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1.
Biosens Bioelectron ; 264: 116645, 2024 Nov 15.
Article in English | MEDLINE | ID: mdl-39142228

ABSTRACT

L-tyrosine is a recognized biomarker of albinism, whose endogenous level in human bodies is directly linked to melanin synthesis while no attention has been paid to its specific diagnosis. To this end, we have developed an electrochemical point-of-care testing device based on a molecularly imprinted gel prepared by a universal paradigm shift design to achieve the enhanced specific recognition of the L-tyrosine. Interestingly, this theoretically optimized molecularly imprinted gel validates the recognition pattern of L-tyrosine and optimizes the structure of the polymer itself with the aid of computational chemistry. Besides, modified extended-layer MXene and Au nanoclusters have significantly improved the sensing activity. As a result, the linear diagnostic range of this electrochemical point-of-care testing device for L-tyrosine is 0.1-100 µM in actual human fluids, which fully covers the L-tyrosine levels of healthy individuals and people with albinism. The diagnosis is completed in 90 s and then the results are transmitted by Bluetooth low energy to the smart mobile terminal. Therefore, we are convinced that this electrochemical point-of-care testing device is a promising tool in the future smart medical system.


Subject(s)
Albinism , Biomarkers , Biosensing Techniques , Electrochemical Techniques , Gold , Point-of-Care Testing , Tyrosine , Humans , Biosensing Techniques/instrumentation , Biosensing Techniques/methods , Biomarkers/analysis , Biomarkers/blood , Electrochemical Techniques/instrumentation , Electrochemical Techniques/methods , Tyrosine/analysis , Tyrosine/blood , Gold/chemistry , Albinism/diagnosis , Equipment Design , Molecular Imprinting/methods , Metal Nanoparticles/chemistry , Limit of Detection , Point-of-Care Systems
2.
Biomacromolecules ; 25(9): 6188-6194, 2024 Sep 09.
Article in English | MEDLINE | ID: mdl-39092916

ABSTRACT

Sequence-selective binding of peptides has been a long-standing goal of chemists. As one of the most abundant amino acids in proteins, lysine plays an important role in protein functions as well as in antimicrobial and cell-penetrating peptides. Herein, we report molecularly imprinted nanoparticles (NPs) with high sequence selectivity for lysine-rich peptides. The NPs are prepared from molecular imprinting of cross-linkable surfactant micelles and postmodification of the imprinted pockets by photoaffinity labeling. The method allows carboxylic acids to be installed precisely near the lysine amino side chains, greatly enhancing the binding strengths of lysine-rich peptides. Small variations in the peptide sequence can be distinguished, and the binding affinity correlates positively with the number of lysine groups in model tripeptides. The method applies to complex lysine-rich biological peptides, achieving hundreds of nanomolar binding affinities and excellent binding specificities.


Subject(s)
Lysine , Molecular Imprinting , Nanoparticles , Peptides , Lysine/chemistry , Nanoparticles/chemistry , Molecular Imprinting/methods , Peptides/chemistry , Micelles
3.
Anal Chim Acta ; 1320: 343002, 2024 Sep 01.
Article in English | MEDLINE | ID: mdl-39142781

ABSTRACT

BACKGROUND: Rapid and sensitive detection of foodborne pathogens in food plays a crucial role in controlling outbreaks of foodborne diseases, of which Listeria monocytogenes and Salmonella typhimurium are representative and notable pathogens. Thus, it's of great importance to achieve the effective detection of these pathogens. However, the most common detection methods (culture-based technique, Polymerase Chain Reaction and immunological methods) have disadvantages that cannot be ignored, such as time-consuming, laborious, complex sample preparation process, and the possibility of cross-reaction. Hence, it is essential to develop a facile detection method for the pathogens with high sensitivity and specificity to avoid the above-mentioned disadvantages. RESULTS: We report a label-free visual platform for the simultaneous capture and detection of Listeria monocytogenes and Salmonella typhimurium. For the first time, we have prepared polydimethylsiloxane-Chromotrope 2R membrane which serves as the substrate for bacterial capture and enrichment through the formation of specific recognition sites. The positively charged Pt-covalent organic framework combines with the pathogens through surface charge interaction, thereby the label-free sandwich platform is formed. Remarkable peroxidase activity of Pt-covalent organic framework converts the conversion of bacterial quantity into amplified color signal by catalyzing 3,3',5,5'-Tetramethylbenzidine to oxidized 3,3',5,5'-Tetramethylbenzidine. The platform demonstrates the capability to identify two representative food-borne pathogens within a time frame of 100 min, exhibiting high sensitivity and excellent specificity without the interference from non-target bacteria. The limit of detection of the visual platform toward Listeria monocytogenes and Salmonella typhimurium was 1.61 CFU mL-1 and 1.31 CFU mL-1, respectively. And the limit of quantification toward Listeria monocytogenes and Salmonella typhimurium was 4.94 CFU mL-1 and 2.47 CFU mL-1, respectively. The relative standard derivations of the visual platform for both bacteria were lower than 4.9 %. Furthermore, our proposed platform has obtained reliable and satisfactory results on analyzing diverse food samples. SIGNIFICANCE: This research expands the application of a label-free platform combined with unlabeled nanocomponents in the rapid isolation and detection of diverse of food-borne pathogens. The platform possesses the advantages of simple operation and real-time monitoring, without complicated sample pretreatment process. The whole detection process can realize the simultaneous monitoring of Listeria monocytogenes and Salmonella typhimurium within 100 min. Furthermore, it is also of reference significance for the detection of other common pathogens.


Subject(s)
Food Microbiology , Listeria monocytogenes , Metal-Organic Frameworks , Molecular Imprinting , Salmonella typhimurium , Molecular Imprinting/methods , Metal-Organic Frameworks/chemistry , Food Microbiology/methods , Listeria monocytogenes/chemistry , Listeria monocytogenes/isolation & purification , Listeria monocytogenes/metabolism , Salmonella typhimurium/chemistry , Salmonella typhimurium/isolation & purification , Salmonella typhimurium/metabolism , Benzidines/chemistry , Benzidines/metabolism , Platinum/chemistry
4.
Compr Rev Food Sci Food Saf ; 23(4): e13399, 2024 Jul.
Article in English | MEDLINE | ID: mdl-39072953

ABSTRACT

Milk, as a widely consumed nutrient-rich food, is crucial for bone health, growth, and overall nutrition. The persistent application of veterinary drugs for controlling diseases and heightening milk yield has imparted substantial repercussions on human health and environmental ecosystems. Due to the high demand, fresh consumption, complex composition of milk, and the potential adverse impacts of drug residues, advanced greener analytical methods are necessitated. Among them, functional materials-based analytical methods attract wide concerns. The magnetic molecularly imprinted polymers (MMIPs), as a kind of typical functional material, possess excellent greenification characteristics and potencies, and they are easily integrated into various detection technologies, which have offered green approaches toward analytes such as veterinary drugs in milk. Despite their increasing applications and great potential, MMIPs' use in dairy matrices remains underexplored, especially regarding ecological sustainability. This work reviews recent advances in MMIPs' synthesis and application as efficient sorbents for veterinary drug extraction in milk followed by chromatographic analysis. The uniqueness and effectiveness of MMIPs in real milk samples are evaluated, current limitations are addressed, and greenification opportunities are proposed. MMIPs show promise in revolutionizing green analytical procedures for veterinary drug detection, aligning with the environmental goals of modern food production systems.


Subject(s)
Drug Residues , Green Chemistry Technology , Milk , Molecularly Imprinted Polymers , Veterinary Drugs , Milk/chemistry , Drug Residues/analysis , Drug Residues/chemistry , Molecularly Imprinted Polymers/chemistry , Animals , Veterinary Drugs/analysis , Veterinary Drugs/chemistry , Green Chemistry Technology/methods , Food Contamination/analysis , Molecular Imprinting/methods , Chromatography/methods
5.
Biosens Bioelectron ; 262: 116570, 2024 Oct 15.
Article in English | MEDLINE | ID: mdl-39018980

ABSTRACT

Molecularly imprinted polymers (MIP) have been widely owing to their specificity, however, their singular structure imposes limitations on their performance. Current enhancement methods, such as doping with inorganic nanomaterials or introducing various functional monomers, are limited and single, indicating that MIP performances require further advancement. In this work, a dual-modification approach that integrates both conductive inorganic nanomaterials and diverse bifunctional monomers was proposed to develop a multifunctional MIP-based electrochemical (MMIP-EC) sensor for diuron (DU) detection. The MMIP was synthesized through a one-step electrochemical copolymerization of silver nanowires (AgNWs), o-phenylenediamine (O-PD), and 3,4-ethylenedioxythiophene (EDOT). DU molecules could conduct fluent electron transfer within the MMIP layer through the interaction between anchored AgNWs and bifunctional monomers, and the abundant recognition sites and complementary cavity shapes ensured that the imprinted cavities exhibit high specificity. The current intensity amplified by the two modification strategies of MMIP (3.7 times) was significantly higher than the sum of their individual values (3.2 times), exerting a synergistic effect. Furthermore, the adsorption performance of the MMIP was characterized by examining the kinetics and isotherms of the adsorption process. Under optimal conditions, the MMIP-EC sensor exhibits a wide linear range (0.2 ng/mL to 10 µg/mL) for DU detection, with a low detection limit of 89 pg/mL and excellent selectivity (an imprinted factor of 10.4). In summary, the present study affords innovative perspectives for the fabrication of MIP-EC sensor with superior analytical performance.


Subject(s)
Biosensing Techniques , Diuron , Electrochemical Techniques , Limit of Detection , Molecularly Imprinted Polymers , Nanowires , Silver , Nanowires/chemistry , Biosensing Techniques/methods , Silver/chemistry , Electrochemical Techniques/methods , Molecularly Imprinted Polymers/chemistry , Diuron/analysis , Diuron/isolation & purification , Molecular Imprinting/methods , Polymers/chemistry , Phenylenediamines/chemistry , Herbicides/analysis , Herbicides/chemistry
6.
Langmuir ; 40(31): 16291-16302, 2024 Aug 06.
Article in English | MEDLINE | ID: mdl-39041625

ABSTRACT

Carboxymethyl Salix psammophila wood powder-imprinted membranes (CMSM-MIPs) were prepared by using wet spinning technology and molecular-imprinting technology for the selective removal of tetracycline from wastewater. Scanning electron microscopy, X-ray diffraction, thermogravimetry, and X-ray photoelectron spectroscopy characterizations demonstrate that CMSM-MIPs retain the membranous structure of Carboxymethyl Salix psammophila wood powder membranes, successfully encapsulate thin layers of imprinted polymers on the membrane surface, and exhibit excellent thermal stability. The adsorption results showed that CMSM-MIPs had the highest selective adsorption capacity for tetracycline, which was 253.8 mg/g. In addition, the adsorption capacities for oxytetracycline and chlortetracycline were 208.8 and 188 mg/g, respectively. It can be observed that CMSM-MIPs not only exhibit a high adsorption capacity for tetracycline but also demonstrate good adsorption capacities for oxytetracycline and chlortetracycline. The experimental results showed that CMSM-MIPs were best fitted with pseudo-second-order kinetics and most consistent with Freundlich fitting. The regeneration experiment showed that CMSM-MIPs still had good regeneration performance after 5 regeneration cycles. In conclusion, the CMSM-MIPs can not only have the natural adsorption performance of Salix psammophila wood powder but also give it higher selectivity through molecular imprinting, so as to achieve efficient removal of target organic pollutants in water.


Subject(s)
Salix , Tetracycline , Wood , Adsorption , Wood/chemistry , Tetracycline/chemistry , Tetracycline/isolation & purification , Salix/chemistry , Powders/chemistry , Membranes, Artificial , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Molecular Imprinting/methods , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/isolation & purification
7.
J Chromatogr A ; 1731: 465196, 2024 Aug 30.
Article in English | MEDLINE | ID: mdl-39047444

ABSTRACT

Magnetic multi-template molecularly imprinted polymers (M-mt-MIPs) were successfully synthesized by surface imprinting and multi-template imprinting strategy, using polydopamine coated magnetic multi-walled carbon nanotubes as supporting materials, five typical chlorophenols (CPs) as templates, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linker. Compared to non-imprinted polymers (NIPs), the as-prepared M-mt-MIPs showed high adsorption capacity (32.58‒80.63 mg g-1), rapid mass transfer and specific selectivity for the five targeted CPs, which were applied as magnetic solid-phase extraction (MSPE) adsorbents. Parameters affecting MSPE efficiency were detailed investigated, such as adsorbents dosage, sample pH, extraction time, type and volume of desorption solvent and salt effect. Combined with HPLC-DAD, a simple, rapid and sensitive method was established, showing good linearity (2‒200 µg L-1), low limits of detection (0.32‒0.49 µg L-1), and high enrichment factors (35.2‒108). The developed M-mt-MIPs-MSPE-HPLC method was applied to enrich and determine CPs in tannery wastewater, wet-blue and crust leather, and satisfactory spiking recoveries were attained in the range of 73.95‒109.7% with relative standard deviations (RSDs) of 2.13-8.48%. This study provided a new alternative material and method to rapid simultaneously extract and analyze low concentration of typical CPs in complicated matrices.


Subject(s)
Chlorophenols , Molecularly Imprinted Polymers , Solid Phase Extraction , Chromatography, High Pressure Liquid/methods , Chlorophenols/analysis , Chlorophenols/isolation & purification , Molecularly Imprinted Polymers/chemistry , Solid Phase Extraction/methods , Adsorption , Limit of Detection , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/isolation & purification , Water Pollutants, Chemical/chemistry , Molecular Imprinting/methods , Nanotubes, Carbon/chemistry , Wastewater/chemistry , Polymers/chemistry , Indoles
8.
J Mol Model ; 30(8): 266, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-39007951

ABSTRACT

CONTEXT: Molecularly imprinted polymers (MIPs) have promising applications as synthetic antibodies for protein and peptide recognition. A critical aspect of MIP design is the selection of functional monomers and their adequate proportions to achieve materials with high recognition capacity toward their targets. To contribute to this goal, we calibrated a molecular dynamics protocol to reproduce the experimental trends in peptide recognition of 13 pre-polymerization mixtures reported in the literature for the peptide toxin melittin. METHODS: Three simulation conditions were tested for each mixture by changing the box size and the number of monomers and cross-linkers surrounding the template in a solvent-explicit environment. Fully atomistic MD simulations of 350 ns were conducted with the AMBER20 software, with ff19SB parameters for the peptide, gaff2 parameters for the monomers and cross-linkers, and the OPC water model. Template-monomer interaction energies under the LIE approach showed significant differences between high-affinity and low-affinity mixtures. Simulation systems containing 100 monomers plus cross-linkers in a cubic box of 90 Å3 successfully ranked the mixtures according to their experimental performance. Systems with higher monomer densities resulted in non-specific intermolecular contacts that could not account for the experimental trends in melittin recognition. The mixture with the best recognition capacity showed preferential binding to the 13-26-α-helix, suggesting a relevant role for this segment in melittin imprinting and recognition. Our findings provide insightful information to assist the computational design of molecularly imprinted materials with a validated protocol that can be easily extended to other templates.


Subject(s)
Molecular Dynamics Simulation , Peptides , Peptides/chemistry , Melitten/chemistry , Polymerization , Molecularly Imprinted Polymers/chemistry , Molecular Imprinting/methods
9.
J Chromatogr A ; 1731: 465193, 2024 Aug 30.
Article in English | MEDLINE | ID: mdl-39047446

ABSTRACT

A pH/temperature bi-responsive gallic acid magnetic imprinted polymer (PTBG-MIP) was synthesized on a Fe3O4@SiO2@KH570 carrier using methacrylic acid (MAA), p-Vinylphenylboronic acid (p-VPBA), and N-isopropyl-acrylamide (NIPAAm) as complex functional monomers. The density functional theory (DFT) was employed to optimize the molar ratio of multi-functional monomers-template complex, which proved to be an effective tool for predicting complex configuration based on electrostatic potential (ESP) analysis and the lowest binding energy. DFT calculation and analysis determined the optimized molar ratio of 2:1:1:1 for GA-MAA-NIPAAm-p-VPBA, which showed good agreement with experimental results. The PTBG-MIP-4 obtained under the optimized conditions exhibited high pH- and temperature- dependence in rebinding the template, displaying a maximum adsorption capacity (Qe) of 62.26 mg g-1 and a highest selection factor (α) of 5.217. Additionally, the PTBG-MIP-4 exhibited exceptional physicochemical properties encompassing magnetization characteristics, morphology, surface sites distribution, and adsorption performance. The application efficiency of this imprinted composite in the extraction and purification of gallic acid from Galla chinensis was remarkably demonstrated.


Subject(s)
Drugs, Chinese Herbal , Gallic Acid , Tannins , Temperature , Acrylamides/chemistry , Adsorption , Biological Products/chemistry , Biological Products/chemical synthesis , Drugs, Chinese Herbal/chemistry , Gallic Acid/chemistry , Gallic Acid/isolation & purification , Hydrogen-Ion Concentration , Molecular Imprinting/methods , Molecularly Imprinted Polymers/chemistry , Polymers/chemistry , Polymers/chemical synthesis , Silicon Dioxide/chemistry , Solid Phase Extraction/methods , Tannins/chemistry
10.
Talanta ; 279: 126558, 2024 Nov 01.
Article in English | MEDLINE | ID: mdl-39047630

ABSTRACT

Although membrane technology has demonstrated outstanding pathogen removal capabilities, current commercial membranes are insufficient for removing small viruses at trace levels due to certain limitations. The theoretical and practical significance of developing a new form of hydrophilic, anti-fouling, and virus-specific ultra-purification membrane with high capturing and separation efficiency, stability, and throughput for water treatment is of the utmost importance. In this study, molecularly imprinted membranes (MIMs) were fabricated from polyvinylidene fluoride (PVDF) membranes utilizing novel surface hydrophilic modification techniques, followed by the immobilization of virus-specific molecularly imprinted nanoparticles (nanoMIPs) as synthetic receptors. Three distinct membrane functionalization strategies were established and optimized for the first time: membrane functionalization with (i) polyethyleneimine (PEI) and dopamine (DOP), (ii) PEI and 3-(chloropropyl)-trimethoxysilane (CTS), and (iii) chitosan (CS). Hydrophilicity was enhanced significantly as a result of these modification strategies. Additionally, the modifications enabled spacer arms between the membrane surface and the nanoMIPs to decrease steric hindrance. The surface chemistry, morphology, and membrane performance results from the characterization analysis of the MIMs demonstrated excellent hydrophilicity (e.g., the functionalized membrane presented 37.84° while the unmodified bare membrane exhibited 128.94° of water contact angle), higher permeation flux (145.96 L m-2 h-1 for the functionalized membrane), excellent uptake capacity (up to 99.99 % for PEI-DOP-MIM and CS-MIM), and recovery (more than 80 % for PEI-DOP-MIM). As proof of concept, the cutting-edge MIMs were able to eliminate the model adenoviruses up to 99.99 % from water. The findings indicate that the novel functionalized PVDF membranes hold promise for implementation in practical applications for virus capture and separation.


Subject(s)
Membranes, Artificial , Polyvinyls , Surface Properties , Ultrafiltration , Polyvinyls/chemistry , Ultrafiltration/methods , Hydrophobic and Hydrophilic Interactions , Viruses/isolation & purification , Molecular Imprinting/methods , Polyethyleneimine/chemistry , Water Purification/methods , Nanoparticles/chemistry , Fluorocarbon Polymers
11.
Int J Biol Macromol ; 277(Pt 2): 134137, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39067725

ABSTRACT

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.


Subject(s)
Aniline Compounds , Electrochemical Techniques , Food Safety , Molecular Imprinting , Serum Albumin, Bovine , Animals , Cattle , Aniline Compounds/chemistry , Biosensing Techniques/methods , Electrochemical Techniques/methods , Food Safety/methods , Limit of Detection , Milk/chemistry , Molecular Imprinting/methods , Molecularly Imprinted Polymers/chemistry , Serum Albumin, Bovine/chemistry
12.
Spectrochim Acta A Mol Biomol Spectrosc ; 322: 124813, 2024 Dec 05.
Article in English | MEDLINE | ID: mdl-39018673

ABSTRACT

Glycoproteins are difficult to be detected by imprinting strategy due to their low natural abundance, high flexible conformation and large size. Herein, a high-density boric acid modified metal-organic framework (MOF) surface molecularly imprinted polymer (SMIP) resonant light scattering sensor was constructed for the high-sensitivity detection of target glycoproteins. A MOF with large specific surface area was selected as the substrate material to support the boric acid group with high loading density (4.66 %). The introduction of the boric acid group in the SMIP provided a high-affinity binding site for the recognition and binding of glycoproteins. Shallow surface cavities with rapid mass transfer (equilibrium time 20 min) were thus formed by surface imprinting. Furthermore, high sensitivity (limit of detection 15 pM) was achieved at physiological pH (7.4), which was conducive to the detection of glycoproteins with low natural abundance in complex biological samples and maintaining physiological activity.


Subject(s)
Boric Acids , Glycoproteins , Metal-Organic Frameworks , Molecularly Imprinted Polymers , Metal-Organic Frameworks/chemistry , Boric Acids/chemistry , Glycoproteins/analysis , Glycoproteins/chemistry , Molecularly Imprinted Polymers/chemistry , Limit of Detection , Light , Molecular Imprinting/methods , Scattering, Radiation , Hydrogen-Ion Concentration
13.
Nano Lett ; 24(28): 8763-8769, 2024 Jul 17.
Article in English | MEDLINE | ID: mdl-38976835

ABSTRACT

Lysine is one of the most abundant residues on the surface of proteins and its site-selective functionalization is extremely challenging. The existing methods of functionalization rely on differential reactivities of lysine on a protein, making it impossible to label less reactive lysines selectively. We here report polymeric nanoparticles that mimic enzymes involved in the posttranslational modifications of proteins that distinguish the chemical and supramolecular contexts of a lysine and deliver the labeling reagent precisely to its ε amino group. The nanoparticles are prepared through molecular imprinting of cross-linkable surfactant micelles, plus an in situ, on-micelle derivatization of the peptide template prior to the imprinting. The procedures encode the polymeric nanoparticles with all the supramolecular information needed for sequence identification and precise labeling, allowing single-site functionalization of a predetermined lysine on the target protein in a mixture.


Subject(s)
Lysine , Nanoparticles , Proteins , Lysine/chemistry , Nanoparticles/chemistry , Proteins/chemistry , Micelles , Molecular Imprinting/methods , Polymers/chemistry , Peptides/chemistry , Protein Processing, Post-Translational
14.
J Chromatogr A ; 1730: 465138, 2024 Aug 16.
Article in English | MEDLINE | ID: mdl-38970874

ABSTRACT

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.


Subject(s)
Aptamers, Nucleotide , Estradiol , Limit of Detection , Molecular Imprinting , Molecularly Imprinted Polymers , Solid Phase Microextraction , Solid Phase Microextraction/methods , Estradiol/analysis , Estradiol/chemistry , Estradiol/isolation & purification , Animals , Aptamers, Nucleotide/chemistry , Molecular Imprinting/methods , Adsorption , Molecularly Imprinted Polymers/chemistry , Meat/analysis , Chromatography, High Pressure Liquid/methods , Polymers/chemistry , Chickens , Reproducibility of Results
15.
Int J Biol Macromol ; 275(Pt 1): 133384, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38917927

ABSTRACT

This study introduces a novel approach for the separation of indacrinone (IC) enantiomers, crucial in treating edema, hypertension, and hyperuricemia. A cationic biopolymer from furan-2-ylmethylhydrazine-cellulose (FUH-CE), derived from cyanoethyl cellulose (CEC), serving as a substrate in molecular imprinting. A key innovation is the use of the Diels-Alder reaction for efficient cross-linking with bis(maleimido)ethane (BME). This chemical strategy resulted in molecularly imprinted microparticles with high selectivity for the S-IC enantiomer, which can be eluted by adjusting the solution's pH. Extensive characterization confirmed the chemical modifications and selective binding efficacy of these biopolymers. Utilizing separation columns, our method achieved an impressive chiral resolution of (±)-IC, with an enantiomeric excess (ee) of 95 % for R-IC during the loading phase and 97 % for S-IC during elution. Under optimized conditions, the biopolymer demonstrated a maximum binding capacity of 131 mg/g at pH 6. This advanced approach represents a significant advancement in chiral separation technology, offering a robust and efficient technique for the selective isolation of enantiomers. This method not only enhances potential targeted therapeutic applications but also provides a scalable solution for industrial chiral separations.


Subject(s)
Cellulose , Cycloaddition Reaction , Furans , Molecular Imprinting , Furans/chemistry , Cellulose/chemistry , Cellulose/analogs & derivatives , Stereoisomerism , Molecular Imprinting/methods , Cations/chemistry , Hydrogen-Ion Concentration
16.
J Chromatogr A ; 1730: 465106, 2024 Aug 16.
Article in English | MEDLINE | ID: mdl-38917678

ABSTRACT

Detecting and quantifying amino acids is vital in biochemical analyses, especially for diagnosing metabolic disorders. L-proline, among these amino acids, holds significant relevance for various metabolic disorders in living organisms, particularly in humans. hyperprolinemia arises when ineffective breakdown of L-proline occurs due to enzyme deficiencies, leading to its accumulation in the body and underscoring the need for precise monitoring. To address this challenge, molecular imprinting offers a reliable single-step technique for detecting target molecules like proteins, peptides, amino acids, or ions with high selectivity. Moreover, nanoparticles, with significant surface area-to-volume ratios, enable high-level mass transfer and binding kinetics, making them ideal for nano-scale sensitive applications. In this study, 2-hydroxyethyl methacrylate-based molecularly imprinted nanoparticles were synthesized via mini-emulsion polymerization, combining the advantages of molecular imprinting technique and nanoparticles for the specific recognition of L-proline, and were well-characterized by Scanning Electron Microscopy, zeta-sizer particle size analysis, and Fourier Transform Infrared Spectroscopy. Based on zeta-sizer analysis, the estimated diameters of L-proline-imprinted and non-imprinted nanoparticles (Pro-MIPs and NIPs) were determined to be approximately 27.51 nm and 20.66 nm, respectively. The adsorption of L-proline onto nanoparticles from aqueous solutions was investigated in a batch system, and the maximum L-proline adsorption capacity was determined to be 26.58 mg/g for Pro-MIPs and 4.65 mg/g for and NIPs. The selectivity of Pro-MIPs was assessed using Liquid Chromatography-Tandem Mass Spectrometry, even in human serum and in the presence of competing molecules (L-histidine and L-phenylalanine). Additionally, Pro-MIPs maintained their adsorption capacity through up to 10 adsorption-desorption cycles without significant decrease.


Subject(s)
Molecular Imprinting , Nanoparticles , Proline , Proline/chemistry , Molecular Imprinting/methods , Humans , Nanoparticles/chemistry , Adsorption , Metabolic Diseases/diagnosis , Methacrylates/chemistry , Chromatography, High Pressure Liquid/methods , Limit of Detection , Particle Size , Molecularly Imprinted Polymers/chemistry
17.
Carbohydr Polym ; 339: 122257, 2024 Sep 01.
Article in English | MEDLINE | ID: mdl-38823923

ABSTRACT

Traditional solid phase extraction (SPE) suffers from a lack of specific adsorption. To overcome this problem, a combination of adsorption method and molecular imprinting technology by polydopamine modification was proposed to realize specific recognition of target compounds in SPE, which is of great significance to improve the separation efficiency of SPE. Cellulose hydrogel beads were prepared by dual cross-linking curing method and modified with polydopamine to make them hydrophilic and biocompatible. Subsequently, cellulose hydrogel-based molecularly imprinted beads (MIBs) were synthesized by surface molecular imprinting technology and used as novel column fillers in SPE to achieve efficient adsorption (34.16 mg·g-1) with specific selectivity towards camptothecin (CPT) in 120 min. The simulation and NMR analysis revealed that recognition mechanism of MIBs involved hydrogen bond interactions and Van der Waals effect. The MIBs were successful used in separating CPT from Camptotheca acuminata fruits, exhibiting impressive adsorption capacity (1.19 mg·g-1) and efficient recovery of CPT (81.54 %). Thus, an environmentally friendly column filler for SPE was developed, offering a promising avenue for utilizing cellulose-based materials in the selective separation of natural products.


Subject(s)
Camptothecin , Cellulose , Hydrogels , Molecular Imprinting , Solid Phase Extraction , Camptothecin/chemistry , Camptothecin/isolation & purification , Cellulose/chemistry , Adsorption , Molecular Imprinting/methods , Hydrogels/chemistry , Solid Phase Extraction/methods , Camptotheca/chemistry , Polymers/chemistry , Hydrophobic and Hydrophilic Interactions , Indoles/chemistry , Fruit/chemistry
18.
Biosens Bioelectron ; 261: 116491, 2024 Oct 01.
Article in English | MEDLINE | ID: mdl-38879900

ABSTRACT

As one class of molecular imprinted polymers (MIPs), surface imprinted polymer (SIP)-based biosensors show great potential in direct whole-bacteria detection. Micro-contact imprinting, that involves stamping the template bacteria immobilized on a substrate into a pre-polymerized polymer matrix, is the most straightforward and prominent method to obtain SIP-based biosensors. However, the major drawbacks of the method arise from the requirement for fresh template bacteria and often non-reproducible bacteria distribution on the stamp substrate. Herein, we developed a positive master stamp containing photolithographic mimics of the template bacteria (E. coli) enabling reproducible fabrication of biomimetic SIP-based biosensors without the need for the "real" bacteria cells. By using atomic force and scanning electron microscopy imaging techniques, respectively, the E. coli-capturing ability of the SIP samples was tested, and compared with non-imprinted polymer (NIP)-based samples and control SIP samples, in which the cavity geometry does not match with E. coli cells. It was revealed that the presence of the biomimetic E. coli imprints with a specifically designed geometry increases the sensor E. coli-capturing ability by an "imprinting factor" of about 3. These findings show the importance of geometry-guided physical recognition in bacterial detection using SIP-based biosensors. In addition, this imprinting strategy was employed to interdigitated electrodes and QCM (quartz crystal microbalance) chips. E. coli detection performance of the sensors was demonstrated with electrochemical impedance spectroscopy (EIS) and QCM measurements with dissipation monitoring technique (QCM-D).


Subject(s)
Bacterial Adhesion , Biosensing Techniques , Escherichia coli , Polymers , Escherichia coli/isolation & purification , Polymers/chemistry , Molecular Imprinting/methods , Surface Properties , Molecularly Imprinted Polymers/chemistry , Escherichia coli Infections/microbiology , Biomimetic Materials/chemistry
19.
Anal Methods ; 16(27): 4524-4533, 2024 Jul 11.
Article in English | MEDLINE | ID: mdl-38913021

ABSTRACT

Taking into account the drug resistance of antibiotics, teicoplanin has been banned in the veterinary field. Also, it brings threat to people's health when they eat foods containing teicoplanin residue. In addition, the abuse of teicoplanin in humans and food animals also poses a potential risk to water. Therefore, it is crucial to purify teicoplanin from food before quantifying its amount. In this study, researchers employed boronate affinity-based controlled oriented surface imprinting technique to produce molecularly imprinted polymers (MIPs) for the isolation of teicoplanin. The 3-fluoro-4-formylphenylboronic acid-functionalized silica nanoparticle substrate was first used as the supporting material for immobilizing teicoplanin. Next, the substrate surface was coated with an imprinting coating whose thickness could be controlled, produced through the self-copolymerization of dopamine and m-aminophenylboronic acid (APBA) in water. After the template was removed, 3D cavities that matched the template were created in the imprinting layer. The prepared teicoplanin-imprinted silica nanoparticles exhibited several significant satisfactory results such as good specificity, high binding capacity (46.9 ± 2.3 mg g-1), moderate binding constant ((5.46 ± 0.18) × 10-5 M-1), fast kinetics (8 min) and low binding pH (pH 5.0) toward teicoplanin. The teicoplanin-imprinted silica nanoparticles could still be reused after seven cycles of adsorption-desorption, which indicated a high chemical stability. In addition, recoveries of the proposed method for teicoplanin at three spiked levels in milk and water ranged from 91.8 to 105.6% and 92.3 to 97.4%, respectively. The teicoplanin-imprinted silica nanoparticles are capable of identifying the target teicoplanin in real samples in a simple, fast, selective and efficient manner.


Subject(s)
Anti-Bacterial Agents , Boronic Acids , Molecular Imprinting , Nanoparticles , Silicon Dioxide , Teicoplanin , Silicon Dioxide/chemistry , Boronic Acids/chemistry , Nanoparticles/chemistry , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/analysis , Teicoplanin/chemistry , Molecular Imprinting/methods , Food Contamination/analysis , Water/chemistry , Glycopeptides/chemistry , Glycopeptides/analysis , Adsorption , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry
20.
Molecules ; 29(11)2024 May 25.
Article in English | MEDLINE | ID: mdl-38893376

ABSTRACT

Ellagic acid (EA) is a natural polyphenol and possesses excellent in vivo bioactivity and antioxidant behaviors, which play an important role in the treatment of oxidative stress-related diseases, such as cancer. Additionally, EA is also known as a skin-whitening ingredient. The content of EA would determine its efficacy. Therefore, the accurate analysis of EA content can provide more information for the scientific consumption of EA-rich foods and cosmetics. Nevertheless, the analysis of EA in these samples is challenging due to the low concentration level and the presence of interfering components with high abundance. Molecularly imprinted polymers are highly efficient pretreatment materials in achieving specific recognition of target molecules. However, the traditional template molecule (EA) could not be absolutely removed. Hence, template leakage continues to occur during the sample preparation process, leading to a lack of accuracy in the quantification of EA in actual samples, particularly for trace analytes. In addition, another drawback of EA as an imprinting template is that EA possesses poor solubility and a high price. Gallic acid (GA), called dummy templates, was employed for the synthesis of MIPs as a solution to these challenges. The approach used in this study was boronate affinity-based oriented surface imprinting. The prepared dummy-imprinted nanoparticles exhibited several significant advantages, such as good specificity, high binding affinity ((4.89 ± 0.46) × 10-5 M), high binding capacity (6.56 ± 0.35 mg/g), fast kinetics (6 min), and low binding pH (pH 5.0) toward EA. The reproducibility of the dummy-imprinted nanoparticles was satisfactory. The dummy-imprinted nanoparticles could still be reused even after six adsorption-desorption cycles. In addition, the recoveries of the proposed method for EA at three spiked levels of analysis in strawberry and pineapple were 91.0-106.8% and 93.8-104.0%, respectively, which indicated the successful application to real samples.


Subject(s)
Ellagic Acid , Molecular Imprinting , Solid Phase Extraction , Ellagic Acid/chemistry , Solid Phase Extraction/methods , Molecular Imprinting/methods , Boronic Acids/chemistry , Molecularly Imprinted Polymers/chemistry , Food Analysis/methods , Nanostructures/chemistry
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