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The solid-phase polymerization synthesis (SPPS) represents one of the most innovative approaches to the preparation of nano-sized molecularly imprinted polymers. One of its main features consists of the use of a solid support on which the template molecule is covalently grafted. It implies that the imprinting process does not involve the target molecule as is, but, rather, a structural modification of it. It is known that the rationally designed mimic N-(4-chloro-1-hydroxy-2-naphthoylamido)-(L)-phenylalanine (CHNA-Phe) is able to generate, by bulk polymerization, imprinted materials capable of recognizing the mycotoxin Ochratoxin A (OTA). In this work, we wanted to verify whether the CHNA-Phe can be a useful mimic template in the SPPS technique. The binding isotherm were measured in the pH range of 4–8 and the binding affinities for CHNA-Phe and OTA were compared, showing that CHNA-Phe-imprinted nanoMIPs recognize, in buffered water, equally well OTA, and that the overall molecular recognition depends markedly from pH-related ionic interactions between the ligand and the binding site. There results confirm that in the SPPS method, it is possible and convenient to use as mimic templates a molecule whose three-dimensional structure is to some extent different from the target without substantial loss of selectivity or binding affinity.

Nanoscale imprinting significantly increases the specific surface area and recognition capabilities of a molecularly imprinted polymer by improving accessibility to analytes, binding kinetics, and template removal. Herein, we present a novel synthetic route for a dual molecularly imprinted polymer (dual-MIP) of the carcinogen oxidative stress biomarkers 3-nitrotyrosine (3-NT) and 4-nitroquinolin-N-oxide (4-NQO) as coatings on graphene quantum-dot capped gold nanoparticles (GQDs-AuNPs). The dual-MIP was successfully coated on the GQDs-AuNPs core via a (3-mercaptopropyl) trimethoxysilane (MPTMS) linkage and copolymerization with the 3-aminopropyltriethoxysilane (APTMS) functional monomer. In addition, we fabricated a facile and compact three-dimensional electrochemical paper-based analytical device (3D-ePAD) for the simultaneous determination of the dual biomarkers using a GQDs-AuNPs@dual-MIP-modified graphene electrode (GQDs-AuNPs@dual-MIP/SPGE). The developed dual-MIP device provides greatly enhanced electrochemical signal amplification due to the improved electrode-specific surface area, electrocatalytic activity, and the inclusion of large numbers of dual-imprinted sites for 3-NT and 4-NQO detection. Quantitative analysis used square wave voltammetry, with an oxidation current appearing at -0.10 V for 4-NQO and +0.78 V for 3-NT. The dual-MIP sensor revealed excellent linear dynamic ranges of 0.01 to 500 μM for 3-NT and 0.005 to 250 μM for 4-NQO, with detection limits in nanomolar levels for both biomarkers. Furthermore, the dual-MIP sensor for the simultaneous determination of 3-NT and 4-NQO provides high accuracy and precision, with no evidence of interference from urine, serum, or whole blood samples.

Fluoroquinolones (FQs) are one of the most important types of antibiotics in the clinical, poultry, and aquaculture industries, and their monitoring is required as the abuse has led to severe issues, such as antibiotic residues and antimicrobial resistance. In this study, we report a voltammetric electronic tongue (ET) for the simultaneous determination of ciprofloxacin, levofloxacin, and moxifloxacin in both pharmaceutical and biological samples. The ET comprises four sensors modified with three different customized molecularly imprinted polymers (MIPs) and a nonimprinted polymer integrated with Au nanoparticle-decorated multiwall carbon nanotubes (Au-fMWCNTs). MWCNTs were first functionalized to serve as a supporting substrate, while the anchored Au nanoparticles acted as a catalyst. Subsequently, MIP films were obtained by electropolymerization of pyrrole in the presence of the different target FQs. The sensors' morphology was characterized by scanning electron microscopy and transmission electron microscopy, while the modification process was followed electrochemically step by step employing [Fe(CN)

Molecularly imprinted ratiometric fluorescence (MIR-FL) nanosensors feature recognition selectivity, detection sensitivity, application universality, visualization accuracy, and device portability, and have gained popularity. However, the fluorescence intensity, nanostructure, color range, and practical application of the sensor still face severe difficulties to be solved. New strategies combined with various technologies have been developed to construct MIR-FL nanosensors for expanded applications. This Perspective highlights current resarch challenges and future prospects involving constructions and applications of MIR-FL nanosensors including dual-emission and triple-emission modes. The postimprinting mixing/modification strategies, microdevices, and multitarget detection are focused, and technology synergy, sensitivity/reproducibility improvement, application diversity/portability, etc. are proposed.

To date, an identification protocol for endocrine disruptors that bind to the thyroid hormone receptor (TR) has not been established. A method for screening and identifying TR-binding substances is highly required due to the existence of unknown TR-binding substances from the environment. Here, we conceived a chromatographic method using a molecularly imprinted polymer (MIP) to create a novel screening protocol for the endocrine disruptors. A receptor-imitating MIP was prepared using

Fluorescence sensing is limited in practical applications owing to multiple autofluorescent substances in complex biological samples such as serum. In this paper, the luminescence decay effect of persistent luminescent nanoparticles (PLNPs) was used to avoid the interference of autofluorescence in complex biological samples, and a non-autofluorescence molecularly imprinted polymer aptamer sensor (MIP-aptasensor) was designed to detect H5N1 virus. The proposed MIP-aptasensor consists of a magnetic MIP and aptamer-functionalized persistent luminescent nanoparticle Zn

Vancomycin is a glycopeptide antibiotic used to treat infections caused by Gram-positive bacteria. Due to the narrow therapeutic index of vancomycin, it is necessary to develop a sensitive and reliable analytical method to monitor the drug concentration in plasma. A novel method based on surface molecularly imprinted solid-phase extraction combined with liquid chromatography-tandem mass spectrometry for the determination of vancomycin in plasma sample was developed. The plasma sample was cleaned up through the solid-phase extraction process before the analysis. The calibration standard of vancomycin in plasma ranged between 1 and 100 ng/mL, and the correlation coefficient (r) was 0.9993. The average recoveries were from 94.3 to 104.0%, and the precision was less than 10.5%. The limit of detection and limit of quantification were 0.5 ng/mL and 1 ng/mL, respectively. The method validated was successfully used for the detection of vancomycin in mice after oral administration.

Molecularly imprinted polymers (MIPs) can exhibit antibody-level affinity for target molecules. However, the nonspecific adsorption of non-imprinted regions for non-target molecules limits the application range of MIPs. Herein, we fabricated PEGylated boronate-affinity-oriented ellagic acid-imprinting magnetic nanoparticles (PBEMN), which first integrated boronate-affinity-oriented surface imprinting and sequential PEGylation for small molecule-imprinted MIPs. The resultant PBEMN possess higher adsorption capacity and faster adsorption rate for template ellagic acid (EA) molecules than the non-PEGylated control. To prove the excellent performance, the PBEMN were linked with hydrophilic boronic acid-modified/fluorescein isothiocyanate-loaded graphene oxide (BFGO), because BFGO could selectively label cis-diol-containing substances by boronate-affinity and output ultrasensitive fluorescent signals. Based on a dual boronate-affinity synergy, the PBEMN first selectively captured EA molecules by boronate-affinity-oriented molecular imprinted recognition, and then the EA molecules were further labeled with BFGO through boronate-affinity. The PBEMN linked BFGO (PBPF) strategy provided ultrahigh sensitivity for EA molecules with a limit of detection of 39.1 fg mL

A kind of molecularly imprinted polymer based on ionic liquids (MIPIL) with flower-like shape was developed for the adsorption of rutin and its deglycosylated product. The MIPIL film was characterized by scanning electron microscope (SEM) and X-ray photo-electron spectroscopy (XPS). The adsorption capacity of quercetin on the proposed imprinted cavity of rutin in the presence of glucose and rhamnose was 3.7 ± 0.017 times as much as that in the absence of glucose and rhamnose. And the adsorption capacity of quercetin varied with the concentration of glucose and rhamnose changing. Thus, the proposed MIPIL film coupled with HPLC was used to explore the deglycosylation of rutin by tracking rutin and quercetin, which confirmed to the pseudo-first-order reaction kinetic with the constant of 0.044 ± 1.5 × 10

In this paper, combining phenylboronic affinity, surface imprinting, and magnetic Fe

18 Pág., 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., The Grant PID2021-122327OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. This article is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society.

A novel kind of three-dimensional ordered macroporous molecular imprinted polymer (3DOM MIP) was prepared and studied. Monodisperse silica microspheres were used to form silica crystal template via simple centrifuge. In the presence of template molecule, acrylamide and trimethylolpropane trimethacrylate were co-polymerized in the interstices of crystal template bisphenol A (BPA). Hydrofluoric acid were employed to etch silica crystal and the mixed solvent of methanol with acetic acid were employed to extract template molecule. The results of SEM and FTIR confirmed the successful synthesis of 3DOM MIP. The obtained 3DOM MIP exhibited a rapid adsorption kinetics and a specific adsorption capacities toward template molecule because of the small size of MIP wall, which possessed much more effective imprinted cavies. Meanwhile, 3DOM MIP could selective recognized BPA from its structural analogues.

Molecularly imprinted polymer (MIP)-based polymeric membrane potentiometric sensors have become an attractive tool for detection of organic species. However, the MIP receptors in potentiometric sensors developed so far are usually prepared by only using single functional monomers. This may lead to low affinities of the MIP receptors due to the lack of diversity of the functional groups, thus resulting in low detection sensitivity of the potentiometric sensors. Additionally, these classical MIP receptors are nonconductive polymers, which are undesirable for the fabrication of an electrochemical sensor. Herein, we describe a novel multifunctional MIP receptor-based potentiometric sensor. The multifunctional MIP receptor is prepared by using two functional monomers, methacrylic acid, and 3-vinylaniline with a dual functionality of both recognition and conduction properties. The poly(aniline) groups are introduced into the methacrylic acid-based MIP by postoxidation of the aniline monomer. Such poly(aniline) groups not only serve as the additional functional groups for selective recognition, but also work as a conducting polymer. The obtained multifunctional MIP receptor shows a high binding capacity and an excellent electron-transfer ability. By using bisphenol A as a model, the proposed multifunctional MIP sensor exhibits a largely improved sensitivity and low noise levels compared to the conventional MIP sensor. We believe that the proposed MIP-based sensing strategy provides a general and facile way to fabricate sensitive and selective MIP-based electrochemical sensors.

We devised, fabricated, and tested differential pulse voltammetry (DPV) and impedance spectroscopy (EIS) chemosensors for duloxetine (DUL) antidepressant determination in human plasma. Polyacrylic nanoparticles were synthesized by precipitation polymerization and were molecularly imprinted with DUL (DUL-nanoMIPs). Then, together with the single-walled carbon nanotube (SWCNT) scaffolds, they were uniformly embedded in polytyramine films, i.e., nanoMIPs-SWCNT@(polytyramine film) surface constructs, deposited on gold electrodes by potentiodynamic electropolymerization. These constructs constituted recognition units of the chemosensors. The molecular dynamics (MD) designing of DUL-nanoMIPs helped select the most appropriate functional and cross-linking monomers and determine the selectivity of the chemosensor. Three different DUL-nanoMIPs and non-imprinted polymer (nanoNIPs) were prepared with these monomers. DUL-nanoMIPs, synthesized from respective methacrylic acid and ethylene glycol dimethyl acrylate as the functional and cross-linking monomers, revealed the highest affinity to the DUL analyte. The linear dynamic concentration range, extending from 10 pM to 676 nM DUL, and the limit of detection (LOD), equaling 1.6 pM, in the plasma were determined by the DPV chemosensor, outperforming the EIS chemosensor. HPLC-UV measurements confirmed the results of DUL electrochemical chemosensing.

Molecularly imprinted polymers (MIPs), often called "synthetic antibodies", are highly attractive as artificial receptors with tailored biomolecular recognition to construct biosensors. Electropolymerization is a fast and facile method to directly synthesize MIP sensing elements

Combating environmental pollution constantly requires new affinity tools to selectively recognize and sensitively detect them. Molecularly imprinted polymers (MIPs) are plastic antibodies that have exhibited great potential as recognition units in optical sensing platforms to monitor wide varieties of environmental pollutants, including ionic species, organic compounds, gases, and even manufactured nanoparticles. The construction, sensing strategies, and applications of molecular-imprinting-based optical sensors (MI-OSs) have been discussed in recent reviews, thus we deliberately set them aside. This Perspective elaborates on unanswered questions and main approaches being taken to address the challenges of MI-OS technologies, which have been less considered until now. Specifically, we highlight obscure technical aspects of MI-OS fabrication and validation that impact their practical applications and importantly offer conceivable solutions to related problems to bridge the research gap.

A composite of the metal-organic framework compound ZIF-8 doped with CdSe quantum dots (QDs) with sensitive and stable luminescence was synthesized, and a molecularly imprinted electrochemiluminescence (ECL) sensor was constructed based on this composite. The ZIF-8@CdSe molecularly imprinted ECL sensor combines the high sensitivity of ECL and the high selectivity of molecular imprinting to realize the sensitive and specific detection of estriol. CdSe QDs and gold nanoparticles were encapsulated within ZIF-8 to obtain the ZIF-8@CdSe QDs/GNP (ZIF@CdSe/GNP) composite. Subsequently, the GNPs were further loaded on the surface of this composite to obtain the GNP/ZIF@CdSe/GNP composite. l-Cysteine was used to immobilize the GNP/ZIF@CdSe/GNP composite on the surface of a gold electrode to obtain the GNP/ZIF@CdSe/GNP-modified gold electrode. A molecularly imprinted polymer (MIP) film was prepared on the surface of the modified electrode by electropolymerization with o-phenylenediamine as the functional monomer and estriol as the template molecule. After elution, estriol could be specifically recognized by the cavities. The readsorption of estriol by the MIP can prevent the coreactant from reaching the electrode surface through the cavities, thereby weakening ECL. A good linear relationship existed between the ∆ECL and lg C of estriol concentrations of 1 × 10

10 Pág., In this work, the preparation and evaluation of water-compatible molecularly imprinted polymers for triazines using 2-hydroxyethyl methacrylate and methacrylic acid as comonomers is described. Four sets of molecularly imprinted and non-imprinted polymers for propazine were prepared at varying monomer molar ratios (from 4:0 to 1:3), and evaluated for the recognition of several triazines directly in aqueous media. The evaluation was performed by loading 1 ml of an aqueous solution containing 500 ng of each selected triazine, washing with 500 μl of acetonitrile, and eluting with 500 μl of methanol followed by 2 × 500 μl of a solution of methanol containing 10% of acetic acid. Final determinations were performed by high-performance liquid chromatography-ultraviolet detection. Improvement in molecular recognition of triazines in water was obtained on those molecularly imprinted polymers incorporating 2-hydroxyethyl methacrylate in 3:1 or 2:2 molar ratios, being the former selected as optimum providing recoveries for propazine up to 80%. A molecularly imprinted solid-phase extraction protocol was developed to ensure that triazines-selective recognition takes place inside selective binding sites in pure water media. Finally, the developed method was successfully applied to the determination of the selected triazines in environmental waters providing limits of detection from 0.16 and the 0.5 μg/L concentration range., This article is based upon work from the National Thematic Network on Sample Treatment (RED-2018-102522-T) funded by the Spanish Ministry of Science, Innovation and Universities, and the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society.

Lupanine is an alkaloid used in the pharma industry as a building block or precursor in the synthesis of sparteine and also explored for drug synthesis in the pharma industry as a chiral selector. This alkaloid is found in lupin bean processing wastewaters originated from the debittering process to make these beans edible. In this work, a computational chemistry approach was taken to design molecularly imprinted polymers (MIPs) selecting itaconic acid, a biobased building block, as a functional monomer that can provide higher affinities for lupanine.

Regulation of nanomaterial-cell interaction is an important requisite for a variety of biomedical applications such as drug delivery systems and theranostics. Here, we demonstrate the regulation of nanomaterial-cell interaction using the oriented adsorption of intrinsic immunoglobulin G (IgG) on molecularly imprinted polymer nanogels (MIP-NGs) capable of recognizing the fragment crystallizable (Fc) domain of IgG. The unique domain recognition property resulted in the suppression of the immune response in Fc domain receptor-possessing macrophages and natural killer cells due to the regulation of protein corona based on the oriented adsorption of IgG. This resulted in the hindrance of the Fc domain, which is the trigger of an immune response. Furthermore, the acquisition of stealth capability was successfully demonstrated in vivo using intravital confocal laser scanning microscopy. The domain imprinting proposed in this study will provide a new strategy for creating nanomaterials capable of domain recognition-based oriented adsorption of intrinsic proteins in situ, thus regulating the protein corona formed on the nanomaterials. Thus, the unique Fc domain-recognition nanomaterial developed in our study can be used for various biomedical applications to target specific cells without triggering an immune response.

A graphitic carbon nitride was synthesised and nalidixic acid (NA) based molecularly imprinted microspheres (MIMs) were polymerised on its surface to create a composite material. After characterisation and evaluation of its absorption ability, the composite was used to prepare a solid-phase extraction (SPE) cartridge for purification of fluoroquinolones in chicken muscle, analysed by ultra-performance liquid chromatography. The cartridge showed high absorption capacities (378-559 μg) and high recoveries (92.1-99.4%) for eight fluoroquinolones, and could be reused at least 20 times. The limits of detection for the 8 drugs were 0.2-0.8 ng g

In this study, morin magnetic molecularly imprinted polymers (Morin-MMIPs) were synthesized based on magnetic nanoparticles and surface molecularly imprinted technology with superparamagnetism and extraction selectivity. The polymers allowed the separating of morin from complex matrices in the presence of an external magnetic field with no need for centrifugation or filtration. The microstructure of the polymers was characterized by scanning electron microscopy and transmission electron microscopy. Meanwhile, the functional group and magnetic properties of the polymers were characterized using Fourier transform infrared spectroscopy (FT-IR) and magnetic vibration meter (VSM). The maximum adsorption capacity of MMIPs was 3.24 mg/g, which was 2.55 times higher than that of MNIPs (1.27 mg/g). Morin was quantified by HPLC-DAD, which showed good linearity in the concentration range of 0.05-60 µg/ml with the correlation coefficient R

A novel molecularly imprinted polymer based on magnetic multiwalled carbon nanotubes was fabricated and applied for selective dispersive micro-solid phase extraction of fenitrothion prior its determination by ion mobility spectrometry. The composite was synthesized using magnetic multiwalled carbon nanotubes as the support. Methacrylic acid was used as the functional monomer, fenitrothion as the template, ethylene glycol dimethacrylate as the cross-linker, and 2,2-azoisobutyronitrile as the initiator. The resultant polymer was characterized by FTIR spectroscopy, X-ray diffraction, field emission scanning electron microscopy, Brunauer-Emmet-Teller analysis, thermogravimetric analysis, and vibrating sample magnetometer techniques. Experimental factors affecting the extraction efficiency such as pH and amount of sorbent were evaluated. Under optimum experimental conditions, the developed method displayed the linear range of 5-220 μg/L with a detection limit of 1.3 μg/L. The intra- and interday relative standard deviations for determination of fenitrothion were 3.6 and 4.7% (n = 6), respectively. Ultimately, the proposed method was used to monitor trace amounts of fenitrothion in fruits, vegetables, and water samples.

Ideal binding ligands for anchoring proteins are essential for the design and assembly of desirable molecularly imprinted polymers (MIPs). In this study, bovine serum albumin-MIPs (BSA-MIPs) were successfully prepared by orchestrating the involvement of orientation-controllable binding ligands via sequential thiol-ene click and thiol-ene-amine conjugation. We showed that the optimal thiol-ene-amine conjugates and binding ligands were decisive in determining the rebinding capacity and selectivity. The pyrrolidinyl MIPs exhibited the best adsorption capacity of 352 ± 22 mg/g and a superior imprinting factor of 4.72 among MIPs with various binding ligands. These favourable results were further studied by computational simulation and isothermal titration calorimetry (ITC). Molecular docking revealed the preferential binding free energy and H-bonds between BSA residues and the thiol-ene-amine conjugates. Meanwhile, the pyrrolidinyl ligand motif enabled entropy-favourable affinity to be achieved via hydrophobic effects with the BSA template by ITC thermodynamics. Because of these favourable bindings, the MIPs exhibited excellent adsorption specificity to BSA over competing proteins. The proof-of-concept of MIPs with orientation-controllable conjugates and proven binding ligands for target proteins demonstrates that this material is promising for use with a real biological sample.

Abstract: Cancer and cardiovascular diseases have become one of the leading causes of death worldwide. Therefore, early detection of these diseases and rapid intervention by medical staff remain a great challenge for clinicians and healthcare providers worldwide. Cancer and cardiovascular disease biomarkers are promising tools for early diagnosis of the disease before it becomes incurable at an advanced stage. They also contribute to monitoring the progress of therapy and surgical treatment. Indeed, sensors have shown great importance for the detection of cancer and cardiovascular biomarkers. Sensors usually require a recognition element for the selective detection of targets. Molecularly imprinted polymer (MIP), as an artificial antibody, has been proposed as an alternative recognition element in sensing fields to overcome the main drawbacks of natural antibodies. With the high need for sensors providing results in a short time and making easier the early diagnosis of these diseases, MIP-based sensors are attracting considerable interest recently, which will undoubtedly be increased in the future due to the sustainability trend. The key aim of this review is to emphasize the recent applications of sensors based on MIP for the detection of cancer and cardiovascular biomarkers and to highlight the key advances related to MIP-based sensors. Furthermore, several key future trends about the applications of MIP-based sensors for the detection of cardiovascular and cancer biomarkers are presented.

A core-shell molecularly imprinted polymer nanoparticle with biological enzyme functional characteristics was developed by oxidative polymerization of template protein and polydopamine on the surface of protease-copper phosphate hybrid nanoflowers by molecular imprinting technology and enzyme immobilization technology. The obtained molecularly imprinted polymer showed specific binding characteristics with the template protein. It recognized and enriched the target molecules through the surface molecularly imprinted sites of the shell structure. In addition, the bound target molecules were further degraded into fragments by nanozymes with biological enzyme characteristics in the core. In this study, molecular imprinting technology and biotechnology were combined to obtain bifunctional molecularly imprinted polymer nanoparticles that can not only enrich template molecules but also degrade them into fragments. Herein, we selected interleukin 6 (IL-6), the target molecule of cytokine release syndrome (CRS), as a template molecule, and reported a molecularly imprinted polymer with degrading enzyme properties that can rapidly reduce IL-6 levels in vivo, including a molecularly imprinted layer that can recognize and bind IL-6 and nanozymes that can degrade IL-6 and deactivate it. It is used to clear the excessive secretion of IL-6 in CRS and reduce the level of IL-6 in the body to achieve the purpose of adjuvant treatment of CRS.

The multi-template molecularly imprinted polymers reinforced with hybrid oxide nanoparticles were developed for the selective separation and determination of the trace level of naproxen (NPX), methocarbamol (MTH), and omeprazole (OMZ) simultaneously from biological and pharmaceutical samples. The polymers were constructed by magnetic core@shell molecularly imprinted polymer nanocomposite (Fe

In this study, a series of molecularly imprinted polymers (MIPs) have been synthesized using separately diclofenac, naproxen, and ibuprofen as templates with three different polymerization approaches. Two functional monomers, methacrylic acid (MAA) and 2-vinylpyridine (2-VP), were tested and ethylene glycol dimethacrylate (EGDMA) was used as crosslinker; also, template-free polymers (NIPs) were synthesized. It was found that the MIP with the highest retention percentage for diclofenac was the one prepared by the emulsion approach and with MAA (98.3%); for naproxen, the one prepared by the bulk polymerization with MAA (99%); and for ibuprofen, the one synthesized by bulk with 2-VP (97.7%). These three MIPs were characterized by scanning electron microscopy, thermogravimetric test, Fourier transform infrared, specific area measurements, and surface charge. It was found that the emulsion method allowed particle size control, while the bulk method gave heterogeneous particles. The three evaluated MIPs exhibited thermal stability up to 300 °C, and it was observed that 2-VP confers greater stability to the material. From the BET analysis, it was demonstrated that the MIPs and NIPs evaluated are mesoporous materials with a pore size between 10 and 20 nm. In addition, the monomer influenced the surface charge of the material, since the MAA conferred an acidic point of zero charge (PZC), while the 2-VP conferred a PZC of basic character. Through adsorption isotherms, it was determined that there is a higher adsorption capacity of the MIPs at acidic pH following a pseudo-second-order kinetic model. Finally, the MIPs were used to determine the non-steroidal anti-inflammatory drugs (NSAIDs) understudy in San Luis Potosí, México, wastewater, finding concentrations of 0.642, 0.985, and 0.403 mg L

Glycoproteins play vital roles in living organisms and often serve as biomarkers for some disease. However, due to the low content of glycoprotein in biological fluids, selective detection of glycoproteins is still a challenging issue that needs to be addressed. In this study, molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under physiological pH was proposed. Monodispersed glycoprotein imprinted particles (SiO2@PEI/MIPs) was first prepared based on surface imprinting strategy using horseradish peroxidase (HRP) as template, and polyethyleneimine (PEI) was used to increase the number of boronic acid groups. The binding experiment indicated that the SiO2@PEI/MIPs hold satisfactory adsorption capacity (1.41 μmol/g), rapid adsorption rate (40 min) and preferable selectivity toward HRP. Then the SiO2@PEI/MIPs was assembled into close-packed colloidal array to construct a label free optical sensor (denoted as GICA). Benefiting from the high ordered photonic crystal structure, binding of HRP onto the GICA could be directly readout from the changes in structure color and diffracted wavelength. The structure color of the GICA changed from bright blue to yellow with the diffraction wavelength red shifted 59 nm when the HRP concentration increased from 2.5 to 15 μmol/L. Importantly, the GICA was capable of detecting HRP from human serum samples. All those results indicated the potential of the GICA for naked-eye detection of glycoprotein.

A novel deep eutectic solvent-magnetic molecularly imprinted polymer (DES-MMIP) for the specific removal of oxalic acid (OA) was prepared by an environmentally friendly deep eutectic solvent, consisting of betaine, citric acid, and glycerol, which acted as the functional monomer for polymerization. The structure and morphology of DES-MMIPs were studied by X-ray diffraction, scanning and transmission electron microscopy, thermal gravimetric analysis, Fourier transform infrared spectroscopy, and vibrating sample magnetometer. DES-MMIPs had a core-shell structure, with magnetic iron oxide as the core, and showed good thermal stability and high adsorption capacity (18.73 mg/g) for OA. The adsorption process of OA by DES-MMIPs followed the pseudo-second-order kinetic model and Langmuir isotherm model. DES-MMIPs had significant selectivity for OA and their imprinting factor was 3.26. When applied to real samples, high performance liquid chromatography analysis showed that DES-MMIPs could remove OA from both spinach and blood serum. These findings provide potential methods for removal of OA from vegetables and for specific removal of OA in renal dialysis.

Monitoring of nanoparticles (NPs) in air and aquatic environments is an unmet challenge accentuated by the rising exposure to anthropogenic or engineered NPs. The inherent heterogeneity in size, shape, and the stabilizing shell of NPs makes their selective recognition a daunting task. Thus far, only a few technologies have shown promise in detecting NPs; however, they are cumbersome, costly, and insensitive to the NPs morphology or composition. Herein, we apply an approach termed nanoparticle-imprinted matrices (NAIM), which is based on creating voids in a thin layer by imprinting NPs followed by their removal. The NAIM was formed on an interdigitated electrode (IDE) and used for the size-selective detection of silica NPs. Three- and 5-fold increases in capacitance were observed for the reuptake of NPs with similar diameter, compared to smaller or larger NPs, in air and liquid phase, respectively. En masse, the proposed approach lays the foundation for the emergence of field-effective, inexpensive, real-life applicable sensors that will allow online monitoring of NPs in air and liquids.

A visual observation of the bending angle changes for the novel and easy detection of proteins is introduced in this study by fabricating bovine serum albumin (BSA) imprinted hydrogel strips with a one sided 3D porous structure using a combination of polystyrene colloidal crystal templating and the molecular imprinting approach using BSA as the template protein and several functional monomers.

This paper proposes a novel electrochemical aptasensor that integrates molecular imprinting techniques for trace analysis of cortisol. This sensor is based on functionalized graphene and nitrogen-doped carbon quantum dots. The morphology and structure of the modified electrode were characterized by scanning electron microscopy and Raman spectroscopy. The functional monomer aptamer and the template molecule cortisol were adsorbed on the electrode by electrostatic adsorption to construct an imprinted sensing platform. Under the optimal conditions, such as the concentration of template molecule, the ratio of template to functional monomer, the elution and adsorption time, the sensor exhibits linearity and a low detection limit of 10

The development of efficient electrochemical sensors of exceptional features, molecularly imprinted polymers (MIPs), has been extensively utilized due to their great vitality as an alternative to bio-recognition elements. MIPs as an artificial bio-recognition element are getting significant attention due to their affordability, easy processability, and scaling-up capabilities. However, the challenge of longer stability and higher sensitivity associated with MIP-based sensing technology is still a remaining challenge. This can be addressed by modifying MIPs with electro-active nano-systems. Correspondingly, MXene is an emerging material of choice to make MIP-based sensing platforms more efficient and develop a bio-active-free sensing system. This review highlights state-of-the-art MXene-modified MIP electrochemical sensing platforms to overcome the associated limitations of pristine MIPs. As a proof-of-concept, the sensitive and selective detection of markers for health monitoring can be efficiently fulfilled by the high-performance MXene-MIP nanocomposite-based electrochemical sensor. Moreover, the challenges associated with this research area along with the potential solutions are also discussed. An attempt has been made to explore MXene-MIP nanocomposites as a next-generation sensing platform suitable for point-of-care testing (POCT) applications.

In this study, a mesoporous silica fluorescence probe co-doped with manganese-doped zinc sulfide quantum dots (Mn:ZnS QDs) and rhodamine B (RB) and coated with molecularly imprinted polymer (MIP) has been prepared by sol-gel methods. The morphology and structure were characterized in detail by transmission electron microscopy (TEM), Fourier transform-infrared absorption spectroscopy (FT-IR) and ultraviolet-visible absorption spectroscopy (UV-vis). The probe exhibited two characteristic emission peaks at 411 nm and 582 nm, and the synchronous ratiometric fluorescence responses

Bio-applied molecularly imprinted polymers (MIPs) are biomimetic materials with tailor-made synthetic recognition sites, mimicking biological counterparts known for their sensitive and selective analyte detection. MIPs, specifically designed for biomarker analysis within biofluids, have the potential to significantly aid patient diagnostics at the point-of-care, enabling self-health monitoring and management. Recent research in this field, facilitated by the hybridisation of materials science and biology, has developed and utilised a variety of different polymerisation synthesis methods tailored to the bio-application of MIPs. This review evaluates the principles of molecular imprinting for disease diagnostics, including recent progress in integrated MIP-sensor technologies for high-affinity analyte detection in complex biofluids from serum and saliva to cerebrospinal fluid, sweat, urine, nasopharyngeal fluid, and tears. The work highlights the state-of-the-art in the progression of MIP-sensor technologies' translation into commercially available sensors and their potential contribution to disease detection systems in healthcare settings.

Molecularly imprinted polymers (MIPs) having the potential to mimic the selectivity and sensitivity of biological molecular recognition are blended here with piezoelectric transducer (EQCM) able to provide ‘real time’ monitoring of molecular level events with extreme sensitivity. In this work, molecularly imprinted polymer nanoparticles selective for a psychoactive drug, cathinone were synthesized, characterized and applied for specific and selective uptake in water. Nanoparticles were separated by centrifugation and characterized for their size and zeta potential. p-Phenylene diamine was chosen as functional monomer to imprint S-cathinone via in silico studies. Molecularly imprinted nanoparticles were eletrodeposited on gold coated quartz crystal electrode of electrochemical quartz crystal microbalance (EQCM). Molecular imprinting experiments were optimized for selective and specific uptake of S-cathinone. Thus fabricated EQCM sensor was able to discriminate between stereoisomers and other close structural analogues also. Imprinting data were successfully fitted to Freundlich adsorption isotherm and curves for non-imprinted and imprinted data were compared. Under optimized conditions, response of nanoMIP-EQCM sensor is linearly proportional to S-cathinone concentration with detection limit as 0.12 ng mL−1 and quantification limit as 0.409 ng mL−1 and imprinting factor as 8. Hence, a highly specific and selective nanoMIP-EQCM sensor is fabricated in a facile manner.

As an efficient and easily available pesticide, imidacloprid (IM) has been widely used in agriculture to kill pests. However, threats to the ecological environment are becoming increasingly prominent, caused by abuse and pesticide residues. This paper reports a sensitive electrochemiluminescence (ECL) sensor based on upconverting nanoparticle functional zeolite imidazolate framework (UCNPs@ZIF-8) nanocomposites combined with molecularly imprinted polymers (MIPs) to successfully achieve the quantitative detection of IM. The composites exhibited a certain multi-faceted prismatic structure and the effective binding of UCNPs was demonstrated by characterization technology. In addition, a sensor with MIPs/UCNPs@ZIF-8/GCE as the working electrode exhibited outstanding ECL performance, including a strong and stable signal and excellent selectivity under optimal conditions. This sensor showed a good linear response to IM over a wide concentration range (0.1 ng L

The benefits of molecularly imprinted polymer (MIP) technology in creating artificial receptors to replace natural counterparts have piqued the interest of numerous researchers in recent years. We propose a biomimetic enrofloxacin-MIP for enrofloxacin (ENRO) antigen detection using gold nanoparticles (AuNPs) and MIP methodologies in this study. A self-assembled monomer layer of aminothiophenol was used to immobilize a pre-formed complex of the anti-enrofloxacin monoclonal antibody and enrofloxacin antigen onto the surface of an AuNP coated screen-printed carbon ink electrode (SPCE). The poly-(aminothiophenol) layer thickness was adjusted to entrap and restrict enrofloxacin antigens near the surface. The imprinting and removal of the enrofloxacin antigen in the MIP film were strongly validated by the Raman spectra. The final mAb-MIP sensor had better sensitivity (302 Ω mL ng

We report a new ready-to-use sensor for simultaneous determination of paraquat (PQ) and glyphosate (GLY) based on a graphite screen-printed electrode modified with a dual-molecularly imprinted polymer coated on a mesoporous silica-platinum core. Amino-mesoporous silica nanoparticles (MSN-NH

3,4-Methylenedioxyamphetamine (MDA) and 3,4-methylenedioxymethamphetamine (MDMA) are the main components of illicit stimulant drugs, also known as "ecstasy", which belong to psychoactive medicine and tend to be increasingly abused among drug addicts worldwide. Herein, an electrochemical sensor based on molecularly imprinted polydopamine (MIP@PDA) was developed to detect MDA and MDMA using differential pulse voltammetry (DPV). An MIP film on a Au electrode was synthesized

As the changes of biomarkers directly reflect the occurrence of degenerative diseases, accurate detection of biomarkers is of great significance for disease diagnosis and control. However, single index detection has high uncertainties to accurately reflect the pathological characteristics because of the complexity of the human internal environment and the extremely trace concentration of indicators. To this end, a method for simultaneous detection of dual-biomarkers based on anti-interference magnetic molecularly imprinted polymers (D-mag-MIPs) is thereby proposed, and successfully applied in human urine analysis for the detection of Parkinson's disease bio-indicators 4-dihydroxyphenylacetic acid (DOPAC) and dopamine (DA). In this work, carboxyl functionalized ferric oxide served as a magnetic core, laying a solid foundation for batch detection. Hyperbranched polyethylenimine, whose abundant amino groups can provide multiple interaction forces to templates with high affinity, is employed as a functional monomer. Relative to single-template MIPs, D-mag-MIPs achieve the detection of dual bio-indicators in a one-time test, reducing the false positive result probability and enhancing the detection accuracy. The proposed methodology has been evaluated to exhibit good anti-interference, satisfactory precision, low detection limits, wide linear ranges and fast batch detection for DA and DOPAC. This work thus offers an alternative and efficient pathway for convenient batch detection of dual bio-indicators from biofluids at once.

Molecularly imprinted nanocomposite membranes with three-dimensional metal–organic frameworks (MOFs)-based structure (MINMs-TM) were successfully prepared by using propranolol as template molecule. Importantly, for the first time, polycarbonate track etch membranes had been used as the supporting surfaces to construct the polydopamine (PDA)-induced MOFs composite structure, in which the as-prepared PDA-modified surface would promote the crystallization and nucleation of ZIF-8-based composite layer. Based on the entire preparation processes of our design, the as-prepared PDA-induced ZIF-8-modified surfaces could be regarded as the imprinted-initiated units of sol–gel imprinting polymerization. Abundant recognition sits of propranolol were achieved in MINMs-TM, which showed characteristic properties of permeability and selectivity. Therefore, high adsorption capacity (41.31 mg/g) and fast adsorption equilibrium rate (within 30 min) had been successfully achieved. Meanwhile, excellent permselectivity rates (β) of MINMs-TM toward propranolol were also obtained as 5.04, 4.79 and 5.14, which MINMs-TM the successful synthesis of high-affinity and high-density propranolol-imprinted sites. Overall, for the practical selective separation and scalability, we had successfully MINMs-TM the preparation of MINMs-TM-based to selective rebinding and separation of propranolol from complex solution system and mimetic water sample, which had further confirmed the desired and potential applications of many environmental pollutants.

Herein, we developed a highly sensitive electrochemical sensor for the trace detection of Sudan I (SDI) dye based on composite molecularly imprinted membranes (MIMs). The pentenyl (lipoic acyl)-isoleucyl-chitosan oligosaccharide (P(L)ICO) and pentenyl-asparaginyl-chitosan oligosaccharide (PASCO) served as bifunctional monomer oligomers. After deposition of gold nanoparticles on a glassy carbon electrode (GCE) surface, a P(L)ICO layer successfully self-assembled on the surface. Subsequently, the primary MIM was polymerised on the electrode surface by using SDI as a template, PASCO as a functional monomer oligomer, and ethylene glycol dimethacrylate as a cross-linking agent. Electrochemical polymerisation was then conducted in an

Carbohydrates are the most abundant organic molecules on Earth and glycosylation is the most common posttranslational modification of proteins. Glycans are involved in a plethora of biological processes including cell adhesion, bacterial and viral infection, inflammation, and cancer development. Coincidently, glycosides were some of the earliest molecules imprinted and have been instrumental in the development of covalent molecular imprinting technology. This perspective illustrates recently developed molecularly imprinted materials for glycan binding and processing. Novel imprinting techniques and postmodification led to development of synthetic glycan-binding materials capable of competing with natural lectins in affinity and artificial glycosidases for selective hydrolysis of complex glycans. These materials are expected to significantly advance glycochemistry, glycobiology, and related areas such as biomass conversion.

The purpose of this work was to apply an electrochemical sensor modified with a molecularly imprinted polymer (MIP) and carbon black (CB) for 17β-estradiol (E2) detection in river water samples. The synthesized MIP was characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM).The modification of the electrode with the MIP and CB contributed to increased sensitivity, an increase of over 173% in relation to that of the bare electrode. The experimental parameters, amount of modifiers, pH and possible interfering species were evaluated. The method showed linearity from 0.10 to 23.0 μmol L

Specific recognition and highly sensitive detection of biomarkers play an essential role in identification, early diagnosis and prevention of many diseases. Magnetic molecularly imprinted polymers (MMIPs) have been widely used to capture biomimetic receptors for targets in various complex matrices due to their superior recognition ability, structural stability, and rapid separation characteristics, which overcome the existing deficiencies of traditional recognition elements such as antibodies, aptamers. The integration of MMIPs as recognition elements with chemical sensors opens new opportunities for the development of advanced analytical devices with improved selectivity and sensitivity, shorter analysis time, and lower cost. Recently, MMIPs-chemical sensors (MMIPs-CS) have made significant progress in detection, but many challenges and development spaces remain. Therefore, this review focuses on the research progress of the sensor based on biomarker detection and introduces the surface modification of the magnetic support material used to prepare high selective MMIPs, as well as the selective extraction of target biomarkers by MMIPs from the complex biological sample matrix. Based on the understanding of optical sensors and electrochemical sensors, the applications of MMIPs-optical sensors (MMIPs-OS) and MMIPs-electrochemical sensors (MMIPs-ECS) for biomarker detection were reviewed and discussed in detail. Moreover, it provides an overview of the challenges in this research area and the potential strategies for the rational design of high-performance MMIPs-CS, accelerating the development of multifunctional MMIPs-CS.

An electrochemical chemosensor for cilostazol (CIL) determination was devised, engineered, and tested. For that, a unique conducting film of the functionalized thiophene-appended carbazole-based polymer, molecularly imprinted with cilostazol (MIP-CIL), was potentiodynamically deposited on a Pt disk electrode by oxidative electropolymerization. Thanks to electro-oxidation potentials lower than that of CIL, the carbazole monomers outperformed pyrrole, thiophene, and phenol monomers, in this electropolymerization. The pre-polymerization complexes quantum-mechanical and molecular dynamics analysis allowed selecting the most appropriate monomer from the three thiophene-appended carbazoles examined. The electrode was then used as a selective CIL chemosensor in the linear dynamic concentration range of 50 to 924 nM with a high apparent imprinting factor, IF = 10.6. The MIP-CIL responded similarly to CIL and CIL's pharmacologically active primary metabolite, 3,4-dehydrocilostazol (dhCIL), thus proving suitable for their determination together. Simulated models of the MIP cavities binding of the CIL, dhCIL, and interferences' molecules allowed predicting chemosensor selectivity. The MIP film sorption of CIL and dhCIL was examined using DPV by peak current data fitting with the Langmuir (L), Freundlich (F), and Langmuir-Freundlich (LF) isotherms. The LF isotherm best described this sorption with the sorption equilibrium constant (

Enzymes, a class of proteins or RNA with high catalytic efficiency and specificity, have inspired generations of scientists to develop enzyme mimics with similar capabilities. Many enzyme mimics have been developed in the past few decades based on small molecules, DNA, and nanomaterials. These artificial enzymes are of great interest because of their low cost and high stability. However, most of these enzyme mimics do not have the desired substrate selectivity. The substrate selectivity of natural enzymes usually stems from a specific binding pocket. A powerful method to create substrate binding cavities is molecular imprinting technology (MIT). Molecularly imprinted polymers (MIPs) have three main characteristics: structural predictability, identification specificity, and application versatility compared with other identification systems. The MIP-based artificial enzymes have the advantages of simple preparation, low cost, and high stability and can realize excellent catalytic activity and selectivity. The development of MIP-based artificial enzymes has been further promoted by optimization methods such as imprinting transition state molecules, post-imprinting modification, opening cross-linked polymers' internal space, and some special preparation methods. Combining molecular imprinting technology with nanozymes, the synergistic effect of both solved the defect of lack of specificity of nanozymes and improved their catalytic activity. This paper summarizes the recent research progress in preparing high-performance artificial enzymes based on MIPs and molecularly imprinted nanozymes. We hope to provide a reference for the design of artificial enzymes, reduce the gap between artificial enzymes and natural enzymes, and thus broaden the application of artificial enzymes in human life and production.

The abuse of antibiotics such as malachite green (MG) has caused its residues in foods and environmental water, and therefore, it is important to establish a rapid and reliable method for sensitive detection of antibiotics. In this work, a novel molecularly imprinted polymer surface-enhanced Raman spectroscopy (SERS) sensor integrating high sensitivity, selectivity, and reusability is fabricated for the detection of trace MG in environmental water. SiO