Hydrophilic molecularly imprinted thermal-responsive polymers based sorbent for ambient ionization mass spectrometric analysis of sulfonamide antibiotics from food samples.

The thermal-responsive magnetic molecularly imprinted polymer (TrMMIP) sorbent was synthesized by surface imprinting method, and then used for magnetic solid-phase extraction (MSPE) and subsequent integrated into the ion source for elution and ionization. The shrinking-strength states change of the thermal-responsive polymer chain on TrMMIP alters the wettability of the sorbent when the working temperature crosses the lower critical solution temperature (LCST) of the polymer, and thus affects its behavior of in the extraction and clean-up process. The targeted analytes could be effectively extracted due to the high selectivity of MIPs and well dispersibility of polymer chain under the open state. Additionally, a hydrophilic polymer chain wrapped on the sorbent surface further protected target substances from co-elution during cleanup. Analytical methods for sulfonamide antibiotics (SAs) detection in complex food samples (milk, honey, fish) were developed, demonstrating potential for rapid and sensitive SAs analysis in diverse food and biological samples.

Surface coupling of molecularly imprinted polymers as strategy to improve sulfamethoxazole removal from water by carbons produced from spent brewery grain.

This work aims to assess the surface coupling of molecularly imprinted polymers (MIP) on carbon adsorbents produced from spent brewery grain, namely biochar (BC) and activated carbon (AC), as a strategy to improve selectivity and the adsorptive removal of the antibiotic sulfamethoxazole (SMX) from water. BC and AC were produced by microwave-assisted pyrolysis, and MIP was obtained by fast bulk polymerization. Two different methodologies were used for the molecular imprinting of BC and AC, the resulting materials being tested for SMX adsorption. Then, after selecting the most favourable molecular imprinting methodology, different mass ratios of MIP:BC or MIP:AC were used to produce and evaluate eight different materials. Molecular imprinting was shown to significantly improve the performance of BC for the target application, and one of the produced composites (MIP1-BC-s(1:3)) was selected for further kinetic and equilibrium studies and comparison with individual MIP and BC. The kinetic behaviour was properly described by both the pseudo-first and pseudo-second order models. Regarding equilibrium isotherms, they fitted the Freundlich and Langmuir models, with MIP1-BC-s(1:3) reaching a maximum adsorption capacity (qm) of 25 ± 1 µmol g-1, 19 % higher than BC. In comparison with other seven pharmaceuticals, the adsorption of SMX onto MIP1-BC-s(1:3) was remarkably higher, as for the specific recognition of this antibiotic by the coupled MIP. The pH study evidenced that SMX removal was higher under acidic conditions. Regeneration experiments showed that MIP1-BC-s(1:3) provided good adsorption performance, which was stable during five regeneration-reutilization cycles. Overall, this study has demonstrated that coupling with MIP may be a suitable strategy to improve the adsorption properties and performance of biochar for antibiotics removal from water, increasing its suitability for practical applications.

Gelatin-based carbon quantum dot-molecularly imprinted polymer: Safe photoluminescent core-shell nano-carrier for the pH-responsive anticancer drug delivery.

This study aims to synthesize a core-shell gelatin-based carbon quantum dot-molecularly imprinted polymer (MIP@g-CQD) via the precipitation free-radical polymerization process using methotrexate (MTX) as a model anticancer template. To investigate the efficiency of the prepared photoluminescent MIP@g-CQD as a pH-responsive nano-carrier, MTX was loaded into MIP@g-CQD by soaking in a drug solution and the release behavior of the loaded drug was evaluated in the necessary pH values (7.4, 5). The successful synthesis of materials was characterized using PL, TEM, FE-SEM, DLS, and FT-IR analyses. Interestingly, the created cavities in the core-shell nano-carriers can interact with the MTX molecules effectively, leading to an increase in the loading capacity. According to the obtained results from Langmuir adsorption isotherms, the imprinting factor was calculated (IF = 4.91). Also, the binding kinetics of MTX revealed the creation of particular recognition sites in the core-shell polymeric network. The MTX-loaded MIP@g-CQD displayed a low rate and limited release at the simulated physiological environment (pH 7.4, 37 °C), but it is increased at tumor tissue (pH 5, 41 °C) conditions, which can lead to long-term and sustained release of MTX in the desired target. This property of MIP@g-CQD could avoid the release of MTX in normal physiological conditions, decreasing the possible side effects of MTX drug. Owing to the existence of amide functional groups in the nano-carrier structure and its negatively charged nature, the MTT assay displayed desirable cytotoxicity against the breast cancer cell line (MCF-7) for the MTX-loaded nano-carrier. According to the obtained results, the prepared safe photoluminescent MIP@g-CQD with appropriate pH-responsivity has a high ability to be applied as an anticancer and bio-detection agent.

Properties, evaluation and application of naringin magnetic molecularly imprinted polymer based on synergistic imprinting strategy.

A novel and facile surface molecularly imprinted polymer coated on magnetic chitosan (Fe3O4@CS@MIP) was fabricated for the selective recognition and enrichment of naringin (NRG). The Fe3O4@CS@MIP was prepared based on covalent-noncovalent synergistic imprinting strategies, utilizing 4-vinyl phenyl boric acid as covalent functional monomer, deep eutectic solvent (choline chloride/methacrylic acid [ChCl/MAA]) as non-covalent functional monomer and Fe3O4@CS nanoparticles as the magnetic support. The obtained Fe3O4@CS@MIP exhibited a uniform morphology, excellent crystallinity, outstanding magnetic properties, and high surface area. Owing to the double recognition abilities, the resultant polymer showed exceptional binding performance and rapid mass transfer in phosphate buffer (pH 7.0). The maximum binding amount of Fe3O4@CS@MIP was found to be 15.08 mg g-1, and the equilibrium adsorption could be achieved within 180 min. Moreover, they also exhibited stronger selectivity for NRG and satisfactory reusability, with only 11.0% loss after five adsorption-desorption cycles. Additionally, the Fe3O4@CS@MIP, serving as an adsorbent, presented practical application potential in the separation and enrichment of NRG from pummelo peel, with extraction efficiency in the range of 79.53% to 84.63%. This work provided a new strategy for improving the performance of MIP and contributed an attractive option for the extraction of NRG in complex samples.

Molecularly imprinted polymer-based electrochemical sensor for rapid detection of masked deoxynivalenol with Mn-doped CeO2 nanozyme as signal amplifier.

Deoxynivalenol-3-glucoside (D3G), the masked form of the important mycotoxin deoxynivalenol (DON), displays potential toxicity but is difficult to control owing to the lack of rapid detection methods. Herein, an innovative molecularly imprinted polymer (MIP)-based electrochemical sensor was developed for the rapid detection of D3G. MIP, an efficient recognition element for D3G, was electropolymerized using o-phenylenediamine based on a surface functional monomer-directing strategy for the first time. CeO2, which contains both Ce3+ and Ce4+ oxidation states, was introduced as a nanozyme to catalyze H2O2 reduction, while Mn doping generated more oxygen vacancies and considerably improved the catalytic activity. Mn-CeO2 also served as a promising substrate material because of its large surface area and excellent conductivity. Under optimal conditions, a good linear relationship was observed for D3G detection over the concentration range of 0.01-50 ng/mL. The proposed sensor could detect D3G down to 0.003 ng/mL with excellent selectivity, even distinguishing its precursor DON in complex samples. The sensor exhibited acceptable stability with high reproducibility and accuracy, and could successfully determine D3G in grain samples. To the best of our knowledge, this is the first electrochemical sensing platform for rapid D3G detection that can easily be expanded to other masked mycotoxins.

Prepared Sandwich structure WS2/ag@MIP composite for ultrasensitive SERS detection of trace 17ß-estradiol in food.

17ß-E2 is used in animal growth regulation and agricultural fertilizer, and even ng L-1 mass concentration levels can show biological effects. In this work, Ag NPs was used as surface-enhanced Raman spectroscopy (SERS) source and WS2 was synthesized by a simple method to provide a uniform distribution platform for Ag NPs. The MIP was the shell, which can selectively enrich the target molecule, pull the distance between the target molecule and SERS source, and protect Ag NPs. A cyclable SERS substrate with high sensitivity for detecting 17ß-E2 in food was constructed. The optimized WS2/Ag@MIP as SERS substrate has the advantages of high Enhanced Factor (EF = 2.78 × 109), low detection limit (LOD = 0. 0958 pM), strong anti-interference ability, and good recycling performance. Moreover, the detection of 17ß-E2 in real samples still has good accuracy. This work provides a new possibility for the trace detection of 17ß-E2 in food.

Self-polymerization silica nanoparticles based molecularly imprinted polymers for selective recognition of protein.

Molecularly imprinted polymers (MIPs) are promising for precise protein separation and purification. However, challenges persist due to their large size, variable configuration, and instability during preparation. Here, a simple silicon self-assembly program was designed to synthesize MIPs without any organic reagents and acid-base catalysis, avoiding the structural damage of protein under severe conditions. In this method, employing hemoglobin (Hb) as a model protein, with tween-20 in emulsification, and tetraethyl orthosilicate (TEOS) as the cross-linking agent, along with co-functional monomers 3-aminopropyltriethoxysilane (APTES) and benzyl(triethoxy)silane (BnTES), enhanced binding efficacy was achieved. Successful imprinting was evidenced through surface morphology observation and physical/chemical property evaluations of the synthesized MIPs. A series of adsorption experiments were performed to investigate the recognition performance of Hb-MIPs. The Hb-MIPs not only exhibited large adsorption capacity (400 µg/mg) and good imprinting factor (6.09) toward template protein, but also showed satisfactory selectivity for reference proteins. Five cycles of adsorption proved that the Hb-MIPs had good reusability. In addition, the successful isolation of HB from bovine blood indicated that Hb-MIPs were an excellent separation and purification material. The mild preparation conditions and good adsorption capacity demonstrated the potential value of this method in separation and purification research.

High performance enrichment and analysis of fluoroquinolones residues in environmental water using cobalt ion mediated paper-based molecularly imprinted polymer chips.

BACKGROUND: Fluoroquinolones (FQs) are widely used for their excellent antimicrobial properties, yet their release into aquatic environments pose risks to ecosystems and public health. The accurate monitoring and analysis of FQs present challenges due to their low concentrations and the complex matrices found in actual environmental samples. To address the need for auto-pretreatment and on-line instrumental analysis, developing new microextraction materials and protocols is crucial. Such advancements will provide better analytical assurance for the effective extraction and determination of FQs at trace levels, which is of great significance to environmental protection and human health. RESULTS: In this work, we presented a Co2+ mediated paper-based molecularly imprinted polymer chip (CMC@Co-MIP), combined with UPLC analysis, to develop an effective analytical method for identifying and quantifying trace amounts of ciprofloxacin (CIP) and enrofloxacin (ENR) in water samples. Notably, the addition of Co2+ in CMC@Co-MIP helped to capture the template molecule CIP through coordination before imprinting, which significantly improved the ordering of the imprinted cavities. CMC@Co-MIP exhibited a maximum adsorption capacity up to 500.20 mg g-1 with an imprinting factor of 4.12, surpassing previous reports by a significant margin. Furthermore, the enrichment mechanism was extensively analyzed by various characterization techniques. The developed method showed excellent repeatability and reproducibility (RSD < 13.0 %) with detection limits ranging from 0.15 to 0.21 µg L-1 and recoveries ranging from 64.9 % to 102.3 % in real spiked water samples. SIGNIFICANCE: We developed a novel microextraction paper-based chip based on Co2+ mediation, which effectively improved the selectivity and convenience of extracting FQs. This breakthrough allowed the chip to have a high enrichment efficiency as well as provide a robust on-line instrumental program. It also confirms that the imprinting scheme based on metal ion coordination is a high-performance strategy.

Boosting Cancer Immunotherapy via Reversing PD-L1-Mediated Immunosuppression with a Molecularly Imprinted Lysosomal Nanodegrader.

Immune checkpoint blockade therapy has achieved important clinical advances in several types of tumors, particularly via targeting the PD-1/PD-L1 axis. However, existing therapeutic strategies that suppress the PD-1/PD-L1 signal pathway usually experience low treatment efficacy and the risk of causing autoimmune diseases. Herein, we report a cancer cell-targeted molecularly imprinted lysosomal nanodegrader (MILND) for boosting immune checkpoint blockade therapy against tumors. The MILND, imprinted with the N-terminal epitope of PD-L1 as an imprinting template, could specifically target the PD-L1 on tumor cells to promote cellular uptake. This process further induces the transport of PD-L1 into lysosomes for degradation, ultimately resulting in the downregulation of PD-L1 expression levels on tumor cells. As a result, a T cell-mediated immune response in the body was activated via the blockade of the PD-1/PD-L1 signaling pathway, which triggered a durable antitumor efficacy. In vivo experiments demonstrated that the MILND could effectively accumulate in tumor sites and exhibit strong tumor growth suppression efficacy in a xenograft tumor model without obvious side effects. Therefore, the MILND provides not only a promising strategy for boosting cancer immunotherapy but also insights for developing molecular imprinting-empowered nanomedicines.

Electroactive Molecularly Imprinted Polymer Nanoparticles (eMIPs) for Label-free Detection of Glucose: Toward Wearable Monitoring.

The diagnosis of diabetes mellitus (DM) affecting 537 million adults worldwide relies on invasive and costly enzymatic methods that have limited stability. Electroactive polypyrrole (PPy)-based molecularly imprinted polymer nanoparticles (eMIPs) have been developed that rival the affinity of enzymes whilst being low-cost, highly robust, and facile to produce. By drop-casting eMIPs onto low-cost disposable screen-printed electrodes (SPEs), sensors have been manufactured that can electrochemically detect glucose in a wide dynamic range (1 µm-10 mm) with a limit of detection (LOD) of 26 nm. The eMIPs sensors exhibit no cross reactivity to similar compounds and negligible glucose binding to non-imprinted polymeric nanoparticles (eNIPs). Measurements of serum samples of diabetic patients demonstrate excellent correlation (>0.93) between these eMIPs sensor and the current gold standard Roche blood analyzer test. Finally, the eMIPs sensors are highly durable and reproducible (storage >12 months), showcasing excellent robustness and thermal and chemical stability. Proof-of-application is provided via measuring glucose using these eMIPs sensor in a two-electrode configuration in spiked artificial interstitial fluid (AISF), highlighting its potential for non-invasive wearable monitoring. Due to the versatility of the eMIPs that can be adapted to virtually any target, this platform technology holds high promise for sustainable healthcare applications via providing rapid detection, low-cost, and inherent robustness.

Smartphone-assisted ratiometric fluorescent sensor for visual detection of chlortetracycline.

The development of a highly selective and sensitive method for detecting chlortetracycline (CTC) is crucial for safeguarding public health and food safety. Herein, a novel ratiometric fluorescence sensor called SiC@ZIF-8@MIP was constructed to specifically recognize and sensitively detect CTC. The sensor has the advantages of fast response speed (7 min), wide linear range (0.1-18 µg mL-1), and low limit of detection (4.56 ng mL-1). With the addition of CTC, the fluorescence of SiC@ZIF-8@MIP is quenched at 410 nm due to the internal filtration effect (IFE) and a new fluorescence signal is generated at 515 nm by CTC due to the aggregation induced emission effect (AIE). Additionally, for rapid on-site detection of CTC, a smartphone is applied to digitize fluorescence images of SiC@ZIF-8@MIP, helping individuals read and analyze the images. This detection method is a promising strategy for on-site assessments of food safety and public health safety.

Computational simulation-assisted template selection of magnetic MOFs molecularly imprinted materials applying the adsorption and detection of multiple fluoroquinolones.

This study utilized computational simulation and surface molecular imprinting technology to develop a magnetic metal-organic framework molecularly imprinted polymer (Fe3O4@ZIF-8@SMIP) capable of selectively recognizing and detecting multiple fluoroquinolones (FQs). The Fe3O4@ZIF-8@SMIP material was synthesized using the "common" template-ofloxacin, identified by computational simulation, demonstrating notable adsorption capacity (88.61-212.93 mg g-1) and rapid mass-transfer features (equilibration time: 2-3 min) for all tested FQs, consistent with Langmuir adsorption model. Subsequently, this material was employed as a magnetic solid-phase-extraction adsorbent for adsorption and detection of multiple FQs by combining with high performance liquid chromatography. The developed method exhibited good linearity for various FQs within the concentration range of 0.1-500 µg L-1, with low limit of detection (0.0605-0.1529 µg L-1) and limit of quantitation (0.2017-0.5097 µg L-1). Satisfactory recoveries (88.38-103.44%) were obtained when applied to spiked food samples, demonstrating the substantial potential of this Fe3O4@ZIF-8@SMIP material for rapid enrichment and identification for multiple FQs residues.

A new SERS quantitative analysis strategy for ultratrace chloramphenicol with Fe3O4@MIP nanocatalytic probe.

Three functional magnetic nanocatalytic probe, which integrates recognition, catalytic amplification, and separation enrichment, is a new approach to construct a simple, fast, highly selective, and sensitive analytical method. In this article, a new magnetic nanosurface molecularly imprinted polymer nanoprobe (Fe3O4@MIP) with trifunctionality was rapidly prepared using a microwave-assisted method with magnetic Fe3O4 nanoparticles as a substrate, chloramphenicol (CAP) as a template molecule, and methacrylic acid as a functional monomer. The characterized nanoprobe was found that could specifically recognize CAP, strongly catalyze the new indicator nanoreaction of fructose (DF)-HAuCl4. The gold nanoparticles (AuNPs) exhibit strong resonance Rayleigh scattering (RRS) and surface enhanced Raman scattering (SERS) effects. Upon addition of CAP, the SERS/RRS signals were linearly weakened. Accordingly, a new SERS/RRS analysis platform for highly sensitive and selective determination of CAP was constructed. The SERS linear range was 0.0125-0.1 nmol/L, with detection limit (DL) of 0.004 nmol/L CAP. Furthermore, it could be combined with magnet-enriched separation to further improve the sensitivity, with a DL of 0.04 pmol/L CAP. The SERS method has been used for the determination of CAP in real samples, with relative standard deviations of 2.37-9.89 % and the recovery of 95.24-107.1 %.

Enhancement in Sensitivity and Selectivity of Electrochemical Technique with CuO/g-C3N4 Nanocomposite Combined with Molecularly Imprinted Polymer for Melamine Detection.

This study focused on enhancing the sensitivity and selectivity to detect melamine by utilizing a photoelectrochemical method. This was achieved by combining a melamine-imprinted polymer with a CuO/g-C3N4 nanocomposite, which was synthesized through chemical precipitation and calcination. The resulting nanocomposite exhibits improved carrier mobility and photoelectrochemical properties. A molecularly imprinted receptor for selective detection was created through bulk polymerization with methacrylic acid and a melamine template. The characterization of the nanocomposite was performed using X-ray photoelectron spectroscopy for the chemical oxidation state, X-ray diffraction patterns for the crystalline structure, and ultraviolet/visible/near-infrared spectroscopy for optical properties. The CuO/g-C3N4 nanocomposite exhibits photoactivity under visible light. The modified electrode, incorporating the CuO/g-C3N4 nanocomposite and melamine-imprinted polymer, demonstrates a linear detection range of 2.5 to 50 nM, a sensitivity of 4.172 nA/nM for melamine, and a low detection limit of 0.42 nM. It shows good reproducibility and high selectivity to melamine, proving effective against interferences and real samples, showcasing the benefits of the molecularly imprinted polymer.

Enhanced Antibacterial Activity of Clindamycin Using Molecularly Imprinted Polymer Nanoparticles Loaded with Polyurethane Nanofibrous Scaffolds for the Treatment of Acne Vulgaris.

Acne vulgaris, a prevalent skin condition, arises from an imbalance in skin flora, fostering bacterial overgrowth. Addressing this issue, clindamycin molecularly imprinted polymeric nanoparticles (Clin-MIP) loaded onto polyurethane nanofiber scaffolds were developed for acne treatment. Clin-MIP was synthesized via precipitation polymerization using methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA), and azoisobutyronitrile (AIBN) as functional monomers, crosslinkers, and free-radical initiators, respectively. MIP characterization utilized Fourier-transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) before being incorporated into polyurethane nanofibers through electrospinning. Further analysis involved FTIR, scanning electron microscopy (SEM), in vitro release studies, and an ex vivo study. Clin-MIP showed strong antibacterial activity against S. aureus, with inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) values of 0.39 and 6.25 µg/mL, respectively. It significantly dropped the bacterial count from 1 × 108 to 39 × 101 CFU/mL in vivo and has bactericidal activity within 180 min of incubation in vitro. The pharmacodynamic and histopathology studies revealed a significant decrease in infected animal skin inflammation, epidermal hypertrophy, and congestion upon treatment with Clin-MIP polyurethane nanofiber and reduced pro-inflammatory cytokines (NLRP3, TNF-α, IL-1ß, and IL-6) conducive to acne healing. Consequently, the recently created Clin-MIP polyurethane nanofibrous scaffold. This innovative approach offers insight into creating materials with several uses for treating infectious wounds caused by acne.

Engineering of dual recognition functional aptamer-molecularly imprinted polymeric solid-phase microextraction for detecting of 17ß-estradiol in meat samples.

In this study, an enhanced selective recognition strategy was employed to construct a novel solid-phase microextraction fiber coating for the detection of 17ß-estradiol, characterized by the combination of aptamer biorecognition and molecularly imprinted polymer recognition. Benefiting from the combination of molecularly imprinted and aptamer, aptamer-molecularly imprinted (Apt-MIP) fiber coating had synergistic recognition effect. The effects of pH, ion concentration, extraction time, desorption time and desorption solvent on the adsorption capacity of Apt-MIP were investigated. The adsorption of 17ß-estradiol on Apt-MIP followed pseudo-second order kinetic model, and the Freundlich isotherm. The process was exothermic and thermodynamically spontaneous. Compared with polymers that only rely on imprinted recognition, non-imprinted recognition or aptamer affinity, Apt-MIP had the best recognition performance, which was 1.30-2.20 times that of these three materials. Furthermore, the adsorption capacity of Apt-MIP for 17ß-estradiol was 885.36-1487.52 times than that of polyacrylate and polydimethylsiloxane/divinylbenzone commercial fiber coatings. Apt-MIP fiber coating had good stability and could be reused for more than 15 times. Apt-MIP solid-phase microextraction coupled with high-performance liquid chromatography was successfully applied to the determination of 17ß-estradiol in pork, chicken, fish and shrimp samples, with satisfactory recoveries of 79.61 %-105.70 % and low limits of detection (0.03 µg/kg). This work provides new perspectives and strategies for sample pretreatment techniques based on molecular imprinting technology and improves analytical performance.

DFT simulated Quercetin imprinted polymer: Selective recovery of Quercetin from onion solid waste.

Onion peels (OP) are byproduct of food processing industries that poses economic and environmental challenges. However, being rich source of bioactive compounds like Quercetin (Qt), a polyphenolic antioxidant with potential health benefits, harnessing value from such waste can imbibe sustainable practices and protect environment. With this view, the present study targets selective recovery of Qt from OP waste using rationally designed molecularly imprinted polymer (MIP). Density Functional Theory (DFT) was used for the theoretical selection of the best conformer of Qt (template), methacrylic acid (MAA) as functional monomer, ratio of Qt-MAA for getting stable pre-polymerization complex, and to avoid hit and trial experiments. The theoretical results were validated experimentally by synthesizing MIP/ control polymer (NIP) using MAA as functional monomer, EGDMA as a cross-linker and AIBN as initiator. Synthesized MIP/NIP were characterized using various characterization techniques to confirm successful imprinting. Prepared MIP and NIP could effectively rebind the Qt molecule with binding capacity of 46.67 and 20.89 mg g-1 respectively. Furthermore, synthesized MIP could selectively recover 62.81 % of Qt from 1 g of dry onion peel powder. This study can be effectually used for sustainable recovery of Qt in large scale for various foods, cosmetic and pharmaceutical applications.

Detection and adsorption of florfenicol in milk using bifunctional carbon dot-doped molecularly imprinted polymers.

Detection of florfenicol (FF) residues in animal-derived foods, as one of the most widely used antibiotics, is critically important to food safety. The fluorescent molecularly imprinted polymer (MIP) was synthesized by surface-initiated atom transfer radical polymerization technique with poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres, 4-vinylpyridine, ethylene glycol dimethacrylate, and FF as the matrix, functional monomer, crosslinker, and template molecule, respectively. Meanwhile, N-S co-doped carbon dot (CD) was synthesized with triammonium citrate and thiourea as precursors under microwave irradiation at 400 W for 2.5 min and then integrated into FF-MIP to obtain CD@FF-MIP. For comparison, non-imprinted polymer (NIP) without FF was also prepared. The adsorption capacity of CD@FF-MIP to FF reached 53.1 mg g-1, which was higher than that of FF-MIP (34.7 mg g-1), whereas the adsorption capacity of NIP was only 17.3 mg g-1. The adsorption equilibrium of three materials was reached within 50 min. Particularly, CD@FF-MIP exhibited an excellent fluorescence quenching response to FF in the concentration range of 3-50 µmol L-1. As a result, CD@FF-MIP was successfully utilized to extract FF in milk samples, which were analyzed by high-performance liquid chromatography. The standard recoveries were 95.8%-98.2%, and the relative standard deviation was 1.6%-4.2%. The method showed the advantages of simple operation, high sensitivity, excellent selectivity, and low cost, and also demonstrated a great application prospect in food detection.

Magnetic molecularly imprinted polymer based on coordination for the determination of trace banned substance furosemide in human urine.

Furosemide (FUR), banned in sports events by the World Anti-Doping Agency, is a key target in drug tests, necessitating a pretreatment material capable of selectively, rapidly, and sufficiently separating/enriching analytes from complex matrices. Herein, a metal-mediated magnetic molecularly imprinted polymer (mMIP) was rationally designed and synthesized for the specific capture of FUR. The preparations involved the utilization of chromium (III) as the binding pivot, (3-aminopropyl)triethoxysilane as functional monomer, and Fe3O4 as core, all assembled via free radical polymerization. Both the morphologies and adsorptive properties of the mMIP were characterized using multiple methods. The resulting Cr(III)-mediated mMIP (ChM-mMIP) presented excellent selectivity and specificity toward FUR. Under optimized conditions, the adsorption capacity reached 128.50 mg/g within 10 min, and the imprinting factor was 10.41. Moreover, it was also successfully applied as a dispersive solid-phase extraction material, enabling the detection of FUR concentration as low as 20 ng/mL in human urine samples when coupled with a high-performance liquid chromatography/photodiode array. Overall, this study offers a valuable strategy for the development of novel recognition material.

A double boronic acid affinity "sandwich" SERS biosensor based on magnetic boronic acid controllable-oriented imprinting for high-affinity biomimetic specific recognition and rapid detection of target glycoproteins.

Transferrin (TRF), recognized as a glycoprotein clinical biomarker and therapeutic target, has its concentration applicable for disease diagnosis and treatment monitoring. Consequently, this study developed boronic acid affinity magnetic surface molecularly imprinted polymers (B-MMIPs) with pH-responsitivity as the "capture probe" for TRF, which have high affinity similar to antibodies, with a dissociation constant of (3.82 ± 0.24) × 10-8 M, showing 7 times of reusability. The self-copolymerized imprinted layer synthesized with dopamine (DA) and 3-Aminophenylboronic acid (APBA) as double monomers avoided nonspecific binding sites and produced excellent adsorption properties. Taking the gold nanostar (AuNS) with a branch tip "hot spot" structure as the core, the silver-coated AuNS functionalized with the biorecognition element 4-mercaptophenylboronic acid (MPBA) was employed as a surface-enhanced Raman scattering (SERS) nanotag (AuNS@Ag-MPBA) to label TRF, thereby constructing a double boronic acid affinity "sandwich" SERS biosensor (B-MMIPs-TRF-SERS nanotag) for the highly sensitive detection of TRF. The SERS biosensor exhibited a detection limit for TRF of 0.004 ng/mL, and its application to spiked serum samples confirmed its reliability and feasibility, demonstrating significant potential for clinical TRF detection. Moreover, the SERS biosensor designed in this study offers advantages in stability, detection speed (40 min), and cost efficiency. The portable Raman instrument for SERS detection fulfills the requirements for point-of-care testing.