumor agents irinotecan and imatinib detection in human plasma samples. MIPs have been prepared by incorporating various fluorescent functional monomers in the polymer matrix, in order to obtain a fluorescent sensor, acting as recognition element and transducer at the same time. Different fluorescent 1,8-naphtalimide and a polymerisable EDANS derivatives have been synthesized; the interactions of these monomers and of fluorescein O-acrylate (commercially available) with each anticancer drug were investigated through NMR experiments. After selection of the best monomer-drug match, several MIPs have been prepared for each target molecule, following a high dilution radical polymerization protocol, and characterized by Dynamic Laser Light Scattering (DLS) and Transmission Electron Microscopy (TEM); nanoparticles with an average diameter of 15 nm were obtained. The MIPs rebinding capacity and specificity were studied through HPLC assays in water, and, exploiting their intrinsic fluorescence properties, it was possible to investigate on their rebinding capabilities in different media, by observing the eventual quenching of fluorescence upon binding.
A MIP designed for irinotecan, in particular, containing a naphtalimide fluorescent dye, showed very promising results, as best specificity in water and an optimal drug sensitivity within its therapeutic concentrations range (17 nM – 17 μM), also in samples of plasma treated with acetonitrile (LOD 9.4 nM with within-run variability 10% and day to day variability 13%).
The bes MIP for imatinib, instead, was obtained by incorporation of EDANS fluorophore in the polymerix matrix; at fluorescence measurements, MIP showed both a good specificity and rebinding capacity toward the imatinib in water (LOD of 1.7 μM and within-run variability 4.4%).
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Mijangos, Irene. "Influence of polymerisation conditions on performance of molecularly imprinted polymers." Thesis, Cranfield University, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.443737.
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Mehamod, Faizatul Shimal Binti. "Molecularly imprinted polymers : rational design, controlled synthesis and novel applications." Thesis, University of Strathclyde, 2011. http://oleg.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=16886.
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Molinelli, Alexandra Lidia. "Molecularly Imprinted Polymers: Towards a Rational Understanding of Biomimetic Materials." Diss., Available online, Georgia Institute of Technology, 2004:, 2004. http://etd.gatech.edu/theses/available/etd-11042004-170626/unrestricted/molinelli%5Falexandra%5Fl%5F200412%5Fphd.pdf.
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Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2005.Weck, Marcus, Committee Member ; Josowicz, Mira, Committee Member ; Janata, Jiri, Committee Member ; Mizaikoff, Boris, Committee Chair ; Huang, Ching-Hua, Committee Member. Includes bibliographical references.
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Wagner, Sabine. "Sensory molecularly imprinted polymer (MIP) coatings for nanoparticle- and fiber optic-based assays." Doctoral thesis, Humboldt-Universität zu Berlin, 2019. http://dx.doi.org/10.18452/19808.
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Für den Nachweis dieser Schadstoffe in niedrigen Konzentrationsbereichen sind schnelle und empfindliche Analysemethoden erforderlich. Molekular geprägte Polymere (MIPs) wurden als synthetische Materialien entwickelt, um die molekulare Erkennung von natürlichen Rezeptoren nachzuahmen, aufgrund ihrer Fähigkeit, selektiv eine Vielzahl von Analyten zu erkennen, ihre Stabilität und ihrer einfachen Herstellung. Sie sind zunehmend in der chemischen Sensorik als Rezeptormaterial für den Nachweis bestimmter Analyten bei niedrigen Konzentrationen zu finden, insbesondere in Kombination mit Fluoreszenz aufgrund dessen hoher Empfindlichkeit.
Ziel dieser Arbeit war die Entwicklung von optischen Sensormaterialien unter Verwendung von MIPs als Erkennungselemente im Zusammenhang mit Fluoreszenz zum sensitiven Nachweis von Herbiziden und Antibiotika in Wasser- und Lebensmittelproben and deren Kombination mit verschiedenen Vorrichtungsformaten für die zukünftige Detektion einer breiten Palette von wichtigen Analyten.For the detection of these contaminants in low concentration ranges fast and sensitive analytical tools are required. Molecularly imprinted polymers (MIPs) have been used as synthetic materials mimicking molecular recognition by natural receptors due to their ability to recognize selectively a wide range of analytes, their stability and ease of synthesis. They have gained more and more attention in chemical sensing as receptor material for the detection of suitable groups of analytes at low concentrations especially in combination with fluorescence due to the latter’s high sensitivity. This work aimed the development of optical sensor materials using MIPs as recognition elements connected with fluorescence for the sensitive detection of herbicides and antibiotics in water and food samples and their combination with various device formats for the future detection of a wide range of analytes.
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Kueh, Alona Swee Hua. "Molecular imprinting of small, poorly functionalised organic compounds." The University of Waikato, 2008. http://hdl.handle.net/10289/2264.
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Molecularly imprinted polymers (MIPs) have been compared to natural antibodies in that they can specifically bind target compounds in a similar way that antibodies specifically bind to an antigen. The attraction of the MIPs technology is the ease of creating binding elements which are relatively cheap compared with the process of isolating natural antibodies. In this research monoterpenes, such as α-terpineol, were chosen to be the model compounds for investigating the molecular imprinting of small, poorly functionalised organic compounds. The conventional non-covalent approach was mainly used to synthesise these MIPs, but the sacrificial-spacer semi-covalent approach was also investigated. A less widely used method, porogen-imprinting - a variant of non-covalent imprinting - was adapted for α-terpineol. The latter novel terpene MIP appeared to specifically bind α-terpineol, by hydrogen bonding, so the polymer was characterised in detail. The main parameters which were altered for preparing non-covalent MIPs included the template (α-terpineol, (-)-menthol or trans-terpin); the functional monomer (methacrylic acid, 2-hydroxyethyl methacrylate, bilirubin and phenol [for the semi-covalent MIP]); the cross-linking monomer (ethylene glycol dimethacrylate, divinylbenzene and trimethylolpropane trimethacrylate); and also the polymerisation method (block or precipitation polymerisation). The binding specificity and cross-reactivity for all the polymers were tested using a liquid batch-binding setup. The batch-binding setup required the detection of analyte that was not bound in order to calculate by difference the fraction of analyte bound to the polymer. Initially the terpenes were to be detected by a colorimetric method; however attempts to make the method sensitive and reliable were not successful. In comparison, gas chromatography was more reliable for the detection of terpenes and was used for the experiments presented in this thesis. 1H-NMR studies of the interaction between α-terpineol and acetic acid (as a non-polymerisable analogue of methacrylic acid) were investigated as a basis for understanding the binding to the carboxyl functional group moiety employed in many of the non-covalent MIPs that were made. The interaction between (-)-menthol and phenol was also investigated because the phenol moiety was employed in the semi-covalent MIP. Only selected MIPs, which appeared to specifically bind the template, were physically characterised. This included optimising the batch-binding parameters, scanning electron microscopy imaging, surface area and pore radius analysis and in some cases Fourier transform-infrared spectroscopy of the polymers.
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Lattach, Youssef. "Development and characterization of sensing layers based on molecularly imprinted conducting polymers for the electrochemical and gravimetrical detection of small organic molecules." Phd thesis, Conservatoire national des arts et metiers - CNAM, 2011. http://tel.archives-ouvertes.fr/tel-00699628.
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In the field of chemical and biological sensors, the increased need for better sensitivity, faster response and higher selectivity during an analysis process, requires the development of more and more efficient transducing sensing layers. In this context, and with the aim to detect small non-electroactive molecules, such as atrazine (ATZ), we designed, characterized and developed sensing layers constituted by functionalized Molecularly Imprinted Conducting Polymers (MICP) and we integrated them into electrochemical and gravimetrical sensors. Starting from acetonitrile pre-polymerization media containing ATZ as template molecules in the presence of thiophene-based functional monomers (FM, namely TMA, TAA, EDOT, TMeOH or Th), differently functionalized and structurally different polythiophene-based FM-MICP films were electrosynthesized onto gold substrates and used for ATZ detection. The sensing properties of FM-MICP layers were shown to result from the presence in their backbones of pre-shaped FM-functionalized imprinted cavities which keep the memory of the targets. Nevertheless, non-specific adsorption onto the surface of the sensing layers takes place systematically, which affects the selectivity of the recognition process. Thanks to surface characterization techniques, we highlighted the influence of the thickness and of the structural properties of the layers on the efficiency of the recognition process. Besides, this latter was shown to operate in the bulk of the polymer matrixes thanks to layers porosity. On another hand, electrochemical measurements correlated with semi-empirical calculations demonstrated the influence of the nature of FM on the strength of the ATZ-FM interaction in the pre-polymerization medium, and then on the number of ATZ molecular imprints and on the sensitivity towards ATZ of the FM-MICP layers. We showed that TAA-MICP, which presents a low limit of detection (10-9 mol L-1) and a large dynamic range (10-8 to 10-4 mol L-1), is the best sensing layer since it offers the best compromise between high level of specific detection of ATZ and low level of non-specific adsorption. Finally, TAA-MICP was used as sensitive layer in an original Electrochemical Surface Acoustic Wave sensor (ESAW) which enabled simultaneous coupled gravimetric and electrochemical measurements.
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Puzio, Kinga. "Towards controlled release of Vanillin and bio-sensing of Adenosine monophosphate using molecularly imprinted polymers." Thesis, Orléans, 2012. http://www.theses.fr/2012ORLE2075.
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Ce mémoire présente une exploration des polymères à empreintes moléculaires (MIP) comme outils d’une libération contrôlée de bioactifs olfactifs ou pour le criblage/préselection de composés à activité antivirales ou anti-tumorales sur le site actif d’une enzyme. La première partie est une étude de la complexation de la vanilline sur des billes polymériques sphériques en vue d’une libération contrôlée (pH, salinité, …). Ces études portent sur les caractéristiques de l'absorption et la libération de la molécule d'intérêt dans le milieu aqueux sur les microsphères fonctionnalisées fourni par Merck ESTAPOR® Microsphères. Nous avons ensuite synthétisé divers MIP de vanilline au format monolithique. Plusieurs stratégies d’impression ont été étudiées: non covalente, covalente et semi-covalente. La composition du MIP préparé dans chaque approche a été optimisée pour obtenir les meilleures propriétés et performances. L'affinité, la sélectivité et la capacité du MIP ont été déterminées. Les MIPs ont été évalués par extraction en phase solide (SPE) d'analogues structuraux de la vanilline dans des échantillons naturels (extrait de vanille, vin). La deuxième partie de ce mémoire concerne l’évaluation de MIPs de l’adénosine 5’-monophosphate (AMP) Le polymère a été préparé par une approche non-covalente et son efficacité de recapture a été caractérisée par analyse frontale (FA). L’analyse frontale est une technique qui permet de discriminer des interactions spécifiques des non spécifiques et de comprendre les mécanismes de liaison dans des cavités spécifiquesThis thesis report presents the exploration of molecularly imprinted polymers (MIP) for the application in controlled release and targeting antivirus and anticancer drugs. The first part of this study describes the imprinting of vanillin as a monolith. Several strategies were studied: non-covalent, covalent and semi-covalent. The composition of the MIP prepared in each approach was optimized to obtain the best properties and performance. The affinity, selectivity and capacity of MIP were determined. MIPs were evaluated in solid-phase extraction (SPE) of structural analogues in natural samples (vanilla extract, wine). We also present the study of the exploration of spherical beads as potential tools for the controlled release of vanillin. These studies concern the characteristics of uptake and release of the molecule of interest in the aqueous medium on functionalised microspheres supplied by Merck ESTAPOR Microspheres®. The second part of this thesis is devoted to studies on the evaluation of MIP of adenosine 5'-monophosphate (AMP). The polymer was prepared in non-covalent approach and efficiency of binding was characterised using frontal analysis (FA). FA is a useful technique that allows discriminate specific and nonspecific interactions and to understand the binding mechanisms in specific cavities
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Hunt, Claire Elizabeth. "New Applications For Molecularly Imprinted Polymers in Fluorescence Assays and Sensors." Thesis, University of Leeds, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.485778.
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Molecular imprinting is a technique used for the construction of synthetic polymers containing binding sites which have a high and selective affinity for a target molecule. Molecularly imprinted polymers (MIPs) can be used in sensors, to bind an analyte and then generate a signal, or in competitive binding assays, where an analyte and a probe molecule compete for .binding to a limited number of binding sites. (MIPs) are often termed 'antibody mimics', although clear advantages of MIPs are apparent when they are used in place of antibodies. MIPs are more stable and robust, inexpensive to produce and can be stored dry at room temperature for substantial periods of time. The development of MIP technologies is also desirable because their production does not require the sacrifice of animals, which is necessary for the generation of antibodies. Methods which could be employed to assess the binding of an analyte to a MIP directly in solution without needing to separate the polymer from solution have been developed, detecting the binding of the drug (S)-propranolol to MIPs, by an increase in fluorescence anisotropy in toluene, or by a shift in the peak fluorescence emission wavelength of (S)-propranolol in aqueous buffer. These methods were used to show that a (S)-propranolol imprinted polymer bound (S)-propranolol more strongly than it did (R)-propranolol, and more strongly than a non-imprinted polymer did. These methods would be particularly useful for rapidly comparing the binding properties of a number of polymers, e.g. where libraries of polymers are being screened to find the one that binds (S)-propranolol most strongly or Joost selectively. The development of competitive binding assays which do not require a time consuming separation step and which do not involve undesirable radiolabels has also been attempted. A fluorescence polarisation immunoassay and a fluorescence intensity based immunoassay for the pesticide 2,4-D were developed. These assays represent a significant advance over previously reporte,d MIP-immunoassays because they use a non-radiolabelled probe and do not .. . . require separation of the polymer from solution. The assay in buffer could be used in the field as a quick screen for 2,4-D related pesticides in contaminated water supplies. It was also attempted to develop MIPs containing a fluorescent acrylarnidofluorescein reporter group as sensors f~r (-)-ephedrine or (S)-propranolol. The binding of analyte to the polymers resulted in an increase in fluorescence, due to deprotonation of the fluorescein moiety. Fluorescence detection methods have shown potential for MIP screening libraries, and MIPs . have been shown to be viable replacements for antibodies in sensor and immunoassay applications.
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Bohan, Fiona Marie. "Synthesis, characterisation and evaluation of molecularly imprinted polymers of small molecules." Thesis, Lancaster University, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.423980.
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Washahi, Aisha Ahmed Yousuf Al. "Novel monomers, dummy templates and binding probes for molecularly imprinted polymers." Thesis, University of Leeds, 2012. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.590503.
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Molecularly imprinted polymers (MIPs) are synthetic receptors containing binding sites selective for a particular analyte molecule. They have been investigated for applications in many of the same analytical techniques where biological antibodies are currently used, such as in binding assays and sensors. MIPs are made using a template which interacts with a functional monomer: after polymerisation the template is extracted to leave the vacant binding sites. In this project, two new amine functional monomers for molecular imprinting were synthesised;4-vinylbenzylarnine (4-VBA) and diethylvinylbenzyl amine (DEVBA). A thorough study of the molecular imprinting of bisphenol A (BPA) template using DEVBA as a monomer has been described. This MIP showed selective binding towards BPA in the presence of structural analogues. These results were in agreement with the NMR titrations data which suggest a hydrogen bond formation between the BPA and DEVBA during imprinting. The new monomers were also used to prepare MIPs for enantioseparation of ibuprofen (IBP). NMR titrations revealed that DEVBA formed strong complexes with the template (S-IBP). However, enantioseparation of IBP was not achieved on either MIP. In chapter 3, MIPs were prepared for the sulphonamide antibiotic sulfamethazine (SMZ). These polymers were successfully used as stationary phases in HPLC for the separation of SMZ and related structures, both in organic and aqueous mobile phases. Two novel derivatives of SMZ were synthesised in chapter 4. Dansylmethazine (DMZ) was designed as a fluorescent analogue of 5MZ and anthraquinonesulfamethazine (AqSMZ) as a dummy template or electroactive analogue. The optical properties of these novel compounds were investigated. A set of AqSMZ-MIPs were prepared and investigated as HPLC stationary phases, in comparison with the MIPs prepared using SMZ as a template. Unlike SMZMIPs, the AqSMZ-MIPs showed very poor recognition of SMZ and its derivatives. This could be due to limited accessibility to the imprinted sites under the investigated conditions due to polymer swelling. The SMZ-MIPs and AqSMZ-MIPs were investigated for use in a competitive binding assay for SMZ using DMZ as a fluorescent probe. Using a MIP based on AqSMZ and glycerol dimethacrylate (GDMA) as cross-linker, some limited evidence for selective binding of the fluorescent probe was obtained. The poor performance of II - the MIP in a competitive assay, however, suggested the need for more optimisation in order to develop a useful sulphonamides assay.
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Subrahmanyam, Sreenath. "Design of molecularly imprinted polymers for sensors and solid phase extraction." Thesis, Cranfield University, 2002. http://dspace.lib.cranfield.ac.uk/handle/1826/7576.
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This thesis presents broadly the applications of molecularly imprinted polymers in sensors and solid phase extraction. Sensors for creatine and creatinine have been reported using a novel method of rational design of molecularly imprinted polymers (MIPs), and solid phase extraction of aflatoxin-B 1 has also been described in the thesis. A method for the selective detection of creataine and creatinine is reported in this thesis, which is based on the reaction between polymerised hemithioacetal, formed by allyl mercaptan, o-phthalic aldehyde, and primary amine leading to the formation of fluorescent isoindole complex. This method was demonstrated for the detection of creatine using creatine-imprinted MIPs. Since MIPs created using traditional methods were unable to differentiate between creatine and creatinine, a new approach to the rational design of a MIP selective for creatinine was developed using computer simulation. A virtual library of functional monomers was assigned and screened against the target molecule, creatinine, using molecular modeling software. The monomers giving the highest binding score were further tested using simulated annealing in order to mimic the complexation of the functional monomers with template in the monomer mixture. The result of this simulation gave an optimised MIP composition. The computationally designed polymer demonstrated superior selectivity in comparison to the polymer prepared using traditional approach, a detection limit of 25 μM and good stability. The 'Bite-and- Switch' approach combined with molecular imprinting can be used for the design of assays and sensors, selective for amino containing substances. MEP for the selective binding properties for aflatoxin-B 1 was prepared using the computational approach. The results obtained demonstrate that the MISPE offers a simple, convenient and a rapid methodology for solid phase extraction of aflatoxin-B 1 even at very low concentrations of 2 ppb. The commercially available C-18 cartridges were able to recover only about 52% of aflatoxin-B 1 at concentrations of 2 ppb when compared with almost complete recovery by the MIP. We have proved here that, MIPs as a solid phase extraction materials offer important and practical advantages with respect to other solid phase extraction methodologies.
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Allender, Christopher John. "Preparation, characterisation and novel applications for non-covalent molecular imprinted polymers." Thesis, Cardiff University, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.248323.
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