A novel surface molecularly imprinted polymer based on the natural biological macromolecule sporopollenin for the specific and efficient adsorption of resveratrol from Polygonum cuspidatum extracts.

Sporopollenin is a natural biological macromolecule consisting of highly cross-linked carbon, hydrogen, and oxygen atoms, with a highly porous structure and multifunctional groups. In this work, a novel surface molecularly imprinted polymer based on magnetically aminated cattail sporopollenin (MACSp-SMIP) was prepared for the specific and efficient adsorption of resveratrol, with the aim of purifying resveratrol from Polygonum cuspidatum extracts. MACSp-SMIP was found to have a porous structure covered with the multi-layered sponge-like imprinted polymers. MACSp-SMIP had a high adsorption capacity for resveratrol (65.77 mg·g-1) and excellent selectivity (imprinting factor 5.64). The adsorption of resveratrol by MACSp-SMIP was a homogeneous diffusion dominated by chemical adsorption with three stages of external diffusion, internal diffusion, and micropore diffusion. MACSp-SMIP was used as an adsorbent in molecularly imprinted solid-phase extraction for the purification of resveratrol from P. cuspidatum extracts, achieving a resveratrol recovery of 94.33 % and a purity of 76.67 % in the final products. MACSp-SMIP maintained a satisfactory recovery of resveratrol (88.18 %) after six cycles. Overall, this work developed a promising biological macromolecule-based adsorbent MACSp-SMIP for the specific and efficient adsorption of resveratrol, and also provided an efficient and simple approach for the selective purification of resveratrol from P. cuspidatum extracts for food/nutraceutical applications.

Electrochemical molecularly imprinted polymer sensor for simple and fast analysis of tetrodotoxin in seafood.

Tetrodotoxin (TTX) is a marine biotoxin whose biosynthesis is associated with the pufferfish. Its distribution is primarily focused in Asian and tropical marine areas. Currently, this group of toxins is classified as emerging in Europe, and its presence could be related to climate change. This incidence has prompted the European Union, with the European Food Safety Authority, to establish control and monitoring mechanisms for TTX in marine products in Europe. In this context, the development of analytical tools capable of ensuring the safety of food products, especially seafood and fish, is a crucial task. This study describes the development of a molecularly imprinted polymer (MIP) based electrochemical sensor for the analysis of TTX. The MIP was synthesized through the electropolymerization of a functional monomer, ortho-phenylenediamine in the presence of a dummy template, voglibose. The MIP sensor was constructed on a screen-printed gold electrode and characterized by cyclic voltammetry. Differential pulse voltammetry, using a redox probe ([Fe(CN)6]3-/4-), was used in the analysis protocol. The developed sensor exhibited a linear response between 5.0 µg mL-1 and 25.0 µg mL-1, with a limit of detection of 1.14 µg mL-1. Its high imprinting efficiency conferred outstanding selectivity towards TTX. The sensor's applicability was confirmed through recovery assays on spiked mussel samples, achieving recoveries of 81.0 %, 110.2 %, and 102.5 % for external standard addition at 30.0, 44.0, and 60.0 µg kg-1, respectively, with relative standard deviations below 15 %. These results are comparable to those obtained using Hydrophilic Interaction Liquid Chromatography coupled with Tandem Mass Spectrometry, a validated method carried out by the European Reference Laboratory for Marine Biotoxins. Thus, the MIP sensor represents a portable, simple, and fast tool with essential analytical functionalities for the sampling phase and pre-selection of laboratory samples for analysis.

A novel Co/Zn-ferrite molecularly imprinted polymer-based electrochemical assay for sensing of gallic acid in plant extracts, wine, and herbal supplement.

In this study, a new molecularly imprinted polymer (MIP)-based sensor platform was developed for the electrochemical determination of gallic acid (GAL) in plant extracts, wine, and herbal supplements. Gallic acid is known for its natural antioxidant properties, which play an important role in preventing cell deterioration that can lead to various diseases. In addition, gallic acid has therapeutic potential due to its anticancer, antiinflammatory, antimicrobial, and neuroprotective properties. Accurate analysis of gallic acid in complex matrices, in mixed samples where different components coexist, is necessary to evaluate the efficacy and safety of this compound. Cobalt ferrite-zinc-dihydro caffeic acid (CFO_Zn_DHCA) nanoparticles, sphere-like in shape and 5 ± 1 nm in size, were incorporated into the MIP-based electrochemical sensor design to enhance the active surface area and porosity of the glassy carbon electrode (GCE) surface. The functional monomer chosen for this study was aminophenyl boronic acid (3-APBA). In the GAL/CFO_Zn_DHCA/3-APBA@MIP-GCE sensor, which was developed using photopolymerization (PP), 3-APBA as a functional monomer was designed, and obtained in the presence of basic monomer (HEMA), cross-linker (EGDMA), and initiator (2-hydroxy-2-methyl propiophenone) by keeping it under a UV lamp at 365 nm. It aims to detect GAL in real samples such as Punica granatum (pomegranate) peel, Camellia sinensis (green and black tea leaves), wine, and herbal supplements. Morphological and electrochemical characterizations of the designed GAL/CFO_Zn_DHCA/3-APBA@MIP-GCE sensor were carried out using scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The linear range for the determination of GAL using the indirect method (5.0 mM [Fe(CN)6]-3/-4) was found to be 1.0 × 10-13 M-1.0 × 10-12 M, and the limit of detection (LOD) and limit of quantification (LOQ) for standard solutions were calculated as 1.29 × 10-14 and 4.29 × 10-14 M, respectively. As a result of the study, the developed MIP-based electrochemical sensor was suitable for detecting GAL with high specificity, selectivity, and sensitivity. Recovery studies were performed to determine the practical applicability of the sensor, and the results were satisfactory. This innovative sensor platform stands out as a reliable and sensitive analytical tool for determining GAL.

An Impedimetric Determination of Zearalenone on MIP-modified Carboceramic Electrode.

Zearalenone (ZEN) is a mycotoxin that poses significant risks to human and animal health due to its mutagenic, immunosuppressive, and carcinogenic properties. This study presents a novel analytical method for detecting ZEN using electrochemical impedance spectroscopy (EIS) combined with a molecularly imprinted polymer (MIP). ZEN, used as the template molecule, was incorporated into polypyrrole on screen-printed electrodes (SPE), and a ZEN-sensitive MIP sensor was created through template removal. The modified sensor surfaces were characterized by EIS and scanning electron microscopy (SEM). An impedimetric MIP sensor for ZEN was developed, offering a detection range from 1 pM to 500 pM. The method's limit of detection (LOD) was established at 1 pM (0.3 pg/mL) with a signal-to-noise ratio of 3 (S/N=3). The method demonstrated high precision and accuracy, with a maximum relative standard deviation (RSD) of less than 4.4% at a 95% confidence level, and relative error (RE) values ranging from -0.8% to -2.7%. The selectivity of the developed MIP sensor was evaluated using ochratoxin A, ochratoxin B, and aflatoxin B1, with no significant interference observed. ZEN recovery from spiked samples was between 95% and 105%, indicating that the method was successfully applied to grain samples, including corn, rice, and wheat.

Hybrid recognition-enabled ratiometric electrochemical sensing of Staphylococcus aureus via in-situ growth of MOF/Ti3C2Tx-MXene and a self-reporting bacterial imprinted polymer.

Rapid and effective analysis of foodborne bacteria is crucial for preventing and controlling bacterial infections. Here, we present the synthesis of a self-reporting molecularly imprinted polymer (MIP) as an inner reference probe (IR), and the in-situ growth of metal-organic frameworks on transition metal carbon nitrides (MOF/Ti3C2TX-MXene) as a signaling nanoprobe (SP). These advancements are then applied in a ratiometric electrochemical bioassay for Staphylococcus aureus (S. aureus) using a hybrid recognition mechanism. When S. aureus is present, the aptamer-integrated MIP (MIP@Apt) efficiently captures it, followed by binding with SP to form a sandwich structure. This leads to decreased current response of IR (IIR) and increased current intensity of SP (Isp), enabling quantification through utilization of the ISP to IIR ratio. The biosensor shows a wide detection range (10-108 CFU mL-1) and low detection limit of 1.2 CFU mL-1. Its feasibility for testing complex samples indicates the potential application in food analysis.

Pharmacokinetics of pulmonary indacaterol in rat lung using molecular imprinting solid-phase extraction coupled with RP-UPLC.

Indacaterol, a ß2 agonist prescribed for long-term management of patients with chronic obstructive pulmonary disease and asthma. In this study the first MISPE cartridges was developed using indacaterol as a template for its selective extraction from rat lung tissues, enabling precise pharmacokinetic evaluation at the drug's site of action. A molecular imprinting polymer was synthesized using indacaterol as a template, methacrylic acid as a functional monomer and ethylene glycol dimethacrylate as a cross-linker with a molar ratio (1: 4: 20). The polymer was characterized by a high binding capacity of 9840 ± 0.86 and high selectivity with an imprinting factor of 4.53 ± 0.12. The synthesized polymer was utilized as a sorbent in solid-phase extraction to purify and extract indacaterol from lung tissue matrix. The optimum molecularly imprinted solid-phase extraction (MISPE) conditions were 20.0 mg of molecular imprinting polymer and non-imprinting polymer, acetonitrile as the loading solvent, acetonitrile: water (20: 80; by volume) as the washing solvent, and methanol: acetic acid (90: 10; by volume) as the eluting solvent. A pharmacokinetic study was performed for indacaterol in rat lungs using the synthesized and optimized MISPE cartridge as a tool for sample purification. These parameters were determined in the lung tissues of rats emphasizing the local exposure of indacaterol to its target organ. The Cmax and Tmax were 51.020 ± 2.810 µg mL- 1 and 0.083 ± 0.001 h, respectively. The AUC 0-24 and AUC0 - inf were 175.920 ± 1.053 and 542.000 ± 5.245 µg h mL- 1, respectively. The elimination rate constant was 0.014 ± 0.00012 h- 1 and the half-life time was 48.510 ± 0.012 h. This study successfully developed and optimized MISPE cartridges using indacaterol as a template, enabling precise pharmacokinetic evaluation in rat lung tissues. The cartridges demonstrated high binding capacity and selectivity, providing crucial insights into the local exposure of indacaterol at its site of action.

A fluorescent nanocomposite probe of quantum dots and zinc oxide embedded in polymer for smartphone-assisted on-site determination of diflunisal.

A fluorescent sensor based on nitrogen-doped graphene quantum dots (N-GQDs) was developed for the smartphone-assisted colorimetric determination of diflunisal. The fluorescence source was embedded with zinc oxide (ZnO) in a molecularly imprinted polymer (ZnO@N-GQDs@MIP). The quantitative analysis was based on the fluorescence quenching caused by electron transfer from the nanoprobe to diflunisal. The sensor demonstrated linearity in the range of 0.10-50.0 µg L-1 with a limit of detection of 0.03 µg L-1. Smartphone-assisted on-site determination produced linearity in the range of 1.0-50.0 µg/L with a limit of detection of 0.30 µg L-1. The developed sensor was applied to determine diflunisal in milk, egg and yogurt samples. Recoveries ranging from 94.8 to 103.7 % were achieved with a RSD below 2.0 % measured by fluorescence spectroscopy, and from 94.9 to 106.9 % with a RSD of <6 % smatphone-assisted measurement. Comparison of the detection outcomes of both methods with those of high-performance liquid chromatography revealed consistent results, demonstrating the accuracy of the developed method, which was also sensitive, selective, and fast. Notably, the portable and easy-to-read smartphone-assisted method is suitable for on-site application.

Hemicellulose-Based Sensors: When Sustainability Meets Complexity.

Hemicelluloses (HCs) are promising sustainable biopolymers with a great natural abundance, excellent biocompatibility, and biodegradability. Yet, their potential sensing applications remain limited due to intrinsic challenges in their heterogeneous chemical composition, structure, and physicochemical properties. Herein, recent advances in the development of HC-based sensors for different chemical analytes and physical stimuli using different transduction mechanisms are reviewed and discussed. HCs can be utilized as carbonaceous precursors, reducing, capping, and stabilizing agents, binders, and active components for sensing applications. In addition, different strategies to develop and improve the sensing capacity of HC-based sensors are also highlighted.

Determination of indole-3-acetic acid using disposable molecularly imprinted electrochemical sensors based on bifunctional monomers.

Stainless steel sheets were coated with carbon ink to obtain disposable carbon electrodes, which were used as supports for moleculary imprinted polymer (MIP) electrochemical sensors by electropolymerizing o-phenylenediamine and o-aminophenol along with indole-3-acetic acid (IAA) as the template. After optimization, the MIP biosensors could be used for sensitive and selective detection of IAA with the limit of quantification of 0.1 µM. Our experimental results showed that stable and reproducible electrochemical responses could be achieved for the disposable MIP biosensors. This approach was successfully used for detection of IAA in different tissues of pea sprouts. This study reveals the potential of MIP electrochemical sensors in practical applications and shrinks the trench between the research and the real world.

Green Synthesis of Molecularly Imprinted Polymers for Selective Extraction of Protocatechuic Acid from Mango Juice.

A novel and environmentally friendly molecularly imprinted polymer (PCA-MIP) was successfully synthesized in an aqueous solution for the selective extraction of protocatechuic acid (PCA). In this study, a deep eutectic solvent (DES, choline chloride/methacrylic acid, 1:2, mol/mol) and chitosan were employed as the eco-friendly functional monomers. These two components interacted with PCA through hydrogen bonding, integrating a multitude of recognition sites within the PCA-MIP. Thus, the resulting PCA-MIP exhibited outstanding adsorption performance, rapid adsorption rate, and better selectivity, with a maximum binding capacity of 30.56 mg/g and an equilibrium time of 30 min. The scanning electron microscope (SEM) and Brunauer-Emmett-Teller (BET) analyses revealed that the synthesized polymers possessed a uniform morphology and substantial surface areas, which were conducive to their adsorption properties. Moreover, the PCA-MIP integrated with HPLC demonstrated its efficacy as an adsorbent for the selective extraction of PCA from mango juice. The PCA-MIP presented itself as an exemplary adsorbent, offering a highly effective and eco-friendly method for the enrichment of PCA from complex matrices.

Chitosan-based hydrogel beads with molecularly imprinted receptors on halloysite nanotubes for tetracycline separation in water and soil.

Tetracycline (TC), a commonly utilized broad-spectrum antibiotic, is frequently detected in water and soil, posing a significant risk to the natural environment and human health. In the present study, the composite hydrogel beads based on chitosan (CS) and halloysite-supported molecularly imprinted polymers, synthesized by two procedures with significantly different solvent volumes (Hal@MIPa(b)), were obtained and used to adsorb the antibiotic. The presence of Hal improved the thermal stability of the hydrogel beads. The system with a thinner polymer layer (CS_Hal@MIPb), containing polymers produced under conditions of significantly higher reagent dilution, was more resistant to higher temperatures than CS_Hal@MIPa. The adsorptive properties were compared with pure CS beads, those containing incorporated Hal, and free polymers obtained by different protocols (MIPa(b)). In the optimized pH 5.0, the maximum adsorption capacities were 175.24 and 178.05 mg g-1 for CS_Hal@MIPa and CS_Hal@MIPb, respectively. The values were slightly lower compared to the systems with free polymers, but the materials achieved equilibrium more rapidly (12 h). The adsorption process was spontaneous and exothermic. Freundlich isotherm and pseudo-second-order kinetic models most accurately described the experimental data. The hydrogel beads retained high selectivity in the presence of other antibiotics, and their high efficiency in the TC removal from real water samples was maintained. Their addition to soil enhanced adsorption capacities, surpassing that of chitosan-based beads containing free polymers. Significantly, the quantity of TC desorption diminished due to the halloysite's presence, which limited its penetration into groundwater. The primary mechanism of tetracycline adsorption on the hydrogel beads studied is pore filling, but other interactions (hydrogen bonding, π-π stacking, electrostatic attraction) are also involved.

Cupric ion coordination-mediated molecularly imprinted electrochemical sensor for the recognition and ratiometric detection of lidocaine.

Molecularly imprinted polymers (MIPs) have been widely used as artificial recognition elements in sensing applications. However, their electrochemical sensing performance is generally hampered by limited affinity and uncontrolled condition change. In this work, a novel MIP electrochemical sensor based on metal coordination interaction was prepared and used for the recognition and ratiometric detection of lidocaine (LC). The sensor was constructed by electrodepositing Cu-coordinated MIP on biomass carbon modified glassy carbon electrode. Herein, Cu2+ ions acted as anchor for the immobilization of LC during the synthesis process, enabling the orderly formation of molecular recognition sites. Reversely, the metal coordination between Cu2+ ions and LC molecules facilitated the recognition of LC. Moreover, the doped cupric ions in the polymer film could provide a reference signal for subsequent ratiometric strategy. Thus the resulting sensor exhibited high selectivity, sensitivity, satisfactory reproducibility, and anti-interference ability. Under the selected conditions, the peak current ratio of LC and cupric ion was linear to LC concentration in the range of 0.008-2.5 µmol L-1 (R2 = 0.9951), and the limit of detection was 1.9 nmol L-1 (S/N = 3). The practical feasibility of the sensor was evaluated by detecting human serum and pharmaceutical samples, and satisfactory outcomes were obtained.

Development and validation of an imprinted polymer based DGT for monitoring ß-blocker drugs in wastewater surveillance.

Wastewater surveillance is an effective and objective approach to monitor contaminant releases and drug usage in the catchment, the estimation requires accurate measurement. In this study, a novel diffusive gradients in thin-film (DGT) technique based on molecularly imprinted polymers (MIPs) for selective measurement of a class of widely prescribed cardiovascular drugs (ß-blockers) in wastewater was developed. The synthesized MIPs showed strong affinity and selectivity for the target compounds. The MIP-DGT had large effective capacities, its performance was independent of a wide range of environmental conditions, including pH (4.58 - 8.89), ionic strength (0.01 - 0.5 M) and dissolved organic matter (< 20 mg L-1). Biofouling had little effect on the uptake of target compounds within 7 days. MIP-DGT devices were applied in a Chinese urban WWTP alongside an auto-sampler. Metoprolol concentrations detected were much higher than other ß-blockers. Concentrations obtained using MIP-DGT were comparable to the 24 h composite samples using an autosampler. The estimated daily consumption calculated based on the data obtained with MIP-DGT implied that metoprolol and propranolol were the most popular ß-blockers in the studied area. Overall, the results in this study demonstrate that the MIP-DGT is a cost-effective, reliable and efficient tool for in situ wastewater monitoring.

Design and fabrication of acorn-like Janus molecularly imprinted materials for highly specific separation and enrichment of oxytetracycline from restaurant oily wastewater.

Molecularly imprinted polymer (MIP) is dedicated to the adsorption of target substances in the aqueous phase, but ignores the adsorption in a more complex environment (oily wastewater). In order to explore the application field of existing MIPs, acorn-like Janus particles were fabricated by photo-initiated seed swelling polymerization. A novel amphiphilic Janus-MIP was prepared with the acorn-like Janus particles as matrix, methacrylic acid, ethylene dimethacrylate and oxytetracycline (OTC) as functional monomers, crosslinking agents and template molecules via surface initiated-atom transfer radical polymerization (SI-ATRP). For comparison, the poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly (GMA-co-EDMA)) microspheres were also utilized as the matrix to prepare common spherical-MIP. The adsorption capacity of Janus-MIP for OTC was 23.8 mg g-1 in oil-water system, while the adsorption capacity of spherical-MIP for OTC was only 12.6 mg g-1 in the same system. At the same time, through high performance liquid chromatography (HPLC) analysis, Janus-MIP can specifically recognize and adsorb trace OTC in restaurant oily wastewater samples, and the proposed method exhibited a lower limit of detection (LOD, 3 ng mL-1) and a higher OTC recovery rate (94.2 %-98.4 %). This work demonstrated great potential for the detection and control of OTC contamination from real samples in an oil-water mixed environment.

Sensitive and selective determination of upadacitinib using a custom-designed electrochemical sensor based on ZnO nanoparticle-assisted molecularly imprinted polymer.

Upadacitinib (UPA) is a selective and reversible oral Janus kinase (JAK) 1 inhibitor and is of great importance in treating inflammatory bowel disease (Zheng et al., Int Immunopharmacol 126:111229, 2024; Foy et al., JAAD Case Rep 42:20-22, 2023). Although there are limitations to the effectiveness of UPA, it has received positive responses in clinical trials and is approved for the treatment of atopy dermatitis (AD) (Li et al., Int Immunopharmacol 125:111193, 2023). In this study, a nanoparticle-doped molecularly imprinted polymer (MIP)-based electrochemical sensor was developed for sensitive and selective detection of UPA. The developed sensor was designed as a thin film layer using the photopolymerization method on the surface of the prepared nanoparticle-doped polymerization solution glassy carbon electrode (GCE). Various nanoparticles, such as multi-walled carbon nanotube, titanium dioxide, oxide, and zinc oxide (ZnO) nanoparticles, were the most suitable for UPA. Surface characterization of the developed sensor was done by scanning electron microscopy (SEM), and electrochemical characterization was done by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The quantitative analysis of UPA was performed in 5.0 mM [Fe (CN)6]3-/4- solution using the differential pulse voltammetry (DPV) technique. Under optimum conditions, the calibration range was between 0.1 and 1 pM. The limit of detection (LOD) and limit of quantification (LOQ) were calculated as 0.005 pM and 0.017 pM, respectively. The sensor's accuracy was proven by performing a recovery study in serum. The sensor's selectivity was also evaluated using common interfering substances such as KNO3, CaCl2, Na2SO4, uric acid, ascorbic acid, dopamine, and paracetamol. According to the results obtained, the performance of the designed sensor was found to be quite sensitive and selective in determining UPA. The developed UPA-ZnO/3-APBA@MIP-GCE sensor showed high sensitivity and selectivity towards UPA. In addition, the selectivity, the most important feature of the MIP-based sensor, was confirmed by imprinting factor (IF) calculations using tofacitinib (TOF) and ruxolitinib (RUX). The sensor's unique selectivity is demonstrated by its successful performance even in the presence of UPA impurities.

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.

All-in-one spot test method for tetracycline using molecularly imprinted polymer-coated paper integrated into a portable 3D printed platform with smartphone-based fluorescent detection.

A molecularly imprinted polymer (MIP) has been synthetized, characterized, impregnated on paper, and integrated into a 3D printed platform with smartphone-based fluorescent detection for the determination of tetracycline in water samples. The MIP synthesis was performed by precipitation polymerization, which was subsequently deposited onto a glass microfiber paper. The synthesized polymer and the MIP@paper have been characterized by FTIR spectroscopy, scanning electron microscopy, and EDS spectroscopy. Afterward, a 3D printed detection platform that houses monochromatic LED strips as radiation source and a smartphone as detector have been used for determination of tetracycline. Digital image processing was based on the RGB colour model using image J software and the red intensity channel was used as analytical signal due to its higher sensitivity. Several factors that affect the adsorption capacity and fluorescent detection have been optimized. Under optimum conditions, detection limit of 0.04 mg L-1 and good linearity up 5 mg L-1 (r = 0.998), were achieved. The intra- and inter-day precision of 4.9 and 7.2 %, respectively, expressed as relative standard deviation (%RSD) were obtained, showing the good precision of the proposed methodology. Satisfactory recoveries between 87 and 98 % were obtained spiking real water sample matrices at different concentrations (0.1-0.3 mg L-1). The portable 3D platform with smartphone-based fluorescent detection exploiting all-in-one spot test method for tetracycline using MIP@paper was evaluated with AGREE and GAPI metrics, evidencing its environmentally friendly approach. Furthermore, the BAGI tool demonstrated the practicality of the method, in terms of functionality and applicability compared to previous HPLC and spectrofluorometric methods.

Bioinspired synergy strategy based on the integration of nanozyme into a molecularly imprinted polymer for improved enzyme catalytic mimicry and selective biosensing.

Nanozymes offer many advantages such as good stability and high catalytic activity, but their selectivity is lower than that of enzymes. This is because most of enzymes have a protein component (apoenzyme) for substrate affinity to enhance selectivity and a non-protein element (coenzyme) for catalytic activity to improve sensitivity. The synergy between molecularly imprinted polymers (MIPs) and nanozymes can mimic natural enzymes, with MIP acting as the apoenzyme and nanozyme as the coenzyme. Despite researchers' attempts to associate MIPs with nanozymes, the full potential of this combination remains not well explored. This study addresses this gap by integrating Fe3O4-Lys-Cu nanozymes with peroxidase-like catalytic activities within appropriate MIPs for L-DOPA and dopamine. The catalytic performance of the nanozyme was improved by the presence of Cu in Fe3O4-Lys-Cu and further enhanced by MIP. Indeed, the exploration of the pre-concentration property of MIP has increased twenty-fold the catalytic activity of the nanozyme. Moreover, this synergistic combination facilitated the template removal process during MIP production by reducing the extraction time from several hours to just 1 min thanks to the addition of co-substrates which trigger the reaction with nanozyme and release the template. Overall, the synergistic combination of MIPs and nanozymes offers a promising avenue for the design of artificial enzymes.

Molecularly Imprinted Polymer Sensor Empowered by Bound States in the Continuum for Selective Trace-Detection of TGF-beta.

The integration of advanced materials and photonic nanostructures can lead to enhanced biodetection capabilities, crucial in clinical scenarios and point-of-care diagnostics, where simplified strategies are essential. Herein, a molecularly imprinted polymer (MIP) photonic nanostructure is demonstrated, which selectively binding to transforming growth factor-beta (TGF-ß), in which the sensing transduction is enhanced by bound states in the continuum (BICs). The MIP operating as a synthetic antibody matrix and coupled with BIC resonance, enhances the optical response to TGF-ß at imprinted sites, leading to an augmented detection capability, thoroughly evaluated through spectral shift and optical lever analogue readout. The validation underscores the MIP-BIC sensor capability to detect TGF-ß in spiked saliva, achieving a limit of detection of 10 fM and a resolution of 0.5 pM at physiological concentrations, with a precision of two orders of magnitude above discrimination threshold in patients. The MIP tailored selectivity is highlighted by an imprinting factor of 52, showcasing the sensor resistance to interference from other analytes. The MIP-BIC sensor architecture streamlines the detection process eliminating the need for complex sandwich immunoassays and demonstrates the potential for high-precision quantification. This positions the system as a robust tool for biomarker detection, especially in real-world diagnostic scenarios.

Preparation of novel magnetic ethylene glycol dimethacrylate-based molecularly imprinted polymer for rapid adsorption of phthalate esters from ethanol aqueous solution.

Phthalate esters (PAEs), as emerging pollutants, pose a serious threat to human health and have become a major concern in the fields of environmental protection and food safety. Selective adsorption using molecularly imprinted polymer (MIP) is feasible, but most MIPs use the potentially toxic methacrylic acid (MAA) as a functional monomer, along with other crosslinking agents. In this study, MIP adsorbent was prepared using only ethylene glycol dimethacrylate (EGDMA) as both the functional monomer and crosslinking agent, without the inclusion of MAA. The adsorbent was utilized for the adsorption of PAEs from an ethanol aqueous solution. The results showed that EGDMA-based MIP (EMIP) achieved better adsorption performance of PAEs than MAA-based MIP (MMIP) due to more interactions of EGDMA with PAEs than MAA with them. For the adsorption of dibutyl phthalate (DBP) using EMIP, 95% of the equilibrium adsorption capacity was achieved within the first 15 min. In the isotherm analysis, the theoretical maximum adsorption capacity of EMIP was obtained as high as 159.24 mg/g at 20 °C in an ethanol (10 v%) aqueous solution. Furthermore, the adsorption of EMIP was not affected by the pH of the solution. The adsorption process of EMIP followed the pseudo-second-order kinetic and Freundlich isotherm model. Ethanol had a significant impact on the adsorption of DBP, and the results of molecular simulation could validate this. In addition, the regeneration experiments indicated that EMIP could be recycled 5 times without significant performance change and had a high recovery efficiency of 94.55%.