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991.
E. Manuela Garrido Josél Costa Lima Cristina M. Delerue-matos Ana Maria Oliveira Brett 《International journal of environmental analytical chemistry》2013,93(1-2):149-157
Abstract Cyclic, differential pulse and square wave voltammetry were applied to develop an electroanalytical procedure for the determination of a group of herbicides used to treat rice crops: molinate, bensul-ruron-methyl, mefenacet and thiobencarb. The oxidation mechanism causes adsorption problems and consequent poisoning of the electrode surface by the products of the electrochemical reaction. Parameters such as pH, frequency and electrochemical electrode surface treatment were optimized. The analytical methodology developed using square wave voltammetry was applied to the determination of molinate and bensulfuron-methyl in simple or mixed commercial products. 相似文献
992.
Nicolás D. Gómez Violeta D'Accurso V. Mariana Freytes Francisco A. Manzano Jorge Codnia M. Laura Azcárate 《国际化学动力学杂志》2013,45(5):306-313
An experimental setup that coupled IR multiple‐photon dissociation (IRMPD) and laser‐induced fluorescence (LIF) techniques was implemented to study the kinetics of the recombination reaction of dichlorocarbene radicals, CCl2, in an Ar bath. The CCl2 radicals were generated by IRMPD of CDCl3. The time dependence of the CCl2 radicals’ concentration in the presence of Ar was determined by LIF. The experimental conditions achieved allowed us to associate the decrease in the concentration of radicals to the self‐recombination reaction to form C2Cl4. The rate constant for this reaction was determined in both the falloff and the high‐pressure regimes at room temperature. The values obtained were k0 = (2.23 ± 0.89) × 10?29 cm6 molecules?2 s?1 and k∞ = (6.73 ± 0.23) × 10?13 cm3 molecules?1 s?1, respectively. 相似文献
993.
994.
A fast procedure has been developed for the direct determination of paint solvents. The method is based on the injection of small volumes of untreated solvent mixtures into a heated Pyrex glass reactor in which the sample is volatilized and introduced by means of a flow of nitrogen into an IR multiple pass gas cell and the spectrum in the mid-IR region is registered as a function of time. Data found for samples are interpolated in calibration graphs obtained by injecting different volumes of pure compounds which constitute the solvent mixture. A methylisobutylketone (MIBK) toluene mixture was used as test system to develop the proposed procedure. The method provides a limit of detection of the order of 1–4 μg, a relative standard deviation of the order of 0.4 to 2% for five independent measurements, and recovery percentage values from 99.8 till 103.6 %. A commercial sample of polyurethane paint solvent has been analysed by the developed procedure. 相似文献
995.
Sonia Dopico‐García Ana Ares‐Pernas Jorge Otero‐Canabal Mar Castro‐López José M. López‐Vilariño Victoria González‐Rodríguez María J. Abad‐López 《先进技术聚合物》2013,24(8):723-731
Nowadays, there is a growing availability of biodegradable industrial materials intended to food contact applications whose service life behavior needs to be further investigated. This article is focused on the degradation of two materials based on polylactic acid. The correlation between the rate of degradation and the amount of trapped degradation products was investigated applying three characterization techniques in parallel, namely rheology, high‐performance liquid chromatography (HPLC), and matrix‐assisted laser desorption/ionization (MALDI). The rate of degradation was studied through the evaluation of their rheological properties and calculation of the number of average molecular weights, and weight‐average molecular weights. Water‐soluble oligomers and lactic acid were quantified by HPLC‐ultraviolet. Changes in cyclic and linear oligomers were monitored by MALDI‐time‐of‐flight mass spectrometry. Specimens of 4‐mm thickness of each biopolymer were subjected to hydrolysis in deionized water up to 6 months at two temperatures, simulating service conditions of food packaging. The diminution in viscosity and consequently in molecular weight distribution (20–60%) showed the degradation of the molecular structure of both polylactic acids. The chain scission was followed through the increasing values of lactic acid and hydrolyzed oligomers (twofold to eightfold), and the predominant signal of the linear oligomers over the cyclic ones with aging. Rheology, HPLC, and MALDI showed to be complementary tools to better understand the changes in the molecular structure. The obtained results showed the necessity of adding suitable stabilizers for each particular food packaging application. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
996.
Abstract The influence of the composition of the initiator system used in the polymerization of PGE is studied. Structural studies of intermediate species by NMR and IR spectroscopies are made which allow confirmation of some characteristics on the previously proposed mechanism and clarification of the mechanism leading to the chlorinated insoluble polymer fraction. This can be explained by the formation of halogenated oligomers in the first stage of the reaction which interchange with different aluminum alkoxides to give another type of initiator system. 相似文献
997.
Dr. Matthieu Autillo Md. Ashraful Islam Julie Héron Laetitia Guérin Dr. Eleonor Acher Dr. Christelle Tamain Dr. Marie-Claire Illy Dr. Philippe Moisy Dr. Eric Colineau Dr. Jean-Christophe Griveau Dr. Claude Berthon Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(24):7138-7153
Actinide +VI complexes ( = , and ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, and complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the 1H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans’ method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the complex. The temperature dependence of the pNMR chemical shifts has a strong contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the complex and a non-Kramers-doublet model for the complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center. 相似文献
998.
Soft molecular electrostatic potentials (SMEP or SEMP) have been recently defined substituting the point-like proton by a Gaussian positive charge distribution. In the present paper an additional step is taken forward, transforming SMEP into a completely soft MEP (CoSMEP). Such transformation is carried out using a charge distributed proton as in SMEP and also a Gaussian positive nuclear charge distribution, instead of the classical point-like nuclear charges. The general form of MEP is roughly preserved, but new features can be noticed. Such new point of view is also associated to the possibility to redefine the molecular charge density. Definition of CoSMEP is thus connected to the definition of total molecular density functions (DF), where to the negative electronic DF is summed up the soft nuclear DF, made of linear combinations of Gaussian distributions of nuclear charges. 相似文献
999.
1000.
Jesús M. Arsuaga José Aguado Amaya Arencibia María S. López-Gutiérrez 《Adsorption》2014,20(2-3):311-319
The aim of this work was to investigate the aqueous mercury adsorption in a fixed bed of mesostructured silica SBA-15 functionalized with propylthiol by co-condensation (SBA-15-SH). Powdered synthesized adsorbents were used to prepare pellets with sizes ranging from 0.5 to 1 mm. The physicochemical properties determined from N2 adsorption and chemical analysis were compared for powder and pellets. Batch static experiments were carried out to obtain the equilibrium mercury adsorption isotherms, resulting that although the maximum adsorption capacity was reduced from powder to pellets, the materials maintained high efficiency for mercury removal even at very low aqueous metal concentration. Dynamic experiments were carried out in a fixed bed column by modifying the volumetric flow rate, bed length, inlet concentration, and amount of propylthiol groups incorporated to the adsorbent, and analyzing the temporal scale and the mercury adsorption capacities. The elution of the fixed bed was carried out chemically by circulating an aqueous 2 M hydrobromic acid stream for 2 h so achieving a complete recovery of the mercury previously adsorbed. Simplified dynamic equations of Bohart–Adams and Wolborska were used for modeling the breakthrough curves. 相似文献