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21.
In situ electrochemical scanning tunneling microscopy (STM) has been used to examine the structures of benzenethiol adlayers on Au(1 0 0) and Pt(1 0 0) electrodes in 0.1 M HClO4, revealing the formation of well-ordered adlattices of Au(1 0 0)-(√2 × √5) between 0.2 and 0.9 V and Pt(1 0 0)-(√2 × √2)R45° between 0 and 0.5 V (versus reversible hydrogen electrode), respectively. The coverage of Au(1 0 0)-(√2 × √5) is 0.33, which is identical to those observed for upright alkanethiol admolecules on Au(1 1 1). In comparison, the coverage of Pt(1 0 0)-(√2 × √2)R45° - benzenethiol is 0.5, much higher than those of thiol molecules on gold surfaces. This result suggests that benzenethiol admolecules on Pt(1 0 0) could stand even more upright than those on Au(1 0 0). All benzenethiol admolecules were imaged by the STM as protrusions with equal corrugation heights, suggesting identical molecular registries on Au(1 0 0) and Pt(1 0 0) electrodes, respectively. Modulation of the potential of a benzenethiol-coated Au(1 0 0) electrode resulted in irreversible desorption of admolecules at E ? 0.1 V (vs. reversible hydrogen electrode) and oxidation of admolecules at E ? 0.9 V. In contrast, benzenethiol admolecule was not desorbed from Pt(1 0 0) at potentials as negative as the onset of hydrogen evolution. Raising the potential rendered deposition of more benzenethiol molecules before oxidation of admolecules commenced at E > 0.9 V.  相似文献   
22.
采用共沉淀法, 固定Mg2+/(Al3++Ti4+)摩尔比为3.00, 改变Ti4+/(Al3++Ti4+)摩尔比(RTi, 0~0.40), 合成了5个Mg-Al-Ti-CO3层状双氢氧化物(LDHs)样品, 并进行了表征. 采用电势滴定、 盐滴定和电势质量滴定法, 测定了其结构电荷密度(σst)、 零净电荷点(pHPZNC)和零净质子电荷点(pHPZNPC)等, 并基于普适1-pK和2-pK模型得出其表面羟基酸碱反应特征平衡常数(pK, pKa1int和pKa2int), 考察了RTi对LDHs晶体结构和界面电化学性质的影响. 研究结果表明, 随着RTi增大,晶胞常数和层间距均增大, 可归因于Ti4+离子间强静电排斥作用. pHPZNC和pHPZNPC以及pK, pKa1int和pKa2int均随RTi的增大而有增大的趋势, 表明表面羟基去质子化趋势降低. 各LDHs样品的pHPZNPC值低于其pHPZNC值, 且随电解质(NaNO3)浓度的增大而升高, 可归因于结构正电荷效应.  相似文献   
23.
In this paper, nonlinear stability of thin elastic circular shallow spherical shell under the.action of uniform edge moment is considered by the modified iteration method to obtain second and third approximations to decide the upper and lower critical loads. Results are plotted in curves for the engineering use and are compared with results of Hu Hai-chang’s. We also investigate the neighbour situation of the critical point, i.e. the double points of the upper and lower critical loads and denote the range of validity of the second approximation. In the end, we obtain the special case, the design formulas of rigidity and stress as well as the corresponding curves as v=0.3 of large deflection of circular plate under the same load. These results are also compared with Huang Tse-yen’s.  相似文献   
24.
Designs, Codes and Cryptography - Recently, Horlemann-Trautmann and Weger (Adv Math Commun, https://doi.org/10.3934/amc.2020089 , 2020) proposed a general framework for a Quaternary McEliece...  相似文献   
25.
Aromatic amines is not used commonly in allylic amination, presumably because of their less nucleophilic nature compared with the more extensively used benzylamine or relatively stable anionic nitrogen nucleophiles. An eco‐friendly method for C–O bond activation of allylic acetates using palladium associated with ligands in water leading to N‐allylation was described in this study. The palladium‐catalyzed allylic amination of allylic acetate with aminonaphthalenes gave 34–95% yields to the corresponding N‐allylic aminonaphthalenes. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   
26.
The asymmetric synthesis of multi-gram quantities of a pseudomonic acid precursor is described. Improvements on the literature synthesis of diacetyl arabinal from arabinose are also reported.  相似文献   
27.
A simple, rapid and accurate high‐performance liquid chromatography method with ultraviolet–visible detection was developed for the determination of five amino acid neurotransmitters – aspartate, glutamic acid, glycine, taurine and γ‐aminobutyric acid – in rat hippocampi with pre‐column derivatization with 4‐fluoro‐7‐nitrobenzofurazan. Several conditions which influenced derivatization and separation, such as pH, temperature, acetonitrile percentage mobile phase and flow rate, were optimized to obtain a suitable protocol for amino acids quantification in samples. The separation of the five neurotransmitter derivatives was performed on a C18 column using a mobile phase consisting of phosphate buffer (0.02 mol/L, pH 6.0)–acetonitrile (84:16, v/v) at a flow rate of 1.0 mL/min with the column temperature at 30°C. The detection wavelength was 472 nm. Without gradient elution, the five neurotransmitter derivatives were completely separated within 15 min. The linear relation was good in the range from 0.50 to 500 µmol/L, and the correlation coefficients were ≥0.999. Intra‐day precision was between 1.8 and 3.2%, and inter‐day precision was between 2.4 and 4.7%. The limits of detection (signal‐to‐noise ratio 3) were from 0.02 to 0.15 µmol/L. The established method was used to determine amino acid neurotransmitters in rat hippocampi with satisfactory recoveries varying from 94.9 to 105.2%. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
28.
The leaves of Cinnamomum reticulatum Hay were extracted successively with hexane and acetone successively. Dipentadecyl ketone, n-dotriaconyl alcohol, 2-(4-hydroxy-3-methoxyphenyl)ethyl hexa- and octacosanoates ( two new esters from hexane extract ), β-sitosterol, fatty acid, vanillin, p-hydroxybenzaldehyde, genkwanin, vanillic acid, p-hydroxybenzoic acid, β-sitosteryl-l-β-glucopyranoside, meso-erythritol, glucose, and 4-(2-hydroxyethyl)-2-methoxyphenyl-l-β-D-glucopyranoside (from the acetone extract) were isolated. The structures of the new esters were elucidated by chemical and physical evidence.  相似文献   
29.
The adsorption of formaldehyde (HCHO) on Pt(111) and Pt(100) electrodes was examined by cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM) in 0.1 M HClO(4). The extent of HCHO adsorption at both Pt electrodes was evaluated by comparing the CVs, particularly for the hydrogen adsorption and desorption between 0.05 and 0.4 V, obtained in 0.1 M HClO(4) with and without HCHO. The adsorption of HCHO on these Pt electrodes was significant only when [HCHO] >/= 10 mM. Adsorbed organic intermediate species acted as poisons, blocking Pt surfaces and causing delays in the oxidation of HCHO. Compared to Pt(111), Pt(100) was more prone to poisoning, as indicated by a 200 mV positive shift of the onset of HCHO oxidation. However, Pt(100) exhibited an activity 3 times higher than that of Pt(111), as indicated by the difference in peak current density of HCHO oxidation. Molecular resolution STM revealed highly ordered structures of Pt(111)-( radical7 x radical7)R19.1 degrees and Pt(100)-( radical2 x radical2) in the potential region between 0.1 and 0.3 V. Voltammetric measurements further showed that the organic poisons produced by HCHO adsorption behaved differently from the intentionally dosed CO admolecules, which supports the assumption for the formation of HCO or COH adspecies, rather than CO, as the poison. On both Pt electrodes, HCHO oxidation commenced preferentially at step sites at the onset potential of this reaction, but it occurred uniformly at the peak potentials.  相似文献   
30.
Many scientists use quantitative measurements to compare the presence and amount, of various proteins and nucleotides among series of one- and two-dimensional (1-D and 2-D) electrophoretic gels. These gels are often scanned into digital image files. Gel spots are then quantified using stand-alone analysis software. However, as more research collaborations take place over the Internet, it has become useful to share intermediate quantitative data between researchers. This allows research group members to investigate their data and share their work in progress. We developed a World Wide Web group-accessible software system, WebGel, for interactively exploring qualitative and quantitative differences between electrophoretic gels. Such Internet databases are useful for publishing quantitative data and allow other researchers to explore the data with respect to their own research. Because intermediate results of one user may be shared with their collaborators using WebGel, this form of active data-sharing constitutes a groupware method for enhancing collaborative research. Quantitative and image gel data from a stand-alone gel image processing system are copied to a database accessible on the WebGel Web server. These data are then available for analysis by the WebGel database program residing on that server. Visualization is critical for better understanding of the data. WebGel helps organize labeled gel images into montages of corresponding spots as seen in these different gels. Various views of multiple gel images, including sets of spots, normalization spots, labeled spots, segmented gels, etc. may also be displayed. These displays are active and may be used for performing database operations directly on individual protein spots by simply clicking on them. Corresponding regions between sets of gels may be visually analyzed using Flicker-comparison (Electrophoresis 1997, 18, 122-140) as one of the WebGel methods for qualitative analysis. Quantitative exploratory data analysis can be performed by comparing protein concentration values between corresponding spots for multiple samples run in separate gels. These data are then used to generate reports on statistical differences between sets of gels (e.g., between different disease states such as benign or metastatic cancers, etc.). Using combined visual and quantitative methods, WebGel can help bridge the analysis of dissimilar gels which are difficult to analyze with stand-alone systems and can serve as a collaborative Internet tool in a groupware setting.  相似文献   
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