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1.
Mikrochim Acta ; 191(6): 332, 2024 05 15.
Article En | MEDLINE | ID: mdl-38748375

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.


Carbon , Dopamine , Fluorescent Dyes , Limit of Detection , Molecularly Imprinted Polymers , Nifedipine , Quantum Dots , Spectrometry, Fluorescence , Quantum Dots/chemistry , Nifedipine/chemistry , Nifedipine/analysis , Fluorescent Dyes/chemistry , Molecularly Imprinted Polymers/chemistry , Dopamine/urine , Dopamine/analysis , Carbon/chemistry , Spectrometry, Fluorescence/methods , Humans , Polymerization , Molecular Imprinting , Tablets/analysis
2.
Mikrochim Acta ; 191(6): 322, 2024 05 10.
Article En | MEDLINE | ID: mdl-38730044

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.


Electrochemical Techniques , Limit of Detection , Molecularly Imprinted Polymers , Zinc , Molecularly Imprinted Polymers/chemistry , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Zinc/chemistry , Graphite/chemistry , Humans , Aminoimidazole Carboxamide/analogs & derivatives , Aminoimidazole Carboxamide/analysis , Aminoimidazole Carboxamide/blood , Aminoimidazole Carboxamide/chemistry , Nanostructures/chemistry , Electrodes
3.
Spectrochim Acta A Mol Biomol Spectrosc ; 316: 124357, 2024 Aug 05.
Article En | MEDLINE | ID: mdl-38692110

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.


Molecularly Imprinted Polymers , Urea , Urethane , Wine , Urethane/analysis , Urethane/chemistry , Molecularly Imprinted Polymers/chemistry , Urea/analysis , Urea/chemistry , Wine/analysis , Spectrometry, Fluorescence/methods , Azides/chemistry , Limit of Detection , Adsorption , Metal-Organic Frameworks/chemistry , Molecular Imprinting/methods
4.
Anal Biochem ; 691: 115551, 2024 Aug.
Article En | MEDLINE | ID: mdl-38702023

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.


Electrochemical Techniques , Molecular Imprinting , Phenylenediamines , Thymol , Phenylenediamines/chemistry , Thymol/analysis , Thymol/chemistry , Electrochemical Techniques/methods , Limit of Detection , Electrodes , Molecularly Imprinted Polymers/chemistry , Carbon/chemistry , Reproducibility of Results
5.
Int J Mol Sci ; 25(9)2024 Apr 23.
Article En | MEDLINE | ID: mdl-38731823

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.


Drug Carriers , Lamotrigine , Molecularly Imprinted Polymers , Lamotrigine/chemistry , Drug Carriers/chemistry , Molecularly Imprinted Polymers/chemistry , Molecularly Imprinted Polymers/chemical synthesis , Molecular Imprinting/methods , Spectroscopy, Fourier Transform Infrared , Drug Liberation , X-Ray Diffraction , Adsorption , Hydrogen-Ion Concentration
6.
J Chromatogr A ; 1726: 464977, 2024 Jul 05.
Article En | MEDLINE | ID: mdl-38735117

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.


Carbon , Fruit and Vegetable Juices , Herbicides , Limit of Detection , Molecularly Imprinted Polymers , Quantum Dots , Triazines , Quantum Dots/chemistry , Triazines/chemistry , Triazines/analysis , Triazines/isolation & purification , Herbicides/analysis , Herbicides/isolation & purification , Herbicides/chemistry , Fruit and Vegetable Juices/analysis , Adsorption , Molecularly Imprinted Polymers/chemistry , Carbon/chemistry , Chromatography, High Pressure Liquid/methods , Magnetite Nanoparticles/chemistry , Solid Phase Microextraction/methods , Molecular Imprinting/methods , Porosity , Graphite/chemistry
7.
Biosens Bioelectron ; 258: 116349, 2024 Aug 15.
Article En | MEDLINE | ID: mdl-38705072

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.


Biosensing Techniques , Exosomes , Gold , Spectrum Analysis, Raman , Humans , Exosomes/chemistry , Gold/chemistry , Spectrum Analysis, Raman/methods , Phospholipids/chemistry , Phospholipids/urine , Limit of Detection , Molecular Imprinting , Molecularly Imprinted Polymers/chemistry , Epitopes/immunology , Epitopes/chemistry , Metal Nanoparticles/chemistry , Tetraspanin 29/urine , Tetraspanin 29/analysis , Antibodies, Immobilized/chemistry
8.
Biosens Bioelectron ; 258: 116348, 2024 Aug 15.
Article En | MEDLINE | ID: mdl-38710143

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.


Biosensing Techniques , Drug Monitoring , Etoposide , Gold , Needles , Etoposide/analysis , Etoposide/administration & dosage , Animals , Rats , Biosensing Techniques/instrumentation , Gold/chemistry , Drug Monitoring/instrumentation , Electrochemical Techniques/methods , Antineoplastic Agents/analysis , Antineoplastic Agents/administration & dosage , Antineoplastic Agents/blood , Metal Nanoparticles/chemistry , Molecularly Imprinted Polymers/chemistry , Limit of Detection , Electrodes , Rats, Sprague-Dawley , Equipment Design
9.
Sci Rep ; 14(1): 10293, 2024 05 04.
Article En | MEDLINE | ID: mdl-38704412

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.


Pesticides , Pyrimidines , Pesticides/analysis , Carbamates/analysis , Carbamates/chemistry , Quantum Dots/chemistry , Molecularly Imprinted Polymers/chemistry , Polymers/chemistry , Spectrometry, Fluorescence/methods , Graphite/chemistry , Molecular Imprinting/methods , Adsorption , Limit of Detection , Spectroscopy, Fourier Transform Infrared , Nanocomposites/chemistry , Nanocomposites/ultrastructure
10.
J Chromatogr A ; 1725: 464876, 2024 Jun 21.
Article En | MEDLINE | ID: mdl-38718697

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.


2,4-Dichlorophenoxyacetic Acid , Microspheres , Molecular Imprinting , Water , Adsorption , Water/chemistry , 2,4-Dichlorophenoxyacetic Acid/analysis , 2,4-Dichlorophenoxyacetic Acid/chemistry , Polymers/chemistry , Kinetics , Molecularly Imprinted Polymers/chemistry
11.
Biosens Bioelectron ; 255: 116269, 2024 Jul 01.
Article En | MEDLINE | ID: mdl-38579624

Saxitoxin (STX), which is produced by certain dinoflagellate species, is a type of paralytic shellfish poisoning toxin that poses a serious threat to human health and the environment. Therefore, developing a technology for the convenient and cost-effective detection of STX is imperative. In this study, we developed an affinity peptide-imprinted polymer-based indirect competitive ELISA (ic-ELISA) without using enzyme-toxin conjugates. AuNP/Co3O4@Mg/Al cLDH was synthesized by calcining AuNP/ZIF-67@Mg/Al LDH, which was obtained by combining AuNPs, ZIF-67, and flower-like Mg/Al LDH. This synthesized nanozyme exhibited high catalytic activity (Km = 0.24 mM for TMB and 132.5 mM for H2O2). The affinity peptide-imprinted polymer (MIP) was imprinted with an STX-specific template peptide (STX MIP) on a multi-well microplate and then reacted with an STX-specific signal peptide (STX SP). The interaction between the STX SP and MIP was detected using a streptavidin-coated nanozyme (SA-AuNP/Co3O4@Mg/Al cLDH). The developed MIP-based ic-ELISA exhibited excellent selectivity and sensitivity, with a limit of detection of 3.17 ng/mL (equivalent: 0.317 µg/g). Furthermore, the system was validated using a commercial ELISA kit and mussel tissue samples, and it demonstrated a high STX recovery with a low coefficient of variation. These results imply that the developed ic-ELISA can be used to detect STX in real samples.


Biosensing Techniques , Cobalt , Metal Nanoparticles , Oxides , Humans , Marine Toxins/analysis , Molecularly Imprinted Polymers , Gold , Hydrogen Peroxide , Shellfish/analysis , Saxitoxin , Enzyme-Linked Immunosorbent Assay/methods , Peptides , Polymers
12.
Molecules ; 29(7)2024 Apr 08.
Article En | MEDLINE | ID: mdl-38611955

Lumpy Skin Disease (LSD) is a notifiable viral disease caused by Lumpy Skin Disease virus (LSDV). It is usually associated with high economic losses, including a loss of productivity, infertility, and death. LSDV shares genetic and antigenic similarities with Sheep pox virus (SPV) and Goat pox (GPV) virus. Hence, the LSDV traditional diagnostic tools faced many limitations regarding sensitivity, specificity, and cross-reactivity. Herein, we fabricated a paper-based turn-on fluorescent Molecularly Imprinted Polymer (MIP) sensor for the rapid detection of LSDV. The LSDV-MIPs sensor showed strong fluorescent intensity signal enhancement in response to the presence of the virus within minutes. Our sensor showed a limit of detection of 101 log10 TCID50/mL. Moreover, it showed significantly higher specificity to LSDV relative to other viruses, especially SPV. To our knowledge, this is the first record of a paper-based rapid detection test for LSDV depending on fluorescent turn-on behavior.


Lumpy skin disease virus , Animals , Cattle , Sheep , Molecularly Imprinted Polymers , Coloring Agents , Cross Reactions , Head
13.
J Hazard Mater ; 470: 134218, 2024 May 15.
Article En | MEDLINE | ID: mdl-38581878

The development of high-performance sensors for doxycycline (DOX) detection is necessary because its residue accumulation will cause serious harm to human health and the environment. Here, a novel tri-emission ratiometric fluorescence sensor was proposed by using "post-mixing" strategy of different emissions fluorescence molecularly imprinted polymers with salicylamide as dummy template (DMIPs). BSA was chosen as assistant functional monomer, and also acted as sensitizers for the aggregation-induced emission (AIE) effect of DOX. The blue-emitting carbon dots and the red-emitting CdTe quantum dots were separately introduced into DMIPs as the response signals. Upon DOX recognition within 2 min, blue and red fluorescence of the tri-emission DMIPs sensor were quenched while green fluorescence of DOX was enhanced, resulting in a wide range of color variations observed over bluish violet-rosered-light pink-orange-yellow-green with a detection limit of 0.061 µM. The sensor possessed highly selective recognition and was successfully applied to detect DOX in complicated real samples. Moreover, with the fluorescent color collection and data processing, the smartphone-assisted visual detection of the sensors showed satisfied sensitivity with low detection limit. This work provides great potential applications for rapid and visual detection of antibiotics in complex substrates.


Anti-Bacterial Agents , Cadmium Compounds , Doxycycline , Molecular Imprinting , Quantum Dots , Spectrometry, Fluorescence , Tellurium , Doxycycline/analysis , Doxycycline/chemistry , Quantum Dots/chemistry , Tellurium/chemistry , Anti-Bacterial Agents/analysis , Cadmium Compounds/chemistry , Limit of Detection , Fluorescence , Carbon/chemistry , Fluorescent Dyes/chemistry , Molecularly Imprinted Polymers/chemistry , Smartphone
14.
Anal Chem ; 96(19): 7602-7608, 2024 May 14.
Article En | MEDLINE | ID: mdl-38671546

Molecular imprinting techniques have attracted a lot of attention as a potential biomimetic technology, but there are still challenges in protein imprinting. Herein, multifunctional nanosized molecularly imprinted polymers (nanoMIPs) for human angiotensin-converting enzyme 2 (ACE2) were prepared by epitope imprinting of magnetic nanoparticles-anchored peptide (magNP-P) templates, which were further applied to construct a competitive displacement fluorescence assay toward ACE2. A cysteine-flanked dodecapeptide sequence was elaborately selected as an epitope for ACE2, which was immobilized onto the surface of magnetic nanoparticles and served as a magNP-P template for imprinting. During polymerization, fluorescent monomers were introduced to endow fluorescence responsiveness to the prepared self-signaling nanoMIPs. A competitive displacement fluorescence assay based on the nanoMIPs was established and operated in a washing-free manner, yielding a wide range for ACE2 (0.1-6.0 pg/mL) and a low detection limit (0.081 pg/mL). This approach offers a promising avenue in the preparation of nanoMIPs for macromolecule recognition and expands potential application of an MIP in the detection of proteins as well as peptides.


Angiotensin-Converting Enzyme 2 , Humans , Angiotensin-Converting Enzyme 2/metabolism , Angiotensin-Converting Enzyme 2/chemistry , Peptidyl-Dipeptidase A/metabolism , Peptidyl-Dipeptidase A/chemistry , Molecular Imprinting , Magnetite Nanoparticles/chemistry , Molecularly Imprinted Polymers/chemistry , Limit of Detection , Peptides/chemistry , Peptides/metabolism
15.
J Chromatogr A ; 1725: 464949, 2024 Jun 21.
Article En | MEDLINE | ID: mdl-38688054

This study introduces an innovative needle trap device (NTD) featuring a molecularly imprinted polymer (MIP) surface-modified Zeolite Y. The developed NTD was integrated with gas chromatography-flame ionization detector (GC-FID) and employed for analysis of fuel ether oxygenates (methyl tert­butyl ether, MTBE, ethyl tert­butyl ether, ETBE, and tert­butyl formate, TBF) in urine samples. To optimize the key experimental variables including extraction temperature, extraction time, salt concentration, and stirring speed, a central composite design-response surface methodology (CCD-RSM) was employed. The optimal values for extraction in the study were found to be 51.2 °C extraction temperature, 46.2 min extraction time, 27 % salt concentration, and 620 rpm stirring speed. Under the optimized conditions, the calibration curves demonstrated excellent linearity within the range of 0.1-100 µg L-1, with correlation coefficients (R2) exceeding 0.99. The limits of detection (LODs) for MTBE, ETBE, and TBF were obtained 0.06, 0.08, and 0.09 µg L-1, respectively. Moreover, the limits of quantification (LOQs) for MTBE, ETBE, and TBF were obtained 0.18, 0.24, and 0.27 µg L-1, respectively. The enrichment factor was also found to be in the range of 98-129.The NTD-GC-FID procedure demonstrated a high extraction efficiency, making it a promising tool for urinary biomonitoring of fuel ether oxygenates with improved sensitivity and selectivity compared to current methods.


Limit of Detection , Methyl Ethers , Zeolites , Zeolites/chemistry , Humans , Methyl Ethers/urine , Methyl Ethers/chemistry , Molecularly Imprinted Polymers/chemistry , Biological Monitoring/methods , Chromatography, Gas/methods , Ethyl Ethers/urine , Ethyl Ethers/chemistry
16.
Anal Methods ; 16(18): 2878-2887, 2024 May 09.
Article En | MEDLINE | ID: mdl-38639924

Shikimic acid (SA) is one of the most effective drugs against the A (H1N1) virus and has high medicinal value. Additionally, it has the ability to generate non-toxic herbicides and antimicrobial medications. The extraction from plants has proven to be the main route of production of SA with economic benefits and environmental efficiency. Therefore, it is necessary to perform purification of SA from these herbal medicines before quantifying it. In this study, researchers employed a boronate affinity-based controlled oriented surface imprinting technique to produce molecularly imprinted polymers (MIPs) as highly effective solid phase extraction (SPE) adsorbents for the isolation and purification of SA. 3-Fluoro-4-formylphenylboronic acid functionalized silica nanoparticles were used as supporting materials for immobilizing SA. Poly(2-anilinoethanol) with a higher hydrophilic domain can be used as an effective imprinting coating. The prepared SA-imprinted silica nanoparticles exhibited several significant results, such as good specificity, high binding capacity (39.06 ± 2.24 mg g-1), moderate binding constant (6.61 × 10-4 M-1), fast kinetics (8 min) and low binding pH (pH 5.0) toward SA. The replication of SA-imprinted silica nanoparticles was deemed satisfactory. The SA-imprinted silica nanoparticles could be still reused after seven adsorption-desorption cycles, which indicated high chemical stability. In addition, the recoveries of the proposed method for SA at three spiked level analysis in star aniseed and meadow cranesbill were 96.2% to 109.0% and 91.6% to 103.5%, respectively. The SA-imprinted silica nanoparticles that have been prepared are capable of identifying the target SA in real herbal medicines. Our approach makes sample pre-preparation simple, fast, selective and efficient.


Boronic Acids , Molecular Imprinting , Nanoparticles , Shikimic Acid , Silicon Dioxide , Solid Phase Extraction , Silicon Dioxide/chemistry , Nanoparticles/chemistry , Molecular Imprinting/methods , Shikimic Acid/chemistry , Shikimic Acid/isolation & purification , Boronic Acids/chemistry , Solid Phase Extraction/methods , Molecularly Imprinted Polymers/chemistry , Adsorption , Herbal Medicine/methods
17.
Mikrochim Acta ; 191(5): 247, 2024 04 08.
Article En | MEDLINE | ID: mdl-38587580

Alumina inorganic molecularly imprinted polymer (MIP) modified multi-walled carbon nanotubes (MWCNTs) on a glassy carbon electrode (MWCNTs-Al2O3-MIP/GCE) was firstly designed and fabricated by one-step electro deposition technique for the detection of uric acid (UA) in sweat. The UA templates were embedded within the inorganic MIP by co-deposition with Al2O3. Through the evaluation of morphology and structure by Field Emission Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM), it was verified that the specific recognition sites can be fabricated in the electrodeposited Al2O3 molecular imprinted layer. Due to the high selectivity of molecular imprinting holes, the MWCNTs-Al2O3-MIP/GCE electrode demonstrated an impressive imprinting factor of approximately 2.338 compared to the non-molecularly imprinted glassy carbon electrode (MWCNTs-Al2O3-NIP/GCE) toward uric acid detection. Moreover, it exhibited a remarkable limit of detection (LOD) of 50 nM for UA with wide detection range from 50 nM to 600 µM. The MWCNTs-Al2O3-MIP/GCE electrode also showed strong interference resistance against common substances found in sweat. These results highlight the excellent interference resistance and selectivity of MWCNTs-Al2O3-MIP/GCE sensor, positioning it as a novel sensing platform for non-invasive uric acid detection in human sweat.


Nanotubes, Carbon , Phosphates , Sweat , Humans , Molecularly Imprinted Polymers , Uric Acid , Aluminum Oxide
18.
Mikrochim Acta ; 191(5): 253, 2024 04 09.
Article En | MEDLINE | ID: mdl-38592400

The development of distance-based paper analytical devices (dPADs) integrated with molecularly imprinted polymers (MIPs) to monitor Escherichia coli (E. coli) levels in food samples is presented. The fluidic workflow on the device is controlled using a designed hydrophilic bridge valve. Dopamine serves as a monomer for the formation of the E. coli-selective MIP layer on the dPADs. The detection principle relies on the inhibition of the E. coli toward copper (II) (Cu2+)-triggered oxidation of o-phenylenediamine (OPD) on the paper substrate. Quantitative detection is simply determined through visual observation of the residual yellow color of the OPD in the detection zone, which is proportional to E. coli concentration. The sensing exhibits a linear range from 25.0 to 1200.0 CFU mL-1 (R2 = 0.9992) and a detection limit (LOD) of 25.0 CFU mL-1 for E. coli detection. Additionally, the technique is highly selective with no interference even from the molecules that have shown to react with OPD to form oxidized OPD. The developed device demonstrates accuracy and precision for E. coli quantification in food samples with recovery percentages between 98.3 and 104.7% and the highest relative standard deviation (RSD) of 4.55%. T-test validation shows no significant difference in E. coli concentration measured between our method and a commercial assay. The proposed dPAD sensor has the potential for selective and affordable E. coli determination  in food samples without requiring sample preparation. Furthermore, this strategy can be extended to monitor other molecules for which MIP can be developed and integrated into paper-microfluidic platform.


Escherichia coli , Phenylenediamines , Polymers , Molecularly Imprinted Polymers , Biological Assay
19.
Mikrochim Acta ; 191(5): 269, 2024 04 17.
Article En | MEDLINE | ID: mdl-38630309

A molecularly-imprinted electrochemiluminescence sensor was constructed for the determination of fenpropathrin (FPT) by molecular imprinting technology. In this sensing platform, the introduction of CdS@MWCNTs significantly enhanced the initial ECL signal of the luminol-O2 system. Specifically, MWCNTs was used as a carrier to adsorb more CdS, in which CdS acted as a co-reaction promoter for luminescence. Molecularly imprinted polymer (MIP) containing specific recognition sites of FPT was used as the material for selective recognition. With increasing amount of FPT the ECL signal decreased. Under the optimum conditions, the ECL response was linearly related to the logarithm of FPT concentration. The developed ECL sensor allowed for sensitive determination of FPT and exhibited a wide linear range from 1.0 × 10- 10 mol L- 1 to 1.0 × 10- 6 mol L- 1. The limit of detection was 3.3 × 10- 11 mol L- 1 (S/N = 3). It can be used for the detection of FPT in vegetable samples.


Luminescence , Molecular Imprinting , Pyrethrins , Luminol , Molecularly Imprinted Polymers
20.
Mikrochim Acta ; 191(5): 270, 2024 04 17.
Article En | MEDLINE | ID: mdl-38630200

A comparative analysis of molecularly imprinted polymers based on different synthesis techniques was performed for the recognition of molnupiravir (MOL). The polymerizations were performed with 3-thienyl boronic acid (3-TBA) as a functional monomer by electropolymerization (EP) and with guanine methacrylate (GuaM) as a functional monomer by photopolymerization (PP). Morphological and electrochemical characterizations of the developed sensors were investigated to verify the constructed sensors. Moreover, quantum chemical calculations were used to evaluate changes on the electrode surface at the molecular and electronic levels. The dynamic linear range of both designed sensors under optimized experimental conditions was found to be 7.5 × 10-12-2.5 × 10-10 M and 7.5 × 10-13-2.5 × 10-11 M for EP and PP, respectively. The effect of various interfering agents on MOL peak current was assessed for the selectivity of the study. In the presence of 100 times more interfering agents, the RSD and recovery values were determined. The RSD values of GuaM/MOL@MIP/GCE and poly(Py-co-3-PBA)/MOL@MIP/GCE sensors were found to be 1.99% and 1.72%, respectively. Furthermore, the recovery values of the MIP-based sensors were 98.18-102.69% and 98.05-103.72%, respectively. In addition, the relative selectivity coefficient (k') of the proposed sensor was evaluated, and it exhibited good selectivity for MOL with respect to the NIP sensor. The prepared sensor was successfully applied to determine MOL in commercial serum samples and capsule form. In conclusion, the developed sensors provided excellent reproducibility, repeatability, high sensitivity, and selectivity against the MOL molecule.


Boronic Acids , Cytidine/analogs & derivatives , Hydroxylamines , Molecularly Imprinted Polymers , Reproducibility of Results , Electrodes , Guanine , Methacrylates
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