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121.
Uhl W Claesener M Haddadpour S Jasper B Hepp A 《Dalton transactions (Cambridge, England : 2003)》2007,(4):417-423
The reactions of bis- and tris(tert-butylethynyl)benzenes with dialkylgallium hydrides afforded two different types of products. 1,4-Di(tert-butylethynyl)benzene and dialkylgallium hydrides R(2)GaH bearing relatively small substituents (R = Et, nPr) gave the expected addition products with each C triple bond C triple bond inserted into a Ga-H bond. The intact GaR(2) groups are attached to those carbon atoms which are in alpha-position to the benzene rings, and intermolecular Ga-C interactions led to the formation of one-dimensional coordination polymers. In contrast secondary reactions with the release of the corresponding trialkylgallium derivatives GaR(3) (R = Et, nPr, iPr, CH(2)tBu, tBu) were observed for all hydrogallation reactions involving the trisalkyne 1,3,5-tris(tert-butylethynyl)benzene. A similar reaction was observed upon treatment of the 1,4-bisalkyne with a dialkylgallium hydride bearing a relatively bulky substituent (R = neopentyl). Cyclophane type molecules are formed in all these cases with two or three gallium atoms in the bridging positions between both benzene rings. 相似文献
122.
Sípos R Szabó-Plánka T Rockenbauer A Nagy NV Sima J Melník M Nagypál I 《The journal of physical chemistry. A》2008,112(41):10280-10286
The copper(II)-3-pyridylmethanol (L) system was investigated in aqueous solution by two-dimensional ESR evaluation at 298 K, and computer simulation of the individual anisotropic spectra at 77 K. The data revealed that the paramagnetic copper(II) complexes [CuL] (2+), [CuL 2] (2+), [CuL 3] (2+), and [CuL 4] (2+) are formed up to pH approximately 7 at a moderate or high excess of ligand. As compared with chelating ligands, two differences were observed for the complexation of 3-pyridylmethanol with copper(II): (1) In contrast with the well-resolved spectra in frozen solution, considerable line-broadening and distortion of the spectral shapes were seen at 298 K, which was interpreted in terms of isomeric equilibria and the medium-rate interconversion of various complexes on the ESR time-scale. (2) At low temperature, there were dramatic changes in the concentration distribution, the minor complexes with higher numbers of coordinating ligands ([CuL 3] (2+) and in particular [CuL 4] (2+)) becoming strongly favored. This phenomenon is explained by the significant differences in the formation enthalpy values of various species, shifting the equilibria according to the van't Hoff equation, and a significant undercooling in the course of fast freezing of the solution, which enhances the changes of the concentration distribution. 相似文献
123.
Multiwalled carbon nanotubes are attractive as sorbents for SPE because they can be used for enrichment of organic compounds and metal ions at trace levels. In this study, multiwalled carbon nanotubes were oxidized with concentrated HNO3, and then the oxidized multiwalled carbon nanotubes were modified with 5-(4'-dimethylamino-benzyliden)-rhodanine. The modified multiwalled carbon nanotubes were used as a solid sorbent for separation and preconcentration of trace amounts of Au(III) ions. The sorption of Au(III) ions was quantitative in the pH range of 2.0-5.0, whereas quantitative desorption occurred instantaneously with 5.0 mL 2.0 M Na2S2O3. The eluted solution was aspirated directly into the flame for atomic absorption spectrometry. The proposed method resulted in an enrichment factor of 94. The RSD of the method was +/- 1.11% (n=10, 2.0 microg/mL) and the LOD was 0.15 ng/mL. The calibration curve for Au(III) was linear between 0.53 ng/mL and 36.0 microg/mL in the initial solution, with an R2 value of 0.9999. The sorbent capacity of the modified multiwalled carbon nanotubes was 7.3 mg Au(III)/g sorbent. The influences of the experimental parameters, including sample pH, sample flow rate, eluent volume and flow rate, sample volume, and interference of some ions on the recoveries of the Au ions, were investigated. The proposed method was applied for preconcentration and determination of Au in different samples. 相似文献
124.
A new modified carbon‐ceramic electrode was prepared by incorporating TiO2 nanoparticle into sol‐gel network by accompanying apple tissue. A mixture of fine graphite powder with 15 wt% of TiO2 nanoparticle was used for the preparation of the carbon matrix and finally modification with a known amount weighted of apple tissue. The apple tissue containing polyphenol oxidase enzyme acts as molecular recognition element. The electrocatalytic oxidation of dopamine was investigated on the surface of the nanobiocomposite modified carbon‐ceramic electrode using cyclic voltammetry, chronoamperometry and amperometry techniques. Effect of pH, scan rate, TiO2 percentage on the response of modified electrode was studied. The prepared modified electrode presented a linear range for dopamine from 5.0×10?6 to 1.2×10?3 M in buffered solutions with pH 7.4 by amperometry. The detection limit was 3.41×10?6 M dopamine. The response of the modified carbon‐ceramic electrode and unmodified carbon‐ceramic electrode was compared. 相似文献
125.
126.
Anca Ramona Croitor Sava M. Carmen Martinez‐Bisbal Diana Maria Sima Jorge Calvar Vicente Esteve Bernardo Celda Uwe Himmelreich Sabine Van Huffel 《Journal of Chemometrics》2012,26(7):406-415
Given high‐resolution magic angle spinning (HR‐MAS) spectra from several glial tumor subjects, our goal is to differentiate between tumor tissue types by separating the different sources that contribute to the profile of each spectrum. Blind source separation techniques are applied for obtaining characteristic profiles for necrosis, highly cellular tumor and border tumor tissue and providing the contribution (abundance) of each of these tumor tissue types to the profile of each spectrum. The problem is formulated as a non‐negative source separation problem. Non‐negative matrix factorization, convex analysis of non‐negative sources and non‐negative independent component analysis methods are considered. The results are in agreement with the pathology obtained by the histopathological examination that succeeded the HR‐MAS measurements. Furthermore, an analysis to verify to which extent the dimension of the input space, the input features and the number of sources to be extracted from the HR‐MAS data could influence the performance of the source separation is presented. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
127.
Daryoush Afzali Rasool Jamshidi Sima Ghaseminezhad Zahra Afzali 《Arabian Journal of Chemistry》2012,5(4):461-466
A method for preconcentration of palladium at trace level on modified multiwalled carbon nanotubes columns and determination by flame atomic absorption spectrometry (FAAS) has been developed. Multiwalled carbon nanotubes (MWCNTs) were oxidized with concentrated HNO3 and the oxidized multiwalled carbon nanotubes were modified with 5-(4′-dimethylamino benzyliden)-rhodanine, and then were used as a solid sorbent for preconcentration of Pd(II) ions. Factors influencing sorption and desorption of Pd(II) ions were investigated. The sorption of Pd(II) ions was quantitative in the pH range of 1.0–4.5, whereas quantitative desorption occurs with 3.0 mL 0.4 mol L?1 thiourea. The amount of eluted palladium was measured using flame atomic absorption spectrometry. The effects of experimental parameters, including sample flow rate, eluent flow rate, and eluent concentration were investigated. The effect of coexisting ions showed no interference from most ions tested. The proposed method permitted a large enrichment factor (about 200). The relative standard deviation of the method was ±2.73% (for eight replicate determination of 2.0 μg mL?1 of Pd(II)) and the limit of detection was 0.3 ng mL?1. The method was applied to the determination of Pd(II) in water, road dust, and standard samples. 相似文献
128.
Local electron mean energy profile of positive primary streamer discharge with pin-plate electrodes in oxygen nitrogen mixtures
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Local electron mean energy (LEME) has a direct effect on the rates of collisional ionization of molecules and atoms by electrons. Electron-impact ionization plays an important role and is the main process for the production of charged particles in a primary streamer discharge. Detailed research on the LEME profile in a primary streamer discharge is extremely important for a comprehensive understanding of the local physical mechanism of a streamer. In this study, the LEME profile of the primary streamer discharge in oxygen-nitrogen mixtures with a pin-plate gap of 0.5 cm under an impulse voltage is investigated using a fluid model. The fluid model includes the electron mean energy density equation, as well as continuity equations for electrons and ions and Poisson’s electric field equation. The study finds that, except in the initial stage of the primary streamer, the LEME in the primary streamer tip tends to increase as the oxygen-nitrogen mole ratio increases and the pressure decreases. When the primary streamer bridges the gap, the LEME in the primary streamer channel is smaller than the first ionization energies of oxygen and nitrogen. The LEME in the primary streamer channel then decreases as the oxygen-nitrogen mole ratio increases and the pressure increases. The LEME in the primary streamer tip is primarily dependent on the reduced electric field with mole ratios of oxygen-nitrogen given in the oxygen-nitrogen mixtures. 相似文献
129.
Sima Alikhanzadeh-Arani Masoud Salavati-Niasari Mohammad Almasi-Kashi 《Journal of magnetism and magnetic materials》2012
A new way of preparing FeCo nanoparticles has been developed using the co-precipitation technique based on the appropriate Co precursors of different types of ligands. These new precursors have been prepared by the reaction of cobalt acetate with three various coordination compositions for forming cobalt complex types. This technique provides proper control on nanoparticle size distribution after annealing to 500 °C. The variation of the magnetic properties with the type of ligands of Co can arise from the changes of the microstructures and crystalline anisotropies. Maximum coercivity values of 480 Oe were obtained. It is found that the precursors with special structures can prevent from agglomeration without presence of any surfactants. 相似文献
130.
Gail Deadwyler Paul D. Sima Yingxian Fu Jeffrey R. Kanofsky 《Photochemistry and photobiology》1997,65(5):884-894
Abstract— We have compared the singlet oxygen-mediated inactivation of acetylcholinesterase (ACE) in solution with the inactivation of ACE on the surface of K562 leukemia cells. In solution, the actions of the singlet-oxygen quenchers, methionine, azide, disodium [ N,N '-ethylene-bis(5-sulfosalicylideneinuninato)]nickelate(II) (Ni-chelate 1) and disodium [( N,N '-2,3-propionic acid)bis(5-sulfosal-icylideneimminato)]nickelate(II) (Ni-chelate 2) could be explained quantitatively by assuming their only mechanism of action was to quench singlet oxygen. The singlet oxygen quenchers, azide, Ni-chelate 1 and Ni-chelate 2, caused smaller inhibitions in the rate of singlet oxygenmediated inactivation of ACE on K562 cells than ACE in solution. The effects of these quenchers and of deuterium oxide were interpreted using a mathematical model of singlet-oxygen quenching and diffusion to estimate the lifetime of singlet oxygen near the cell surface. The azide quenching data and the deuterium-oxide data gave lifetimes of 0.9 ± 0.2 μs and 0.45 ± 0.15 μs, respectively. The increases in ACE inactivation lifetime caused by the nickel chelates were anomalously large. The unexpectedly large quenching due to the nickel chelates may have been due to a nonuniform distribution of the chelates in the cytoplasm with a large concentration of the chelate near the cell membrane. 相似文献