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RSC Advances Dec 2022In recent years, graphene quantum dots (GQDs) received huge attention due to their unique properties and potential applicability in different area. Here, we report...
In recent years, graphene quantum dots (GQDs) received huge attention due to their unique properties and potential applicability in different area. Here, we report simple and facile method for the synthesis of GQDs and their functionalization by doping and co-doping using different heteroatom under the optimized conditions. The doping and co-doping of GQDs using boron and nitrogen have been confirmed by FTIR and TEM. The UV-visible and fluorescence techniques have been used to study the optical properties and stability of functionalized GQDs. Further, the screening for enhancement of quantum yields of all GQDs were performed with fluorescence and UV-visible spectra under the optimized conditions. The average QY was obtained as 16.0%, 83.6%, 18.2% and 29.6% for GQDs, B-GQDs, N-GQDs and B,N-GQDs, respectively. The sensor was used to determine paraoxon in water samples. The LOD was observed to be 1.0 × 10 M with linearity range of 0.001 to 0.1 M. The RSD was calculated for the developed B,N-GQDs based sensor and observed to be 2.99% with the regression coefficient as 0.997. All the doped, co-doped and un-doped GQDs possess remarkable properties as a fluorescent probe.
PubMed: 36605643
DOI: 10.1039/d2ra05275j -
ACS Applied Nano Materials Dec 2022Nanoscale cerium-bismuth oxides/oxynitrates were prepared by a scalable low-temperature method at ambient pressure using water as the sole solvent. Solid solutions were...
Nanoscale cerium-bismuth oxides/oxynitrates were prepared by a scalable low-temperature method at ambient pressure using water as the sole solvent. Solid solutions were formed up to a 1:1 Ce/Bi molar ratio, while at higher doping levels, bismuth oxynitrate photocatalysts with a pronounced layered structure were formed. Bismuth caused significant changes in the structure and surface properties of nanoceria, such as the formation of defects, oxygen-containing surface groups, and Lewis and Brønsted acid sites. The prepared bifunctional adsorbents/photocatalysts were efficient in the removal of toxic organophosphate (methyl paraoxon) from water by reactive adsorption followed by photocatalytic decomposition of the parent compound and its degradation product (-nitrophenol). Bi-doped ceria also effectively adsorbed and photodegraded the endocrine disruptors bisphenols A and S and outperformed pure ceria and the P25 photocatalyst in terms of efficiency, durability, and long-term stability. The very low toxicity of Bi-nanoceria to mammalian cells, aquatic organisms, and bacteria has been demonstrated by comprehensive in vivo/in vitro testing, which, in addition to its simple "green" synthesis, high activity, and durability, makes Bi-doped ceria promising for safe use in abatement of toxic chemicals.
PubMed: 36583119
DOI: 10.1021/acsanm.2c03926 -
Food Chemistry May 2023An enzyme-free, sensitive, and convenient approach was reported for the P-nitrophenyl substituent organophosphorus pesticides (NSOPs) of paraoxon-methyl (PM),...
An enzyme-free, sensitive, and convenient approach was reported for the P-nitrophenyl substituent organophosphorus pesticides (NSOPs) of paraoxon-methyl (PM), paraoxon-ethyl (PE), parathion-methyl (PTM) and parathion-ethyl (PTE)) by indirectly quantification of the 4-nitrophenol (4-NP, hydrolysis product of the NSOPs). NaOH instead of hydrolase/nanozyme was applied, and temperature, pH, ultrasound was investigated to improve the NSOPs hydrolysis. Under the optimized conditions, the hydrolysis efficiencies were up to 99.9 %, 99.9 %, 99.6 %, 96.0 % for PM (10 min), PE (30 min), PTM (90 min) and PTE (120 min), based on which a low detection limits of 0.06 (PM), 0.07 (PE), 0.06 (PTM) and 0.07 (PTE) ppb were calculated with the 4-NP detection limit (0.03 ppb). Furthermore, the method exhibited good performance for the NSOPs with recoveries from 88.87 % to 100.33 % in real samples. This indirect approach offered an ultrasensitive alternative for the NSOPs detection, which holds great potential in practical application for the assessment of food safety and environmental risks.
Topics: Pesticides; Paraoxon; Organophosphorus Compounds; Methyl Parathion; Parathion
PubMed: 36563621
DOI: 10.1016/j.foodchem.2022.135218 -
Pharmaceutics Dec 2022Chitosan-decorated liposomes were proposed for the first time for the intranasal delivery of acetylcholinesterase (AChE) reactivator pralidoxime chloride (2-PAM) to the...
Chitosan-decorated liposomes were proposed for the first time for the intranasal delivery of acetylcholinesterase (AChE) reactivator pralidoxime chloride (2-PAM) to the brain as a therapy for organophosphorus compounds (OPs) poisoning. Firstly, the chitosome composition based on phospholipids, cholesterol, chitosans (Cs) of different molecular weights, and its arginine derivative was developed and optimized. The use of the polymer modification led to an increase in the encapsulation efficiency toward rhodamine B (RhB; ~85%) and 2-PAM (~60%) by 20% compared to conventional liposomes. The formation of monodispersed and stable nanosized particles with a hydrodynamic diameter of up to 130 nm was shown using dynamic light scattering. The addition of the polymers recharged the liposome surface (from -15 mV to +20 mV), which demonstrates the successful deposition of Cs on the vesicles. In vitro spectrophotometric analysis showed a slow release of substrates (RhB and 2-PAM) from the nanocontainers, while the concentration and Cs type did not significantly affect the chitosome permeability. Flow cytometry and fluorescence microscopy qualitatively and quantitatively demonstrated the penetration of the developed chitosomes into normal Chang liver and M-HeLa cervical cancer cells. At the final stage, the ability of the formulated 2-PAM to reactivate brain AChE was assessed in a model of paraoxon-induced poisoning in an in vivo test. Intranasal administration of 2-PAM-containing chitosomes allows it to reach the degree of enzyme reactivation up to 35 ± 4%.
PubMed: 36559339
DOI: 10.3390/pharmaceutics14122846 -
Biological & Pharmaceutical Bulletin Mar 2023Carbapenem-resistant bacterial infections pose an urgent threat to public health worldwide. Horizontal transmission of the β-lacatamase Klebsiella pneumoniae...
Carbapenem-resistant bacterial infections pose an urgent threat to public health worldwide. Horizontal transmission of the β-lacatamase Klebsiella pneumoniae carbapenemase (blaKPC) multidrug resistance gene is a major mechanism for global dissemination of carbapenem resistance. Here, we investigated the effects of baicalein, an active ingredient of a Chinese herbal medicine, on plasmid-mediated horizontal transmission of blaKPC from a meropenem-resistant K. pneumoniae strain (JZ2157) to a meropenem-sensitive Escherichia coli strain (E600). Baicalein showed no direct effects on the growth of JZ2157 or E600. Co-cultivation of JZ2157 and E600 caused the spread of meropenem resistance from JZ2157 to E600. Baicalein at 40 and 400 µg/mL significantly inhibited the spread of meropenem resistance. Co-cultivation also resulted in plasmid-mediated transmission of blaKPC from JZ2157 to E600, which was inhibited by baicalein. Therefore, baicalein may be used in clinical practice to prevent or contain outbreaks of carbapenem-resistant infections by inhibiting the horizontal transfer of resistance genes across bacteria species.
Topics: Humans; Klebsiella pneumoniae; Escherichia coli; Meropenem; Genes, MDR; Paraoxon; beta-Lactamases; Bacterial Proteins; Plasmids; Carbapenems; Klebsiella Infections; Anti-Bacterial Agents; Microbial Sensitivity Tests
PubMed: 36543225
DOI: 10.1248/bpb.b22-00500 -
EFSA Journal. European Food Safety... Dec 2022The utility of pesticides in the agricultural field is unquestionable, but at the same time pesticide use presents serious hazards to the environment and the human...
The utility of pesticides in the agricultural field is unquestionable, but at the same time pesticide use presents serious hazards to the environment and the human health. For that reason, detection of pesticides and their biotransformation products in food is of utmost importance. According to previous studies, esterase-based biosensors have been proposed as a viable and efficient solution for the detection of organophosphate pesticides. In this project, a double mutant of the thermostable esterase-2 (EST2) from was studied as a potential biosensor, for its ability to detect residual amounts of pesticides. Initial characterisation of the enzyme was performed, that included determination of optimal pH, thermophilicity, as well as kinetic analysis. Subsequently, the enzyme was studied by enzymatic activity assays with and without the presence of various organophosphate compounds. The effect of the organophosphates on the enzymatic activity was measured and complete inhibition of the enzyme was observed after incubation with paraoxon. These experiments were followed by an additional method involving labelling of the enzyme with a fluorescent probe. In this case, the effect of different pesticides on the EST2 enzyme was monitored by measuring the fluorescence quenching upon addition to the enzyme. Fourteen compounds were screened with this method and significant fluorescence quenching was observed in the presence of paraoxon and methyl-paraoxon when used in equimolar amounts with the enzyme in the range of nanomolar. This biosensor has been also used to test the presence of pesticides in real food samples, like fruits and juices. This research represents a starting point to develop effective fluorescence-based biosensors aiming at the screening of mutants with different pesticide selectivity profiles. The use of this enzyme-based biosensor can have applications in the field of food traceability as well as environmental monitoring, to control the presence of toxic chemicals, in particular organophosphate pesticides.
PubMed: 36531285
DOI: 10.2903/j.efsa.2022.e200922 -
Drug and Chemical Toxicology Jan 2024A series of uncharged salicylaldehyde oximes were synthesized and evaluated for the reactivation of organophosphorus (OP) nerve agents simulants Diethylchlorophosphonate...
A series of uncharged salicylaldehyde oximes were synthesized and evaluated for the reactivation of organophosphorus (OP) nerve agents simulants Diethylchlorophosphonate (DCP) & Diethylcyanophosphonate (DCNP) and pesticides (paraoxon & malaoxon) inhibited Acetylcholinesterase AChE). The computational software Swiss ADME and molinspiration were used to unfold the probability of drug-likeness properties of the oximes derivatives. Substituted aromatic oximes with diethylamino or bromo group with free hydroxyl group ortho to oxime moiety were found efficient to regenerate the enzymatic activity in AChE assay. The alkylation of the ortho hydroxyl group of derivatives led to the loss of reactivation potential. The derivatives with a hydroxyl group and without oxime group and vice versa did not show significant reactivation potency against tested OP toxicants. Further, we also evaluated the reactivation potential of these selected molecules on the rat brain homogenate against different OPs inhibited ChE and found maximum reactivation potency of oxime . The results were further validated by molecular docking and dynamic studies which showed that the hydroxyl group interacted with serine amino acids in the catalytic anionic site of AChE enzyme and was stable up to 200 ns consequently providing proper orientation to oxime moiety for reactivating the OP inhibited enzyme. It has thus been proved by the structure-activity relationship of oximes derivatives that hydroxyl group ortho to oxime is essential for reactivating OP inhibited AChE. Amongst the twenty-one oximes derivatives, was found to be most active in regenerating the paraoxon, malaoxon, DCP and DCNP inhibited AChE enzyme.
Topics: Cholinesterase Inhibitors; Paraoxon; Cholinesterase Reactivators; Acetylcholinesterase; Molecular Docking Simulation; Oximes; Organophosphorus Compounds; Malathion; Nitrophenols
PubMed: 36514993
DOI: 10.1080/01480545.2022.2150210 -
Analytical Chemistry Dec 2022Due to the fascinating properties such as high porosity, large surface areas, and tunable chemical components, metal-organic frameworks (MOFs) have emerged in many...
Due to the fascinating properties such as high porosity, large surface areas, and tunable chemical components, metal-organic frameworks (MOFs) have emerged in many fields including catalysis, energy storage, and gas separation. However, the intrinsic electrical insulation of MOFs severely restricts their application in electrochemistry. Here, we synthesize a series of 2D conductive MOFs (cMOFs) through tuning the structure with atomic precision using simple hydrothermal methods. Various electroactive probes are used to reveal the structure-property relationships in 2D cMOFs. Then, we demonstrate the first exploration and implementation of 2D cMOFs toward the construction of electrochemical biosensors. In particular, the biosensor based on Cu(tetrahydroxy-1,4-quinone) [Cu(THQ)] displays a remarkably improved electrocatalytic performance at a much lower potential. The mechanism study reveals the essential role of charge-transfer interactions between the dense catalytic sites of Cu(THQ) and analytes. Furthermore, the Cu(THQ)-based biosensor demonstrates robust anti-interference capability, good stability, fast response speed, and an ultralow detection limit for paraoxon. These promising results indicate the great potential of cMOFs in biomedical, food safety, and environmental sensing applications.
Topics: Metal-Organic Frameworks; Electric Conductivity; Paraoxon; Catalysis; Electricity; Biosensing Techniques
PubMed: 36454682
DOI: 10.1021/acs.analchem.2c03766 -
Journal of Hazardous Materials Feb 2023The development of high-performance catalyst materials with high catalytic activity for the hydrolysis of organophosphorus toxicants without additional pH buffer...
The development of high-performance catalyst materials with high catalytic activity for the hydrolysis of organophosphorus toxicants without additional pH buffer conditions has become an urgent need for practical application. Here, a multifunctional molecularly imprinted polymer double network hydrogel (MIP-DN) material has been prepared by integrating the first polymer network containing the functional group of bi-amidoxime as the catalytic active center and the cationic polymer polyethyleneimine (PEI) with pH buffer function as the main component of the second network. Advantageously, the resultant MIP-DN hydrogel showed excellent catalytic performance without additional pH buffer conditions, exhibiting a half-life of 25 min for the hydrolysis of paraoxon in pure water. Together with multi-functions of high catalytic activity, self-buffering function and excellent processability, the MIP-DN hydrogel prepared in this work provides a new strategy for the preparation of catalytic materials with practical application value toward toxic organophosphates.
Topics: Organophosphates; Hydrogels; Hydrolysis; Polymers
PubMed: 36423451
DOI: 10.1016/j.jhazmat.2022.130332 -
ACS Applied Materials & Interfaces Nov 2022The development of a portable, quantitative, and user-friendly sensor for on-site monitoring of organophosphorus pesticides (OPs) is significantly urgent to guarantee...
The development of a portable, quantitative, and user-friendly sensor for on-site monitoring of organophosphorus pesticides (OPs) is significantly urgent to guarantee food safety. Herein, a carbon dot/cobalt oxyhydroxide composite (CD/CoOOH)-based fluorescent hydrogel sensor is constructed for precisely quantifying OPs using a homemade portable auxiliary device. As a fluorescence signal indicator, the orange-emissive CD/CoOOH composite is encapsulated into an agarose hydrogel kit for amplifying the detection signals, shielding background interference, and enhancing stability. Acetylcholinesterase (AChE) catalyzes the hydrolysis of the substrate to produce thiocholine, which induces the decomposition of CoOOH and makes the fluorescence enhancement of the hydrogel platform possible. OPs can specifically block the AChE activity to limit thiocholine production, resulting in a decrease in platform fluorescence. The image color of the fluorescent hydrogel kit is transformed into digital information using a homemade auxiliary device, achieving on-site quantitative detection of paraoxon (model target) with a detection limit of 10 ng mL. Harnessing CD/CoOOH composite signatures, hydrogel encapsulation, and portable optical devices, the proposed fluorescence hydrogel platform demonstrated high sensitivity and good anti-interference performance in agricultural sample analysis, indicating considerable potential in the on-site application.
Topics: Pesticides; Organophosphorus Compounds; Acetylcholinesterase; Carbon; Hydrogels; Biosensing Techniques; Cobalt; Thiocholine
PubMed: 36380517
DOI: 10.1021/acsami.2c17450