Search

Nowadays, molecularly imprinted polymers (MIPs) are well established and are considered excellent materials for performing selective extractions. However, with the progressive implementation of the principles of green chemistry, it is necessary to find greener alternatives for both the synthesis and further use of MIPs in sample preparation. Accordingly, in the present work, different deep eutectic solvents (DES, both hydrophilic and hydrophobic), as an alternative to conventional organic solvents (i.e., toluene), were evaluated as porogens for the synthesis of imprinted fibers (monoliths), using fused silica capillaries as molds, for solid-phase microextraction (SPME). From this study, the polymer prepared with propazine (dummy template), methacrylic acid (monomer), ethylene glycol dimethacrylate (cross-linker), and a formic acid:L-menthol (1:1) DES (porogen) showed the best performance for selective rebinding of triazines. After optimization of the different variables involved in SPME, the new imprinted fibers were successfully applied to the extraction of target analytes (desisopropylatrazine, desethylatrazine, simazine, and atrazine) from soil sample extracts, providing relative recoveries ranging from 75.7 to 120.1%, reaching limits of detection within the range of 6.2-15.7 ng g-1, depending upon the analyte.

Over the last decades, an increasing demand for new specific molecular recognition elements has emerged in order to improve analytical methods that have already been developed in order to reach the detection/quantification limits of target molecules. Molecularly imprinted polymers (MIPs) have molecular recognition abilities provided by the presence of a template molecule during their synthesis, and they are excellent materials with high selectivity for sample preparation. These synthetic polymers are relatively easy to prepare, and they can also be an excellent choice in the substitution of antibodies or enzymes in different kinds of assays. They have been properly applied to the development of chromatographic or solid-phase extraction methods and have also been successfully applied as electrochemical, piezoelectrical, and optical sensors, as well as in the catalysis process. Nevertheless, new formats of polymerization can also provide new applications for these materials. This paper provides a comprehensive comparison of the new challenges in molecular imprinting as materials of the future in Spain, Ministerio de Ciencia, Innovación y Universidades (España), Depto. de Química Analítica, Fac. de Ciencias Químicas, TRUE, pub

Although photothermal therapy is of significance in therapeutic strategies for fighting bacterial infection, the precise target of photothermal agents to bacterial sites is still a challenge. In this work, lipopolysaccharide (LPS) imprinted photothermal molecularly imprinted polymers (PMIP) were prepared for the efficient capture and elimination of Pseudomonas aeruginosa. The LPS derived from Pseudomonas aeruginosa was selected as a template due to its cis-diol structure, which can provide active sites to direct the boronate affinity-mediated synthesis of molecularly imprinted polymers. Polydopamine with good biocompatibility and photothermal effect was used as an imprinting matrix to achieve good photothermal function and imprinting efficiency. The combination of bacteria-imprinting with photothermal ability allowed PMIP to deactivate target bacteria with enhanced precision and efficiency. Taken together, our study offers a promising strategy to design synthetic materials for targeting and treating pathogens for various infectious diseases and expands the application of molecular imprinting technology in the field of antimicrobials.

Molecular imprinting technology is a well-established technique for the obtainment of tailor-made polymers, so-called molecularly imprinted polymers, with a predetermined selectivity towards a target analyte or structurally related compounds. Accordingly, molecularly imprinted polymers are considered excellent materials for sample preparation providing unprecedented selectivity to analytical methods. However, the use of molecularly imprinted polymers in sample preparation still presents some shortcomings derived from the synthesis procedure itself limiting its general applicability. In this regard, molecularly imprinted polymers use to display binding sites heterogeneity and slow diffusion mass transfer of analytes to the imprinted sites affecting their overall performance. Besides, the performance of molecularly imprinted polymers in organic solvents is excellent, but their selective binding ability in aqueous media is considerably reduced. Accordingly, the present review pretends to provide an updated overview of the recent advances and trends of molecularly imprinted polymers-based extraction, focusing on those strategies proposed for the improvement of mass transfer and selective recognition in aqueous media. Besides, with the progressive implementation of Green Chemistry principles, the different steps and strategies for the preparation of molecularly imprinted polymers are reviewed from a green perspective.

This paper describes the synthesis of novel molecularly imprinted magnetic nano-beads for the selective extraction (MISPE) of zearalenone mycotoxin in river and tap waters and further analysis by high-performance liquid chromatography (HPLC) with fluorescence detection (FLD). A semi-covalent imprinting approach was achieved for the synthesis of the molecularly imprinted polymers (MIP). The nanoparticles were prepared by covering the starting Fe3O4 material with a first layer of tetraethyl orthosilicate (TEOS) and then with a second layer using cyclododecyl 2-hydroxy-4-(3-triethoxysilylpropylcarbamoyloxy) benzoate. The last was used with a dual role, template and functional monomer after the extraction of the template molecule. The material was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopies (FT-IR). The solid phase extraction was optimized in all the steps: loading, washing and elution. The optimal conditions allowed the determination of zearalenone in trace levels of 12.5, 25 and 50 µg L−1 without significant differences between the fortified and found level concentrations., MICIN, Depto. de Química Analítica, Fac. de Ciencias Químicas, TRUE, pub

Molecularly imprinted polymers (MIPs) display intriguing recognition properties and can be used as sensor recognition elements or in separation. In this work, we investigated the formation of hierarchical porosity of compositionally varied MIPs using 129Xe Nuclear Magnetic Resonance (NMR) and 1H Time Domain Nuclear Magnetic Resonance (TD-NMR). Variable temperature 129Xe NMR established the morphological variation with respect to the degree of cross-linking, supported by 1H TDNMR determination of polymer chain mobility. Together, the results indicate that a high degree of cross-linking stabilizes the porous structure: highly cross-linked samples display a significant amount of accessible mesopores that instead collapse in less structured polymers. No significant differences can be detected due to the presence of templated pores in molecularly imprinted polymers: in the dry state, these specific shapes are too small to accommodate xenon atoms, which, instead, probe higher levels in the porous structure, allowing their study in detail. Additional resonances at a high chemical shift are detected in the 129Xe NMR spectra. Even though their chemical shifts are compatible with xenon dissolved in bulk polymers, variable temperature experiments rule out this possibility. The combination of 129Xe and TDNMR data allows attribution of these resonances to softer superficial regions probed by xenon in the NMR time scale. This can contribute to the understanding of the surface dynamics of polymers.

Molecularly imprinted polymers (MIPs) display intriguing recognition properties and can be used as sensor recognition elements or in separation. In this work, we investigated the formation of hierarchical porosity of compositionally varied MIPs using 129Xe Nuclear Magnetic Resonance (NMR) and 1H Time Domain Nuclear Magnetic Resonance (TD-NMR). Variable temperature 129Xe NMR established the morphological variation with respect to the degree of cross-linking, supported by 1H TD-NMR determination of polymer chain mobility. Together, the results indicate that a high degree of cross-linking stabilizes the porous structure: highly cross-linked samples display a significant amount of accessible mesopores that instead collapse in less structured polymers. No significant differences can be detected due to the presence of templated pores in molecularly imprinted polymers: in the dry state, these specific shapes are too small to accommodate xenon atoms, which, instead, probe higher levels in the porous structure, allowing their study in detail. Additional resonances at a high chemical shift are detected in the 129Xe NMR spectra. Even though their chemical shifts are compatible with xenon dissolved in bulk polymers, variable temperature experiments rule out this possibility. The combination of 129Xe and TD-NMR data allows attribution of these resonances to softer superficial regions probed by xenon in the NMR time scale. This can contribute to the understanding of the surface dynamics of polymers.

Biological recognition sites are very useful for biomedical purposes and, more specifically, for polymeric scaffolds. However, synthetic polymers are not capable of providing specific biological recognition sites. To solve this inconvenience, functionalization of biological moieties is typically performed, oftentimes via peptide binding. In this sense, the main task is capturing the biological complexity of a protein. This study proposes a possible alternative solution to this challenge. Our approach is based on the combination of molecular imprinting (MI) and electrospinning processes. We propose here an alternative MI approach with polymeric structures, instead of using cross-linkers and monomers as conventionally performed. Different PCL–protein scaffolds were produced via electrospinning before performing MI. Gelatin, collagen, and elastin were used as proteins. Results evidenced that the MI process conducted with PCL electrospun membranes was carried out with ionic interactions between the desired molecules and the recognition sites formed. In addition, it has been proved that MI was more efficient when using gelatin as a template. This approach opens a new stage in the development of recognition sites in scaffolds obtained with synthetic polymers and their application for biomedical purposes.

Molecular imprinting is a powerful, generic, and cost-effective technique; however, challenges still remain related to the fabrication and development of these systems involving nonhomogeneous binding sites, insufficient template removing, incompatibility with aqueous media, low rebinding capacity, and slow mass transfer. The vapor-phase deposition of polymers is a unique technique because of the conformal nature of coating and offers new possibilities in a number of applications including sensors, microfluidics, coating, and bioaffinity platforms. Herein, we demonstrated a simple but versatile concept to generate one-dimensional surface-imprinted polymeric nanotubes within anodic aluminum oxide (AAO) membranes based on initiated chemical vapor deposition (iCVD) technique for biorecognition of immunoglobulin G (IgG). It is reported that the fabricated surface-imprinted nanotubes showed high binding capacity and significant specific recognition ability toward target molecules compared with the nonimprinted forms. Given its simplicity and universality, the iCVD method can offer new possibilities in the field of molecular imprinting.

Molecular imprinting is a powerful, generic, and cost-effective technique; however, challenges still remain related to the fabrication and development of these systems involving nonhomogeneous binding sites, insufficient template removing, incompatibility with aqueous media, low rebinding capacity, and slow mass transfer. The vapor-phase deposition of polymers is a unique technique because of the conformal nature of coating and offers new possibilities in a number of applications including sensors, microfluidics, coating, and bioaffinity platforms. Herein, we demonstrated a simple but versatile concept to generate one-dimensional surface-imprinted polymeric nanotubes within anodic aluminum oxide (AAO) membranes based on initiated chemical vapor deposition (iCVD) technique for biorecognition of immunoglobulin G (IgG). It is reported that the fabricated surface-imprinted nanotubes showed high binding capacity and significant specific recognition ability toward target molecules compared with the nonimprinted forms. Given its simplicity and universality, the iCVD method can offer new possibilities in the field of molecular imprinting.

Pseudophakic cystoid macular edema (PCME), caused by chronic inflammation, is the most common cause of visual impairment in the medium-term after cataract surgery. Therefore, the prophylactic topical administration of combined steroidal and non-steroidal anti-inflammatory drugs is commonly done. Drug-eluting intraocular lenses (IOLs) gained interest as an efficient way to overcome the compliance issues related to the use of ocular drops without the need for additional surgical steps. The incorporation of functional monomers and molecular imprinting were herein applied to design hydrogels suitable as IOLs and able to co-deliver steroidal (dexamethasone sodium phosphate) and non-steroidal (bromfenac sodium) drugs. The incorporation of N-(2-aminopropyl) methacrylamide (APMA) increased the drug uptake and improved the in vitro release kinetics. Imprinting with bromfenac resulted in a decreased drug release due to permanent drug bonding, while imprinting with dexamethasone increased the amount of dexamethasone released after dual-drug loading. The application of a mathematical model to predict the in vivo drug release behavior suggests the feasibility of achieving therapeutic drug concentrations of bromfenac and dexamethasone in the aqueous humor for about 2 and 8 weeks, respectively, which is compatible with the current topical prophylaxis after cataract surgery

The use of molecularly imprinted polymers in sample preparation as selective sorbent materials has received great attention during the last years leading to analytical methods with unprecedented selectivity. However, with the progressive implementation of Green Analytical Chemistry principles, it is necessary to critically review the greenness of synthesis and further use of molecularly imprinted polymers in sample preparation. Accordingly, in the present review, the different steps and strategies for the preparation of molecularly imprinted polymers, the used reagents, as well as their incorporation to microextraction techniques are reviewed from a green perspective and recent alternatives to make the use of molecularly imprinted polymers more sustainable are provided.

Molecular dynamics (MD) simulations of prepolymerization mixtures can provide detailed insights concerning the molecular-level mechanisms underlying the performance of molecularly imprinted polymers (MIPs) and can be used for the in silico screening of candidate polymer systems. Here, we describe the use of MD simulations of all-atom, all-component MIP prepolymerization mixtures and procedures for the evaluation of the simulation data using the Amber simulation software suite.

Recent years have witnessed a dramatic increase in the use of theoretical and computational approaches in the study and development of molecular imprinting systems. These tools are being used to either improve understanding of the mechanisms underlying the function of molecular imprinting systems or for the design of new systems. Here, we present an overview of the literature describing the application of theoretical and computational techniques to the different stages of the molecular imprinting process (pre-polymerization mixture, polymerization process and ligand-molecularly imprinted polymer rebinding), along with an analysis of trends within and the current status of this aspect of the molecular imprinting field.

Selective serotonin reuptake inhibitors (SSRIs) are a class of antidepressants regularly detected in the environment. This indicates that the existing wastewater treatment techniques are not successfully removing them beforehand. This study investigated the potential of molecularly imprinted polymers (MIPs) to serve as sorbents for removal of SSRIs in water treatment. Sertraline was chosen as the template for imprinting. We optimized the composition of MIPs in order to obtain materials with highest capacity, affinity, and selectivity for sertraline. We report the maximum capacity of MIP for sertraline in water at 72.6 mg g-1, and the maximum imprinting factor at 3.7. The MIPs were cross-reactive towards other SSRIs and the metabolite norsertraline. They showed a stable performance in wastewater-relevant pH range between 6 and 8, and were reusable after a short washing cycle. Despite having a smaller surface area between 27.4 and 193.8 m2·g-1, as compared to that of the activated carbon at 1400 m2·g-1, their sorption capabilities in wastewaters were generally superior. The MIPs with higher surface area and pore volume that formed more non-specific interactions with the targets considerably contributed to the overall removal efficiency, which made them better suited for use in wastewater treatment.

A novel method is successfully tested for non-covalent imprinting. Conditions are used which practically exclude the formation of prepolymerization complexes. The template is cholesterol, and no so-called functional monomer is used. The polymers contain only an acrylic diester crosslinker. The porogen isopropanol prevents even hydrogen bonding between the template and the monomer in the prepolymerization solution. Despite of these apparently very disadvantageous conditions, appreciable imprinting factors for cholesterol and imprinted selectivity against some other steroids are observed, similar to other cholesterol MIPs with proven analytical usefulness.

Magnetic nanoparticles have been surface modified by molecular imprinting and evaluated as selective sorbents for the extraction of triazines from environmental waters. The use of propazine as template allowed us to synthesize a selective material able to simultaneously recognize and selective extract not only the template but also several other herbicides of the same family. A magnetic molecularly imprinted-based dispersive solid-phase extraction procedure was developed and fully optimized. Magnetic molecularly imprinted polymer particles can be easily collected and separated from liquid solvents and samples with the help of an external magnetic field, avoiding in that way any centrifugation or filtration steps, which represents a remarkable advantage over traditional procedures. Under optimum conditions, selective extraction of several triazines (cyanazine, simazine, atrazine, propazine, and terbutylazine) from environmental water samples was performed prior to final determination by high-performance liquid chromatography with diode-array detection. Recoveries for the studied triazines were within the range of 75.2–94.1%, with relative standard deviations lower than 11.3% (n = 3). The limits of detection were within 0.16–0.51 µg/L, depending upon the triazine and the type of sample analyzed.

In this work, a novel molecularly imprinted stir-bar was developed for the stir-bar sorptive extraction (SBSE) of thiabendazole (TBZ) and carbendazim (CBZ) from orange samples. Magnetic nanoparticles were surface modified with oleic acid and then encapsulated by a silica shell using a conventional sol-gel procedure. Subsequently, nanoparticles were functionalized with methacrylate functionalities by grafting onto the particles surface. Finally, the modified magnetic nanoparticles were entrapped in a polymer monolith synthetized by copolymerization with the imprinting polymerization mixture using a glass vial insert as a mold. Variables affecting the polymerization and rebinding conditions of target analytes were optimized. The uptake capacity for the template (TBZ) was evaluated as well as the cross-reactivity for the related compound CBZ by rebinding experiments. Finally, the proposed magnetic imprinted monolith was applied to the SBSE of TBZ and CBZ from orange sample extracts providing a remarkable clean-up ability. The calculated detection limit were 0.13 and 0.10 mg kg−1 for CBZ and TBZ respectively, low enough to satisfactory analysis of both compounds in orange samples according to current European Union regulations.

Materials that can mimic the molecular recognition-based functions found in biology are a significant goal for science and technology. Molecular imprinting is a technology that addresses this challenge by providing polymeric materials with antibody-like recognition characteristics. Recently, significant progress has been achieved in solving many of the practical problems traditionally associated with molecularly imprinted polymers (MIPs), such as difficulties with imprinting of proteins, poor compatibility with aqueous environments, template leakage, and the presence of heterogeneous populations of binding sites in the polymers that contribute to high levels of non-specific binding. This success is closely related to the technology-driven shift in MIP research from traditional bulk polymer formats into the nanomaterial domain. The aim of this article is to throw light on recent developments in this field and to present a critical discussion of the current state of molecular imprinting and its potential in real world applications.

In this study, a novel photoluminescence material for the detection of tributyltin (TBT) was developed by using a paper-based nanocomposite system. For this purpose, molecularly imprinted polymeric nanoparticles (MIN) were synthesized with mini-emulsion polymerization technique. Graphene quantum dots obtained by the hydrothermal pyrolysis were immobilized to the nanoparticle surface via EDC-NHS coupling. The fabrication of sensing platform for TBT can be divided into two steps that are the preparation of nanocomposite and the applying the nanocomposite onto nitrocellulose membrane. The selectivity constant and association kinetics were calculated to analyze the interaction of TBT with immobilized MINs. The results proved that the developed nanosensor is promising for the determination of TBT with high selectivity and sensitivity reaching a detection limit of 0.23 ppt in seawater. This novel photoluminescent nanosensor has the potential to pave the way for further studies and applications.

The fabrication of bioactive scaffolds able to mimic the in vivo cellular microenvironment is a challenge for regenerative medicine. The creation of sites for the selective binding of specific endogenous proteins represents an attractive strategy to fabricate scaffolds able to elicit specific cell response. Here, electrospinning (ESP) and soft-molecular imprinting (soft-MI) techniques were combined to fabricate a soft-molecular imprinted electrospun bioactive scaffold (SMIES) for tissue regeneration. Scaffolds functionalized using different proteins and growth factors (GFs) arranged onto the surface were designed, fabricated and validated with different polyesters, demonstrating the versatility of the developed approach. The scaffolds bound selectively each of the different proteins used, indicating that the soft-MI method allowed fabricating high affinity binding sites on ESP fibers compared to non-imprinted ones. The imprinting of ESP fibers with several GFs resulted in a significant effect on cell behavior. FGF-2 imprinted SMIES promoted cell proliferation and metabolic activity. BMP-2 and TGF-beta 3 imprinted SMIES promoted cellular differentiation. These scaffolds hold the potential to be used in a cell-free approach to steer endogenous tissue regeneration in several regenerative medicine applications.

The application of molecular imprinting technology in the separation and purification of active ingredients in natural products was widely reported, but remains a challenge. Enrichment and separation are especially limited. A surface imprinting technique was reported to synthesize molecularly imprinted microspheres (MIMs) in this article. With paeoniflorin (PF) as the template molecule, β-cyclodextrin (β-CD) and acrylamide (AA) as the functional monomers, and poly(glycidyl methacrylate, GMA) microspheres (PGMA) as the backing material. MIMs have been characterized by FTIR and FESEM. Adsorption experiments indicated the adsorption capacity of MIMs was superior to those comparative non-imprinted microspheres (NIMs) and the binding isotherm of MIMs was in good agreement with the two-site binding model. The baseline separation of PF and its structural analogue albiflorin (AF) were achieved on the new MIMs packed column. MIMs showed good affinity and efficiency for separation of PF and AF compared with those comparative NIMs. The approach of fabricating MIMs is simple, rapid, and inexpensive, and may shed new light on the application of MIMs as a liquid chromatography stationary phase to separate and analyze PF and AF from the Red peony root extracts. © 2017 by the authors.

Protein phosphorylation is a reversible post-translational modification (PTM)playing a central role in numerous biological events including disease pathogenesis.Thus, the analysis of phosphoproteome is crucial for understandingcellular regulation processes and can facilitate the development of new diagnosticand therapeutic tools.Phosphoproteins are typically analyzed using liquid chromatography coupledwith mass spectrometry (LC-MS) after proteolytic processing. However,phosphopeptides are notoriously difficult to analyze by LC-MS due their lowabundance and transient nature. This creates a need for effective enrichmenttools for phosphorylated proteins and peptides prior to mass spectrometryanalysis.The work presented in this thesis is focused on development and validationof methods and tools for enrichment of phosphopeptides with the use of molecularimprinting technology. In particular, the targeted PTMs include phosphorylationon tyrosine (pTyr) and histidine (pHis).The key recognition element employed in developed synthetic receptors was1,3-diaryl urea functional monomer FM1. This monomer is a potent hydrogenbond donor forming strong cyclic hydrogen bonds with oxyanions such asphosphates. The bias of the imprinted urea-based receptor towards differentphosphorylated residues can be programmed by selection of the template. Thus, the N, C-protected phosphotyrosine and phosphonotriazolylalaninewere used as templates to generate phosphotyrosine (pTyr MIP) and phosphohistidine(pHis MIP) selective molecularly imprinted polymers, respectively.The application of previously reported pTyr MIP for phosphoproteomicstudies was validated on complex biological samples of the mouse brain lysatedigest spiked with standard peptides and HeLa cells digested proteins. Furthermore,the pTyr MIP was developed in the format of microspherical porous beads characterized by uniformly sized and shaped particles with increasedsurface area and pore size as well as improved binding affinity and sel

In this work, we developed an efficient “molecularly imprinted polymer microzymes and inorganic magnetic nanozymes” synergistic catalysis strategy for the formation of disulfide bonds in peptides. The polymeric microzymes showed excellent selectivity toward the template peptide as well as the main reactant (linear peptide), and the Fe3O4 magnetic nanoparticle (MNP) nanozymes inhibited the intermolecular reaction during the formation of disulfide bonds in peptides. As a result, the integration of the two different artificial enzymes in one process facilitates the intramolecular cyclization in high product yields (59.3%) with excellent selectivity. Mechanism study indicates the synergistic effect was occurred by using a “reversed solid phase synthesis” strategy with an enhanced shift of reaction balance to product generation. We believe the synergistic catalysis by “polymeric microzymes and inorganic nanozymes” presented in the present work may open new opportunities in creation of multifunctional enzyme mimics for sensing, imaging, and drug delivery.

Self-organized nano-and microstructures of soft materials are attracting considerable attention because most of them are stimuli-responsive due to their soft nature. In this regard, topological defects in liquid crystals (LCs) are promising not only for self-assembling colloids and molecules but also for electro-optical applications such as optical vortex generation. However, there are currently few bottom-up methods for patterning a large number of defects periodically over a large area. It would be highly desirable to develop more effective techniques for high-throughput and low-cost fabrication. Here, a micropixelated LC structure consisting of a square array of topological defects is stabilized by photopolymerization. A polymer network is formed on the structure of a self-organized template of a nematic liquid crystal (NLC), and this in turn imprints other nonpolymerizable NLC molecules, which maintains their responses to electric field and temperature. Photocuring of specific local regions is used to create a designable template for the reproducible selforganization of defects. Moreover, a highly diluted polymer network (approximate to 0.1 wt% monomer) exhibits instant on-off switching of the patterns. Beyond the mere stabilization of patterns, these results demonstrate that the incorporation of self-organized NLC patterns offers some unique and unconventional applications for anisotropic polymer networks.

Self-organized nano-and microstructures of soft materials are attracting considerable attention because most of them are stimuli-responsive due to their soft nature. In this regard, topological defects in liquid crystals (LCs) are promising not only for self-assembling colloids and molecules but also for electro-optical applications such as optical vortex generation. However, there are currently few bottom-up methods for patterning a large number of defects periodically over a large area. It would be highly desirable to develop more effective techniques for high-throughput and low-cost fabrication. Here, a micropixelated LC structure consisting of a square array of topological defects is stabilized by photopolymerization. A polymer network is formed on the structure of a self-organized template of a nematic liquid crystal (NLC), and this in turn imprints other nonpolymerizable NLC molecules, which maintains their responses to electric field and temperature. Photocuring of specific local regions is used to create a designable template for the reproducible selforganization of defects. Moreover, a highly diluted polymer network (approximate to 0.1 wt% monomer) exhibits instant on-off switching of the patterns. Beyond the mere stabilization of patterns, these results demonstrate that the incorporation of self-organized NLC patterns offers some unique and unconventional applications for anisotropic polymer networks.

The preparation of molecularly imprinted core–shell magnetic nanoparticles and their subsequent use in the solid-phase extraction of thiabendazole from citrus sample extracts is described. Molecularly imprinted core–shell magnetic nanoparticles were prepared by the precipitation copolymerization of the imprinting polymerization mix_x0002_ture on the surface of vinyl-modified silica magnetic nanoparticles and were charac_x0002_terized by Fourier transform infrared spectroscopy and scanning electron microscopy. The obtained molecularly imprinted core–shell magnetic nanoparticles exhibited a high selectivity for thiabendazole and were easily collected and separated by an exter_x0002_nal magnetic field without additional centrifugation or filtration steps. Under opti_x0002_mum conditions, a magnetic molecularly imprinted solid-phase extraction method was developed allowing the extraction of thiabendazole from citrus sample extracts and final determination by high-performance liquid chromatography with fluores_x0002_cence detection. The detection limit was 0.2 mg/kg, far lower than the maximum residue limit established within the European Union for thiabendazole in citrus samples.

In this report, the crosslinking density of bupivacaine molecularly imprinted methacrylic acid (MAA)-ethylene glycol dimethacrylate (EGDMA) copolymers was investigated through replacement of EGDMA by methyl methacrylate (MMA). The effects were examined using a series of full-scale MD simulations of pre-polymerization mixtures, equilibrium rebinding studies on the corresponding synthesized polymers and morphology characterization through nitrogen sorption measurements. While the extent of hydrogen bonding between the functional monomer MAA and bupivacaine observed in the MD pre-polymerization mixtures was comparable in each of the systems studied, the decrease in degree of crosslinking impacted directly on polymer morphology as observed in BET and BJH studies of surface area and porosity. Further, decreases in the crosslinking density induced reductions in template rebinding capacity as seen from a series of radio-ligand binding studies, demonstrating the importance of crosslinking on the performance of molecularly imprinted MAA-EGDMA copolymers, the polymer system most commonly used in molecular imprinting science and technology.

Molecular genetic testing for the 11p15-associated imprinting disorders Silver-Russell and Beckwith-Wiedemann syndrome (SRS, BWS) is challenging because of the molecular heterogeneity and complexity of the affected imprinted regions. With the growing knowledge on the molecular basis of these disorders and the demand for molecular testing, it turned out that there is an urgent need for a standardized molecular diagnostic testing and reporting strategy. Based on the results from the first external pilot quality assessment schemes organized by the European Molecular Quality Network (EMQN) in 2014 and in context with activities of the European Network of Imprinting Disorders (EUCID.net) towards a consensus in diagnostics and management of SRS and BWS, best practice guidelines have now been developed. Members of institutions working in the field of SRS and BWS diagnostics were invited to comment, and in the light of their feedback amendments were made. The final document was ratified in the course of an EMQN best practice guideline meeting and is in accordance with the general SRS and BWS consensus guidelines, which are in preparation. These guidelines are based on the knowledge acquired from peer-reviewed and published data, as well as observations of the authors in their practice. However, these guidelines can only provide a snapshot of current knowledge at the time of manuscript submission and readers are advised to keep up with the literature.Copyright © 2016 Macmillan Publishers Limited, part of Springer Nature. All rights reserved.

El reconocimiento molecular constituye actualmente una de las ramas de estudio más prometedora, fruto de la combinación de las ciencias químicas y biológicas. Este concepto está involucrado en numerosos procesos biológicos que se dan en la naturaleza y que, al contrario de lo que se cree, raramente ocurren al azar, sino que a menudo ocurren entre moléculas seleccionadas, sobretodo en sistemas altamente organizados, lo que implica asociaciones intermoleculares más o menos complejas que pueden ser vistas como el sistema de comunicación molecular del mundo químico. La creación de macromoléculas sintéticas capaces de realizar reconocimiento molecular ha aumentado espectacularmente en los últimos años. Estos compuestos tienen aplicación en el análisis clínico, medioambiental y agroalimentario. En el campo farmacéutico abre un amplio abanico de posibilidades a la hora de diseñar nuevas terapias. De los métodos de obtención de macromoléculas sintéticas capaces de reconocimiento molecular, en este trabajo de fin de grado, se ha elegido la impresión molecular por su bajo coste, resistencia, versatilidad, alta selectividad y sencillez de preparación. En esta revisión se pretende dar una visión general de cómo se efectúa el reconocimiento molecular y de las interacciones no covalentes que lo hacen posible, y, además, explicar uno de los métodos más importante de obtención de macromoléculas sintéticas, la impresión molecular. Se hace un repaso de las ventajas con respecto a los receptores biológicos y las limitaciones de los polímeros impresos molecularmente. Las cuatro formas de impresión molecular que revisamos pueden optimizarse en aspectos como los monómeros funcionales, agentes de entrecruzamiento, disolvente porógeno e iniciador. Dedicamos, por ello, un último apartado a los nuevos enfoques para la optimización, Molecular recognition is currently one of the most promising study fields, resulting from the combination of the chemical and biological sciences. It is involved in many biological processes that occur in nature. Contrary to popular belief, these processes rarely occur randomly, especially in highly organized systems involving intermolecular associations. These associations, more or less complex, can be seen as the molecular communication system of the chemical world. The creation of synthetic macromolecules capable of molecular recognition has increased dramatically in recent years. These compounds have applications in the clinical, environmental and food analysis. In the pharmaceutical world, they open up a wide range of possibilities when designing new therapies. Of the methods existing to obtain synthetic macromolecules capable of molecular recognition, Molecular Imprinting was chosen for its low cost, strength, versatility, high selectivity and ease of preparation. This review aims to give an overview on how the molecular recognition is made and of the non-covalent interactions that make it possible as well as explain one of the most important methods of obtaining synthetic macromolecules, molecular printing. A review of the advantages against biological receptors and the limitations of molecularly imprinted polymers is made. Four forms of molecular impression are reviewed, and these can be optimised in aspects such as functional monomers, crosslinking agents, pore-forming solvent and initiator. This is addressed in the last chapter of this work

Sulfonamides are known not only to be antimicrobial drugs that lead to antimicrobial resistance but also to be chemotherapeutic agents that may be allergenic and potentially carcinogenic, which represents a potentially hazardous compound once present in soil or water. Herein, a hybrid material based on molecularly imprinted polymer (MIP)-decorated magnetite nanoparticles for specific and label-free sulfonamide detection is reported. The composite has been characterized using different spectroscopic and imaging techniques. The magnetic properties of the composite are used to separate, preconcentrate, and manipulate the analyte which is selectively captured by the MIP onto the surface of the composite. Screen printed electrodes have been employed to monitor the impedance levels of the whole material, which is related to the amount of the captured analyte, via electrochemical impedance spectroscopy. This composite-based sensing system exhibits an extraordinary limit of detection of 1 × 10 mol L (2.8 × 10 ppb) (S/N = 3), which is close to those obtained with liquid chromatography and mass spectrometry, and it was demonstrated to screen sulfamethoxazole in a complex matrix such as seawater, where according to the literature sulfonamides content is minimum compared with other environmental samples.

Dopamine (DA) can be detected by electrochemical oxidation in conventional electrodes. However, the presence of other oxidizable species (interferents) usually present in physiological fluids at high concentrations (like ascorbic acid) makes very difficult its electrochemical detection. In the present work, glassy carbon electrodes have been modified with molecularly imprinted silica (MIS) films prepared by electroassisted deposition of sol–gel precursors. The production of MIS films was performed by adding the template molecule (DA) to the precursor sol. The molecular impression of silica was assessed showing a high coherency allowing a filtering capacity in the molecular scale. The MIS-modified electrodes present a high selectivity for the detection of DA in neutral or acidic solutions. The MIS-modified electrodes allow the amperometric determination of dopamine in solutions containing ascorbic acid with molar ratios lower than 1:50,000.

Molecularly imprinted nanofiber membranes were fabricated from chitin and print molecule of phenylalanine derivative by simultaneously applying an alternative molecular imprinting and an electrospinning. The D-enantiomer imprinted nanofiber membrane preferentially incorporated the D-enantiomer and selectively transported D-enantiomer and vice versa. The permselectivity was exponentially increased with the increase in the membrane thickness, implying that multi-stage cascade membrane separation was carried out within the nanofiber membrane. The present study led to the conclusion that a molecularly imprinted nanofiber membrane is one of suitable membrane forms for the separation membrane with relatively high flux and permselectivity.

In this work, novel molecularly imprinted stir-bars based upon the entrapment of modified magnetic nanoparticles within an imprinted polymer monolith is developed for stir-bar sorptive extraction (SBSE). Firstly, magnetic nanoparticles were surface modified with oleic acid followed by encapsulation inside a silica network. Then, vinyl-groups were grafted onto the particles surface for the subsequent copolymerization with the imprinting polymerization mixture using a glass vial insert as a mold. As a result, the obtained imprinted monolith presented magnetic properties allowing its use as magnetic stir-bar. Variables affecting both polymer morphology (i.e.;amount of magnetic nanoparticles, polymerization time) and binding-elution conditions of target analytes (i.e.;solvents, time) was carefully optimized. Optimum imprinted stir-bars were evaluated for the SBSE of triazines in soil sample extracts. Recoveries, at 16 ng g−1 concentration level, ranged from 2.4 to 8.7% with relative standard deviations lower than 15% (n = 3). Although low recoveries were obtained, the high selectivity provided by the new molecularly imprinted stir-bars allowed reaching detection limits below 7.5 ng g−1 by liquid chromatography coupled to UV detection. © 2016 Elsevier B.V.

The development of in silico strategies for the study of the molecular imprinting process and the properties of molecularly imprinted materials has been driven by a growing awareness of the inherent complexity of these systems and even by an increased awareness of the potential of these materials for use in a range of application areas. Here we highlight the development of theoretical and computational strategies that are contributing to an improved understanding of the mechanisms underlying molecularly imprinted material synthesis and performance, and even their rational design.

This report demonstrates that the diversity of hydrogen bond interactions present in molecularly imprinted polymer pre-polymerization mixtures, typically associated with binding-site heterogeneity, can also contribute to morphological characteristics that may influence polymer-template recognition. Comparisons have been made between a series of bupivacaine molecularly imprinted methacrylic acid (MAA)-ethylene glycol dimethacrylate (EGDMA) copolymers and a series of analogous methyl methacrylate (MMA)-EGDMA copolymers using comprehensive molecular dynamics studies of the respective pre-polymerization mixtures, template-polymer binding studies and detailed BET surface area and BJH porosity analyses. The role of the carboxylic acid functionality of MAA, and in particular the acidic proton, in generating morphological features conducive to analyte access (slit-like rather than ink bottle-like structures) and recognition is discussed.

Development of stem cell delivery system with ability of control over mutilineage differentiation and improved engraft efficiency is imperative in regenerative medicine. We herein report transfer stamping of human mesenchymal stem cells (hMSCs) patches using thermally expandable hydrogels with tunable cell-adhesive properties. The hydrogels were prepared from functionalized four arm copolymer of Tetronic(®), and the cell adhesion on the hydrogel was modulated by incorporation of fibronectin (FN) or cell-adhesive peptide (RGD). The resulting hydrogels showed spontaneous expansion in size within 10 min in response to the temperature reduction from 37 to 4°C. The adhesion and proliferation of hMSCs on FN-hydrogels were positively tunable in proportion to the amount of FN within hydrogels with complete monolayer of hMSCs (hMSC patch) being successfully achieved. The hMSC patch on the hydrogel was faced to the target substrate, which was then easily detached and re-attached to the target when the temperature was reduced from 37°C up to 4°C. We found that the transfer stamping of cell patch was facilitated at lower temperature of 4°C relative to 25°C, with the use of thinner hydrogels (0.5 mm in thickness relatively to 1.0 or 1.5 mm) and longer transfer time (>15 min). Notably, the hMSC patch was simply transferred from the hydrogel to the subcutaneous mouse skin tissue within 15 min with cold saline solution being dropped to the hydrogel. The hMSC patch following osteogenic or adipogenic commitment was also achieved with long-term culture of hMSCs on the hydrogel, which was successfully detached to the target surface. These results suggest that the hydrogels with thermally expandable and tunable cell-adhesive properties may serve as a universal substrate to harvest hMSC patch in a reliable and effective manner, which could potentially be utilized in many cell-sheet based therapeutic applications.

Testosterone imprinted co-polymer membranes of acrylonitrile with acrylic acid, methacrylic acid and acrylamide were synthesised by phase inversion technique. The developed membranes were characterised by FT-IR, XRD and SEM techniques. Imprinted membranes showed specificity towards the template testosterone. Among the various co-polymers, the acrylamide incorporated co-polymer showed high binding towards the used template. Investigation of the selectivity characteristics revealed that the developed membranes showed selectivity toward the template testosterone than similar compounds. The bound template could be totally recovered and regenerated membranes maintain their recognition property after repeated use. On the basis of the results, the imprinted membranes can be applied for the direct extraction of testosterone in clinical analysis.

A novel chiral sorbent for D-mandelic acid (D-MA) has been fabricated on vinyl functionalized multiwalled carbon nanotube (MWCNT) by molecular imprinting technology. Molecular imprinted polymers (MIPs) were formed by D-MA as a template molecule on the surface of the vinyl functionalized MWCNT with 4-vinyl pyridine (functional monomer) and ethylene glycol dimethacrylate (crosslinking agent) with a thermal polymerization technique. FTIR, X-ray diffraction technique (XRD) and transmission electron microscopy (TEM) were used to characterize the composite structure, morphology and determine the grafted MIP quantities in the composite. Properties like adsorption dynamics, specific binding and selective recognition capacity were evaluated. The resulting MWCNT-MIP demonstrated favorable selectivity, good stability and a higher adsorption capacity for the template molecule compared to products created by bulk polymerization. For comparison, blank polymer (MWCNT-NIP) was prepared by the same procedure, only without using the template molecule in the polymerization process. To get an insight into the role of MWCNT on chiral recognition, D-MA imprinted and non-imprinted polymers without MWCNT were also prepared.

Aspects of the molecular-level basis for the function of ethylene glycol dimethacrylate and trimethylolproprane trimethacrylate crosslinked methacrylic acid copolymers molecularly imprinted with (S)-propranolol have been studied using a series of all-component and all-atom molecular dynamics studies of the corresponding prepolymerization systems. The crosslinking agents were observed to contribute to template complexation, and the results were contrasted with previously reported template-recognition behavior of the corresponding polymers. Differences in the extent to which the two crosslinkers interacted with the functional monomer were identified, and correlations were made to polymer-ligand recognition behavior and the results of nuclear magnetic resonance spectroscopic studies studies. This study demonstrates the importance of considering the functional monomer-crosslinker interaction when designing molecularly imprinted polymers, and highlights the often neglected general contribution of crosslinker to determining the nature of molecularly imprinted polymer-template selectivity.

In this report, principal component analysis (PCA) has been used to explore the influence of template complexation in the pre-polymerization phase on template molecularly imprinted polymer (MIP) recognition and polymer morphology. A series of 16 bupivacaine MIPs were studied. The ethylene glycol dimethacrylate (EGDMA)-crosslinked polymers had either methacrylic acid (MAA) or methyl methacrylate (MMA) as the functional monomer, and the stoichiometry between template, functional monomer and crosslinker was varied. The polymers were characterized using radioligand equilibrium binding experiments, gas sorption measurements, swelling studies and data extracted from molecular dynamics (MD) simulations of all-component pre-polymerization mixtures. The molar fraction of the functional monomer in the MAA-polymers contributed to describing both the binding, surface area and pore volume. Interestingly, weak positive correlations between the swelling behavior and the rebinding characteristics of the MAA-MIPs were exposed. Polymers prepared with MMA as a functional monomer and a polymer prepared with only EGDMA were found to share the same characteristics, such as poor rebinding capacities, as well as similar surface area and pore volume, independent of the molar fraction MMA used in synthesis. The use of PCA for interpreting relationships between MD-derived descriptions of events in the pre-polymerization mixture, recognition properties and morphologies of the corresponding polymers illustrates the potential of PCA as a tool for better understanding these complex materials and for their rational design.

Herein, we present a survey of the literature covering the development of molecular imprinting science and technology over the years 2004-2011. In total, 3779 references to the original papers, reviews, edited volumes and monographs from this period are included, along with recently identified uncited materials from prior to 2004, which were omitted in the first instalment of this series covering the years 1930-2003. In the presentation of the assembled references, a section presenting reviews and monographs covering the area is followed by sections describing fundamental aspects of molecular imprinting including the development of novel polymer formats. Thereafter, literature describing efforts to apply these polymeric materials to a range of application areas is presented. Current trends and areas of rapid development are discussed.

In this work, we report a method that allows the deterministic, photo-controlled covalent assembly of nanoparticles directly on surface. As a model system, we study the conjugation of molecularly imprinted polymer (MIP) nanoparticles on a glass surface and confirm that the immobilized nanoparticles maintain their molecular recognition functionality. The glass slide was first modified with perfluorophenylazide and then used to bind MIP nanoparticles under UV irradiation. After each step the surface was analyzed by water contact angle measurement, fluorescence microscopy, scanning electron microscopy, and/or synchrotron-based X-ray photoelectron spectroscopy. The MIP nanoparticles immobilized on the glass surface remained stable and maintained specific binding for the template molecule, propranolol. The method developed in this work allows MIP nanoparticles to be directly coupled to a flat surface, offering a straightforward means to construct robust chemical sensors. Using the reported photo conjugation method, it is possible to generate patterned assembly of nanoparticles using a photomask. Since perfluorophenylazide-based photochemistry works with all kinds of organic material, the method developed in this work is expected to enable immobilization of not only MIPs but also other kinds of organic and inorganic-organic core-shell particles for various applications involving photon or electron transfer., QC 20140428

Dyes are used in different industries as textile, paper, food processing, cosmetic, leather tanning, rubber, printing and so on. These chemical substances have negative effect on the quality of the water and food, causing human diseases and environmental problems. In view of these aspects, colorant have attracted the interest of the scientists in developing efficient routes for their detection and/or removal from the polluted sites. Although traditional technologies used for removal of dyes are efficient, there is the necessity of developing innovative systems both more cheaply and of easy performance. In this scenario, the integration of the membrane science with the molecular imprinting technology is an alternative way that present many advantages such us the removal or detection of a specific dye or a class of dyes and cost reduction processes. In fact, exploiting the benefits of these two technologies it is possible to develop molecularly imprinted membranes able to recognize a dye of interest in specific mode. This potential is promising for combatting the illegal use of dyes in food, drinks and aquaculture as well as for their removal. The main positive aspects of the imprinted membranes are their chemical stability, reusability, as well as the resistance to the pH and temperature. In addition, their preparation requires short operation time and it is not expensive. All these properties have an encouraging impact in dealing with the problem of dyes contamination. This short review offers a description of the concept of molecular imprinting, starting from the approach of the synthesis of imprinted polymers until the description of the preparation of imprinted membranes. The application of imprinted polymers and membranes for the detection and/or removal of dyes from polluted sites will be also discussed.

Two types of molecularly imprinted nanofiber membrane were fabricated from chitosan, adopting D-phenylalanine (D-Phe) or L-phenylalanine (L-Phe) as a print molecule. Molecularly imprinted nanofiber membranes were fabricated by applying a co-axial, two capillary spinneret so that molecular recognition sites could be localized on the surface of formed nanofiber. Though the effect was not so prominent, the amount of molecular recognition site for nanofibers with localized molecular recognition site (core-shell molecularly imprinted nanofiber membranes) was higher than that with delocalized one (usual molecularly imprinted nanofiber membranes). Those membranes showed permselectivity. The enantiomer preferentially incorporated into membrane was selectively transported.

The thesis focuses on fundamental studies aimed at elucidating factors that influence molecularly imprinted polymer (MIP) formation and ligand recognition. To this end, a series of computational techniques, in particular chemometrics and molecular dynamics (MD) in conjunction with polymer synthesis and physical characterization studies have been employed. In Paper I, the multivariate analysis method principal component analysis (PCA) was used to investigate the role of incubation media on polymer-ligand recognition, and results highlighted the importance of several solvent parameters on recognition. In Paper II, all-component MD simulations were used to examine the role of polymerization mixture stoichiometry on MIP-template recognition. Correlations between nature and extent of template complexation and recognition were observed. The influence of the acidic functionality of the methacrylic acid used in these polymers on polymer-template recognition and morphology was examined in Paper III. PCA was then used in Paper IV to identify relationships between interactions in the pre-polymerization mixture, polymer functionality, recognition and morphology using the polymers described in Paper II and III.