Molecularly Imprinted Polymer Research Articles

Novel Conductive and Redox-Active Molecularly Imprinted Polymer for Direct Quantification of Perfluorooctanoic Acid.

This study developed a novel molecularly imprinted polymer (MIP) that is both conductive and redox-active for directly quantifying perfluorooctanoic acid (PFOA) electrochemically. We synthesized the monomer 3,4-ethylenedioxythiophene-2,2,6,6-tetramethylpiperidinyloxy (EDOT-TEMPO) for electropolymerization on a glassy carbon electrode using PFOA as a template, which was abbreviated as PEDOT-TEMPO-MIP. The redox-active MIP eliminated the need for external redox probes. When exposed to PFOA, both anodic and cathodic peaks of MIP showed a decreased current density. This observation can be explained by the formation of a charge-assisted hydrogen bond between the anionic PFOA and MIP's redox-active moieties (TEMPO) that hinder the conversion between the oxidized and reduced forms of TEMPO. The extent of the current density decrease showed excellent linearity with PFOA concentrations, with a method detection limit of 0.28 ng·L-1. PEDOT-TEMPO-MIP also exhibited high selectivity toward PFOA against other per- and polyfluoroalkyl substances (PFAS) at environmentally relevant concentrations. Our results suggest electropolymerization of MIPs was highly reproducible, with a relative standard deviation of 5.1% among three separate MIP electrodes. PEDOT-TEMPO-MIP can also be repeatedly used with good stability and reproducibility for PFOA detection. This study provides an innovative platform for rapid PFAS quantification using redox-active MIPs, laying the groundwork for developing compact PFAS sensors.

One-Pot Preparation of Ratiometric Fluorescent Molecularly Imprinted Polymer Nanosensor for Sensitive and Selective Detection of 2,4-Dichlorophenoxyacetic Acid.

The development of fluorescent molecular imprinting sensors for direct, rapid, and sensitive detection of small organic molecules in aqueous systems has always presented a significant challenge in the field of detection. In this study, we successfully prepared a hydrophilic colloidal molecular imprinted polymer (MIP) with 2,4-dichlorophenoxyacetic acid (2,4-D) using a one-pot approach that incorporated polyglycerol methacrylate (PGMMA-TTC), a hydrophilic macromolecular chain transfer agent, to mediate reversible addition-fragmentation chain transfer precipitation polymerization (RAFTPP). To simplify the polymerization process while achieving ratiometric fluorescence detection, red fluorescent CdTe quantum dots (QDs) and green fluorescent nitrobenzodiazole (NBD) were introduced as fluorophores (with NBD serving as an enhancer to the template and QDs being inert). This strategy effectively eliminated background noise and significantly improved detection accuracy. Uniform-sized MIP microspheres with high surface hydrophilicity and incorporated ratiometric fluorescent labels were successfully synthesized. In aqueous systems, the hydrophilic ratio fluorescent MIP exhibited a linear response range from 0 to 25 μM for the template molecule 2,4-D with a detection limit of 0.13 μM. These results demonstrate that the ratiometric fluorescent MIP possesses excellent recognition characteristics and selectivity towards 2,4-D, thus, making it suitable for selective detection of trace amounts of pesticide 2,4-D in aqueous systems.

Amelioration of Smoke Taint in Wine via Addition of Molecularly Imprinted Polymers during or after Fermentation.

The adsorbents used to remove taint compounds from wine can also remove constituents that impart desirable color, aroma, and flavor attributes, whereas molecularly imprinted polymers (MIPs) are tailor-made to selectively bind one or more target compounds. This study evaluated the potential for MIPs to ameliorate smoke taint in wine via removal of volatile phenols during or after fermentation. The addition of MIPs to smoke-tainted Pinot Noir wine (for 24 h with stirring) achieved 35-57% removal of guaiacol, 4-methylguaiacol, cresols, and phenol, but <10% of volatile phenol glycoconjugates were removed and some wine color loss occurred. Of the MIP treatments that were subsequently applied to Semillon and Merlot fermentations or wine, MIP addition post-inoculation of yeast yielded the best outcomes, both in terms of volatile phenol removal and wine sensory profiles. Despite some impact on other aroma volatiles and red wine color, the findings demonstrate that MIPs can ameliorate smoke-tainted wine.

Investigation of electrochemical behaviour and determination of Riociguat with bare GCE and molecularly imprinted polymer-based electrochemical sensor

Pulmonary Arterial Hypertension (PAH) causes death due to ventricular overload and heart failure. Calcium channel blockers, anticoagulants, digoxin and diuretics are the standards of care for PAH. Riociguat (RIO) is an oral soluble guanylate cyclase stimulator approved for the treatment of PAH by World Health Organization (WHO) Group 1 patients. In this study, the electrochemical behavior of RIO was investigated using a bare glassy carbon electrode (GCE). In addition, RIO was determined using GCE and a molecularly imprinted polymer (MIP)-based electrochemical sensor. The MIP-based electrochemical sensor was prepared by photopolymerization of methacrylic acid in the presence of a basic monomer, crosslinker, target molecule, and photoinitiator. The polymer film was characterised by a scanning electron microscope (SEM) and cyclic voltammetry (CV). Under the optimized conditions, the results obtained with GCE and MIP sensor were compared. The analytical performance of GCE and MIP-based electrochemical sensors was evaluated. The linear ranges of RIO were 1.0 × 10–6 – 1.0 × 10–4 M and 1.0 × 10–13 – 1.0 × 10–12 M, with a limit of detection (LOD) of 1.40 × 10–8 M and 2.12 × 10–14 by bare GCE and MIP-based electrochemical sensor using differential pulse voltammetry (DPV), respectively. The results show that the MIP sensor has higher sensitivity than the bare GCE. Both were applied to commercial human serum samples and pharmaceutical dosage forms. The recovery studies were performed, and the recovery% and RSD% results are within the acceptable range. Therefore, the GCE and MIP sensors have good selectivity, accuracy and precision.

Fluorescent probe based on GO/g-C3N4-PEG@Cu NPs/MIP for the detection of dopamine in banana.

Graphene oxide (GO) and copper nanoparticles (Cu NPs) were incorporated to modulate and enhance the fluorescence properties of pegylated graphite phase carbon nitride (g-C3N4-PEG). Combined with the specific recognition capability of a molecular imprinted polymer (MIP), a highly sensitive and selective fluorescent molecular imprinted probe for dopamine detection was developed. The fluorescent g-C3N4-PEG was synthesized from melamine and modified with GO and Cu NPs to obtain GO/g-C3N4-PEG@Cu NPs. Subsequently, MIP was prepared on the surface of GO/g-C3N4-PEG@Cu NPs using dopamine as the template molecule. Upon elution of the template molecule, a dopamine-specific GO/g-C3N4-PEG@Cu NPs/MIP fluorescence probe was obtained. The fluorescence intensity of the probe was quenched through the adsorption of different concentrations of dopamine by the MIP, thus establishing a novel method for the detection of dopamine. The linear range of dopamine detection was from 5 × 10-11 to 6 × 10-8mol L-1, with a detection limit of 2.32 × 10-11mol L-1. The sensor was utilised for the detection of dopamine in bananas, achieving a spiked recovery rate between 90.3% and 101.3%. These results demonstrate that the fluorescence molecular imprinted sensor developed in this study offers a highly sensitive approach for dopamine detection in bananas.

Designing A Selective Electrochemical Nanosensor Based on Molecularly Imprinted Polymer for Detection of Pirfenidone

In this study, an electrochemical determination of pirfenidone(PIR), an antifibrotic drug, was developed for the first time with a bare glassy carbon electrode(GCE) and a molecularly imprinted polymer(MIP)-based nanosensor. A molecularly imprinted polymer(MIP) incorporating o-phenylenediamine(o-PD), chitosan(CHIT), ionic liquid(IL), and diamond nanoparticles(DiaNPs) was utilized to modify a glassy carbon electrode(GCE), developing a stable and selective electrochemical nanosensor(MIP/CHIT@IL@DiaNPs/GCE) for PIR detection. The designed MIP/CHIT@IL@DiaNPs/GCE was characterized by electrochemical impedance spectroscopy(EIS), cyclic voltammetry(CV), scanning electron microscopy(SEM) and atomic force microscopy(AFM). The [Fe(CN)6]3−/4− redox couple was used as a probe to characterize the nanosensor by using voltammetric methods. Under optimum conditions, the bare GCE showed a linear response in the concentration range of 9.90 μM to 260.0 μM for the determination of PIR, and the detection limit was calculated to be 2.48 μM. While, the MIP/CHIT@IL@DiaNPs/GCE nanosensor exhibited good sensitivity with a linear range of 30.0 pM−1.0 nM and a detection limit of 9.29 pM. To demonstrate the applicability of the developed nanosensors to real samples, the determination was made from Pirfect® tablet and human serum.

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.

Dual Template Molecularly Imprinted Polymers Targeting Blockade of CD47 for Enhanced Macrophage Phagocytosis and Synergistic Antimetabolic Therapy.

Glycinamide ribonucleotide formyltransferase (GARFT) is an important enzyme in the folate metabolism pathway, and chemical drugs targeting GARFT have been used in tumor treatments over the past few decades. The development of novel antimetabolism drugs that target GARFT with improved performance and superior activity remains an attractive strategy. Herein, we proposed a targeted double-template molecularly imprinted polymer (MIP) for enhancing macrophage phagocytosis and synergistic antimetabolic therapy. The double-template MIP was prepared by imprinting the exposed peptide segment of the extracellular domain of CD47 and the active center of GARFT. Owing to the imprinted cavities on the surface of MIP, it can actively target cancer cells and mask the "do not eat me" signal upon binding to CD47 thereby blocking the CD47-SIRPα pathway and ultimately enhancing phagocytosis by macrophages. In addition, MIP can specifically bind to the active center of GARFT upon entry into the cells, thereby inhibiting its catalytic activity and ultimately interfering with the normal expression of DNA. A series of cell experiments demonstrated that MIP can effectively target CD47 overexpressed 4T1 cancer cells and inhibit the growth of 4T1 cells. The enhanced phagocytosis ability of macrophages-RAW264.7 cells was also clearly observed by confocal imaging experiments. In vivo experiments also showed that the MIP exhibited a satisfactory tumor inhibition effect. Therefore, this study provides a new idea for the application of molecular imprinting technology to antimetabolic therapy in conjunction with macrophage-mediated immunotherapy.

Computer simulation‐guided template selection for a molecularly imprinted polymer for selective trifluralin adsorption

AbstractTo meet selective adsorption toward trifluralin, a novel molecularly imprinted polymer (MIP) was fabricated by the dummy template molecular imprinting technology. First, computational simulation was performed to select a suitable dummy template, 3,5‐dinitro‐4‐methylbenzoic acid (T1), based on the maximum basis set superposition error (BSSE)‐corrected binding interaction energy (ΔE) of the monomer N‐vinylpyrrolidone (NVP)‐T1 complex and its structural overlap with trifluralin. Then, the MIP was prepared via the bulk polymerization. The adsorption experiments showed the MIP exhibited a trifluralin adsorption capacity of 5.1 mg g−1, an imprinting factor (IF) of 2.2, and short adsorption equilibrium time of 5 min. The adsorption of trifluralin conformed to the Freundlich adsorption (R2 = 0.985) and pseudo‐second‐order model (R2 = 0.999). In addition, the MIP exhibited selectivity to trifluralin over other adsorbents, including structural analogs (pendimethalin and oryzalin), pesticide (carbendazim), and nitrocompounds (nitrofurantoin, furazolidone, and furaltadone), with the selectivity factor (β) in the range of 1.2–3.0, respectively. In trifluralin/oryzalin mixture, the IF toward oryzalin was still as high as 1.9. The removal rate of the MIP to trifluralin in environmental water samples ranged from 90.08% to 99.04%. This study provides theoretical and experimental insights for the preparation of MIP using dummy templates.

Development of a Molecularly Imprinted Polymer for Determination of Atenolol Based on Selective Solid Phase Extraction and Application in Pharmaceutical Samples

This paper demonstrates the synthesis and storage of molecular-imprinted polymers (MIP) at room temperature using bulk polymerization of atenolol (Ate), which is characterized by high sensitivity, low costs, and high stability. The research used 0.99:6:20 mmol ratios of template, monomer, and cross-linking agents for the polymerization in order to ensure an appropriate adsorption capacity. By making MIP for atenolol as Ate-MIP, which could be looked at with a UV-VIS spectrophotometer at 276 nm, Fourier- transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM), a functional monomer of allyl chloride with cross-linking ethylene glycol dimethyl acrylate was made. Mass spectrometric (MS) detection may use allyl chloride to determine atenolol levels in pharmaceutical preparations. The GC/MS methods developed in this study are accurate, sensitive, and precise and can be easily applied to (NOVATEN/India and ATENOIOI/U.K.) tablets in pharmaceutical preparation. The elution process was applied to the template (Ate) from the Ate-MIP, which developed cavities, caused by using porogenic solutions of methanol, chloroform, and acetic acid (70:20:10, respectively). The maximum adsorption capacity of Ate-MIP was 2.9957 µmol/g, and the ratio of template to monomer was 1:1 in adherence to the Langmuir isotherm model. A solid-phase extraction (SPE) syringe packed with molecular imprinted polymers (MIPs) was used to selectively separate and pre-concentrate Ate from aqueous solutions and estimations of atenolol.

High-precision flexible sweat self-collection sensor for mental stress evaluation

As a stress hormone existing in the human body, cortisol can reflect the psychological stress and health status in daily life, and is a potential biomarker of the body’s stress response. To effectively collect sweat and accurately identify the target, this paper reports a flexible wearable cortisol detection device with outstanding reliability and sensitivity. Molecular imprinted polymer (MIP) ensures cortisol specificity. And carbon nanotubes (CNT) on electrodes increase sensitivity, expanding the detection range to 10−3 to 104 nM, with sensitivity at 189.2 nA/lg(nM). In addition, porous chitosan hydrogel (PCSH) collects sweat effectively, its adhesive properties and 80% swelling rate offer a low-cost alternative to microfluidics. Flexible printed circuit board (FPCB) and serpentine electrode (SE) ensure device durability. This non-invasive, highly sensitive device offers a novel method for mental stress monitoring and clinical diagnosis, advancing human physiological state monitoring.

Application of piezoelectric sensors to aspartame determination in fluids

The study touches the development of piezoelectric sensors based on molecularly imprinted polymers (MIPs) with an aspartame imprint. The values of the imprinting factors and the selectivity coefficients of the developed sensor MIP-E951 in relation to target molecules and other sweeteners were calculated to confirm the ability of MIP -951 to selective detection of aspartame. The range of determined concentrations is 1 – 1 × 10–3 g/liter, the detection limit of aspartame is 5 × 10–4 g/liter. When analyzing model solutions, it was found that foreign components usually present in soft drinks do not interfere with the determination of aspartame using the developed sensor. The obtained sensors were tested for the determination of aspartame in soft drinks. Chromatographic analysis was used as a reference method. The results obtained by both methods indicate that piezo sensors can be successfully used for the analysis of aspartame in liquid media. The error of determination does not exceed 8%.

Integration of miniaturized sample preparation and molecularly imprinted polymers in food analysis

The use of innumerable chemical compounds in food production to enhance agricultural quality and yield has raised significant global concerns regarding food safety. To address these concerns, miniaturized solid sample preparation techniques have emerged as an appealing strategy for analyzing chemical residues in complex samples, notably those found in food matrices. The efficacy of these miniaturized solid extraction procedures hinges largely on the choice of the sorbent phase. Molecularly imprinted polymers (MIPs) have been introduced as highly selective and versatile sorbent phases for a wide range of miniaturized solid techniques. Their remarkable selectivity is attributed to the creation of distinct cavities during the synthesis process, which subsequently accommodate the target analyte when the sample is applied. This unique characteristic empowers MIP polymers to exhibit exceptional specificity toward the desired analyte. The use of MIPs as sorbent phases in miniaturized sample preparation methods has shown great potential to increase the analytical performance of residue evaluation in food matrices. Therefore, here we present a comprehensive overview of the current landscape of miniaturized solid sample techniques employing MIPs as sorbent phases for the assessment of residues in food samples. Moreover, this review is primarily on recent reports concerning the application of MIPs in solid-phase microextraction (SPME), in-tube SPME, microextraction by packed sorbent (MEPS), disposable pipette extraction (DPX), solid-phase extraction in pipette tip (SPE-PT) and stir bar sorptive extraction (SBSE). Lastly, we will bring some future topics concerning the use of MIPs in miniaturized sample preparation methods for food analysis in order to bring some new avenues for enhancing food products' safety and quality assessment.

Polyaniline-based bovine serum albumin imprinted electrochemical sensor for ultra-trace-level detection in clinical and food safety applications

Monitoring bovine serum albumin (BSA) at ultra-low levels is crucial for clinical and food safety applications, as it plays a significant role in identifying various health conditions and potential risks, necessitating fast, trace-level detection of BSA. This study proposes an approach to address these challenges by employing molecularly imprinted polymer (MIP) to develop an ultra-trace-level and cost-effective BSA sensing platform. The MIP electrochemical sensor was developed using polyaniline (PANI) combined with the protein crosslinker glutaraldehyde (GA) to optimize BSA surface imprinting in the MIP. As a result, the sensor achieves a sensitivity of 1.24 μA/log(pg/mL), with a picomolar detectable limit of 2.3 pg/mL (0.035 pM) and a wide detection range from 20 pg/mL to 200,000 pg/mL (0.303 pM to 3030 pM), making it suitable for clinical and food safety applications. Additionally, the study explores the interaction between an acidic surfactant protein eluent (acetic acid with sodium dodecyl sulfate, AcOH-SDS) and BSA vacant sites, enhancing recognition and re-binding. The PANI-based MIP sensor demonstrates initial feasibility and practicality in commercial milk and real human serum, opening avenues for early disease detection and ensuring food safety in BSA-related immune responses.

Molecularly imprinted Ag2S quantum dots with high photocatalytic activity for dye removal: Experimental and DFT insights

Molecular imprinted polymers (MIPs) were developed by carrying out the cocktail solution of Template ((Salata, 2004)-Gingerol), monomer, crosslinker, and Ag2S Quantum Dots (QDs) by ex-situ dissolved in an appropriate solvent, resulting in an efficient crosslinked polymer composite. Degradation of Alizarin red S (ARS) dye and yellowish sunset (SY) azo dye under visible light irradiation was reported first time by the introduction of prepared MIPs composite. In this research, the result shows efficient photocatalyt activity of Ag2S-MIPs composite for the degradation of AR and SY dye with degradation% (80%) and (84%) in the aqueous wastewater. The degradation efficiency of the Ag2S-MIPs composite and the Ag2S QD associated with non-imprinted polymers (NIPs) (i.e.Ag2S-NIPs composite) were calculated by using different parameters such as catalyst dose, pH value, optimum time and concentration variation and the observations are evocative. Moreover, the density functional theory (DFT) approach was also used to analyze the structural, stability/energetics, and electronic features of the organic-inorganic hybrid composites of the Ag2S QD with the MIPs based on (Salata, 2004)-gingerol extract. The proposed QD and MIPs (EGDMA and (Salata, 2004)-Gingerol) composite model has been detected to be the most stable because it shows the largest binding energy (BE) among the three chosen composite models. It was found out that imprinted polymers were superior in enhancing the degradation of dyes when compared to non imprinted polymers. Introducing MIPs into the valence band accelerates the catalysis properties to stabilize newly fashioned excitons that are basically generated as a result of light excitation in presence of Ag2S Quantum Dots (QDs) and molecular imprinted polymer (MIPs). Motivation behind this work is to address the challenges related to environmental pollution causing by organic dyes. These toxins are known to cause diverse symptoms (e.g., skin irritation, eye infection, respiratory disorders, and even cancer) once exposed through ingestion and inhalation. Through incorporation of Ag2S QD into MIP,the purpose of this research is to enhance the selectivity, specificity and photocatalytic activity for dyes and that work holds a potential towards environmental remediation by developing a cost effective and sustainable method for controlling pollution in water.

Enhanced detection of 4-nitrophenol in drinking water: ECL sensor utilizing velvet-like graphitic carbon nitride and molecular imprinting

In this work, a molecularly imprinted electrochemiluminescence (ECL) sensor was developed for selective detection of 4-nitrophenol (4-NP) in drinking water for the first time. By synthesizing velvet-like graphitic carbon nitride (V-g-C3N4) via one-step thermal polycondensation and integrating it with a molecularly imprinted polymer (MIP), the ECL sensor was fabricated. The MIP-modified V-g-C3N4 composites (MIP/V-g-C3N4) were synthesized using a sol-gel method with 4-NP as the template molecule. Under optimal conditions, the ECL sensor exhibited a wide detection range (5 × 10−10-1 × 10−5 mol/L) and a low detection limit (1.8 × 10−10 mol/L). In testing with actual drinking water samples, it displayed high accuracy (recoveries for intraday and inter-day: 93.50–106.2% and 97.00–107.3%, separately) and precision (RSDs for intraday and inter-day: 1.54–4.59% and 1.53–4.28%, respectively). The developed MIP-based ECL sensor demonstrated excellent selectivity, stability, and reproducibility, offering a promising and reliable approach for highly sensitive and selective determination of 4-NP in drinking water.

Molecularly imprinted polymer based on covalent organic framework coated steel substrate as the mass spectrometric ionization source for the direct detect of aflatoxins in complex food matrices

Ambient mass spectrometry allows direct analysis of various sample types with minimal or no pretreatment. However, due to the influence of matrix effects, there are sensitivity and issues in analyzing trace analytes in complex food samples. In this work, we developed a spray mass spectrometry platform based on SSS@TPBD-TPA@MIPs (Stainless steel substrate (SSS), terephthalaldehyde (TPA), N, N, N′, N′-tetrakis(p-aminophenyl)-p-phenylenediamine (TPBD), molecularly imprinted polymer (MIP)), for rapid, in situ, high-throughput, highly enrichment efficiency and highly selective trace analysis of aflatoxins. By simplifying the sample pretreatment and directly applying high voltage for ESI-MS, the analysis can be completed within 1 min. The established method base on SSS@TPBD-TPA@MIPs exhibited high sensitivity and accuracy when determine trace level AFs in maize and peanuts. The results demonstrated a good linear relationship within the range of 0.01–10 μg/L, with the determination coefficient (R2) ≥ 0.9956. The limits of detection (LODs) was 0.035–0.3 ng/mL and limits of quantitation (LOQs) was 0.12–0.99 ng/mL, with acceptable recovery rate of 82.09–115.66 % and good repeatability represented by the relative standard deviation (RSD) less than 17.43 %. Furthermore, SSS@TPBD-TPA@MIPs exhibited excellent reusability, with more than 8 repeated uses, and showed good adsorption performance.

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 400W for 2.5min 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 53.1mgg-1, which was higher than that of FF-MIP (34.7mgg-1), whereas the adsorption capacity of NIP was only 17.3mgg-1. The adsorption equilibrium of three materials was reached within 50min. Particularly, CD@FF-MIP exhibited an excellent fluorescence quenching response to FF in the concentration range of 3-50 µmolL-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.

Integrated microfluidic chip with a MIP-gated organic electrochemical transistor for continuous, selective, and label-free quantification of tumor marker

Early diagnosis of cancer is crucial to effective treatment of the patients and to higher survival rates. Tumor marker detection as an effective and noninvasive cancer diagnosis method has important clinical significance. N1, N12-diacetylspermine (DAS) is a new tumor marker. The development of its detection methods is an urgent need for medical diagnosis and human health monitoring. The conventional detection methods of DAS are labor-intensive and time-consuming approaches. In this work, a novel electrochemical detection platform was established by integrating an organic electrochemical transistor (OECT) with a microfluidic chip and applied for trace measurement of DAS. The sensing unit is a gate electrode in the OECT modified with molecularly imprinted polymers (MIPs), which can be used as an artificial receptor to realize label-free detection. The high specific recognition ability of MIPs films combined with the amplified function of an OECT yielded a highly sensitive and selective electrochemical detection chip. The integrated microfluidic channel controlledthe exact amount of solution to be delivered and provided real-time detection of DAS. The experimental results indicated that changes in channel current was proportional to DAS concentrations from 1 nM to 10 μM, with the detection limits of 0.8 nM. It is the first demonstration of the integration of a microfluidic system with a MIP-gated OECT for real-time tumor marker detection. The study results of this work helped to develop Point-Of-Care (POC) tools for the early diagnosis of lung cancer, colon cancer and breast cancer.

A High-Throughput Screening Strategy for Synthesizing Molecularly Imprinted Polymer Nanoparticles Selectively Targeting Tumors.

Molecularly imprinted polymers (MIPs) show significant promise as effective alternatives to antibodies in disease diagnosis and therapy. However, the challenging process of screening extensive libraries of monomer combinations and synthesis conditions to identify formulations with enhanced selectivity and affinity presents a notable time constraint. The need for expedient methods becomes clear in accelerating the strategic development of MIPs tailored for precise molecular recognition purposes. In this study, an innovative high-throughput screening methodology designed to identify the optimal MIP formulation for targeting tumors is presented. Employing a microtiter plate format, over 100 polymer syntheses are conducted, incorporating diverse combinations of functional monomers. Evaluation of binding performance utilizes fluorescence-based assays, focusing on an epitope of the epidermal growth factor receptor (EGFR). Through this meticulously structured screening process, synthesis conditions that produced MIP nanoparticles exhibiting substantial specificity for EGFR targeting (KD = 10-12m) are identified. These "bionic antibodies" demonstrate selective recognition of cancer cells in whole blood samples, even at concentrations as low as 5cellsmL-1. Further validation through fluorescent imaging confirms the tumor-specific localization of the MIPs in vivo. This highly efficient screening approach facilitates the strategic synthesis of imprinted polymers functioning as precision bioprobes.