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Physical Chemistry Chemical Physics :... May 2023Guest molecules containing chromophore groups encapsulated by β-cyclodextrin (β-CD) generate circular dichroism (CD) signals, which enables a preliminary prediction of...
Guest molecules containing chromophore groups encapsulated by β-cyclodextrin (β-CD) generate circular dichroism (CD) signals, which enables a preliminary prediction of their binding modes. However, the accurate determination of the representative binding conformation (RC) remains a challenging task due to the complex conformational space of these host-guest systems. Here, we combine a molecular dynamics/quantum mechanics/continuum solvent model (MD/QM/CSM) with induced circular dichroism (ICD) data (N. L. Pacioni, A. B. Pierini and A. V. Veglia., 2013, , 319-324.) to explore the binding mechanism of β-CD with four -methylcarbamate molecules: promecarb (PC), bendiocarb (BC), carbaryl (CY) and carbofuran (CF). In aqueous solution, their stability decreases as: PC > BC > CY > CF. Comparing the ECD spectra computed from TD-DFT with the ICD data can help eliminate many common binding configurations and identify the RC. The host-guest binding affinities (BAs) estimated using a ONIOM2(B971:PM6)/SMD model reproduce the measured binding trend, reveal the competition between the non-covalent interaction and solvent effect and explain the large difference in their binding modes. We also examine the fluctuations in the computed BA using similar structures.
Topics: beta-Cyclodextrins; Molecular Dynamics Simulation; Solvents
PubMed: 37184134
DOI: 10.1039/d3cp01252b -
ACS Omega Apr 2022Magnetic sorbents based on iron-aluminum-mixed metal hydroxides composited with metal-organic frameworks (MOFs) were designed and synthesized using different benzoate...
Magnetic Solid-Phase Extraction of Carbamate Pesticides Using Magnetic Metal-Organic Frameworks Derived from Benzoate Ligands, Followed by Digital Image Colorimetric Screening and High-Performance Liquid Chromatography Analysis.
Magnetic sorbents based on iron-aluminum-mixed metal hydroxides composited with metal-organic frameworks (MOFs) were designed and synthesized using different benzoate ligands, including terephthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,3,5-benzenetricarboxylic acid, and 1,2,4,5-benzenetetracarboxylic acid. The magnetic MOF derived from terephthalic acid ligand exhibited an excellent extraction efficiency, with adsorption capacities in the range of 2193-4196 mg kg, and was applied for magnetic solid-phase extraction (MSPE) of carbamate pesticides, that is, bendiocarb, carbosulfan, carbofuran, carbaryl, propoxur, isoprocarb, and promecarb. Simple digital image colorimetry based on the diazotization reaction and high-performance liquid chromatography (HPLC) were utilized for fast screening and quantification purposes, respectively. A good analytical performance for a simple screening approach using portable equipment was obtained with detection limits in the range of 1.0-18.0 μg L. Under the optimized MSPE-HPLC conditions, the entire developed procedure provided a wide linear range between 0.015 and 1000 μg L, low limits of detection, and limits of quantitation ranging from 0.005 to 0.090 and 0.015-0.300 μg L, respectively. Enrichment factors up to 184 were achieved. The intra- and interday relative standard deviations were below 6.7 and 9.4%, respectively. The proposed MSPE-digital image colorimetry and MSPE-HPLC methods were successfully applied for screening and determining carbamate pesticides in fruits and vegetables. The recoveries were obtained in a satisfactory range of 71.5-122.8%. This discovery has led to the development of integration methods using newly synthesized sorbent materials for the enrichment of carbamate pesticides prior to their analysis in complicated samples. The developed MSPE coupled with digital image colorimetry was efficient for fast carbamate contamination screening, while MSPE-HPLC offered a sensitive analytical methodology for quantifying contaminated samples.
PubMed: 35449973
DOI: 10.1021/acsomega.2c00596 -
Electrophoresis Mar 2015The applicability of an ionic liquid-based cationic surfactant 1-dodecyl-3-methyl-imidazolium tetrafluoroborate (C12 MImBF4 ) as pseudostationary phase in MEKC has been...
The applicability of an ionic liquid-based cationic surfactant 1-dodecyl-3-methyl-imidazolium tetrafluoroborate (C12 MImBF4 ) as pseudostationary phase in MEKC has been evaluated for the analysis of 11 carbamate pesticides (promecarb, carbofuran, metolcarb, fenobucarb, aldicarb, propoxur, asulam, benomyl, carbendazim, ethiofencarb, isoprocarb) in juice samples. Under optimum conditions (separation buffer, 35 mM NaHCO3 and 20 mM C12 MImBF4 , pH 9.0; capillary temperature 25°C; voltage -22 kV) the analysis was carried out in less than 12 min, using hydrodynamic injection (50 mbar for 7.5 s) and detection at 200 nm. For the extraction of these CRBs from juice samples, a dispersive liquid-liquid microextraction (DLLME) procedure has been proposed, by optimization of variables affecting the efficiency of the extraction. Following this treatment, sample throughput was approximately 12 samples per hour, obtaining a preconcentration factor of 20. Matrix-matched calibration curves were established using tomato juice as representative matrix (from 5 to 250 μg/L for CBZ, BY, PX, CF, FEN, ETH, ISP, and 25-250 μg/L for ASL, ALD, PRC, MTL), obtaining quantification limits ranging from 1 to 18 μg/L and recoveries from 70 to 96%, with RSDs lower than 9%.
Topics: Beverages; Borates; Carbamates; Chromatography, Micellar Electrokinetic Capillary; Imidazoles; Ionic Liquids; Linear Models; Solanum lycopersicum; Models, Chemical; Reproducibility of Results; Sensitivity and Specificity; Surface-Active Agents
PubMed: 25546365
DOI: 10.1002/elps.201400311