The course of aniline oxidation with ammonium peroxydisulfate in aqueous solutions has been investigated. The reaction was terminated at various times and the intermediates collected. Besides the precipitates, the films deposited in situ on silicon windows have also been studied. The kinetic course of polymerization is controlled by the acidity level, which changes during the polymerization from pH 8 to a final value close to pH 1. It has two distinct exothermic phases. Gel-permeation chromatography indicates that aniline oligomers are produced at first at high pH, while polyaniline follows after the pH becomes sufficiently low. The growth of polyaniline nanotubes was observed by optical microscopy and confirmed by electron microscopy. The molecular structure of the reaction intermediates was studied in detail by FTIR spectroscopy. Oxidation products are markedly sulfonated, and they contain phenazine units. Aniline oligomers are more soluble in chloroform than the polymer fraction, which contains nanotubes. 相似文献
We propose the use of the Si atom in the experimentally observed C59Si molecule as a possible way to controllably anchor fullerene molecules on a Si surface, due to the formation of a strong bond to one of the Si surface atoms. All our results are based on ab initio total energy density functional theory, and we obtain that the binding energy is on the order of 2.1 eV, approximately 1.4 eV more stable than a C60 bonded in a similar situation. A possible route to obtain such adsorption via a (C59Si)2 dimer is examined, and we find the whole process to be exothermic by approximately 0.2 eV. 相似文献
A series of planar-chiral ferrocene alkenylphosphines, (S(p))-2-(diphenylphosphino)-1-vinylferrocene (2), (S(p))-2-(diphenylphosphino)-1-(prop-1-en-1-yl)ferrocene (3; as a mixture of Z and E isomers in ca. 5:1 ratio), and (E,S(p))-2-(diphenylphosphino)-1-(2-phenylethen-1-yl)ferrocene ((E)-4), was obtained by Wittig and Horner-Wadsworth-Emmons reactions from the common precursor, (S(p))-2-(diphenylphosphino)ferrocene-1-carboxaldehyde (1). Coordination properties of these novel ferrocene donors were studied in their palladium(II) and tungsten(0)-carbonyl complexes. The reaction between 2 and [{Pd(mu-Cl)(L(NC))}2] (5, L(NC) = 2-{(dimethylamino)methyl-kappaN}phenyl-kappaC(1)) gave the bridge-cleavage product [PdCl(L(NC))(2-kappaP)] (6) while the reaction with [Pd(L(NC))(MeCN)2]ClO4 (7) yielded the cationic bis(chelate) [Pd(L(NC))(2-eta2:kappaP)]ClO4 (8). Chelate complexes of the type [W(CO)4(L-eta2:kappaP)] (9 with L = 2; (Z/E)-10 with L = (Z/E)-3) were obtained by reacting [W(CO)4(cod)] (cod = eta2:eta2-cycloocta-1,5-diene) with the appropriate phosphinoalkene in refluxing toluene while a similar reaction with (E)-4 yielded mixtures of [W(CO)5(4-kappaP)] ((E)-11) and [W(CO)4(4-eta2:kappaP)] ((E)-12). All compounds were characterized by spectral methods (multinuclear NMR, IR, MS, and CD), and the structures of 1, 2, 8, 9, (Z/E)-10, and (E)-11 were corroborated by X-ray diffraction analysis. Ligands 2 and (E)-4 as well as their complexes 6, 8, 9, (E)-11, and (E)-12 were further studied by electrochemical methods. 相似文献
A graphite–polyurethane composite electrode with Santa Barbara Amorphous 15, SBA-15, mesoporous silica organofunctionalized with 2-benzothiazolethiol (BTSBA) as bulk modifier has been characterized electrochemically by voltammetry and electrochemical impedance spectroscopy (EIS) in the presence of cadmium ions, as an example of a toxic trace heavy metal, as well as by solid-state 13C-NMR and by scanning electron microscopy. EIS measurements performed on the modified composite electrodes to investigate the influence of BTSBA on the deposition of cadmium during square wave anodic stripping voltammetry showed that organofunctionalization of the SBA-15 bulk modifier in the composite electrode facilitates heavy metal deposition. Experiments were also carried out with a mixture of submicromolar cadmium, lead, copper and mercury ions and led to similar conclusions. 相似文献
Kept in the dark : The non‐photocatalytic generation of free radicals from fine and ultrafine TiO2 particles has been studied by means of a spin‐trapping/ESR spectroscopy technique (see figure). The amount and kind of free radicals generated depends on the crystalline structure, but not on the particle dimensions.
Electrochemical oxidation of (?)‐epigallocatechin gallate (EGCG), the main monomer flavanol found in green tea, has been investigated over a wide pH range at a glassy‐carbon electrode using square‐wave voltammetry (SWV). Square‐wave voltammograms of (?)‐epigallocatechin (EGC) and gallic acid have been studied as well. The I–E profile of EGCG, i.e. the oxidation potentials and the current responses of the first and the second peak, is pH dependent. The oxidation of EGCG is a quasireversible process over the studied pH range, which was also confirmed by the non‐linear relationship between the peak currents and squre root of frequency. The best SWV responses for EGCG were obtained at pH 2.0, frequency of 100 Hz, step of 2 mV and amplitude of 50 mV. Under these conditions, linear responses for EGCG were obtained for concentrations from 1×10?7 M to 1×10?6 M, and calculated LOD and LOQ for the first oxidation peak were 6.59×10?8 M and 2.19×10?7 M, respectively. The proposed electroanalytical procedure was applied for the determination of EGCG content in green tea. Developed SWV methodology represents a potential analytical tool in determination of catechins in tea samples. 相似文献
New bimetallic compound [CuxNi1?x(bpy)2(ox)]·4H2O (x = 0.05, ox = oxalato, bpy = 2,2′-bipyridine) was synthesized and chemically characterized. Its crystal structure is molecular. The octahedron around the metal central atom is deformed due to coordination by one bidentate oxalate anion and two bpy ligands. There are four uncoordinated water molecules in the asymmetric unit. The metal site is occupied by both Cu(II) and Ni(II) atoms in the 5:95 ratio. The complex molecules interact with water molecules through hydrogen bonds and, moreover, π–π interactions between aromatic rings lead to a 1D arrangement of molecules. The susceptibility data measured down to 2 K were analyzed using strong-coupling theory and the best agreement with the experimental data were found for g = 2.1, D/k = 5.6, E/k = 0.35, J/k = 0.2. The dehydration starts at 30 °C. As a final product of its thermal decomposition a solid solution of CuxNi1?xO was detected by X-ray powder diffraction. 相似文献
We propose a Lemaître–Tolman–Bondi system mimicking a two-body system to address the problem of the cosmological expansion versus local dynamics. This system is strongly bound but participates in the cosmic expansion and is exactly comoving with the cosmic substratum. 相似文献
There has been increasing interest in nuclear magnetic resonance (NMR) techniques that are sensitive to diffusion of molecules containing NMR visible nuclei for the estimation of microstructure parameters. A microstructure parameter of particular interest is pore radius distribution. A recent in silico study optimised the shape of the gradient waveform in diffusion weighted spin-echo experiments for estimating pore size. The study demonstrated that optimised gradient waveform (GEN) protocols improve pore radius estimates compared to optimised pulse gradient spin-echo (PGSE) protocols, particularly at shorter length scales. This study assesses the feasibility of implementing GEN protocols on a small bore 9.4 T scanner and verifies their additional sensitivity to pore radius. We implement GEN and PGSE protocols optimised for pore radii of 1, 2.5, 5, 7.5, 10 μm and constrained to maximum gradient strengths of 40, 80, 200 mT m(-1). We construct microstructure phantoms, which have a single pore radius for each phantom, using microcapillary fibres. The measured signal shows good agreement with simulated signal, strongly indicating that the GEN waveforms can be implemented on a 9.4 T system. We also demonstrate that GEN protocols provide improved sensitivity to the smaller pore radii when compared to optimised PGSE protocols, particularly at the lower gradient amplitudes investigated in this study. Our results suggest that this improved sensitivity of GEN protocols would be reflected in clinical scenarios. 相似文献