Molecularly Imprinted Polymer Research Articles

Sensitive Coatings Based on Molecular-Imprinted Polymers for Triazine Pesticides' Detection.

Triazine pesticide (atrazine and its derivatives) detection sensors have been developed to thoroughly check for the presence of these chemicals and ultimately prevent their exposure to humans. Sensitive coatings were designed by utilizing molecular imprinting technology, which aims to create artificial receptors for the detection of chlorotriazine pesticides with gravimetric transducers. Initially, imprinted polymers were developed, using acrylate and methacrylate monomers containing hydrophilic and hydrophobic side chains, specifically for atrazine, which shares a basic heterocyclic triazine structure with its structural analogs. By adjusting the ratio of the acid to the cross-linker and introducing acrylate ester as a copolymer, optimal non-covalent interactions were achieved with the hydrophobic core of triazine molecules and their amino groups. A maximum sensor response of 546 Hz (frequency shift/layer height equal to 87.36) was observed for a sensitive coating composed of 46% methacrylic acid and 54% ethylene glycol dimethacrylate, with a demonstrated layer height of 250 nm (6.25 kHz). The molecularly imprinted copolymer demonstrated fully reversible sensor responses, not only for atrazine but also for its metabolites, like des-ethyl atrazine, and structural analogs, such as propazine and terbuthylazine. The efficiency of modified molecularly imprinted polymers for targeted analytes was tested by combining them with a universally applicable quartz crystal microbalance transducer. The stable selectivity pattern of the developed sensor provides an excellent basis for a pattern recognition procedure.

COF-COOH@MIP as solid-phase extraction adsorbent for selective and sensitive detection of metamitron in environmental water

Metamitron (MET) is a selective herbicide widely used in agriculture but can persist in the environment and potentially contaminate water resources. This study reports the successful synthesis of a composite adsorbent, COF-COOH@MIP, specifically designed for MET preconcentration via solid-phase extraction (SPE) before high-performance liquid chromatography (HPLC) analysis. COF-COOH@MIP integrates the advantages of covalent organic frameworks (COFs) with their high surface area and stability and molecularly imprinted polymers (MIP) with their tailored recognition cavities. The adsorbent achieved a maximum adsorption capacity of 4.67 μg mg−1. The SPE column packed with COF-COOH@MIP demonstrated excellent reusability, with recovery rates of MET around 100 % after six consecutive cycles. The limit of detection (LOD) and limit of quantification (LOQ) of the established method were remarkably low, at 2.94 ng mL−1 and 9.80 ng mL−1, respectively. The linearity was credible within 0.03-400 μg mL−1 (R2 = 0.9999). The method’s applicability to real-world samples was validated by analyzing water from a farm, a ditch, and a river. This method offers a valuable tool for environmental monitoring programs to safeguard water quality from MET pollution.

Low-tech innovation: biomimetic solid-contact potentiometric sensor for nanomolar-level atrazine detection.

Despite the fact that there are already a number of solid-contact-based ion-selective electrodes designed for atrazine detection, our ground-breaking contribution lies in introducing the first-ever atrazine potentioselectrode, enabling the ultra-sensitive detection of atrazine at nanomolar levels. Solid-contact ion-selective electrodes can offer advantages, such as improved stability, reproducibility, sensitivity, and selectivity compared to their liquid-contact counterparts. Here, a biomimetic potentiometric sensor for Atrazine was developed using economic, light weight, and flexible carbon cloth as solid-contact material. Our methodology entails the synthesis of a molecularly imprinted polymer (MIP) through straightforward precipitation polymerization, showcasing a streamlined and efficient method for creating highly specific molecular recognition elements. The validation of template removal is confirmed via meticulous analysis employing EDX and FTIR techniques, ensuring the efficacy of our methodology. The resulting sensing membrane are casted by dispersing the MIP in 2-nitrophenyl octyl ether plasticizer and embedding it within a PVC matrix containing sodium tetraphenyl borate as a lipophilic additive. The developed sensor responds to atrazine in the pH range of 2.8-3.3 over a wide concentration range of 1 × 10-8M to 1 × 10-5M & 1 × 10-5M to 1 × 10-1M with respective slopes of 29.2 mv & 58.7mV and a limit of detection of 1 × 10-9M. An impressive feature of this sensor lies in its swift response time, registering a rapid reaction within a mere 10s. Emphasize the sensor's commendable attributes of reproducibility, selectivity, and sensitivity underscoring its successful application in field monitoring.

ZIF-12-derived nitrogen doped porous carbon nanosheets-functionalized with silver nanoparticles for ratiometric molecularly-imprinted electrochemical sensing of D-penicillamine

In this work, an electrochemical platform was developed for detection of D-pencillamine utilizing highly responsive molecularly imprinted polymers (MIPs). This platform operates on a ratiometric principle and is constructed on nitrogen-doped porous carbon nanosheets (N-PCNS) derived from zeolite imidazolate frameworks (ZIF-12) in the presence of saturated solution of zinc sulfate. Subsequently, silver nanoparticles (Ag) were introduced onto the surface of N-PCNS/GCE to enhance conductivity and surface area, and serve as a standard signal. The MIP layer was formed on the Ag@N-PCNS/GCE surface through o-phenylenediamine (o-phen) electro-polymerization in the presence of the D-pencillamine (D-PAN) as a template. Detection of D-PAN relies on measuring ID-PAN/IAg response ratio employing differential pulse voltammetry (DPV). This ratio exhibits a linear correlation with the concentration of D-PAN in the dynamic linear range of 0.161–170 µM, exploiting LOD of 38.0 nM (S/N = 3). The electrochemical sensor offers numerous advantages including low detection limit, accuracy, stability, and sufficient degree of selectivity. Utilizing this platform, D-PAN-containing samples were efficiently analyzed with recovery percentages of 98.0–102.0 % and RSDs of 2.78–3.89 %, demonstrating the accuracy of the method.

A facile colorimetric sensor for ketoprofen detection in milk: Integrating molecularly imprinted polymers with Cu-doped Fe3O4 nanozymes

A facile and efficient detection method is required to address the potential health risks of ketoprofen (KP) in animal-derived foods. Herein, we integrated molecularly imprinted polymers (MIPs) with Cu-doped Fe3O4 nanozymes (Fe3O4–Cu) to develop a selective colorimetric sensor for KP detection. Chitosan and glutaraldehyde were used as functional monomers and cross-linkers to fabricate proposed the MIPs@Fe3O4–Cu. On KP addition, it was specifically captured by the imprinted cavities, thereby blocking the channels between chromogenic substrates and Fe3O4–Cu. Based on this rationale, a selective colorimetric sensor utilizing MIPs@Fe3O4–Cu was established, exhibiting a linear range of 0.25–100 μM and a detection limit of 0.073 μM. The developed method was validated through its application in milk samples, yielding satisfactory recoveries with low relative standard deviations. This efficient and selective colorimetric sensor holds immense significance for KP detection in complex samples.

Molecular Imprinting‐involving Highly Selective Tetracycline Detection Platform Based on Mn2V2O7 with Excellent Oxidase‐mimicking Activity

AbstractNanozymes‐involving colorimetry may represent an effective solution to tetracycline detection due to its affordability and simplicity. To improve the performance in selectivity, molecular imprinting technology has emerged as a promising approach to simulating the interaction between antibodies and receptors. Herein, Mn2V2O7, a form of nanozyme with oxidase‐mimicking activity, was synthesized. With tetracycline as the template, the cavities with unique dimensions were constructed through the self‐polymerization of dopamine (DA) on Mn2V2O7. In Mn2V2O7@MIP, polydopamine (PDA) acts as molecularly imprinted polymer (MIP) and its cavities are compatible with tetracycline in dimension. It also exhibits oxidase‐mimicking activity. With the introduction of tetracycline, the cavity of PDA is blocked, which leads to obvious color fading, which enables precise tetracycline detection with colorimetry. The range of linear detection is from 10 to 100 μM, and the lower limit of detection is 0.82 μM. It is anticipated that the combination between nanozymes‐involving colorimetry and molecular imprinting technology would contribute to the accurate detection of organic pollutants in the aquatic environment.

Paper-Based Fluorescent Sensor for Rapid Multi-Channel Detection of Tetracycline Based on Graphene Quantum Dots Coated with Molecularly Imprinted Polymer.

In this paper, we developed a paper-based fluorescent sensor using functional composite materials composed of graphene quantum dots (GQDs) coated with molecularly imprinted polymers (MIPs) for the selective detection of tetracycline (TC) in water. GQDs, as eco-friendly fluorophores, were chemically grafted onto the surface of paper fibers. MIPs, serving as the recognition element, were then wrapped around the GQDs via precipitation polymerization using 3-aminopropyltriethoxysilane (APTES) as the functional monomer. Optimal parameters such as quantum dot concentration, grafting time, and elution time were examined to assess the sensor's detection performance. The results revealed that the sensor exhibited a linear response to TC concentrations in the range of 1 to 40 µmol/L, with a limit of detection (LOD) of 0.87 µmol/L. When applied to spiked detection in actual water samples, recoveries ranged from 103.3% to 109.4%. Overall, this paper-based fluorescent sensor (MIPs@GQDs@PAD) shows great potential for portable, multi-channel, and rapid detection of TC in water samples in the future.

3D inkjet printing of hybrid electroactive ink based on molecularly imprinted polymers for lipopolysaccharides detection

A hybrid electroactive ink based on molecularly imprinted polymer (MIP) hollow microparticles, zinc oxide nanoparticles (ZnO NPs) and conductive carbon paste (CP) is reported herein for the first time. The MIP/ZnO NPs/CP and corresponding non-imprinted NIP/ZnONPs/CP modified inks were screen-printed on plastic substrates via 3D inkjet technology to cover around 40 working screen-printed carbon electrodes (SPCE) pieces in a single batch. The custom-made electrochemical MIP/ZnONPs/CP@SPCE sensor was designed for the detection of bacterial endotoxins, i.e., lipopolysaccharides (LPS), derived from Pseudomonas aeruginosa. Hollow MIP silica microparticles with specific properties for 3D printing application, in terms of granulation and morphology, were synthesized via sol-gel method using tetraethyl orthosilicate and (3-aminopropyl) triethoxysilane as monomers. Following the structural and morphological characterization of microparticles, the evaluation of template rebinding indicated a clear specificity of MIPs for LPS compared to the NIPs. Hybrid MIP/ZnONPs/CP and NIP/ZnONPs/CP inks were characterized using morphological and structural methods, which confirmed a viscosity of 25.000 mPa.s, a granulation of <20 µm, and a solid powder content of <27 %, as well as a homogenous incorporation of MIP particles and ZnONPs in the conductive CP. Finally, the electrochemical evaluation of the modified MIP/ZnONPs/CP@SPCE sensor revealed a good sensitivity to LPS molecules in PBS at pH 7.4, in the linear working range 1 - 100 µM, where a 0.058 µM limit of detection (LOD) and a response time less than or equal to 1 min were determined. The selectivity of the MIP/ZnONPs/CP@SPCE sensor towards LPS from Salmonella enterica and Escherichia coli was also assessed, highlighting a clear difference between these structural resembling species.

Computational and Experimental Comparison of Molecularly Imprinted Polymers Prepared by Different Functional Monomers-Quantitative Parameters Defined Based on Molecular Dynamics Simulation.

In recent years, the advancement of computational chemistry has offered new insights into the rational design of molecularly imprinted polymers (MIPs). From this aspect, our study tried to give quantitative parameters for evaluating imprinting efficiency and exploring the formation mechanism of MIPs by combining simulation and experiments. The pre-polymerization system of sulfadimethoxine (SDM) was investigated using a combination of quantum chemical (QC) calculations and molecular dynamics (MD) simulations. MIPs were prepared on the surface of silica gel by a surface-initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA ATRP). The results of the QC calculations showed that carboxylic monomers exhibited higher bonding energies with template molecules than carboxylic ester monomers. MD simulations confirmed the hydrogen bonding sites predicted by QC calculations. Furthermore, it was observed that only two molecules of monomers could bind up to one molecule of SDM, even when the functional monomer ratio was up to 10. Two quantitative parameters, namely, the effective binding number (EBN) and the maximum hydrogen bond number (HBNMax), were defined. Higher values of EBN and HBNMax indicated a higher effective binding efficiency. Hydrogen bond occupancies and RDF analysis were performed to analyze the hydrogen bond formation between the template and the monomer from different perspectives. Furthermore, under the influence of the EBN and collision probability of the template and the monomers, the experimental results show that the optimal molar ratio of template to monomer is 1:3. The method of monomer screening presented in this study can be extended to future investigations of pre-polymerization systems involving different templates and monomers.

Molecularly Imprinted Wearable Sensor with Paper Microfluidics for Real-Time Sweat Biomarker Analysis.

The urgent need for real-time and noninvasive monitoring of health-associated biochemical parameters has motivated the development of wearable sweat sensors. Existing electrochemical sensors show promise in real-time analysis of various chemical biomarkers. These sensors often rely on labels and redox probes to generate and amplify the signals for the detection and quantification of analytes with limited sensitivity. In this study, we introduce a molecularly imprinted polymer (MIP)-based biochemical sensor to quantify a molecular biomarker in sweat using electrochemical impedance spectroscopy, which eliminates the need for labels or redox probes. The molecularly imprinted biosensor can achieve sensitive and specific detection of cortisol at concentrations as low as 1 pM, 1000-fold lower than previously reported MIP cortisol sensors. We integrated multimodal electrochemical sensors with an iontophoresis sweat extraction module and paper microfluidics for real-time sweat analysis. Several parameters can be simultaneously quantified, including sweat volume, secretion rate, sodium ion, and cortisol concentration. Paper microfluidic modules not only quantify sweat volume and secretion rate but also facilitate continuous sweat analysis without user intervention. While we focus on cortisol sensing as a proof-of-concept, the molecularly imprinted wearable sensors can be extended to real-time detection of other biochemicals, such as protein biomarkers and therapeutic drugs.

A disposable electrochemical sensor for amyloid-β42 protein based on molecular imprinted polymers with nitrogen doped carbon dots-graphene nanohybrid

This work presented a molecularly imprinted polymer (MIP) electrochemical sensor for determination of amyloid-β42 (Aβ42) as an Alzheimer’s disease (AD) biomarker. A nitrogen-doped carbon-dot-graphene (NCD-G) nanohybrid was synthesized through a simple ultrasonic method. Polypyrrole (PPY) was used as an imprinted polymer with an Aβ42 template for the electropolymerization process. The NCD-G and MIP were modified on a screen-printed carbon electrode (SPCE) without binding agent. The morphology and electrochemical properties of MIP/NCD-G modified SPCE were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and square wave voltammetry (SWV). The developed sensor exhibited good linear response in a range from 5 to 70 pg/mL with a limit of detection (LOD) of 1 pg/mL under optimal conditions. This sensor shows excellent performance due to the enhancement of effective surface area, electrical conductivity, and electrocatalytic activity. This MIP sensor takes advantage of molecularly imprinted technique combined with nanohybrid to achieve high selectivity and sensitivity. Moreover, it possessed good reproducibility and miniaturization that could be applied as a platform for portable devices in healthcare in the future. Novelty statementThis work provides the combination of a zero-dimensional and two-dimensional materials, nitrogen doped carbon dots-graphene nanohybrid (NCD-G) by self-assembly through a simple ultrasonication method and applied as a molecularly imprinted polymer (MIP) sensor for determination of amyloid-β42 protein. We propose a minimum number of preparation steps which NCD-G could enhance the MIP sensor performance, owing to the synergistic effects with high selectivity and sensitivity. The hybrid formation of the carbon dots with graphene using their π-π interactions in carbon nanostructures. NCD-G nanohybrid and MIP modified on screen printed carbon electrode (SPCE) for the determination of amyloid-β42 have not been previously investigated. Moreover, this disposable strip is a single-use tool that might be essential for on-site devices.

Comparative study of two MIP-based electrochemical sensors for selective detection and quantification of the antiretroviral drug lopinavir in human serum

Thermal polymerization (TP) and electropolymerization (EP) are the two methods used in this study to explore the molecular imprinting process. To detect the antiviral medication lopinavir (LPV), an inhibitor of enzyme HIV-1 protease that is co-formulated with ritonavir (RTV) to extend its half-life in the body, with greater precision, these methods were merged with an electrochemical sensor. The sensors were created on glassy carbon electrodes (GCE) based on molecularly imprinted polymers (MIP) using TP with methacrylic acid (MAA) functional monomer and EP with p-aminobenzoic acid (PABA) functional monomer. Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and electrochemical methods were utilized to examine the technical features of the suggested sensors. For both approaches, the necessary optimization investigations were carried out. Different LPV concentrations, ranging from 1.0 pM to 17.5 pM in drug solution and commercial human serum samples, were used to validate the analytical efficiency of the two sensors and compare their electroanalytical behaviour. For TP-LPV@MIP/GCE and EP-LPV@MIP/GCE, the corresponding limit of detection (LOD) was 2.68 × 10−13 M (0.169 pg mL−1) and 1.79 × 10−13 M (0.113 pg mL−1) in standard solutions, and 2.87 × 10−13 M (0.180 pg mL−1) and 2.91 × 10−13 M (0.183 pg mL−1) in serum samples. For the measurement of LPV in tablet form and serum samples, the proposed TP-LPV@MIP/GCE and EP-LPV@MIP/GCE sensors provide good recovery, demonstrating 99.85–101.16 % and 100.36–100.97 % recovery, respectively. The imprinting factor was utilized to demonstrate the selectivity of the suggested sensors by utilizing several anti-viral drugs that are structurally comparable to LPV. Additionally, the constructed sensors were examined for the potential impacts of interferences and the stability during the storage.

Ingestible Sensor Based on Fluorescent Gold Nanopaticles and Molecularly Imprinted Polymers on Thread for Localized Quantification of Escherichia Coli in the Gastrointestinal Tract

AbstractThe small intestinal (SI) microbiota plays an important role in human health and disease. Current methods based on fecal analysis do not provide an accurate representation of the SI microbiome. This article introduces an ingestible sensor for the quantification of Escherichia coli (E. coli) in the SI by developing the fluorescent thread‐based ingestible pill analytical device (TPAD) using fluorescent gold nanoclusters (AuNCs) coupled with molecularly imprinted polymers (MIPs). Quantitative detection lies in the change in fluorescence signal on thread as proportional to target bacteria concentrations using a smartphone. Utilizing a pH‐sensitive enteric coating, this device facilitates localized sampling of the SI microbiome. Hydrophilic beads are employed to autonomously seal the device after sampling, offering a self‐locking mechanism. The sensor demonstrates a linear range for E. coli detection between 2.0 × 103 and 14.0 × 103 CFU mL−1 with an R2 of 0.9975 and a detection limit (LOD) of 400.0 × 102 CFU mL−1. The sensor also shows remarkable precision and acceptable accuracy for monitoring E. coli levels in in vivo animal studies compared to commercially available test kits. The developed TPAD, therefore, offers a novel, low‐cost, and non‐invasive method for rapidly diagnosing gastrointestinal (GI)‐related medical conditions and studying host–microbiome interactions.

Selective and sensitive molecularly imprinted polymer-based electrochemical sensor for detection of deltamethrin

Electrochemical sensors have a broad range of industrial applications due to their sensitivity, speed, and cost-effectiveness. These sensors enable the continuous monitoring and control of critical parameters in various industrial processes. For instance, they are essential in food safety, environmental monitoring, biomedical applications, and pharmaceutical production. In the food industry, electrochemical sensors facilitate the rapid and reliable detection of contaminants and pathogens in food products, thus enhancing product quality and consumer safety. An electrochemical sensor was developed with the molecularly imprinted polymer (MIP) technique to detect deltamethrin with high sensitivity and selectivity. The sensor was fabricated by electrodeposition of Co3O4 on indium tin oxide (ITO), followed by electropolymerization of o-phenylenediamine with deltamethrin as a template molecule. The template molecules were then removed from the modified electrode by a methanol. The MIP-based electrochemical sensor exhibited high sensitivity and selectivity towards deltamethrin. Under the optimized conditions, the LOD values for the MIP/Co3O4/ITO electrode in the first and second linear regressions were 1.53 nM for linear range of 2.82 nM to 56.5 nM and 0.34 μM for linear range of 0.25 μM to 3.98 μM. Moreover, the LOD values for the NIP/Co3O4/ITO electrode in the first and second regressions were 2.43 nM for the linear range of 3.91 nM to 65.0 nM and 726.0 nM for the linear range of 0.023 μM to 4.5 μM. The developed electrochromic pesticide sensor, being an electrochemical-based molecularly imprinted polymer (MIP) sensor incorporating electrochromic materials, enables both target-specific pesticide detection and visual pesticide identification based on color changes dependent on pesticide concentration. Consequently, this system is more advantageous compared to electrochemical-based MIP sensors, as it provides both qualitative and quantitative determinations. The qualitative assessment aims to enhance the ease of use of the sensor, thereby increasing the potential for it to become a commercially viable product by reducing the need for instrumental devices.

Selective solid phase extraction of folic acid from tomato as a biological source with a magnetic molecularly imprinted polymer measured by fluorescence spectroscopy

AbstractA novel magnetic molecular-imprinted polymer (MMIP) was used to selectively extract folic acid directly from real samples. Folic acid was used as template molecule, Fe3O4/SiO2-3-triethoxysilyl-propyl-acrylamide as functional monomer, azobisisobutyronitrile as initiation, ethylene glycol dimethacrylate as crosslinker agent, and acrylamide as the secondary monomer in a mixed ethanol-water solvent. The effect of different parameters on the extraction efficiency was studied, and the optimum conditions were established as follows: the concentrations of crosslinking and template were fixed at 0.05 and 0.06 g, absorption percentage was 96.5, pH was adjusted to 8, and extraction time was 8 h with a temperature of 25 °C. By examining the effect of pH, we tried to investigate the effect of the amide groups that present in MMIP and its intermolecular hydrogen interaction with folic acid. After optimising the effective parameters in polymer synthesis and adsorption rate, a magnetic imprinting dispersive solid-phase extraction method combined with fluorescence spectrophotometry at λem = 367 nm (MMIP-DSPE-FL) was constructed for sensitive determination of folic acid in tomato samples. The limit of quantification (LOQ) and limit of detection (LOD) values were 30.00 ± 0.01 μg L−1 and 10.00 ± 0.03 μg L−1, respectively, after the MMIP-DSPE preconcentration. Three tomato samples were analysed to give recoveries in the range of 80.2–81.6%, with relative standard deviation values below 0.6% (n = 3). The prepared MMIP-DSPE showed high selectivity toward folic acid, which could be used six times without changing adsorption capacity. The adsorption isotherm of the folic acid-imprinted polymer pursued the Langmuir model (RL = 0.029), and the kinetics model followed pseudo-first-order (R2 = 0.9974).

Versatile and reliable extraction of phytosterols employing sonochemical synthesized molecularly imprinted polymer

Phytosterols (PSs) are bioactive compounds in the sterol family, present in numerous complex food and plant matrices in free and conjugated forms. The interest in these compounds arises for phytotherapeutic purposes, particularly for their action on cholesterol metabolism and impact on cardiovascular diseases. There is a need to develop approaches that can selectively extract target analytes and accurately identify and quantify them with high precision. This work proposed the synthesis of molecularly imprinted polymers (MIPs) for PSs with a sonochemical approach, enabling a rapid polymerization step (5 min). This proposed MIP was able to extract 8 PSs (brassicasterol, stigmastanol, campesterol, campestanol, stigmasterol, β-sitosterol, Δ5-avenasterol, α-spinasterol) from a wide range of plant and food matrices belonging to different classes (Brassicaceae, dried fruits and Leguminosae) and was coupled to ultra-high liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). MIP based on dispersed solid phase extraction (dSPE-MIP) and targeted analysis has proven to be particularly effective in addressing the challenges associated with the complexity of plant-derived matrices, minimising interferences. This was demonstrated by the excellent control of the matrix effect, which was within ±15 %, ensuring the robustness and reliability of the method. The identification and quantification of 8 different PSs was successfully achieved with satisfactory recovery values ranging from 65 % to 100 %. The proposed strategy offers an affordable alternative to classical methods, providing enhanced sensitivity, selectivity and overall performance.

Molecular docking and molecular dynamics study of 3-hydroxybutyrate with polymers for diabetic ketoacidosis-targeted molecularly imprinted polymers

Context: Molecularly imprinted polymers (MIPs) are promising materials with tailored binding sites that can selectively recognize and bind target molecules. The combined approach of molecular docking and molecular dynamics (MD) simulation provides valuable insights into the interactions between 3-hydroxybutyrate (3HB) and the designed MIPs, shedding light on the intricate details of their binding mechanisms. This information is crucial for designing MIPs with high selectivity and affinity for 3HB, which is a key biomarker of diabetic ketoacidosis (DKA). Aims: To examine the interactions and dynamic behavior of 3HB in a complex with ten polymers by employing molecular docking and MD simulations. Methods: Initially, molecular docking was employed to predict the binding orientations and affinities of the 3HB molecule within the active sites of the polymers. Subsequently, molecular dynamics simulation was utilized to explore the dynamic behavior, stability, and interactions within these complexes for 100 ns. Metabolic and toxicological properties of 3HB using SwissADME were also predicted. Results: N-(hydroxymethyl)acrylamide (NHMAm), hydroxyethyl methacrylate (HEMA), itaconic acid (ITA), and N-[tris(hydroxymethyl)methyl]acrylamide (TrisNHMAm) displayed the strongest interactions with 3HB, with binding affinities of -2.64, 2.523, 2.469, and 2.305 kcal/mol, respectively. Various kinds of molecular interactions influence ligand-polymer binding in a variety of ways, as illustrated by the four polymers with the lowest binding affinities. In molecular dynamics, 4-vinylpyridine (4VP), N,N-dimethylacylamide (DMAm), N-(hydroxyethyl)acrylamide (NHEAm), and hydroxyethyl methacrylate (HEMA) suggest a strong stable complex with 3HB with an overall ΔTOTAL of -0.56, -0.35, -0.32, and -0.27 kcal/mol, respectively. The ADME prediction indicated that 3HB has favorable pharmacokinetic properties. Conclusions: HEMA shows the ability to interact well with 3HB both by molecular docking and molecular dynamics.

Efficient synthesis of the undiluted vegetable juice-compatible hydrophilic quantum dot-labeled fluorescent molecularly imprinted polymer microspheres via facile one-pot surface-initiated ARGET ATRP

The development of fluorescent molecularly imprinted polymers (MIPs) applicable for herbicide optosensing in the undiluted vegetable juices is highly important for food safety control, but still remains a challenging task. Herein, we report on a facile and efficient new strategy for the synthesis of hydrophilic quantum dot (QD)-labeled fluorescent MIP microspheres capable of directly and selectively optosensing a widely used herbicide (i.e., 2,4-dichlorophenoxyacetic acid, 2,4-D) in the undiluted vegetable juices. Such fluorescent MIP particles were readily prepared through one-step grafting of a red CdTe QD-labeled 2,4-D-MIP layer with hydrophilic polyethylene glycol brushes onto the preformed uniform “living” polymer microspheres (with surface-bound alkyl halide groups) via one-pot surface-initiated activator regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) (SI-ARGET ATRP). They proved to be a highly useful optosensor with high 2,4-D selectivity and sensitivity (the limit of detection ≤ 0.14 μM) in the undiluted Chinese cabbage and cucumber juices. They also showed excellent photostability and reusability and could be directly utilized for 2,4-D detection with high recoveries (98.2 %-102.4 %) and accuracy (RSD≤3.8 %) in the undiluted Chinese cabbage and cucumber juices at three spiking levels of both 2,4-D and its mixtures with several analogues. The use of SI-ARGET ATRP significantly reduced the applied copper catalyst concentration (about 5 μM), which greatly alleviated the quenching effect of the copper catalyst on the fluorescence of the QD-labeled MIP (usually observed for those prepared via normal ATRPs that typically use several hundreds of μM of copper catalysts), thus making this facile new strategy highly efficient for developing advanced fluorescent MIPs that hold much promise in various bioanalytical and diagnostic applications.

Preparation of a surface molecularly imprinted thermo-sensitive polymer for selective trypsin capture

Molecularly imprinted polymers (MIPs) are innovative porous materials created through polymerization templating methods for highly selective, sensitive detection and separation of the desired chemical species, known as template molecules. Surface imprinting over nano-sized substrates with special functional groups is an effective approach for improving the mass transfer and rebinding capacity. In this study, we successfully performed surface imprinting using methacrylic acid (MAA) and thermoresponsive N-isopropyl acrylamide (NIPAm) as functional monomers on acrylic-functionalized silica nanoparticles and served as a Trypsin artificial receptor. The resulting Trypsin imprinted polymer exhibited a binding capacity of 1022.44 mg/g, surpassing the non-imprinted polymer’s capacity of 292.41 mg/g within 45 min. Moreover, the imprinting factor, the main influence factor in MIP performance, was 3.5, demonstrating the significant selectivity of the polymeric products. In addition, due to the temperature sensitivity of NIPAm the template removing process was simply done by changing pore size. The silica nanoparticles and the synthesized MIP particles had diameters of approximately 95 nm and 105 nm, respectively, with the polymer layer thickness being around 5 nm. The MIP adsorption model followed the Freundlich isotherm and pseudo-second-order kinetics resulting in efficiencies of 93.0 % and 95.4 %, respectively. The developed Trypsin imprinted polymer was reusable for four consecutive uses,demonstrating both resilience and selectivity towards Trypsin.

Endosulfan as Potentiometric Sensor in a Kinetic Model of Molecularly Imprinted Polymer (MIP)

Indonesia is an agrarian country with abundant agricultural and plantation land, where farmers often face severe challenge of pests damaging crop yields. To address this challenge, chemical agents such as pesticides and herbicides are used for plant management and care. However, the inappropriate use of these chemical agents poses significant risks to the environment when the prevalence surpasses environmental and human tolerance limits. Pesticides and herbicides containing endosulfan components require proper management to prevent adverse effects on humans and the environment. Therefore, this research aimed to develop Molecularly Imprinted Polymer (MIP) endosulfan pollutant sensors to assess the kinetics of MIP adsorption to endosulfan analyte. Among the various models used for assessment, the Freundlich Isotherm showed optimal results, with an AT value of 1.79 × 107 L/mg, B (Constant related to heat of sorption) of 6 x 10-8 J/mol, and b (Freundlich Isotherm constant) of 4.13×1010. Furthermore, the obtained distribution coefficient (R2) at 0.9768 was more effective compared to other models.