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1.
Sci Rep ; 14(1): 10293, 2024 05 04.
Artículo en Inglés | MEDLINE | ID: mdl-38704412

RESUMEN

In this study, a sensitive and selective fluorescent chemosensor was developed for the determination of pirimicarb pesticide by adopting the surface molecular imprinting approach. The magnetic molecularly imprinted polymer (MIP) nanocomposite was prepared using pirimicarb as the template molecule, CuFe2O4 nanoparticles, and graphene quantum dots as a fluorophore (MIP-CuFe2O4/GQDs). It was then characterized using X-ray diffraction (XRD) technique, Fourier transforms infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), and transmission electron microscopy (TEM). The response surface methodology (RSM) was also employed to optimize and estimate the effective parameters of pirimicarb adsorption by this polymer. According to the experimental results, the average particle size and imprinting factor (IF) of this polymer are 53.61 nm and 2.48, respectively. Moreover, this polymer has an excellent ability to adsorb pirimicarb with a removal percentage of 99.92 at pH = 7.54, initial pirimicarb concentration = 10.17 mg/L, polymer dosage = 840 mg/L, and contact time = 6.15 min. The detection of pirimicarb was performed by fluorescence spectroscopy at a concentration range of 0-50 mg/L, and a sensitivity of 15.808 a.u/mg and a limit of detection of 1.79 mg/L were obtained. Real samples with RSD less than 2 were measured using this chemosensor. Besides, the proposed chemosensor demonstrated remarkable selectivity by checking some other insecticides with similar and different molecular structures to pirimicarb, such as diazinon, deltamethrin, and chlorpyrifos.


Asunto(s)
Plaguicidas , Pirimidinas , Plaguicidas/análisis , Carbamatos/análisis , Carbamatos/química , Puntos Cuánticos/química , Polímeros Impresos Molecularmente/química , Polímeros/química , Espectrometría de Fluorescencia/métodos , Grafito/química , Impresión Molecular/métodos , Adsorción , Límite de Detección , Espectroscopía Infrarroja por Transformada de Fourier , Nanocompuestos/química , Nanocompuestos/ultraestructura
2.
Anal Biochem ; 691: 115551, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38702023

RESUMEN

A molecularly imprinted electrochemical sensor was facilely fabricated for the detection of thymol (THY). o-Phenylenediamine (oPD) was used as the functional monomer and electropolymerized on the surface of the glassy carbon electrode (GCE) by using THY as the templates. After the THY templates were removed with 50 % (v/v) ethanol, imprinted cavities complementary to the templates were formed within the poly(o-phenylenediamine) (PoPD) films. The resultant molecularly imprinted PoPD/GCE (MI-PoPD/GCE) was used for the detection of THY, and a wide linear range from 0.5 to 100 µM with a low limit of detection (LOD) of 0.084 µM were obtained under the optimal conditions. The developed MI-PoPD/GCE also displays high selectivity, reproducibility and stability for THY detection. Finally, the content of THY in the real samples was accurately determined by the as-fabricated MI-PoPD/GCE, demonstrating its high practicability and reliability.


Asunto(s)
Técnicas Electroquímicas , Impresión Molecular , Fenilendiaminas , Timol , Fenilendiaminas/química , Timol/análisis , Timol/química , Técnicas Electroquímicas/métodos , Límite de Detección , Electrodos , Polímeros Impresos Molecularmente/química , Carbono/química , Reproducibilidad de los Resultados
3.
J Chromatogr A ; 1725: 464876, 2024 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-38718697

RESUMEN

Herein, 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model template in a rational design strategy to produce water-compatible noncovalent imprinted microspheres. The proposed approach involved computational modelling for screening functional monomers and a simple method for preparing monodisperse and highly cross-linked microspheres. The fabricated non-imprinted polymer (NIP) and 2,4-d-imprinted polymer (2,4-d-MIP) were characterised, and their adsorption capabilities in an aqueous environment were evaluated. Results reveal that the pseudo-second-order kinetics model was appropriate for representing the adsorption of 2,4-D on NIP and 2,4-d-MIP, with R2 values of 0.97 and 0.99, respectively. The amount of 2,4-D adsorbed on 2,4-d-MIP (97.75 mg g-1) was considerably higher than those of phenoxyacetic acid (35.77 mg g-1), chlorogenic acid (9.72 mg g-1), spiramycin (1.56 mg g-1) and tylosin (1.67 mg g-1). Furthermore, it exhibited strong resistance to protein adsorption in an aqueous medium. These findings confirmed the feasibility of the proposed approach, providing a reference for the development of water-compatible noncovalent imprinted polymers.


Asunto(s)
Ácido 2,4-Diclorofenoxiacético , Microesferas , Impresión Molecular , Agua , Adsorción , Agua/química , Ácido 2,4-Diclorofenoxiacético/análisis , Ácido 2,4-Diclorofenoxiacético/química , Polímeros/química , Cinética , Polímeros Impresos Molecularmente/química
4.
Mikrochim Acta ; 191(6): 322, 2024 05 10.
Artículo en Inglés | MEDLINE | ID: mdl-38730044

RESUMEN

The first electrochemical sensor application in the literature is described for the sensitive and selective determination of the selective Janus kinase (JAK)-1 inhibitor abrocitinib (ABR). ABR is approved by the U.S. Food and Drug Administration (FDA) for the treatment of atopic dermatitis. The molecularly imprinted polymer (MIP)-based sensor was designed to incorporate zinc nanoflower (ZnNFs)-graphene oxide (GO) conjugate (ZnNFs@GO), synthesized from the root methanolic extract (RME) of the species Alkanna cappadocica Boiss. et Bal. to improve the porosity and effective surface area of the glassy carbon electrode (GCE). Furthermore, the MIP structure was prepared using ABR as a template molecule, 4-aminobenzoic acid (4-ABA) as a functional monomer, and other additional components. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) were used to characterize the surface and structure of the synthesized nanomaterial and MIP-based surface. Among the electrochemical methods, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were preferred for detailed electrochemical characterization, and differential pulse voltammetry (DPV) was preferred for all other electrochemical measurements using 5.0 mM [Fe(CN)6]3-/4- solution as the redox probe. The MIP-based sensor, which was the result of a detailed optimization phase, gave a linear response in the 1.0 × 10-13 - 1.0 × 10-12 M range in standard solution and serum sample. The obtained limit of detection (LOD) and limit of quantification (LOQ) values and recovery studies demonstrated the sensitivity, accuracy, and applicability of the sensor. Selectivity, the most important feature of the MIP-based sensor, was verified by imprinting factor calculations using ibrutinib, ruxolitinib, tofacitinib, zonisamide, and acetazolamide.


Asunto(s)
Técnicas Electroquímicas , Límite de Detección , Polímeros Impresos Molecularmente , Zinc , Polímeros Impresos Molecularmente/química , Técnicas Electroquímicas/métodos , Técnicas Electroquímicas/instrumentación , Zinc/química , Grafito/química , Humanos , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análisis , Aminoimidazol Carboxamida/sangre , Aminoimidazol Carboxamida/química , Nanoestructuras/química , Electrodos
5.
Int J Mol Sci ; 25(9)2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38731823

RESUMEN

This study presents the initial attempt at introducing a magnetic molecularly imprinted polymer (MIP) designed specifically for lamotrigine with the purpose of functioning as a drug carrier. First, the composition of the magnetic polymer underwent optimization based on bulk polymer adsorption studies and theoretical analyses. The magnetic MIP was synthesized from itaconic acid and ethylene glycol dimethacrylate exhibiting a drug loading capacity of 3.4 ± 0.9 µg g-1. Structural characterization was performed using powder X-ray diffraction analysis, vibrating sample magnetometry, and Fourier transform infrared spectroscopy. The resulting MIP demonstrated controlled drug released characteristics without a burst effect in the phospahe buffer saline at pH 5 and 8. These findings hold promise for the potential nasal administration of lamotrigine in future applications.


Asunto(s)
Portadores de Fármacos , Lamotrigina , Polímeros Impresos Molecularmente , Lamotrigina/química , Portadores de Fármacos/química , Polímeros Impresos Molecularmente/química , Polímeros Impresos Molecularmente/síntesis química , Impresión Molecular/métodos , Espectroscopía Infrarroja por Transformada de Fourier , Liberación de Fármacos , Difracción de Rayos X , Adsorción , Concentración de Iones de Hidrógeno
6.
J Chromatogr A ; 1726: 464977, 2024 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-38735117

RESUMEN

A magnetic molecularly imprinted polymer (MMIP) adsorbent incorporating amino-functionalized magnetite nanoparticles, nitrogen-doped graphene quantum dots and mesoporous carbon (MIP@MPC@N-GQDs@Fe3O4NH2) was fabricated to extract triazine herbicides from fruit juice. The embedded magnetite nanoparticles simplified the isolation of the adsorbent from the sample solution. The N-GQDs and MPC enhanced adsorption by affinity binding with triazines. The MIP layer provided highly specific recognition sites for the selective adsorption of three target triazines. The extracted triazines were determined by high-performance liquid chromatography (HPLC) coupled with diode-array detection (DAD). The developed method exhibited linearity from 1.5 to 100.0 µg L-1 with a detection limit of 0.5 µg L-1. Recoveries from spiked fruit juice samples were in the range of 80.1- 108.4 %, with a relative standard deviation of less than 6.0 %. The developed MMIP adsorbent demonstrated good selectivity, high extraction efficiency, ease of fabrication and use, and good stability.


Asunto(s)
Carbono , Jugos de Frutas y Vegetales , Herbicidas , Límite de Detección , Polímeros Impresos Molecularmente , Puntos Cuánticos , Triazinas , Puntos Cuánticos/química , Triazinas/química , Triazinas/análisis , Triazinas/aislamiento & purificación , Herbicidas/análisis , Herbicidas/aislamiento & purificación , Herbicidas/química , Jugos de Frutas y Vegetales/análisis , Adsorción , Polímeros Impresos Molecularmente/química , Carbono/química , Cromatografía Líquida de Alta Presión/métodos , Nanopartículas de Magnetita/química , Microextracción en Fase Sólida/métodos , Impresión Molecular/métodos , Porosidad , Grafito/química
7.
Biosens Bioelectron ; 258: 116349, 2024 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-38705072

RESUMEN

Detection of cancer-related exosomes in body fluids has become a revolutionary strategy for early cancer diagnosis and prognosis prediction. We have developed a two-step targeting detection method, termed PS-MIPs-NELISA SERS, for rapid and highly sensitive exosomes detection. In the first step, a phospholipid polar site imprinting strategy was employed using magnetic PS-MIPs (phospholipids-molecularly imprinted polymers) to selectively isolate and enrich all exosomes from urine samples. In the second step, a nanozyme-linked immunosorbent assay (NELISA) technique was utilized. We constructed Au/Na7PMo11O39 nanoparticles (NPs) with both surface-enhanced Raman scattering (SERS) property and peroxidase catalytic activity, followed by the immobilization of CD9 antibodies on the surface of Au/Na7PMo11O39 NPs. The Au/Na7PMo11O39-CD9 antibody complexes were then used to recognize CD9 proteins on the surface of exosomes enriched by magnetic PS-MIPs. Lastly, the high sensitivity detection of exosomes was achieved indirectly via the SERS activity and peroxidase-like activity of Au/Na7PMo11O39 NPs. The quantity of exosomes in urine samples from pancreatic cancer patients obtained by the PS-MIPs-NELISA SERS technique showed a linear relationship with the SERS intensity in the range of 6.21 × 107-2.81 × 108 particles/mL, with a limit of detection (LOD) of 5.82 × 107 particles/mL. The SERS signal intensity of exosomes in urine samples from pancreatic cancer patients was higher than that of healthy volunteers. This bidirectional MIPs-NELISA-SERS approach enables noninvasive, highly sensitive, and rapid detection of cancer, facilitating the monitoring of disease progression during treatment and opening up a new avenue for rapid early cancer screening.


Asunto(s)
Técnicas Biosensibles , Exosomas , Oro , Espectrometría Raman , Humanos , Exosomas/química , Oro/química , Espectrometría Raman/métodos , Fosfolípidos/química , Fosfolípidos/orina , Límite de Detección , Impresión Molecular , Polímeros Impresos Molecularmente/química , Epítopos/inmunología , Epítopos/química , Nanopartículas del Metal/química , Tetraspanina 29/orina , Tetraspanina 29/análisis , Anticuerpos Inmovilizados/química
8.
Biosens Bioelectron ; 258: 116348, 2024 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-38710143

RESUMEN

Therapeutic drug monitoring (TDM) serves as a potent tool for adjusting drug concentration within a reasonable range. However, continuous monitoring of anticancer drugs in-vivo presents a significant challenge. Herein, we propose a needle-in-needle electrochemical sensor based on an acupuncture needle electrode, capable of monitoring the anticancer drug etoposide in the peritoneal cavity of living rats. The acupuncture needle was modified with Au nanoparticles and etoposide-templated molecularly imprinted polymer (MIP), resulting in high sensitivity and selectivity in the electrochemical detection of etoposide. The modified acupuncture needle (0.16 mm diameter) was anchored inside a syringe needle (1.40 mm diameter), allowing the outer syringe needle to protect the modified materials of the inner acupuncture needle during skin piercing. Due to the unique needle-in-needle design, high stability was obtained during in-vivo etoposide monitoring. Connecting to a smartphone-controlled portable electrochemical workstation, the needle-in-needle sensor offers great convenience in point-of-care TDM. Moreover, the electrode materials on the acupuncture needle were carefully characterized and optimized. Under the optimized conditions, low detection limits and wide linear range were achieved. This work provides new insights into acupuncture needle electrochemical sensors and further expands the feasibility for real-time and in-vivo detection.


Asunto(s)
Técnicas Biosensibles , Monitoreo de Drogas , Etopósido , Oro , Agujas , Etopósido/análisis , Etopósido/administración & dosificación , Animales , Ratas , Técnicas Biosensibles/instrumentación , Oro/química , Monitoreo de Drogas/instrumentación , Técnicas Electroquímicas/métodos , Antineoplásicos/análisis , Antineoplásicos/administración & dosificación , Antineoplásicos/sangre , Nanopartículas del Metal/química , Polímeros Impresos Molecularmente/química , Límite de Detección , Electrodos , Ratas Sprague-Dawley , Diseño de Equipo
9.
Anal Methods ; 16(20): 3240-3248, 2024 May 23.
Artículo en Inglés | MEDLINE | ID: mdl-38726550

RESUMEN

Currently, Nernstian-response-based polymeric membrane potentiometric sensors using molecularly imprinted polymers (MIPs) as receptors have been successfully developed for determination of organic ionic species. However, the preparation of these MIP receptors usually involves tedious and time-consuming template-removal procedures. Herein, a template-removal-free MIP is proposed and used as a receptor for fabrication of a potentiometric sensor. The proposed methodology not only significantly shortens the preparation time of MIP-based potentiometric sensors but also improves the batch-to-batch reproducibility of these sensors. By using antibiotic vancomycin as a model, the new concept offers a linear concentration range of 1.0 × 10-7 to 1.0 × 10-4 mol L-1 with a detection limit of 2.51 × 10-8 mol L-1. It can be expected that the template-removal-free MIP-based sensing strategy could lay the foundation for simple fabrication of electrochemical sensors without the need for template removal such as potentiometric and capacitive sensors and ion-sensitive field-effect transistors.


Asunto(s)
Antibacterianos , Polímeros Impresos Molecularmente , Potenciometría , Vancomicina , Potenciometría/métodos , Potenciometría/instrumentación , Antibacterianos/análisis , Polímeros Impresos Molecularmente/química , Vancomicina/química , Vancomicina/análisis , Membranas Artificiales , Impresión Molecular/métodos , Límite de Detección , Polímeros/química , Reproducibilidad de los Resultados
10.
Anal Methods ; 16(20): 3278-3286, 2024 May 23.
Artículo en Inglés | MEDLINE | ID: mdl-38738557

RESUMEN

Dextromethorphan (DXM) is a widely utilized central antitussive agent, which is frequently abused by individuals seeking its recreational effect. But DXM overdose can cause some adverse effects, including brain damage, loss of consciousness, and cardiac arrhythmias, and hence its detection is significant. Herein, an electrochemical sensor based on a Cu-coordinated molecularly imprinted polymer (Cu-MIP) was fabricated for its detection. For constructing the sensor, nitrogen-doped carbon nanosheets (CCNs) were prepared through calcining chitin under an argon atmosphere, and molybdenum disulfide (MoS2) was allowed to grow on their surface. Subsequently, the obtained MoS2/CCNs composite was employed to modify a glassy carbon electrode (GCE), and the Cu-MIP was electrodeposited on the electrode in a Cu-1,10-phenanthroline (Cu-Phen) solution containing DXM, where Cu2+ played a role in facilitating electron transfer and binding DXM. Due to the large specific surface area, good electrocatalytic properties and recognition of the resulting composite, the resulting Cu-MIP/MoS2/CCNs/GCE showed high selectivity and sensitivity. Under optimized experimental conditions, the peak current of DXM and its concentration exhibited a good linear relationship over the concentration range of 0.1-100 µM, and the limit of detection (S/N = 3) was 0.02 µM. Furthermore, the electrochemical sensor presented good stability, and it was successfully used for the determination of DXM in pharmaceutical, human serum and urine samples.


Asunto(s)
Carbono , Cobre , Dextrometorfano , Disulfuros , Técnicas Electroquímicas , Polímeros Impresos Molecularmente , Molibdeno , Molibdeno/química , Disulfuros/química , Dextrometorfano/análisis , Dextrometorfano/química , Dextrometorfano/orina , Cobre/química , Técnicas Electroquímicas/métodos , Carbono/química , Polímeros Impresos Molecularmente/química , Quitina/química , Humanos , Límite de Detección , Electrodos , Antitusígenos/química , Antitusígenos/análisis , Antitusígenos/orina
11.
Molecules ; 29(10)2024 May 12.
Artículo en Inglés | MEDLINE | ID: mdl-38792139

RESUMEN

In the past few decades, considerable scientific strides have been made in the subject of drug analysis in human biological samples. However, the risk caused by incorrect drug plasma levels in patients still remains an important concern. This review paper attempts to investigate the advances made over the last ten years in common sample preparation techniques (SPT) for biological samples based on solid sorbents, including solid-phase extraction (SPE) and solid-phase micro-extraction (SPME), and in particular in the field of molecularly imprinted polymers (MIPs), including non-stimuli-responsive and stimuli-responsive adsorbents. This class of materials is known as 'smart adsorbents', exhibiting tailored responses to various stimuli such as magnetic fields, pH, temperature, and light. Details are provided on how these advanced SPT are changing the landscape of modern drug analysis in their coupling with liquid chromatography-mass spectrometry (LC-MS) analytical techniques, a general term that includes high-performance liquid chromatography (HPLC) and ultra-high performance liquid chromatography (UHPLC), as well as any variation of MS, such as tandem (MS/MS), multiple-stage (MSn), and high-resolution (HRMS) mass spectrometry. Some notes are also provided on coupling with less-performing techniques, such as high-performance liquid chromatography with ultraviolet (HPLC-UV) and diode array detection (HPLC-DAD) detection. Finally, we provide a general review of the difficulties and benefits of the proposed approaches and the future prospects of this research area.


Asunto(s)
Extracción en Fase Sólida , Humanos , Extracción en Fase Sólida/métodos , Preparaciones Farmacéuticas/análisis , Preparaciones Farmacéuticas/química , Microextracción en Fase Sólida/métodos , Cromatografía Líquida de Alta Presión/métodos , Polímeros Impresos Molecularmente/química , Cromatografía Liquida/métodos , Espectrometría de Masas en Tándem/métodos
12.
Biosensors (Basel) ; 14(5)2024 Apr 30.
Artículo en Inglés | MEDLINE | ID: mdl-38785696

RESUMEN

This work presents a novel approach for tailoring molecularly imprinted polymers (MIPs) with a preliminary stage of atom transfer radical polymerization (ATRP), for a more precise definition of the imprinted cavity. A well-defined copolymer of acrylamide and N,N'-methylenebisacrylamide (PAAm-co-PMBAm) was synthesized by ATRP and applied to gold electrodes with the template, followed by a crosslinking reaction. The template was removed from the polymer matrix by enzymatic/chemical action. The surface modifications were monitored via electrochemical impedance spectroscopy (EIS), having the MIP polymer as a non-conducting film designed with affinity sites for CA15-3. The resulting biosensor exhibited a linear response to CA15-3 log concentrations from 0.001 to 100 U/mL in PBS or in diluted fetal bovine serum (1000×) in PBS. Compared to the polyacrylamide (PAAm) MIP from conventional free-radical polymerization, the ATRP-based MIP extended the biosensor's dynamic linear range 10-fold, improving low concentration detection, and enhanced the signal reproducibility across units. The biosensor demonstrated good sensitivity and selectivity. Overall, the work described confirmed that the process of radical polymerization to build an MIP material influences the detection capacity for the target substance and the reproducibility among different biosensor units. Extending this approach to other cancer biomarkers, the methodology presented could open doors to a new generation of MIP-based biosensors for point-of-care disease diagnosis.


Asunto(s)
Técnicas Biosensibles , Polímeros Impresos Molecularmente , Polimerizacion , Polímeros Impresos Molecularmente/química , Impresión Molecular , Humanos , Espectroscopía Dieléctrica , Polímeros/química , Acrilamidas/química , Reproducibilidad de los Resultados , Oro/química , Resinas Acrílicas/química
13.
ACS Appl Mater Interfaces ; 16(21): 27714-27727, 2024 May 29.
Artículo en Inglés | MEDLINE | ID: mdl-38717953

RESUMEN

Rapid and accurate quantification of metabolites in different bodily fluids is crucial for a precise health evaluation. However, conventional metabolite sensing methods, confined to centralized laboratory settings, suffer from time-consuming processes, complex procedures, and costly instrumentation. Introducing the MXene/nitrogen-doped electrochemically exfoliated graphene (MXene@N-EEG) nanocomposite as a novel biosensing platform in this work addresses the challenges associated with conventional methods, leveraging the concept of molecularly imprinted polymers (MIP) enables the highly sensitive, specific, and reliable detection of metabolites. To validate our biosensing technology, we utilize agmatine as a significant biologically active metabolite. The MIP biosensor incorporates electrodeposited Prussian blue nanoparticles as a redox probe, facilitating the direct electrical signaling of agmatine binding in the polymeric matrix. The MXene@N-EEG nanocomposite, with excellent metal conductivity and a large electroactive specific surface area, effectively stabilizes the electrodeposited Prussian blue nanoparticles. Furthermore, increasing the content of agmatine-imprinted cavities on the electrode enhances the sensitivity of the MIP biosensor. Evaluation of the designed MIP biosensor in buffer solution and plasma samples reveals a wide linear concentration range of 1.0 nM-100.0 µM (R2 = 0.9934) and a detection limit of 0.1 nM. Notably, the developed microfluidic biosensor offers low cost, rapid response time to the target molecule (10 min of sample incubation), good recovery results for detecting agmatine in plasma samples, and acceptable autonomous performance for on-chip detection. Moreover, its high reliability and sensitivity position this MIP-based biosensor as a promising candidate for miniaturized microfluidic devices with the potential for scalable production for point-of-care applications.


Asunto(s)
Técnicas Biosensibles , Técnicas Electroquímicas , Grafito , Polímeros Impresos Molecularmente , Nanocompuestos , Nitrógeno , Grafito/química , Técnicas Biosensibles/métodos , Nanocompuestos/química , Nitrógeno/química , Polímeros Impresos Molecularmente/química , Técnicas Electroquímicas/métodos , Humanos , Límite de Detección , Impresión Molecular , Polímeros/química
14.
J Hazard Mater ; 472: 134469, 2024 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-38691995

RESUMEN

The scarcity of selective adsorbents for efficient extraction and removal of microcystins (MCs) from complex samples greatly limits the precise detection and effective control of MCs. Three-dimensional covalent organic frameworks (3D COFs), characterized by their large specific surface areas and highly ordered rigid structure, are promising candidates, but suffer from lack of specific recognition. Herein, we design to engineer molecularly imprinted cavities within 3D COFs via molecularly imprinted technology, creating a novel adsorbent with exceptional selectivity, kinetics and capacity for the efficient extraction and removal of MCs. As proof-of-concept, a new CC bond-containing 3D COF, designated JNU-7, is designed and prepared for copolymerization with methacrylic acid, the pseudo template L-arginine and ethylene dimethacrylate to yield the JNU-7 based molecularly imprinted polymer (JNU-7-MIP). The JNU-7-MIP exhibits a great adsorption capacity (156 mg g-1) for L-arginine. Subsequently, the JNU-7-MIP based solid-phase extraction coupled with high performance liquid chromatography-mass spectrometry achieves low detection limit of 0.008 ng mL-1, wide linear range of 0.025-100 ng mL-1, high enrichment factor of 186, rapid extraction of 10 min, and good recoveries of 92.4%-106.5% for MC-LR. Moreover, the JNU-7-MIP can rapidly remove the MC-LR from 1 mg L-1 to levels (0.26-0.35 µg L-1) lower than the WHO recommended limit for drinking water (1 µg L-1). This work reveals the considerable potential of 3D COF based MIPs as promising adsorbents for the extraction and removal of contaminants in complex real samples.


Asunto(s)
Microcistinas , Impresión Molecular , Extracción en Fase Sólida , Contaminantes Químicos del Agua , Microcistinas/aislamiento & purificación , Microcistinas/química , Microcistinas/análisis , Adsorción , Extracción en Fase Sólida/métodos , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/aislamiento & purificación , Contaminantes Químicos del Agua/análisis , Estructuras Metalorgánicas/química , Arginina/química , Polímeros Impresos Molecularmente/química , Cromatografía Líquida de Alta Presión , Límite de Detección
15.
Mikrochim Acta ; 191(6): 344, 2024 May 27.
Artículo en Inglés | MEDLINE | ID: mdl-38802523

RESUMEN

A molecularly imprinted electrochemiluminescent sensor is developed for the sensitive detection of tetracycline in environmental and food samples. The sensor uses an ionic liquid (i.e. [APMIM]Br) modified graphene-carbon nanotube composite (GMI) material as substrate, a double-layered core-shell metal-organic framework NH2-UiO-66@ZIF-8 (NUZ) loaded bipyridyl ruthenium (NUZ@Ru) as luminescent material, and a molecularly imprinted copolymer of o-phenylenediamine and hydroquinone as recognition element. The ionic liquid-modified graphene-carbon nanotube composite has a favorable three-dimensional structure, high specific surface area, and good hydrophilicity; the core-shell structured metal-organic framework has high stability and plentiful reaction sites for loading; the molecularly imprinted copolymer film has enhanced stability and recognition effect. Hence, the resulting sensor combines the merits of several materials and presents improved performance. Under the optimum detection conditions, it shows a wide linear range of 0.05 µM - 1 mM, a low detection limit of 20 nM, high selectivity, and excellent stability. It has been successfully applied to the detection of tetracycline in different samples.


Asunto(s)
Técnicas Electroquímicas , Límite de Detección , Mediciones Luminiscentes , Estructuras Metalorgánicas , Polímeros Impresos Molecularmente , Tetraciclina , Tetraciclina/análisis , Tetraciclina/química , Polímeros Impresos Molecularmente/química , Estructuras Metalorgánicas/química , Mediciones Luminiscentes/métodos , Técnicas Electroquímicas/métodos , Grafito/química , Nanotubos de Carbono/química , Contaminación de Alimentos/análisis , Líquidos Iónicos/química , Antibacterianos/análisis , Antibacterianos/química , Contaminantes Químicos del Agua/análisis , Impresión Molecular
16.
Anal Chem ; 96(21): 8641-8647, 2024 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-38716697

RESUMEN

Pathogenic bacterial infections, even at extremely low concentrations, pose significant threats to human health. However, the challenge persists in achieving high-sensitivity bacterial detection, particularly in complex samples. Herein, we present a novel sandwich-type electrochemical sensor utilizing bacteria-imprinted polymer (BIP) coupled with vancomycin-conjugated MnO2 nanozyme (Van@BSA-MnO2) for the ultrasensitive detection of pathogenic bacteria, exemplified by Staphylococcus aureus (S. aureus). The BIP, in situ prepared on the electrode surface, acts as a highly specific capture probe by replicating the surface features of S. aureus. Vancomycin (Van), known for its affinity to bacterial cell walls, is conjugated with a Bovine serum albumin (BSA)-templated MnO2 nanozyme through EDC/NHS chemistry. The resulting Van@BSA-MnO2 complex, serving as a detection probe, provides an efficient catalytic platform for signal amplification. Upon binding with the captured S. aureus, the Van@BSA-MnO2 complex catalyzes a substrate reaction, generating a current signal proportional to the target bacterial concentration. The sensor displays remarkable sensitivity, capable of detecting a single bacterial cell in a phosphate buffer solution. Even in complex milk matrices, it maintains outstanding performance, identifying S. aureus at concentrations as low as 10 CFU mL-1 without requiring intricate sample pretreatment. Moreover, the sensor demonstrates excellent selectivity, particularly in distinguishing target S. aureus from interfering bacteria of the same genus at concentrations 100-fold higher. This innovative method, employing entirely synthetic materials, provides a versatile and low-cost detection platform for Gram-positive bacteria. In comparison to existing nanozyme-based bacterial sensors with biological recognition materials, our assay offers distinct advantages, including enhanced sensitivity, ease of preparation, and cost-effectiveness, thereby holding significant promise for applications in food safety and environmental monitoring.


Asunto(s)
Compuestos de Manganeso , Óxidos , Polímeros , Staphylococcus aureus , Vancomicina , Staphylococcus aureus/aislamiento & purificación , Compuestos de Manganeso/química , Óxidos/química , Vancomicina/química , Polímeros/química , Albúmina Sérica Bovina/química , Técnicas Electroquímicas/métodos , Análisis de la Célula Individual , Antibacterianos/química , Antibacterianos/farmacología , Animales , Límite de Detección , Polímeros Impresos Molecularmente/química , Humanos
17.
Spectrochim Acta A Mol Biomol Spectrosc ; 316: 124357, 2024 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-38692110

RESUMEN

This study described the preparation of an azide covalent organic framework-embedded molecularly imprinted polymers (COFs(azide)@MIPs) platform for urea adsorption and indirect ethyl carbamate (EC) removal from Chinese yellow rice wine (Huangjiu). By modifying the pore surface of COFs using the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, COFs(azide) with a high fluorescence quantum yield and particular recognition ability were inventively produced. In order to selectively trap urea, the COFs(azide) were encased in an imprinted shell layer via imprinting technology. With a detection limit (LOD) of 0.016 µg L-1 (R2 = 0.9874), the COFs(azides)@MIPs demonstrated a good linear relationship with urea in the linear range of 0-5 µg L-1. Using real Huangjiu samples, the spiking recovery trials showed the viability of this sensing platform with recoveries ranging from 88.44 % to 109.26 % and an RSD of less than 3.40 %. The Huangjiu processing model system achieved 38.93 % EC reduction by COFs(azides)@MIPs. This research will open up new avenues for the treatment of health problems associated with fermented alcoholic beverages, particularly Huangjiu, while also capturing and removing hazards coming from food.


Asunto(s)
Polímeros Impresos Molecularmente , Urea , Uretano , Vino , Uretano/análisis , Uretano/química , Polímeros Impresos Molecularmente/química , Urea/análisis , Urea/química , Vino/análisis , Espectrometría de Fluorescencia/métodos , Azidas/química , Límite de Detección , Adsorción , Estructuras Metalorgánicas/química , Impresión Molecular/métodos
18.
Int J Mol Sci ; 25(10)2024 May 18.
Artículo en Inglés | MEDLINE | ID: mdl-38791542

RESUMEN

Molecularly imprinted polymers (MIPs) are established artificial molecular recognition platforms with tailored selectivity towards a target molecule, whose synthesis and functionality are highly influenced by the nature of the solvent employed in their synthesis. Steps towards the "greenification" of molecular imprinting technology (MIT) has already been initiated by the elaboration of green MIT principles; developing MIPs in a solvent-free environment may not only offer an eco-friendly alternative, but could also significantly influence the affinity and expected selectivity of the resulting binding sites. In the current study the first solvent-free mechanochemical synthesis of MIPs via liquid-assisted grinding (LAG) is reported. The successful synthesis of the imprinted polymer was functionally demonstrated by measuring its template rebinding capacity and the selectivity of the molecular recognition process in comparison with the ones obtained by the conventional, non-covalent molecular imprinting process in liquid media. The results demonstrated similar binding capacities towards the template molecule and superior chemoselectivity compared to the solution-based MIP synthesis method. The adoption of green chemistry principles with all their inherent advantages in the synthesis of MIPs may not only be able to alleviate the potential environmental and health concerns associated with their analytical (e.g., selective adsorbents) and biomedical (e.g., drug carriers or reservoirs) applications, but might also offer a conceptual change in molecular imprinting technology.


Asunto(s)
Impresión Molecular , Polímeros Impresos Molecularmente , Polímeros Impresos Molecularmente/química , Polímeros Impresos Molecularmente/síntesis química , Impresión Molecular/métodos , Técnicas de Síntesis en Fase Sólida/métodos , Polímeros/química , Polímeros/síntesis química , Solventes/química
19.
Mikrochim Acta ; 191(6): 332, 2024 05 15.
Artículo en Inglés | MEDLINE | ID: mdl-38748375

RESUMEN

Nifedipine (NIF), as one of the dihydropyridine calcium channel blockers, is widely used in the treatment of hypertension. However, misuse or ingestion of NIF can result in serious health issues such as myocardial infarction, arrhythmia, stroke, and even death. It is essential to design a reliable and sensitive detection method to monitor NIF. In this work, an innovative molecularly imprinted polymer dual-emission fluorescent sensor (CDs@PDA-MIPs) strategy was successfully designed for sensitive detection of NIF. The fluorescent intensity of the probe decreased with increasing NIF concentration, showing a satisfactory linear relationship within the range 1.0 × 10-6 M ~ 5.0 × 10-3 M. The LOD of NIF was 9.38 × 10-7 M (S/N = 3) in fluorescence detection. The application of the CDs@PDA-MIPs in actual samples such as urine and Qiangli Dingxuan tablets has been verified, with recovery ranging from 97.8 to 102.8% for NIF. Therefore, the fluorescent probe demonstrates great potential as a sensing system for detecting NIF.


Asunto(s)
Carbono , Dopamina , Colorantes Fluorescentes , Límite de Detección , Polímeros Impresos Molecularmente , Nifedipino , Puntos Cuánticos , Espectrometría de Fluorescencia , Puntos Cuánticos/química , Nifedipino/química , Nifedipino/análisis , Colorantes Fluorescentes/química , Polímeros Impresos Molecularmente/química , Dopamina/orina , Dopamina/análisis , Carbono/química , Espectrometría de Fluorescencia/métodos , Humanos , Polimerizacion , Impresión Molecular , Comprimidos/análisis
20.
Mikrochim Acta ; 191(5): 242, 2024 04 04.
Artículo en Inglés | MEDLINE | ID: mdl-38573524

RESUMEN

Molecularly imprinted polymer (MIP) nanofilms for alpha-fetoprotein (AFP) and the receptor binding domain (RBD) of the spike protein of SARS-CoV-2 using either a peptide (epitope-MIP) or the whole protein (protein-MIP) as the template were prepared by electropolymerization of scopoletin. Conducting atomic force microscopy revealed after template removal and electrochemical deposition of gold a larger surface density of imprinted cavities for the epitope-imprinted polymers than when using the whole protein as template. However, comparable affinities towards the respective target protein (AFP and RBD) were obtained for both types of MIPs as expressed by the KD values in the lower nanomolar range. On the other hand, while the cross reactivity of both protein-MIPs towards human serum albumin (HSA) amounts to around 50% in the saturation region, the nonspecific binding to the respective epitope-MIPs is as low as that for the non-imprinted polymer (NIP). This effect might be caused by the different sizes of the imprinted cavities. Thus, in addition to the lower costs the reduced nonspecific binding is an advantage of epitope-imprinted polymers for the recognition of proteins.


Asunto(s)
COVID-19 , alfa-Fetoproteínas , Humanos , SARS-CoV-2 , Epítopos , Polímeros Impresos Molecularmente , Polímeros
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