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排序方式: 共有209条查询结果,搜索用时 15 毫秒
51.
Barros TC Cuccovia IM Farah JP Masini JC Chaimovich H Politi MJ 《Organic & biomolecular chemistry》2006,4(1):71-82
The study of highly conjugated, carbonyl-containing molecules such as 1,4,5,8-naphthalene tetracarboxylic dianhydride, III, is of interest since reactivity differences and transmission of electronic effects through the conjugated framework can be evidenced. The kinetics of hydrolysis of III in aqueous solution were determined from 5 M acid to pH 10. In basic solution hydrolysis of III yields, sequentially, 1,4,5,8-naphthalene diacid monoanhydride, II, and 1,4,5,8-naphthalene tetracarboxylic acid, I. The second order rate constant for alkaline hydrolysis is 200 fold higher for the first ring opening. The water-catalyzed hydrolysis of III yields a pH-dependent mixture of ionic forms of I and II. The rate constant for water-catalyzed hydrolysis of III is 25 fold higher than that for II. In concentrated acid the rates for reaching equilibrium (I, II and III) increase and III is the major product. The pK(a)s of I (3.24, 5.13 and 6.25) and II (3.05, 5.90) were determined by potentiometric, fluorescence and UV spectroscopy titrations and by quantitative fit of the kinetic and equilibrium data. The apparent, pH-dependent, equilibrium constants, K(EqII), for anhydride formation between I and II were obtained from the UV spectra. The quantitative fit of kinetic and equilibrium data are consistent with the assumption that anhydride formation only proceeds with the fully protonated species for both I and II and permitted the estimation of the equilibrium constants for anhydride formation, K(EqII). The value of K(EqII) (I <==> II) between pH 1 and 6 was ca. 5. Geometry optimization calculations in the gas phase of the reactions of III in alkaline, neutral and acid conditions, at the DFT level of theory, gave electronic distributions that were qualitatively consistent with the experimental results. 相似文献
52.
The design and synthesis of two novel quinoxalinophenanthrophenazine-based anion sensors are reported. Binding studies of these sensors with an array of mono- and polyatomic anions using UV-vis, fluorescence, and NMR titrations have shown 1:1 and 1:2 sensor-to-anion ratios. Binding constants were calculated for anions, which exhibited high affinity for the sensors, including acetate, benzoate, cyanide, and fluoride ions. 相似文献
53.
Belarmino AT Froehner S Zanette D Farah JP Bunton CA Romsted LS 《The Journal of organic chemistry》2003,68(3):706-717
Hydrolyses of benzaldehyde acetals, PhCH(OR)(2), are specific hydrogen-ion catalyzed when R = methyl, n-butyl, but with secondary and tertiary alkyl derivatives, R = i-propyl, s-butyl, t-butyl, t-amyl, hydrolyses are general-acid catalyzed. The Br?nsted alpha values for both secondary and tertiary alkyl groups are in the range: alpha = 0.57-0.61. A simple iterative procedure was developed to estimate the individual rate constants for general-acid catalysis by the diacid and monoacid forms of succinic acid buffer. Plots of log k(obs) (at [buffer] = 0 M) against pH are linear for the secondary and tertiary acetals, and plots of log k(H) for the H(3)O(+)-catalyzed reaction, (13)C and (1)H chemical shifts, and (1)J(CH) coupling constants against the Charton steric parameter, nu, for alkoxy groups are linear. The second-order rate constant, k(H), increases about 100-fold on going from R = Me to R = t-amyl, indicating the significant role of steric effects on reactivity. Steric effects upon (13)C NMR chemical shifts and coupling constants indicate that increasing the bulk of the alkoxy moiety increases the electron density at the carbon reaction center, which accelerates hydrolysis. Analysis of the Jencks-More-O'Ferrall free energy diagram for the reaction provides support for concerted proton transfer and C-O bond breaking in the transition state for hydrolyses of benzaldehyde acetals with secondary and tertiary alkyl groups in contrast to specific hydrogen catalysis with R = Me and n-Bu. All our results are consistent with rate-determining acid hydrolysis of benzaldehyde dialkyl acetals to hemiacetal intermediates that breakdown rapidly to benzaldehyde. 相似文献
54.
Microwave synthesis of polymer-embedded Pt-Ru catalyst for direct methanol fuel cell 总被引:2,自引:0,他引:2
Bensebaa F Farah AA Wang D Bock C Du X Kung J Le Page Y 《The journal of physical chemistry. B》2005,109(32):15339-15344
Platinum-ruthenium nanoparticles stabilized within a conductive polymer matrix are prepared using microwave heating. Polypyrrole di(2-ethylhexyl) sulfosuccinate, or PPyDEHS, has been chosen for its known electrical conductivity, thermal stability, and solubility in polar organic solvents. A scalable and quick two-step process is proposed to fabricate alloyed nanoparticles dispersed in PPyDEHS. First a mixture of PPyDEHS and metallic precursors is heated in a microwave under reflux conditions. Then the nanoparticles are extracted by centrifugation. Physical characterization by TEM shows that crystalline and monodisperse alloyed nanoparticles with an average size of 2.8 nm are obtained. Diffraction data show that crystallite size is around 2.0 nm. Methanol electro-oxidation data allow us to propose these novel materials as potential candidates for direct methanol fuel cells (DMFC) application. The observed decrease in sulfur content in the polymer upon incorporation of PtRu nanoparticles may have adversely affected the measured catalytic activity by decreasing the conductivity of PPyDEHS. Higher concentration of polymer leads to lower catalyst activity. Design and synthesis of novel conductive polymers is needed at this point to enhance the catalytic properties of these hybrid materials. 相似文献
55.
I. S. El-yamani M. Y. Farah E. N. Abd El-Messieh 《Journal of Radioanalytical and Nuclear Chemistry》1978,45(2):357-364
The distribution of Be(II) between aqueous sulphuric acid solutions and organic phases of di-(2-ethyl hexyl)-phosphoric acid
(HDEHP) has been described. The dependence of extraction on contact time, acidity, metal and extractant concentration, diluent
type and temperature was thoroughly investigated. The possible mechanism of the extraction is discussed on the basis of results
obtained. 相似文献
56.
Lattice mismatch plays a determining role in surface atomic diffusion in epitaxy. One effect is the increasing anisotropy of diffusion along close-packed steps of adsorbed islands on (1 1 1) surfaces with increasing strain in the layer as shown by previous works on homoepitaxy and heteroepitaxy where the adlayer is under compressive strain. In most of these investigations the barrier of diffusion along steps with triangular microfacets (B steps) is greater than the barrier of diffusion along steps with square microfacets (A steps). Through atomistic simulations of a system under tensile strain, Co/Pt(1 1 1), we evidence reversal behaviour with a much smaller barrier obtained for diffusion at B step. Such effect results from a particular diffusion path along B step having a low cost in energy and being specific to tensile strain systems. 相似文献
57.
Lee TM Oldenburg AL Sitafalwalla S Marks DL Luo W Toublan FJ Suslick KS Boppart SA 《Optics letters》2003,28(17):1546-1548
Contrast agents are utilized in virtually every imaging modality to enhance diagnostic capabilities. We introduce a novel class of optical contrast agent, namely, encapsulating microspheres, that are based not on fluorescence but on scattering nanoparticles within the shell or core. The agents are suitable for reflection- or scattering-based techniques such as optical coherence tomography, light microscopy, and reflectance confocal microscopy. We characterize the optical properties of gold-, melanin-, and carbon-shelled contrast agents and demonstrate enhancement of optical coherence tomography imaging after intravenous injection of such an agent into a mouse. 相似文献
58.
59.
Co-extraction and separation of zirconium and hafnium by long-chain amines from sulphate media 总被引:1,自引:0,他引:1
The extraction of Zr and Hf from sulphuric acid systems by solutions of Primene JMT (a long-chain primary amine) in kerosene, is described. The effect of contact time, free acidity, solvent concentration and temperature, has been thoroughly examined. A rapid improved method for HfZr separation is suggested. 相似文献
60.
Dr. Farah Benyettou Dr. Katia Nchimi‐Nono Dr. Mustapha Jouiad Dr. Yoann Lalatonne Dr. Irena Milosevic Prof. Laurence Motte Prof. John‐Carl Olsen Prof. Na'il Saleh Prof. Ali Trabolsi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4607-4613
Magnetic and fluorescent assemblies of iron‐oxide nanoparticles (NPs) were constructed by threading a viologen‐based ditopic ligand, DPV2+, into the cavity of cucurbituril (CB[7]) macrocycles adsorbed on the surface of the NPs. Evidence for the formation of 1:2 inclusion complexes that involve DPV2+ and two CB[7] macrocycles was first obtained in solution by 1H NMR and emission spectroscopy. DPV2+ was found to induce self‐assembly of nanoparticle arrays (DPV2+?CB[7]NPs) by bridging CB[7] molecules on different NPs. The resulting viologen‐crosslinked iron‐oxide nanoparticles exhibited increased saturation magnetization and emission properties. This facile supramolecular approach to NP self‐assembly provides a platform for the synthesis of smart and innovative materials that can achieve a high degree of functionality and complexity and that are needed for a wide range of applications. 相似文献