全文获取类型
收费全文 | 20337篇 |
免费 | 3225篇 |
国内免费 | 2611篇 |
专业分类
化学 | 17250篇 |
晶体学 | 471篇 |
力学 | 1461篇 |
综合类 | 121篇 |
数学 | 380篇 |
物理学 | 6490篇 |
出版年
2024年 | 63篇 |
2023年 | 259篇 |
2022年 | 1001篇 |
2021年 | 878篇 |
2020年 | 996篇 |
2019年 | 729篇 |
2018年 | 628篇 |
2017年 | 676篇 |
2016年 | 954篇 |
2015年 | 848篇 |
2014年 | 1033篇 |
2013年 | 1674篇 |
2012年 | 1168篇 |
2011年 | 1153篇 |
2010年 | 1069篇 |
2009年 | 1170篇 |
2008年 | 1183篇 |
2007年 | 1305篇 |
2006年 | 1190篇 |
2005年 | 1070篇 |
2004年 | 1085篇 |
2003年 | 954篇 |
2002年 | 712篇 |
2001年 | 630篇 |
2000年 | 616篇 |
1999年 | 550篇 |
1998年 | 468篇 |
1997年 | 354篇 |
1996年 | 302篇 |
1995年 | 276篇 |
1994年 | 231篇 |
1993年 | 147篇 |
1992年 | 143篇 |
1991年 | 103篇 |
1990年 | 71篇 |
1989年 | 71篇 |
1988年 | 62篇 |
1987年 | 47篇 |
1986年 | 44篇 |
1985年 | 47篇 |
1984年 | 33篇 |
1983年 | 13篇 |
1982年 | 24篇 |
1981年 | 24篇 |
1980年 | 31篇 |
1979年 | 23篇 |
1978年 | 11篇 |
1977年 | 11篇 |
1975年 | 11篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
Several phenoxy-imine ligands bearing o-trityl group in phenoxy moiety RN=CHArOH (Ar = C6H2(CPh3)tBu, R = 2,6-Me2C6H3 ( L 1 H ); 2,6-iPr2C6H3 ( L 2 H ); 3,5-(CF3)2C6H3 ( L 3 H ); 3,5-(OMe)2C6H3 ( L 4 H ); CHPh2 ( L 5 H ); CPh3 ( L 6 H )) were synthesized and characterized by1H NMR and 13C NMR spectroscopy. The vanadium complexes based on these ligands LVCl2(THF)2 ( 1–6 ) were synthesized via conventional transmetalation reaction in moderate to high yields. Complexes 1–6 were fully characterized by FT-IR, elemental analyses and the molecular structures of 1 , 2 ·H2O, (2 ·H2O ) 2 (μ-Cl) 2 , 4 , and 5 were confirmed by X-ray crystallographic analysis in which the six-coordinated vanadium centers are in a typical octahedral geometry. Upon activation with Et2AlCl in toluene, complexes 1–6 showed high activities in ethylene polymerization affording polymers with moderate molecular weight (5.9–11.8 × 104 Da). Moreover, in hexane or CH2Cl2, 1–6 /Et2AlCl exhibited enhanced activities. When activated with MAO or MMAO in toluene, these complexes showed relatively low activities but afforded polymers with ultra-high molecular weight (up to 3.30 × 106 Da). 1–6 /Et2AlCl also showed high activities in ethylene/1-hexene copolymerization at room temperature giving moderate molecular-weight polymers (6.5–11.4 × 104 Da) with co-monomer incorporation being of 6.0 ~ 7.8%. 相似文献
12.
Xiao Sun Li Zhang Yu Cao Jinhua Li Atanas G. Atanasov Linfang Huang 《Biomedical chromatography : BMC》2020,34(12):e4949
Balanophora involucrata J. D. Hooker has been known to possess potential anti-inflammatory and antibacterial activities; however, its antiviral activity has not been evaluated so far. In order to find new neuraminidase inhibitors (NAIs), the neuraminidase (NA) inhibition activity of different B. involucrata extracts was evaluated. In this study, an in vitro NA inhibition assay was performed to identify which extract of B. involucrata exhibits (maximal) inhibitory activity against NA. Ultra high performance liquid chromatography/quadrupole time-of-flight–tandem mass spectroscopy (MS/MS) and molecular docking techniques were used to identify the specific compounds responsible for the anti-influenza activity of the extract, and to explore the potential natural NAIs. The ethyl acetate extract of B. involucrata exhibited significant inhibitory activity against NA with 50% inhibitory concentration (IC50) value of 159.5 μg/mL. Twenty compounds were identified according to the MS/MS spectra; among them two compounds (quercitrin and phloridzin) showed obvious inhibitory activity against NA, with IC50 of 311.76 and 347.32 μmol/L, respectively. This study suggested that B. involucrata can be a potential natural source of NAIs and may be useful in the fight against ferocious influenza viruses. 相似文献
13.
Umie F.M. Haziz Rosenani A. Haque Shun-Ze Zhan Hassan H. Abdallah Mohd R. Razali 《应用有机金属化学》2020,34(10):e5818
The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, 1H- and 13C-NMR data. The 13C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]2·2PF6 is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λem = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm. 相似文献
14.
Bijian Lan Chunming Liu Xiang Yin Hua Zhang Wei Xu Zhongyi Hua 《Frontiers of Chemistry in China》2006,1(3):296-299
Organic materials of D-π-A type MR-X (MR-1: p-dimethylaminophenylethenetrica-rbonitrile and MR-2: p-diphenylaminophenylethene tricarbonitrile) were designed and synthesized. The device with a sandwich structure shows good
rectificative phenomena. The highest rectification ratio 10000 was achieved in device Cu/MR-1/Ag, and about 100 in other device
M/MR-X/M (M: Cu, Ag). It has been found that rectificative phenomena exist only in the atmosphere-liquid interface region
by means of liquid adsorption, and electric field could help form the oriented molecular film.
__________
Translated from Journal of Fudan University (Natural Science), 2005, 44(4) (in Chinese) 相似文献
15.
16.
Jong Uhn Kim 《Transactions of the American Mathematical Society》2002,354(3):1117-1135
In this paper we discuss an initial-boundary value problem for a stochastic nonlinear equation arising in one-dimensional viscoelasticity. We propose to use a new direct method to obtain a solution. This method is expected to be applicable to a broad class of nonlinear stochastic partial differential equations.
17.
使用SAC/SAC-CI方法,利用D95(d),6-311g**以及cc-PVTZ等基组,对B2分子的基态(X3Σg-)和第一激发态(A3Σu-)的平衡结构和谐振频率进行了优化计算.通过对3个基组的计算结果的比较,得出了D95(d)基组为3个基组中的最优基组的结论;使用D95(d)基组,利用SAC的GSUM(Group Sum of Operators)方法对基态(X3Σg-),SAC-CI的GSUM方法对激发态(A3Σu-)进行单点能扫描计算,用正规方程组拟合Murrell-Sorbie函数,得到了相应电子态的完整势能函数;从得到的势能函数计算了与基态(X3Σg-)和第一激发态(A3Σu-)相对应的光谱常数(Be,αe,ωe和ωeχe),结果与实验数据吻合. 相似文献
18.
根据GaN氢化物气相外延生长(HVPE)的原理,设计制作了双温区卧式HVPE系统.根据实际生长中出现的问题和CaN样品的测试情况,对系统进行了逐步的调试和改进. 相似文献
19.
20.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献