Synthesis and application of imprinted polyvinylimidazole-silica hybrid copolymer for Pb2+ determination by flow-injection thermospray flame furnace atomic absorption spectrometry

A novel ion imprinted polyvinylimidazole-silica hybrid copolymer (IIHC) was synthesized and used as a selective solid sorbent for Pb(2+) ions preconcentration using an on-line solid phase extraction (SPE) system coupled to TS-FF-AAS. The ionic hybrid sorbent was prepared using 1-vinylimidazole and 3-(trimethoxysilyl)propylmethacrylate as monomers, Pb(2+) ions as template, tetraethoxysilane as reticulating agent and 2,2'-azobis-isobutyronitrile as initiator. The best on-line SPE conditions concerning sorption behavior, including sample pH (6.46), buffer concentration (9.0 mmol L(-1)), eluent (HNO(3)) concentration (0.5 mol L(-1)) and preconcentration flow rate (4.0 mL min(-1)), were optimized by means of full factorial design and Doehlert matrix. The analytical curve ranged from 2.5 to 65.0 μg L(-1) (r=0.999) with limit of detection of 0.75 μg L(-1); the precision (repeatability) calculated as relative standard deviation (n=10) was 5.0 and 3.6% for Pb(2+) concentration of 10.0 and 60.0 μg L(-1), respectively. From on-line breakthrough curve, column capacity was 3.5 mg g(-1). Preconcentration factor (PF), consumptive index (CI) and concentration efficiency (CE) were 128.0, 0.16 mL and 25.6 min(-1), respectively. The selective performance of the sorbent, based on relative selectivity coefficient, was compared to NIC (non imprinted copolymer) for the binary mixture Pb(2+)/Cd(2+), Pb(2+)/Cu(2+) and Pb(2+)/Zn(2+). The results showed that ion imprinted polyvinylimidazole-silica hybrid polymer had higher selectivity for Pb(2+) than NIC at 64.9, 16.0 and 8.8 folds. The developed method was successfully applied for highly sensitive and selective Pb(2+) determination in different kinds of water samples, parenteral solutions and urine. Accuracy was also assessed by analyzing certified reference fish protein (DORM-3) and marine sediment (MESS-3 and PACS-2) with satisfactory results.     

Kinetics and mechanism of the reactions of O‐aryl S‐(4‐nitrophenyl) dithiocarbonates with anilines in aqueous ethanol

The reactions of O‐(4‐methylphenyl) S‐(4‐nitrophenyl) dithiocarbonate and O‐(4‐chlorophenyl) S‐(4‐nitrophenyl) dithiocarbonate with a series of anilines are subjected to a kinetic investigation in 44 wt% ethanol–water, at 25.0 °C and an ionic strength of 0.2 M. The reactions are followed spectrophotometrically at 420 nm (appearance of 4‐nitrobenzenethiolate anion). Under excess amine, pseudo‐first‐order rate coefficients (k_obs) are found. For the reactions of both substrates with anilines, plots of k_obs versus free amine concentration at constant pH are nonlinear upwards, according to a second‐order polynomial equation. This kinetic behavior is in agreement with a stepwise mechanism consisting of two tetrahedral intermediates, one zwitterionic (T^±) and the other anionic (T^?), with a kinetically significant proton transfer from T^± to an aniline to yield T^?. The rate equation was derived from the proposed mechanism. By nonlinear least‐squares fitting of the rate equation to the experimental data, values of the rate micro‐coefficients involved in both steps were determined. Copyright © 2009 John Wiley & Sons, Ltd.     

Magnetic properties of RCr2Si2 compounds (R=Tb,Er)

We report on magnetic properties of RCr₂Si₂ compounds with R=Tb, Er. The polycrystalline samples were characterized by powder X-ray diffraction and found to be isostructurally crystallizing in the ThCr₂Si₂-type tetragonal structure. The samples were further investigated by specific heat, AC-susceptibility and magnetization methods in the temperature range 2–900 K and in magnetic fields up to 9 T. The magnetic measurements revealed the magnetic ordering of the rare-earth moments below about 2 K, whilst no high-temperature ordering of the Cr moments was observed. The evidence of for Cr magnetism is corroborated by results of first-principles calculations based on the density functional theory (DFT).     

New PEPTIR-2.0 Peptide Designed for Use as Recognition Element in Electrochemical Biosensors with Improved Specificity towards E. coli O157:H7

The detection of pathogens through alternative methodologies based on electrochemical biosensors is being studied. These devices exhibit remarkable properties, such as simplicity, specificity, and high sensitivity in monitoring pathogens. However, it is necessary to continue conducting studies that adequately improve these characteristics, especially the recognition molecule. This work aims to design and evaluate a new peptide, named PEPTIR-2.0, as a recognition molecule in electrochemical biosensors to detect E. coli O157:H7 in water. PEPTIR-2.0 was obtained from modifications of the PEPTIR-1.0 peptide sequence, which was previously reported and exhibited excellent properties for detecting and quantifying this pathogenic microorganism. PEPTIR-1.0 is a peptide analogous to the TIR (Translocated Intimin Receptor) protein capable of interacting with the Intimin outer membrane. The basis of this study was to obtain, by using bioinformatics tools, a molecule analogous to PEPTIR-1.0 that maintains its three-dimensional structure but increases the hydrophobic interactions between it and Intimin, since these intermolecular forces are the predominant ones. The designed PEPTIR-2.0 peptide was immobilized on screen-printed electrodes modified with gold nanoparticles. The detection capacity of E. coli O157:H7 in water was evaluated using electrochemical impedance spectroscopy in the presence of other microorganisms, such as P. aeruginosa, S. aureus, and non-pathogenic E. coli. The results showed that PEPTIR-2.0 confers remarkable specificity to the biosensor towards detecting E. coli, even higher than PEPTIR-1.0.     

In Silico and Experimental Investigation of the Biological Potential of Some Recently Developed Carprofen Derivatives

The efficient regioselective bromination and iodination of the nonsteroidal anti-inflammatory drug (NSAID) carprofen were achieved by using bromine and iodine monochloride in glacial acetic acid. The novel halogenated carprofen derivatives were functionalized at the carboxylic group by esterification. The regioselectivity of the halogenation reaction was evidenced by NMR spectroscopy and confirmed by X-ray analysis. The compounds were screened for their in vitro antibacterial activity against planktonic cells and also for their anti-biofilm effect, using Gram-positive bacteria (Staphylococcus aureus ATCC 29213, Enterococcus faecalis ATCC 29212) and Gram-negative bacteria (Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853). The cytotoxic activity of the novel compounds was tested against HeLa cells. The pharmacokinetic and pharmacodynamic profiles of carprofen derivatives, as well as their toxicity, were established by in silico analyses.     

Evaluation of the Photocatalytic Properties of Copper Oxides/Graphene/TiO2 Nanoparticles Composites

Easy and cost-efficient modifications of titanium dioxide nanoparticles that improve their efficiency in the visible light domain represent a continuous and challenging research topic. In addition, the effect of graphene on the overall photocatalytic process is still debated. Consequently, herein, we prepared a series of TiO₂ nanoparticle-based composites with different copper oxide mass content (1–3%) and co-doped with graphene of different oxidation degrees. Different characterization techniques were used to analyze the structural and physico-chemical properties of the obtained composites: Scanning Electron Microscopy (SEM)/Transmission Electron Microscopy (TEM)/Energy-dispersive X-ray spectroscopy (EDX) analysis, X-ray powder diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic performance was evaluated by the degradation of methylene blue under both UVA and visible light irradiation. The nanocomposites show very good photocatalytic activity independent of the presence of reduced graphene oxide, due to the Cu₂O/CuO-TiO₂ heterojunctions. This finding has been confirmed by the very efficient visible-light-driven degradation of amoxicillin and ciprofloxacin.     

Nanocrystalline Skinnerite (Cu3SbS3) Prepared by High-Energy Milling in a Laboratory and an Industrial Mill and Its Optical and Optoelectrical Properties

Copper, antimony and sulfur in elemental form were applied for one-pot solid-state mechanochemical synthesis of skinnerite (Cu₃SbS₃) in a laboratory mill and an industrial mill. This synthesis was completed after 30 min of milling in the laboratory mill and 120 min in the industrial mill, as corroborated by X-ray diffraction. XRD analysis confirmed the presence of pure monoclinic skinnerite prepared in the laboratory mill and around 76% monoclinic skinnerite, with the secondary phases famatinite (Cu₃SbS₄; 15%), and tetrahedrite (Cu_11.4Sb₄S₁₃; 8%), synthesized in the industrial mill. The nanocrystals were agglomerated into micrometer-sized grains in both cases. Both samples were nanocrystalline, as was confirmed with HRTEM. The optical band gap of the Cu₃SbS₃ prepared in the laboratory mill was determined to be 1.7 eV with UV–Vis spectroscopy. Photocurrent responses verified with I–V measurements under dark and light illumination and Cu₃SbS₃ nanocrystals showed ~45% enhancement of the photoresponsive current at a forward voltage of 0.6 V. The optical and optoelectrical properties of the skinnerite (Cu₃SbS₃) prepared via laboratory milling are interesting for photovoltaic applications.     

ChemInform Abstract: H2O Nucleation Around Au+

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