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981.
The adsorption/desorption process of borate was studied at Pt(111) in acidic solution by cyclic voltammetry. A so-called butterfly
wave in the cyclic voltammogram of Pt(111) in HClO4 shifted to negative direction upon the addition of boric acid with the disappearance of its sharp spikes. The shift in potential
was found to be −57 mV with a tenfold increase of boric acid concentration. This illustrates that this anomalous wave is due
to borate adsorption/desorption by a one-electron transfer process. The borate adsorption/desorption wave was observed to
shift by −63 mV/pH. At pH>3, the anomalous wave splits forming two separate waves, depending on the pH and the scan rate.
The appearance of two waves is assigned to the change in the adsorption mode of borate or the participation of OH in the adsorption
process. 相似文献
982.
Vijayasarathi Nagarajan Barbara Müller Oksana Storcheva Klaus Köhler Andreas Pöppl 《Research on Chemical Intermediates》2007,33(8):705-724
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin
echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data
of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental
and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands. 相似文献
983.
The technique of bead injection has been adapted for surface enhanced Raman scattering (SERS) to substantially improve precision, long term stability and sensitivity of SERS detection in analytical chemistry. For this purpose a fully automated flow system comprising a dedicated flow-cell has been developed and tested. With the developed flow-cell, which contains two inlet and two outlet channels, it is possible to retain, perfuse and discharge minute amounts of polymer beads while monitoring all steps by Raman spectroscopy. First, beads carrying cation exchanger moieties were retained in the flow-cell and subsequently perfused with a silver nitrate and a hydroxylamine solution using one inlet of the flow cell. By this sequence homogeneous SERS active silver layers were formed on the beads. The uniformity of the achieved silver layer was studied by secondary electron microscopy. For measurement, the analyte was then introduced from the second inlet channel such that the interaction between the activated SERS beads and analyte occurred in close proximity and within the focus of the laser excitation beam. Due to the complete computer control of all experimental steps, including bead entrapment, SERS layer generation, sample introduction and final bead removal, highly reproducible conditions for SERS were achieved. The method was developed using 9-aminoacridine as a test molecule. Quantitative studies were carried out for 9-aminoacridine and acridine showing linear calibrations from 1-100 nmol l(-1) and 50-1,000 nmol l(-1), respectively, using a sample volume of 200 microl each. Typical relative standard deviations were 4.7% for 9-aminoacrine and 5.8% for acridine. 相似文献
984.
Regás D Afonso MM Rodríguez ML Palenzuela JA 《The Journal of organic chemistry》2003,68(20):7845-7852
The reaction of vinyl allenes with imines under Lewis acid catalysis has been explored. Vinyl allenes in which the allenic portion of the molecule is tri- or tetrasubstituted gave octahydroquinoline derivatives as single isomers together with a minor compound formed by an ene reaction of the imine with the allene. Compounds in which the allene is 1,3-disubstituted do not react under the conditions assayed. 相似文献
985.
Elena Blanco J. M. Ruso J. Sabín G. Prieto F. Sarmiento 《Journal of Thermal Analysis and Calorimetry》2007,87(1):211-215
The interactions of lysozyme and myoglobin with anionic surfactants
(hydrogenated and fluorinated), at surfactant concentrations below the critical
micelle concentration, in aqueous solution were studied using spectroscopic
techniques. The temperature conformational transition of globular proteins
by anionic surfactants was analysed as a function of denaturant concentration
through absorbance measurements at 280 nm. Changes in absorbance of protein-surfactant
system with temperature were used to determine the unfolding thermodynamics
parameters, melting temperature, T
m,
enthalpy, ΔH
m,
entropy, ΔS
m
and the heat capacity change, ΔC
p,
between the native and denatured states. 相似文献
986.
Koichi Kikuta Koji Noda Shin Okumura Toshiaki Yamaguchi Shin-ichi Hirano 《Journal of Sol-Gel Science and Technology》2007,42(3):381-387
Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets.
An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa2Nb3O10 oxide grains. A seed layer composed of (TBA)Ca2Nb3O10 nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds
of perovskite compounds, LaNiO3 (LNO) and Pb(Zr,Ti)O3 (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical
properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by
use of this orientation control. 相似文献
987.
The data clustering problem consists in dividing a data set into prescribed groups of homogeneous data. This is an NP-hard problem that can be relaxed in the spectral graph theory, where the optimal cuts of a graph are related to the eigenvalues of graph 1-Laplacian. In this paper, we first give new notations to describe the paths, among critical eigenvectors of the graph 1-Laplacian, realizing sets with prescribed genus. We introduce the pseudo-orthogonality to characterize m3(G), a special eigenvalue for the graph 1-Laplacian. Furthermore, we use it to give an upper bound for the third graph Cheeger constant h3(G), that is, h3(G) 6 m3(G). This is a first step for proving that the k-th Cheeger constant is the minimum of the 1-Laplacian Raylegh quotient among vectors that are pseudo-orthogonal to the vectors realizing the previous k - 1 Cheeger constants. Eventually, we apply these results to give a method and a numerical algorithm to compute m3(G), based on a generalized inverse power method. 相似文献
988.
John M. Charnes Howard Marmorstein Walter Zinn 《The Journal of the Operational Research Society》1995,46(8):1006-1013
We consider a periodic-review inventory replenishment model with an order-up-to-R operating doctrine for the case of deterministic lead times and a covariance-stationary stochastic demand process. A method is derived for setting the inventory safety stock to achieve an exact desired stockout probability when the autocovariance function for Gaussian demand is known. Because the method does not require that parametric time-series models be fit to the data, it is easily implemented in practice. Moreover, the method is shown to be asymptotically valid when the autocovariance function of demand is estimated from historical data. The effects on the stockout rate of various levels of autocorrelated demand are demonstrated for situations in which autocorrelation in demand goes undetected or is ignored by the inventory manager. Similarly, the changes to the required level of safety stock are demonstrated for varying levels of autocorrelation. 相似文献
989.
This paper studies the optimal operation of an M/E k /1 queueing system with a removable service station under steady-state conditions. Analytic closed-form solutions of the controllable M/E k /1 queueing system are derived. This is a generalization of the controllable M/M/1, the ordinary M/E k /1, and the ordinary M/M/1 queueing systems in the literature. We prove that the probability that the service station is busy in the steady-state is equal to the traffic intensity. Following the construction of the expected cost function per unit time, we determine the optimal operating policy at minimum cost. 相似文献
990.
Kun-Jen Chung 《The Journal of the Operational Research Society》1995,46(11):1374-1385
Chiu, in 1976, studied the economic design of np charts for processes subject to a multiplicity of assignable causes. Chiu developed a two-step minimization procedure to obtain the three control variables, namely, the sampling interval, the sample size and the acceptance number. Although Chiu's two-step minimization procedure is simple, applicable and down to earth, it is rather inefficient and has some drawbacks. This paper presents an algorithm to overcome these drawbacks. The results and the execution times of all numerical examples show that the accuracy and the efficiency of the algorithm is reasonably good. 相似文献