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61.
62.
Density functional theory and ab initio computations elucidated the ring-opening of substituted (R = –CF3, –CN, –CH3, –H, –NH2, –OCH3, –OH, –SiH3) 1-bromo–1-lithiosilirane 1 and 2-bromo–2-lithiosilirane 2 to LiBr complexes of 2-silaallene and 1-silaallene, respectively. Formally, two competitive pathways can be considered. The ring-opening reaction can take place through a concerted manner via TS3. Alternatively, the reaction may proceed in a stepwise fashion with the intermediacy of a free silacyclopropylidene–LiBr complex 7. In both cases, the position of the substituents determines the kinetic of the reactions. The structures with an electron-donating group are generally unstable, whereas the silacyclopropylidenoids bearing electron-withdrawing substituents are particularly stable species. Here, we propose the ring-opening of 5a–h to corresponding LiBr complexes of 2-silaallenes can proceed in both concerted and stepwise mechanism except for –H, –CH3, and –SiH3. The obtained activation energies for the ring-openings of 5a–h to related 2-silaallenes are too high for a reaction at room temperature with up to 61.4 kcal/mol. In contrast, the activation energy barriers for the isomerization of 6a–h to the LiBr complexes of 1-silaallenes was determined to be relatively low at the B3LYP/6-31+G(d,p), M06/6-31+G(d,p), and MP2/6-31+G(d,p) levels. Moreover, we have also investigated the solvent effect on the unsubstituted models using both implicit and explicit solvation models. The energy barriers of the solvated models are found to be slightly higher than the results of gas phase calculations. Additionally, the ring-opening of dimer 6 (6–Dim) is also calculated for the ring-opening mechanism with the energy barrier of 3.7 kcal/mol at B3LYP/6-31+G(d,p) level of theory. 相似文献
63.
Shou-Nian Ding Chun-Mei Li Bu-Hong Gao Osman Kargbo Neng Wan Xi Chen Chan Zhou 《Mikrochimica acta》2014,181(15-16):1957-1963
Fluorescent gold nanoclusters (Au-NCs) were synthesized by a one-pot method using 11-mercaptoundecanoic acid as a reducing and capping reagent. It is found that the red fluorescence of the Au-NCs is quenched by the introduction of Eu(III) at pH 7.0, but that fluorescence is restored on addition of phosphate. The Au-NCs were investigated by transmission electron microscopy and fluorescence photographs. The effect of pH on fluorescence was studied in the range from pH 6 to 10 and is found to be strong. Based on these findings, we have developed an assay for phosphate. Ions such as citrate, Fe(CN)6 3?, SO4 2?, S2O8 2?, Cl?, HS?, Br?, AcO?, NO2 ?, SCN?, ClO4 ?, HCO3 ?, NO3 ?, Cd2+, Ba2+, Zn2+, Mg2+, and glutamate do not interfere, but ascorbate and Fe3+ can quench Au-NCs fluorescence. The fluorescent nanocluster probe responds to phosphate in the range from 0.18 to 250 μM, and the detection limit is 180 nM. The probe also responds to pyrophosphate and ATP. Figure
Off/on fluorescence sensor for phosphate based on Eu3+-modulated Au NCs thanks to the competition of oxygen-donor atoms from phosphate with those from the carboxylate groups was developed 相似文献
64.
Mohamed M. El-Galy Farage A. Issa Osman A. Desouky Hanan M. Diab Mahmoud R. Khattab 《Journal of Radioanalytical and Nuclear Chemistry》2011,288(3):805-811
The present study aims to use the ??-spectrometry, at NMA. A radiochemical technique [1, 2] for analysis of U-isotopes was carried out for some granite samples from Gabal Gattar and El Missikat localities and also for some reference soil samples of IAEA. Several steps of sample preparation, radiochemical separation, and source preparation were performed before analysis. The concerned sample was leached by HNO3, HF and H2O2 acids after ashing. The ashed sample was spiked with uranium tracer (232U) for chemical yield and activity calculation. Then uranium was extracted from the matrix elements with trioctylphosphine oxide (TOPO) and stripped with 1 M NH4F/0.1 M HCl solution. The uranium fraction was purified by co-precipitation with LaF3 to ensure complete removal of thorium and traces of resolution degrading elements. This was followed by a final clean-up step using an anion exchange. The pure uranium fraction was electrodeposited on a stainless steel disc from HCl/oxalate solution. The obtained results from the soil reference samples indicate general similarities between the techniques of ??-spectrometers of NMA, EAEA and IAEA for analysis of U-isotopes. The U-isotopes in the granite samples of high radioactivity levels need more attempts after dilution process to be in the limit detection of ??-spectrometry. 相似文献
65.
Xianglei Mao Alexander A. Bol'shakov Dale L. Perry Osman Sorkhabi Richard E. Russo 《Spectrochimica Acta Part B: Atomic Spectroscopy》2011,66(8):604-609
Laser Ablation Molecular Isotopic Spectrometry (LAMIS) was recently reported for optical isotopic analysis of condensed samples in ambient air and at ambient pressure. LAMIS utilizes molecular emissions which exhibit larger isotopic spectral shits than in atomic transitions. For boron monoxide 10BO and 11BO, the isotopic shifts extend from 114 cm−1 (0.74 nm) to 145–238 cm−1 (5–8 nm) at the B2Σ+ (v = 0) → X2Σ+ (v = 2) and A2Πi (v = 0) → X2Σ+ (v = 3) transitions, respectively. These molecular isotopic shifts are over two orders of magnitude larger than the maximum isotopic shift of approximately 0.6 cm−1 in atomic boron. This paper describes how boron isotope abundance can be quantitatively determined using LAMIS and how atomic, ionic, and molecular optical emission develops in a plasma emanating from laser ablation of solid samples with various boron isotopic composition. We demonstrate that requirements for spectral resolution of the measurement system can be significantly relaxed when the isotopic abundance ratio is determined using chemometric analysis of spectra. Sensitivity can be improved by using a second slightly delayed laser pulse arriving into an expanding plume created by the first ablation pulse. 相似文献
66.
Yasemin Oztekin Zafer Yazicigil Ali Osman Solak Zafer Ustundag Zeynel Kilic Selen Bilge 《Surface and interface analysis : SIA》2011,43(5):923-930
Modification of glassy carbon (GC) surfaces with phenanthroline derivatives (PDs) such as 5‐amino‐1,10‐phenanthroline (5AP) and 5,6‐diamino‐1,10‐phenanthroline (56DAP) is described in this study. Surface modification experiments were performed by cyclic voltammetry (CV) scanning from + 1.2 to + 2.7 V at scan rate of 100 mV/s applying 30 potential scans in acetonitrile (CH3CN) containing 1 mM PDs and 100 mM tetrabutylammoniumtetrafluoroborate (TBATFB). The presence of PDs on GC electrode was confirmed using CV, electrochemical impedance spectroscopy (EIS), contact angle measurements and ellipsometry and comparing with the results of bare GC electrode. A mechanism was proposed for the electrochemical modification of the GC electrode surface with PDs. The structure of the 5AP and 56DAP films was also discussed in the light of electrochemical and spectroscopic data. The complex‐forming ability of the modified surfaces against metal cations was investigated by square‐wave voltammetry (SWV). It was shown that surfaces having 1,10‐phenanthroline ligands with different functional groups were quite useful for the determination of transition metal ions. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
67.
68.
In this study, extracts of the flowers of the folk medicinal plant Bombax malabaricum DC were biologically and chemically screened. Chemical constituents in the n-hexane fraction from the flowers of B. malabaricum DC were investigated using gas-liquid chromatography (GLC) analysis, affording 14 compounds, including cholesterol, stigmasterol, campesterol and α-amyrin, while the residual 10 compounds are hydrocarbons. GLC analysis of the fatty acid (FA) esters established the majority abundance of the saturated FA over their unsaturated analogues. The polar methanol fraction afforded seven flavones: vicenin 2 (1), linarin (2), saponarin (3), cosmetin (4), isovitexin (5), xanthomicrol (6) and apigenin (7). Structures 1-7 were established by intensive studies of various spectral data (H-NMR, mass spectroscopy and UV) and comparison with authentic samples. Compounds 1-7 are described here for the first time from this plant. Extracts of n-hexane and methanol exhibited significant antioxidant and antimicrobial activities. 相似文献
69.
In the present paper, we consider the classical Widder transform, the Hν-transform, the Kν-transform, and the Yν-transform. Some identities involving these transforms and many others are given. By making use of these identities, a number of new Parseval-Goldstein type identities are obtained for these and other well-known integral transforms. 相似文献
70.
Osman Ra?it I?ikMehmet Sezer Zekeriya Güney 《Applied mathematics and computation》2011,217(22):9438-9450
We introduce a new method to solve high order linear differential equations with initial and boundary conditions numerically. In this method, the approximate solution is based on rational interpolation and collocation method. Since controlling the occurrence of poles in rational interpolation is difficult, a construction which is found by Floater and Hormann [1] is used with no poles in real numbers. We use the Bernstein series solution instead of the interpolation polynomials in their construction. We find that our approximate solution has better convergence rate than the one found by using collocation method. The error of the approximate solution is given in the case of the exact solution f ∈ Cd+2[a, b]. 相似文献