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1.
Molecules ; 26(2)2021 Jan 07.
Article in English | MEDLINE | ID: mdl-33430495

ABSTRACT

We developed a method for determination of imidacloprid and its metabolites 5-hydroxy imidacloprid, olefin imidacloprid, imidacloprid urea and 6-chloronicotinic acid in Procambarus clarkii (crayfish) tissues using quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography-triple quadrupole mass spectrometry. Samples (plasma, cephalothorax, hepatopancrea, gill, intestine, and muscle) were extracted with acetonitrile containing 0.1% acetic acid and cleaned up using a neutral alumina column containing a primary secondary amine. The prepared samples were separated using reverse phase chromatography and scanned in the positive and negative ion multiple reaction-monitoring modes. Under the optimum experimental conditions, spiked recoveries for these compounds in P. clarkii samples ranged from 80.6 to 112.7% with relative standard deviations of 4.2 to 12.6%. The limits of detection were 0.02-0.5 µg·L-1, the limits of quantification were 0.05-2.0 µg·L-1 and the method of quantification was 0.05-2.0 µg·kg-1. The method is rapid, simple, sensitive and suitable for rapid determination and analysis of imidacloprid and its metabolites in P. clarkii tissues.


Subject(s)
Astacoidea/chemistry , Chromatography, High Pressure Liquid , Metabolome , Neonicotinoids/chemistry , Nitro Compounds/chemistry , Tandem Mass Spectrometry , Animals , Astacoidea/metabolism , Chemical Fractionation/methods , Chromatography, High Pressure Liquid/methods , Metabolomics/methods , Neonicotinoids/isolation & purification , Neonicotinoids/metabolism , Nitro Compounds/isolation & purification , Nitro Compounds/metabolism , Solvents , Tandem Mass Spectrometry/methods
2.
Int J Biol Macromol ; 168: 116-123, 2021 Jan 31.
Article in English | MEDLINE | ID: mdl-33309655

ABSTRACT

Wide dissemination of pesticides for protecting plants against pests has resulted in high production of un-infected crops but higher environmental pollution. High percentages of pesticides are released to the environment and finally use water as the final destination. The current study is concerning by removal of Imidacloprid pesticide from water using pressure-free passage through polymeric membrane integrated design. Both of chitosan and chitosan functionalized silver nanoparticles (AgNPs @chitosan) membranes were prepared, characterized and applied as adsorbent matrix for Imidacloprid. SEM, TEM and PSA analysis revealed the biosynthesis of AgNPs in the range of 25-50 nm. However, SEM and FTIR analysis revealed the proper formation of chitosan membrane and its proper functionalization with silver nanoparticles. Both of chitosan and AgNPs @chitosan membranes succeeded to remove 40 and 85% of Imidacloprid at slightly acidic pH, respectively. Moreover, the amount of removed Imidacloprid was proportional with the amount of its initial concentration indicating the successful removal of Imidacloprid by AgNPs @chitosan membrane even at higher pesticide concentrations. The obtained results indicate the promising use of AgNPs @chitosan membranes for removal of Imidacloprid pesticide from contaminated water depending on the pressure-free design that lacks external energy support.


Subject(s)
Chitosan/chemistry , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Silver/chemistry , Anti-Bacterial Agents/chemistry , Metal Nanoparticles/chemistry , Neonicotinoids/chemistry , Nitro Compounds/chemistry , Pesticides/chemistry , Pesticides/isolation & purification , Polymers
3.
J Sep Sci ; 43(12): 2467-2476, 2020 Jun.
Article in English | MEDLINE | ID: mdl-32212382

ABSTRACT

Dummy template surface molecularly imprinted polymers based on silica gel were prepared through the surface molecular imprinting technique. Nonpoisonous nicotinamide, which is a structural analogue of imidacloprid and acetamidine, was chosen as the dummy template molecule. The obtained polymers were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The results showed that the polymers exhibited high adsorption capacity and selectivity for imidacloprid and acetamiprid. The maximum adsorption capacities of the polymers toward imidacloprid and acetamiprid were 42.05 and 22.99 mg/g, and the adsorption could reach binding equilibrium within 150 min. The polymers were successfully applied as column-filling materials to extract imidacloprid and acetamiprid from tea polyphenols with a relatively high removal rate (92.36 and 95.20%). The polymers also showed great stability and reusability during the application. The obtained polymers possessed good application prospects for removing imidacloprid and acetamiprid in tea polyphenol production processes.


Subject(s)
Molecularly Imprinted Polymers/chemistry , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Polyphenols/chemistry , Silicon Dioxide/chemistry , Tea/chemistry , Gels/chemistry , Molecular Structure , Neonicotinoids/chemistry , Nitro Compounds/chemistry , Particle Size , Surface Properties
4.
Biosens Bioelectron ; 154: 112091, 2020 Apr 15.
Article in English | MEDLINE | ID: mdl-32093897

ABSTRACT

This work presents a signal on-off ratiometric electrochemical sensor coupled with a molecular imprinted polymer (MIP) for imidacloprid (IMI) determination. The ratiometric strategy corrects the detection results by setting 6-(Ferrocenyl)hexanethiol (FcHT) as an internal reference. The MIP membrane, as a molecular recognition receptor, has a three-dimensional structure and is complementary in the shape and chemical functionality to the template. The combination of a ratiometric strategy and MIP improves the sensitivity and selectivity of the sensors. The experimental parameters, such as monomer/template ratio, electropolymerization cycle and adsorption time, are optimized to improve the IMI sensing performance of the as-fabricated electrode. Under optimal electrochemical conditions, the proposed sensor is used to detect IMI in laboratory and real samples. In a range as wide as 5 × 10-7-1 × 10-4 mol L-1, a linear relationship is well established, and the value of the correlation coefficient is 0.9984. The limit of detection (LOD, S/N = 3) is well defined as 4.7 × 10-8 mol L-1. The recovery rates range from 97.4% to 103.5% while testing real samples. The fabricated electrode shows superior anti-interference ability for IMI determination in the presence of analogs at a higher level.


Subject(s)
Biosensing Techniques , Electrochemical Techniques , Molecular Imprinting , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Neonicotinoids/chemistry , Nitro Compounds/chemistry , Polymers/chemistry
5.
Sci Rep ; 10(1): 2586, 2020 02 13.
Article in English | MEDLINE | ID: mdl-32054936

ABSTRACT

Exploring the new catalytic systems for the reduction of organic and inorganic pollutants from an indispensable process in chemical, petrochemical, pharmaceutical and food industries, etc. Hence, in the present work, authors motivated to synthesize bare reduced graphene oxide (rGO), polyaniline (PANI), three different ratios of rGO-PANI(80:20, 50:50, 10:90) composites and rGO-PANI(80:20, 50:50, 10:90) supported mono (Pd) & bimetallic [Pd: Au(1:1, 1:2, 2:1)] nanocomposite by a facile chemical reduction method. Also, it investigated their catalytic performances for the reduction of organic/inorganic pollutants and antimicrobial activities. All the freshly prepared bare rGO, PANI, three different ratios of rGO-PANI(80:20, 50:50, 10:90) composites and rGO-PANI(80:20, 50:50, 10:90)/Pd & Pd: Au(1:1, 1:2, 2:1) nanocomposite hybrid catalysts were characterized using UV-Vis, FT-IR, SEM, FE-SEM, EDAX, HR-TEM, XRD, XPS and Raman spectroscopy analysis. Among them, an optimized best composition of rGO-PANI(80:20)/Pd: Au(1:1) bimetallic nanocomposite hybrid catalyst exhibits better catalytic reduction and antimicrobial activities than other composites, as a result of strong electrostatic interactions between rGO, PANI and bimetal (Pd: Au) NPs through a synergistic effect. Hence, an optimized rGO-PANI(80:20)/Pd:Au(1:1) bimetallic nanocomposite catalyst would be considered as a suitable catalyst for the reduction of different nitroarenes, organic dyes, heavy metal ions and also significantly inhibit the growth of S. aureus, S. Typhi as well as Candida albicans and Candida kruesi in wastewater.


Subject(s)
Aniline Compounds/chemistry , Gold/chemistry , Graphite/chemistry , Nanocomposites/chemistry , Palladium/chemistry , Aniline Compounds/pharmacology , Bacteria/drug effects , Catalysis , Coloring Agents/isolation & purification , Environmental Pollutants/isolation & purification , Fungi/drug effects , Gold/pharmacology , Graphite/pharmacology , Nanocomposites/ultrastructure , Nitro Compounds/isolation & purification , Oxidation-Reduction , Palladium/pharmacology
6.
Crit Rev Anal Chem ; 50(6): 513-537, 2020.
Article in English | MEDLINE | ID: mdl-31559830

ABSTRACT

Polymer microgels loaded with inorganic nanoparticles have gained much attention as catalytic systems for reduction of toxic chemicals. Enhanced catalytic properties of hybrid microgels are related to the stimuli responsive nature of microgels and extraordinary stability of nanoparticles within network of polymer microgels. Catalytic properties of hybrid microgels can be tuned very easily by slight variation in environmental conditions. Herein we have reviewed catalytic reduction of toxic chemicals such as nitroarenes and organic dyes in the presence of appropriate hybrid microgel catalytic systems under different operating conditions of reaction. Recent advancements in catalytic behavior of hybrid microgels with special emphasis on their ability to catalytically degrade various toxic chemicals has been presented in this review.


Subject(s)
Coloring Agents/chemistry , Coloring Agents/isolation & purification , Microgels/chemistry , Nitro Compounds/chemistry , Nitro Compounds/isolation & purification , Photochemical Processes , Water/chemistry , Catalysis
7.
Molecules ; 24(16)2019 Aug 12.
Article in English | MEDLINE | ID: mdl-31408943

ABSTRACT

A multi-residue method for the determination of 107 pesticide residues in wolfberry has been developed and validated. Similar pretreatment approaches were compared, and the linearity, matrix effect, analysis limits, precision, stability and accuracy were validated, which verifies the satisfactory performance of this new method. The LODs and LOQs were in the range of 0.14-1.91 µg/kg and 0.46-6.37 µg/kg, respectively. The recovery of analytes at three fortification levels (10 µg/kg, 50 µg/kg, 100 µg/kg) ranged from 63.3-123.0%, 72.0-118.6% and 67.0-118.3%, respectively, with relative standard deviations (RSDs) below 15.0%. The proposed method was applied to the analysis of fifty wolfberry samples collected from supermarkets, pharmacies and farmers' markets in different cities of Shandong Province. One hundred percent of the samples analyzed included at least one pesticide, and a total of 26 pesticide residues was detected in fifty samples, which mainly were insecticides and bactericide. Several pesticides with higher detection rates were 96% for acetamiprid, 82% for imidacloprid, 54% for thiophanate-methyl, 50% for blasticidin-S, 42% for carbendazim, 42% for tebuconazole and 36% for difenoconazole in wolfberry samples. This study proved the adaptability of the developed method to the detection of multiple pesticide residues in wolfberry and provided basis for the research on the risks to wolfberry health.


Subject(s)
Liquid-Liquid Extraction/methods , Lycium/chemistry , Pesticide Residues/isolation & purification , Benzimidazoles/isolation & purification , Carbamates/isolation & purification , Chromatography, High Pressure Liquid/methods , Humans , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Nucleosides/isolation & purification , Pesticide Residues/classification , Tandem Mass Spectrometry/methods , Thiophanate/isolation & purification , Triazoles/isolation & purification
8.
J Environ Sci Health B ; 54(2): 118-128, 2019.
Article in English | MEDLINE | ID: mdl-30285549

ABSTRACT

The paper reports the kinetics and adsorption isotherm modeling for imidacloprid (IMIDA) and azoxystrobin (AZOXY) in rice straw (RS)/corn cob (CC) and peat (P)/compost (C) based biomixtures. The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intraparticle diffusion models were used to describe the kinetics. The adsorption data were subjected to the Langmuir and the Freundlich isotherms. Results (r2Adj values) suggested that the modified Elovich model was the best suited to explain the kinetics of IMIDA sorption while different models explained AZOXY sorption kinetics in different biomixtures (PFO in RS + C and RS + P; PSO in CC + P and Elovich in CC + C). Biomixtures varied in their capacity to adsorb both pesticides and the adsorption coefficient (Kd) values were 116.8-369.24 (AZOXY) and 24.2-293.4 (IMIDA). The Freundlich isotherm better explained the sorption of both pesticides. Comparison analysis of linear and nonlinear method for estimating the Freundlich adsorption constants was made. In general, r2Adj values were higher for the nonlinear fit (AZOXY = 0.938-0.982; IMIDA = 0.91-0.970) than the linear fit (AZOXY = 0.886-0.993; IMIDA = 0.870-0.974) suggesting that the nonlinear Freundlich equation better explained the sorption. The rice straw-based biomixtures performed better in adsorbing both the pesticides and can be used in bio-purification systems.


Subject(s)
Models, Chemical , Neonicotinoids/chemistry , Nitro Compounds/chemistry , Pyrimidines/chemistry , Strobilurins/chemistry , Adsorption , Composting , Diffusion , Kinetics , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Oryza/chemistry , Pesticides/chemistry , Pesticides/isolation & purification , Plant Stems/chemistry , Pyrimidines/isolation & purification , Soil , Strobilurins/isolation & purification , Zea mays/chemistry
9.
J Sci Food Agric ; 99(3): 1267-1274, 2019 Feb.
Article in English | MEDLINE | ID: mdl-30073655

ABSTRACT

BACKGROUND: Coffee is one of the most popular beverages in the world. However, as daily consumables, coffee beans may contain pesticide residues that are capable of causing adverse health effects. Thus, we investigated residue dynamics in coffee beans using supervised field trials under Good Agricultural Practice conditions and determined the effects of household coffee processing on the coffee-bean pesticide residues dinotefuran and its metabolites 1-methyl-3-(tetrahydro-3-furylmethyl) urea (UF) and 1-methyl-3-(tetrahydro-3-furylmethyl) guanidine (DN). RESULTS: The recovery rate of dinotefuran and its metabolites UF and DN was in the range 73.5%-106.3%, with a relative SD < 10%. The limits of detection and limits of quantification for dinotefuran, UF and DN were all 0.003 and 0.01 mg kg-1 , respectively. Dissipation experiments were conducted over 2015 and 2016 and showed a mean half-life of 40.8 days. Coffee processing procedures were performed as described for traditional household coffee processing in Ethiopia. Dinotefuran contents were reduced by 44.4%-86.7% with washing of coffee beans and the roasting process reduced these contents by 62.2%-100%. DN residues were not detected in roasted coffee beans before day 21 or in brewed coffee before day 35 and UF residues were not detected in brewed coffee before day 35. Kruskal-Wallis analyses indicated large variations in the stability of pesticide residues between processing methods (P ≤ 0.05). Reductions of pesticide concentrations with washing were also significantly lower than those following roasting (P = 0.0001) and brewing processes (P = 0.002). Moreover, processing factors were less than one for all processing stages, indicating reductions of pesticides contents for all processing stages. CONCLUSION: The cumulative effects of the three processing methods are of paramount importance with respect to an evaluation of the risks associated with the ingestion of pesticide residues, particularly those in coffee beans. © 2018 Society of Chemical Industry.


Subject(s)
Coffea/chemistry , Guanidines/chemistry , Neonicotinoids/chemistry , Nitro Compounds/chemistry , Pesticide Residues/chemistry , Chromatography, Liquid , Coffea/metabolism , Coffee/chemistry , Coffee/metabolism , Ethiopia , Food Contamination/analysis , Food Handling , Guanidines/isolation & purification , Guanidines/metabolism , Neonicotinoids/isolation & purification , Neonicotinoids/metabolism , Nitro Compounds/isolation & purification , Nitro Compounds/metabolism , Pesticide Residues/isolation & purification , Pesticide Residues/metabolism , Seeds/chemistry , Seeds/metabolism , Solid Phase Extraction , Tandem Mass Spectrometry
10.
Free Radic Biol Med ; 129: 430-439, 2018 12.
Article in English | MEDLINE | ID: mdl-30321702

ABSTRACT

Alzheimer's disease (AD) is a progressive form of dementia characterized by increased production of amyloid-ß plaques and hyperphosphorylated tau protein, mitochondrial dysfunction, elevated oxidative stress, reduced protein clearance, among other. Several studies showed systemic modifications of immune and inflammatory systems due, in part, to decreased levels of CD3+ lymphocytes in peripheral blood in AD. Considering that oxidative stress, both in the brain and in the periphery, can influence the activation and differentiation of T-cells, we investigated the 3-nitrotyrosine (3-NT) proteome of blood T-cells derived from AD patients compared to non-demented (ND) subjects by using a proteomic approach. 3-NT is a formal protein oxidation and index of nitrosative stress. We identified ten proteins showing increasing levels of 3-NT in CD3+ T-cells from AD patients compared with ND subjects. These proteins are involved in energy metabolism, cytoskeletal structure, intracellular signaling, protein folding and turnover, and antioxidant response and provide new insights into the molecular mechanism that impact reduced T-cell differentiation in AD. Our results highlight the role of peripheral oxidative stress in T-cells related to immune-senescence during AD pathology focusing on the specific targets of protein nitration that conceivably can be suitable to further therapies. Further, our data demonstrate common targets of protein nitration between the brain and the periphery, supporting their significance as disease biomarkers.


Subject(s)
Alzheimer Disease/diagnosis , Lymphocytes/chemistry , Nitro Compounds/immunology , Proteome/immunology , Tyrosine/analogs & derivatives , Aged , Aged, 80 and over , Alzheimer Disease/immunology , Alzheimer Disease/metabolism , Antioxidants/chemistry , Antioxidants/metabolism , Biomarkers/metabolism , CD3 Complex/genetics , CD3 Complex/immunology , Case-Control Studies , Cell Separation , Cytoskeletal Proteins/chemistry , Cytoskeletal Proteins/immunology , Energy Metabolism/genetics , Female , Gene Expression , Humans , Lymphocytes/immunology , Male , Middle Aged , Nitro Compounds/chemistry , Nitro Compounds/isolation & purification , Nitrosative Stress , Oxidative Stress , Primary Cell Culture , Proteome/genetics , Proteome/metabolism , Signal Transduction , Tyrosine/metabolism
11.
Food Chem ; 268: 264-270, 2018 Dec 01.
Article in English | MEDLINE | ID: mdl-30064756

ABSTRACT

The aim of this study was to determine the insecticide residue processing factor (PF) from plums to prunes and the effect of the industrial processing of prunes residue concentrations. Our results show an increase of insecticide concentrations during plum dehydration that is explained by fruit water loss; however, the normalized insecticide residue concentration, based on plum dry weights to compensate dehydration, was reduced. The water washing and tenderizing of prunes produced insecticide residue reductions of 22.9 ±â€¯4.5% and 21.9 ±â€¯4.2%, respectively. PF were: 1.157, 1.872, 1.316, 0.192, 2.198, 0.775 and 0.156 for buprofezin, l-cyhalothrin, spirodiclofen, indoxacarb, acetamiprid, imidacloprid and emamectin benzoate, respectively, being directly related to water solubility, aqueous hydrolysis and degradation point and inversely related to molecular mass and melting point. In plums for the dehydrated agroindustry the final product is prunes, therefore, it is crucial to consider the PF to determine the specific preharvest interval for this important agroindustry.


Subject(s)
Gas Chromatography-Mass Spectrometry , Pesticide Residues/analysis , Prunus domestica/chemistry , Fruit/chemistry , Fruit/metabolism , Ivermectin/analogs & derivatives , Ivermectin/analysis , Ivermectin/chemistry , Ivermectin/isolation & purification , Neonicotinoids/analysis , Neonicotinoids/chemistry , Neonicotinoids/isolation & purification , Nitriles/analysis , Nitriles/chemistry , Nitriles/isolation & purification , Nitro Compounds/analysis , Nitro Compounds/chemistry , Nitro Compounds/isolation & purification , Oxazines/analysis , Oxazines/chemistry , Oxazines/isolation & purification , Oxidation-Reduction , Pesticide Residues/chemistry , Pesticide Residues/isolation & purification , Prunus domestica/metabolism , Pyrethrins/analysis , Pyrethrins/chemistry , Pyrethrins/isolation & purification , Solid Phase Extraction
12.
J S Afr Vet Assoc ; 89(0): e1-e5, 2018 Jul 09.
Article in English | MEDLINE | ID: mdl-30035593

ABSTRACT

Reports were received that Cape spurfowl (Pternistis capensis) fell during flight and scrambled uncoordinatedly for cover and some died. Three carcases were submitted for necropsy examination, which revealed mainly congestion of the carcases and haemorrhages. Common causes of acute mortalities in birds were first excluded, but there was a history of possible exposure to imidacloprid-treated barley seeds. Imidacloprid, a neonicotinoid insecticide, is used to protect various crops against invertebrate pests. The combined crop contents and pooled liver samples collected from the Cape spurfowl during necropsy were submitted for liquid chromatography-high-resolution mass spectrometry (LC-HRMS) for imidacloprid analysis. Imidacloprid and several of its metabolites were detected in the samples. Farmers should cover sown seeds with a layer of soil and remove any spilled seeds, as granivorous birds are susceptible to imidacloprid intoxication. Regulatory authorities should re-evaluate the risk posed by imidacloprid-treated seeds for pollinators and granivorous birds.


Subject(s)
Bird Diseases/chemically induced , Insecticides/poisoning , Neonicotinoids/poisoning , Nervous System Diseases/veterinary , Nitro Compounds/poisoning , Animals , Autopsy/veterinary , Bird Diseases/pathology , Birds , Gas Chromatography-Mass Spectrometry , Insecticides/isolation & purification , Liver/pathology , Neonicotinoids/isolation & purification , Nervous System Diseases/chemically induced , Nervous System Diseases/pathology , Nitro Compounds/isolation & purification , South Africa
13.
Bull Environ Contam Toxicol ; 101(1): 137-143, 2018 Jul.
Article in English | MEDLINE | ID: mdl-29858622

ABSTRACT

Environmental contamination with neonicotinoid insecticides represents an issue of wide concern due to their negative effects on pollinators. The goal of this work was to evaluate the potential use of biomixtures employed in biopurification systems (BPS) to remove two neonicotinoid pesticides, imidacloprid and thiamethoxam, from wastewater of agricultural origin. The removal was assayed by quantification of the parent compounds and the detection of putative transformation products of imidacloprid by means of LC-MS/MS, and mineralization of radiolabeled imidacloprid. Two biomixtures (B1, B2) were prepared using coconut fiber, compost and two soils pre-exposed to imidacloprid (volumetric composition 50:25:25). After spiking of neonicotinoids and 228 days of treatment, the removal ranged from 22.3%-30.3% and 38.6%-43.7% for imidacloprid and thiamethoxam, respectively. Transformation products imidacloprid-urea, desnitro-imidacloprid and desnitro-olefin-imidacloprid were detected in both biomixtures. The mineralization of 14C-imidacloprid revealed DT50 (mineralization half-lives) values of 3466 and 7702 days in the biomixtures B1 and B2, respectively, markedly lower than those in the soil used in their preparation (8667 and 9902 days, respectively). As demonstrated by these findings, the high persistence of these compounds in the BPS suggests that additional biological (or physicochemical) approaches should be explored in order to decrease the impact of neonicotinoid-containing wastewater of agricultural origin.


Subject(s)
Insecticides/isolation & purification , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Water Purification , Agriculture , Biodegradation, Environmental , Carbon Radioisotopes/chemistry , Chemical Phenomena , Chromatography, Liquid , Half-Life , Limit of Detection , Oxazines/isolation & purification , Soil/chemistry , Soil Pollutants/isolation & purification , Tandem Mass Spectrometry , Thiamethoxam , Thiazoles/isolation & purification , Wastewater/chemistry , Water Pollutants, Chemical/isolation & purification
14.
Food Chem ; 255: 81-88, 2018 Jul 30.
Article in English | MEDLINE | ID: mdl-29571502

ABSTRACT

A magnetic molecularly imprinted polymer (MMIP) adsorbent for imidacloprid was prepared using non-covalent approach with functionalized nano Fe3O4 particles (magnetic cores), imidacloprid (template), acrylic acid (functional monomer), ethylene glycol dimethacrylate (cross linker) and azobisisobutyronitrile (initiator) and used for selective separation of imidacloprid from honey and vegetable samples. The polymers were characterized using FT-IR spectroscopy, SEM and TEM images. For analysis of imidacloprid LC-MS/MS equipment was used. Adsorption kinetics was best explained by pseudo-second-order kinetic model. Adsorption data fitted well into linearized Freundlich equation (R2 > 0.98). Scatchard plot analysis indicates the presence of two classes of binding sites in the MMIPs with the Cmax of 1889.6 µg g-1 and 65448.9 µg g-1, respectively. MMIPs demonstrated much higher affinity for imidacloprid over structurally similar analogues acetamiprid (α = 23.59) and thiamethoxam (α = 17.15). About 87.1 ±â€¯5.0% and 90.6 ±â€¯5.6% of the added imidacloprid was recovered from MMIPs in case of fortified eggplant and honey samples, respectively.


Subject(s)
Honey , Molecular Imprinting/methods , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Polymers/chemistry , Solanum melongena/chemistry , Adsorption , Food Contamination/analysis , Magnetics , Methacrylates/chemistry , Microscopy, Electron, Scanning , Microscopy, Electron, Transmission , Nitriles/chemistry , Oxazines/isolation & purification , Polymers/chemical synthesis , Solid Phase Extraction/instrumentation , Solid Phase Extraction/methods , Spectroscopy, Fourier Transform Infrared , Tandem Mass Spectrometry , Thiamethoxam , Thiazoles/isolation & purification
15.
Biosens Bioelectron ; 102: 464-469, 2018 Apr 15.
Article in English | MEDLINE | ID: mdl-29182929

ABSTRACT

One major marker of nitrosative stress is the formation of 3-Nitrotyrosine (3-NT) from Tyrosine (Tyr) by adding a nitro group (-NO2) with nitrating agents. Nitration of Tyr often causes loss of protein activity and is linked with many diseases. In this article, we detect 3-NT and discriminate it from Tyr with Differential Pulse Voltammetry (DPV) as it is a very important biomarker. We first examined redox (oxidation/reduction) properties and stability of 3-NT in detail. Second, we provided the Tyr and 3-NT discrimination with DPV and compared with the chromatography. We then explored the interaction of 3-NT and DNA oligonucleotides. Our findings demonstrate that 3-NT can be used as a new electrochemical indicator, which is able to detect hybridization of probe (single stranded DNA-ssDNA) and hybrid (double stranded DNA-dsDNA) both via 3-NT reduction and guanine oxidation signal changes at the same time. The signal differences enabled us to distinguish ssDNA and dsDNA without using a label or a tag. Moreover, we achieved to detect hybridization of DNA by using the reduction signal of 3-NT obtained at -0.4V vs. Ag/AgCl. More importantly, we observed the changes of the reduction signals of 3-NT after the interaction of probe and hybrid sequences. We showed that 3-NT signal decreases more with hybrid than the probe. Our platform, for the first time, demonstrates the detection of hybridization both guanine oxidation and indicator reduction signal changes at the same time. Moreover, we, for the first time, demonstrated the interaction between 3-NT and DNA.


Subject(s)
Biosensing Techniques/methods , Nitro Compounds/chemistry , Nucleic Acid Hybridization/methods , Tyrosine/chemistry , DNA, Single-Stranded/chemistry , Electrochemistry , Nitro Compounds/isolation & purification , Oligonucleotides/chemistry , Oxidation-Reduction , Tyrosine/analogs & derivatives , Tyrosine/isolation & purification
16.
J Environ Sci Health B ; 52(9): 671-682, 2017 Sep 02.
Article in English | MEDLINE | ID: mdl-28679066

ABSTRACT

Low cost agro-waste biosorbents namely eucalyptus bark (EB), corn cob (CC), bamboo chips (BC), rice straw (RS) and rice husk (RH) were characterized and used to study atrazine and imidacloprid sorption. Adsorption studies suggested that biosorbents greatly varied in their pesticide sorption behaviour. The EB was the best biosorbent to sorb both atrazine and imidacloprid with KF values of 169.9 and 85.71, respectively. The adsorption isotherm were nonlinear in nature with slope (1/n) values <1. The Freundlich constant Correlating atrazine/imidacloprid sorption parameter [KF.(1/n)] with the physicochemical properties of the biosorbents suggested that atrazine adsorption correlated significantly to the aromaticity, polarity, surface area, fractal dimension, lacunarity and relative C-O band intensity parameters of biosorbents. Probably, both physisorption and electrostatic interactions were responsible for the pesticide sorption. The eucalyptus bark can be exploited as low cost adsorbent for the removal of these pesticides as well as a component of on-farm biopurification systems.


Subject(s)
Agriculture/methods , Atrazine/isolation & purification , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Pesticides/isolation & purification , Adsorption , Atrazine/chemistry , Eucalyptus , Neonicotinoids/chemistry , Nitro Compounds/chemistry , Oryza , Pesticides/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Zea mays
17.
Water Environ Res ; 89(5): 440-450, 2017 May 01.
Article in English | MEDLINE | ID: mdl-28442004

ABSTRACT

In this study, a multi-response optimization method using Taguchi's robust design approach is proposed for imidacloprid removal by reverse osmosis. Tests were conducted with different membrane type (BW30, LFC-3, CPA-3), transmembrane pressure (TMP = 20, 25, 30 bar), volume reduction factor (VRF = 2, 3, 4), and pH (3, 7, 11). Quality and quantity of permeate are optimized with the multi-response characteristics of the total dissolved solid (TDS), conductivity, imidacloprid, and total organic carbon (TOC) rejection ratios and flux of permeate. The optimized conditions were determined as membrane type of BW30, TMP 30 bar, VRF 3, and pH 11. Under these conditions, TDS, conductivity, imidacloprid, and TOC rejections and permeate flux were 97.50 97.41, 97.80, 98.00% and 30.60 L/m2·h, respectively. Membrane type was obtained as the most effective factor; its contribution is 64%. The difference between the predicted and observed value of multi-response signal/noise (MRSN) is within the confidence interval.


Subject(s)
Imidazoles/isolation & purification , Insecticides/isolation & purification , Nitro Compounds/isolation & purification , Water Pollutants, Chemical/isolation & purification , Water Purification/methods , Neonicotinoids , Osmosis
18.
Nat Prod Rep ; 34(4): 343-360, 2017 04 05.
Article in English | MEDLINE | ID: mdl-28271107

ABSTRACT

Covering up to September 2016This review reports on natural compounds that derive from the isoxazolinone ring as well as the 3-nitropropanoic acid (3-NPA) moiety. These structural elements occur in compounds that have been identified in plants, insects, bacteria and fungi. In particular, plants belonging to the family of legumes produce such compounds. In the case of insects, isoxazolin-5-one and 3-NPA derivatives were found in leaf beetles of the subtribe Chrysomelina. A number of these natural products have been synthesized so far. In the case of the single compound 3-NPA, several synthetic strategies have been reported and some of the most efficient routes are reviewed. The toxicity of 3-NPA results from its ability to bind covalently to the catalytic center of succinate dehydrogenase causing irreversible inhibition of mitochondrial respiration. As a motif that is produced by many species of plants, leaf beetles and fungi, different detoxification mechanisms for 3-NPA have evolved in different species. These mechanisms are based on amide formation of 3-NPA with amino acids, reduction to ß-alanine, ester formation or oxidation to malonic acid semialdehyde. The biosynthetic pathways of 3-NPA and isoxazolin-5-one moieties have been studied in fungi, plants and leaf beetles. In the case of fungi, 3-NPA derives from aspartate, while leaf beetles use essential amino acids such as valine as ultimate precursors. In the case of plants, it is supposed that malonate serves as a precursor of 3-NPA, as indicated by feeding of 14C-labeled precursors to Indigofera spicata. In other leguminous plants it is suggested that asparagine is incorporated into compounds that derive from isoxazolin-5-one, which was indicated by 14C-labeled compounds as well. In the case of leaf beetles it was demonstrated that detection of radioactivity after 14C-labeling from a few precursors is not sufficient to unravel biosynthetic pathways.


Subject(s)
Biological Products/chemistry , Isoxazoles/chemistry , Nitro Compounds/chemistry , Propionates/chemistry , Animals , Biological Products/isolation & purification , Isoxazoles/isolation & purification , Molecular Structure , Nitro Compounds/isolation & purification , Propionates/isolation & purification
19.
J Environ Sci Health B ; 52(5): 326-337, 2017 May 04.
Article in English | MEDLINE | ID: mdl-28277079

ABSTRACT

Bentonite was modified by quaternary ammonium cations viz. cetytrimethylammonium (CTA), cetylpyridinium (CP), rioctylmethylammonium (TOM) and pcholine (PTC) at 100% cation exchange capacity of bentonite and was characterized by X-ray diffraction, CHNS elemental analyser and Fourier transform infrared spectroscopy. The sorption of imidacloprid on organobentonites/bentonite was studied by batch method. Normal bentonite could adsorb imidacloprid only upto 19.31-22.18% while all organobentonites except PTC bentonite (PTCB), enhanced its adsorption by three to four times. Highest adsorption was observed in case of TOM bentonite (TOMB) (76.94-83.16%). Adsorption kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models. For normal bentonite data were best fitted to pseudo-first-order kinetic, while for organobentonites fitted to pseudo-second-order kinetics. Sorption data were analysed using Freundlich, Langmuir, Temkin and Dubinin-Radushkevich isotherm models. Data were well fitted to Freundlich adsorption isotherm. Product of Freundlich adsorption constant and heterogeneity parameter (Kf.1/n) was in following order: TOMB (301.87) > CTA bentonite (CTAB) (152.12) > CP bentonite (CPB) (92.58) > bentonite (27.25). Desorption study confirmed hysteresis and concentration dependence. The present study showed that the organobentonite could be a good sorbent for removal of imidacloprid from natural water sample also. Percentage adsorption and Distribution coefficient (mL g-1) value of different adsorbent was in following order: TOMB (74.85% and 297.54) > CTAB (55.78% and 126.15) > CPB (45.81% and 84.55) > bentonite (10.65% and 11.92).


Subject(s)
Bentonite/chemistry , Imidazoles/chemistry , Nitro Compounds/chemistry , Water Pollutants, Chemical/chemistry , Adsorption , Imidazoles/isolation & purification , Kinetics , Models, Chemical , Neonicotinoids , Nitro Compounds/isolation & purification , Spectroscopy, Fourier Transform Infrared , Water/chemistry , Water Pollutants, Chemical/isolation & purification , X-Ray Diffraction
20.
Sci Total Environ ; 577: 376-385, 2017 Jan 15.
Article in English | MEDLINE | ID: mdl-27817922

ABSTRACT

Agri-wastes biochars viz. eucalyptus bark (EBBC), corn cob (CCBC), bamboo chips (BCBC), rice husk (RHBC) and rice straw (RSBC) and acid treated RSBC (T-RSBC), were characterized for their physico-chemical properties and sorption behaviour of atrazine and imidacloprid was studied. Kinetics study suggested that except atrazine adsorption on RSBC, which was best explained by the pseudo second order model, sorption of atrazine and imidacloprid on biochars was well explained by the modified Elovich model. Among the five normal biochars, the RSBC showed the maximum atrazine (37.5-70.7%) and imidacloprid (39.9-77.8%) sorption. The phosphoric acid treatment of RSBC further enhanced the sorption of both pesticides in T-RSBC. The Freundlich adsorption isotherms were highly nonlinear and percent adsorption decreased with increase in pesticide concentration in solution. Pesticide adsorption on biochars was affected by their aromaticity, polarity, pore diameter, pH and weak acid fraction. Thus, rice straw biochars have great potential for environmental implications and can be exploited as adsorbents for pesticide industry spewed waste water purification.


Subject(s)
Atrazine/isolation & purification , Charcoal/chemistry , Neonicotinoids/isolation & purification , Nitro Compounds/isolation & purification , Pesticides/isolation & purification , Water Pollutants, Chemical/isolation & purification , Water Purification , Adsorption , Wastewater
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