全文获取类型
收费全文 | 92021篇 |
免费 | 5133篇 |
国内免费 | 11884篇 |
专业分类
化学 | 71044篇 |
晶体学 | 1169篇 |
力学 | 2493篇 |
综合类 | 868篇 |
数学 | 13197篇 |
物理学 | 20267篇 |
出版年
2024年 | 116篇 |
2023年 | 698篇 |
2022年 | 1894篇 |
2021年 | 1833篇 |
2020年 | 2257篇 |
2019年 | 2187篇 |
2018年 | 1881篇 |
2017年 | 2748篇 |
2016年 | 2860篇 |
2015年 | 2402篇 |
2014年 | 3376篇 |
2013年 | 6694篇 |
2012年 | 6271篇 |
2011年 | 5071篇 |
2010年 | 4286篇 |
2009年 | 5860篇 |
2008年 | 6058篇 |
2007年 | 6319篇 |
2006年 | 5743篇 |
2005年 | 4825篇 |
2004年 | 4474篇 |
2003年 | 3714篇 |
2002年 | 4936篇 |
2001年 | 2877篇 |
2000年 | 2644篇 |
1999年 | 2480篇 |
1998年 | 2152篇 |
1997年 | 1700篇 |
1996年 | 1440篇 |
1995年 | 1360篇 |
1994年 | 1213篇 |
1993年 | 1009篇 |
1992年 | 956篇 |
1991年 | 644篇 |
1990年 | 543篇 |
1989年 | 524篇 |
1988年 | 383篇 |
1987年 | 310篇 |
1986年 | 280篇 |
1985年 | 228篇 |
1984年 | 244篇 |
1983年 | 140篇 |
1982年 | 214篇 |
1981年 | 175篇 |
1980年 | 195篇 |
1979年 | 183篇 |
1978年 | 171篇 |
1977年 | 123篇 |
1976年 | 109篇 |
1973年 | 68篇 |
排序方式: 共有10000条查询结果,搜索用时 9 毫秒
991.
Complex films of crosslinked poly(methylsiloxane-co-ethylene oxide) and lithium perchlorate were prepared. These solid state polymeric electrolytes show a markedly higher ionic conductivity, and excellent flexibility. The ionic conductivity of the network films closed to 10~(-5) Scm~(-1) at room temperature. The effects of Li~+ content, species and contents of crosslinking agents, molecular weight of poly(ethylene oxide) and temperature on the ionic conductivity of the network films were also investigated. 相似文献
992.
12-钼磷酸—聚乙烯醇的光电子转移反应 总被引:4,自引:0,他引:4
12-钼磷酸—聚乙烯醇体系具有不可逆光致变色的特性。根据X射线光电子能谱、电子自旋共振谱、紫外及可见光谱的测试结果,笔者认为:在PMo_(12)-PVA的光电子转移反应中,PMo_(12)既是氧化剂也是光敏剂。PMo_(12)分子中氧可分成O_p、O_b和O_t三种情况.其中O_t可成为光化学的活性位置,它和PVA羟基上的氧均较易被紫外光激活。激活的0_t边使周围的一个电荷向金属原子(Mo~(Ⅵ))转移,边与PVA羟基上被激活的氧作用,电子就由此羟基上的氧向O_t转移,致使体系中部分PMo_(12)与PVA发生二电子或四电子氧化还原反应,形成Mo(Ⅵ、Ⅴ)配合物而变色,同时,PVA分子的部分羟基及该羟基位的碳上脱氢形成羰基而具有酮结构。此外,从Mo(V)的ESR特征信号随时间变化而减弱,但其吸收光谱的吸光度未变,于是推断该光化学反应过程中尚有Mo(Ⅳ)生成,已由XPS谱证实。 相似文献
993.
A method has been developed for highly sensitive determination of haloperidol in human serum involving a simple extraction procedure followed by gas chromatographic separation. Target components were separated from the extracting solvents with a Van den Berg type solventless sample injector before introduction Into a DB-1 capillary separation column. A surface ionization detector (SID), which has highly selective sensitivity for Substituted amines, was employed for quantitation using bromperidol as an internal standard. Chloroform proved to be the best extracting solvent, yielding a quantitative detection limit of 5 ng/ml (S/N = 2). Comparison of the response to target compounds obtained by the SID, FTD (flame thermionic detector), and FID (flame ionization detector) showed the SID to be superior. 相似文献
994.
Haoshuang Gu Yongming Hu Hao Wang Xiangrong Yang Zhenglong Hu Ying Yuan Jin You 《Journal of Sol-Gel Science and Technology》2007,42(3):293-297
Single crystalline nanowires of lead titanate (PbTiO3) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure
and optical properties of PbTiO3 nanowires were investigated. The PbTiO3 nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO3 with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm.
The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy
(XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition
of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed
at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies
are responsible for the light emission of PbTiO3 nanowires. 相似文献
995.
J.S. Yadav B.V. Subba Reddy K.V. Raghavendra Rao G.G.K.S. Narayana Kumar 《Tetrahedron letters》2007,48(31):5573-5576
Indoles undergo smooth alkylation with propargylic alcohols in the presence of 10 mol % of scandium triflate under mild conditions to produce 3-propargylated indoles in excellent yields with high selectivity. 相似文献
996.
ZENG Xiang-Chao② XU Shi-Hai LIU Po-Runa DENG Qin-Ying 《结构化学》2005,24(3):299-302
1 INTRODUCTION Indole and its derivatives have attracted much at-tention due to their chemical properties as well asbiological activities[1, . They have been widely used 2]as the materials for producing pigment, perfume,plant growth regulators, etc. Recently, it has alsobeen found that some indole derivatives present anti-tumor and antiviral activities[3~5]. During our sear-ches for bioactive compounds, a series of indole deri-vatives were synthesized, among … 相似文献
997.
The synthesis of dendrons with the end-capped 5-(N,N-dimethylamino)naphthyl-1-ethynyl unit connected to conjugated naphthylethynyl or p-phenylethynyl chains, as the branches of the 1,3,5-substituted benzene core, have been undertaken by heterocoupling reaction between 1,3,5-triiodobenzene and the convenient end-capped 5-(N,N-dimethylamino)naphthylacetylene or 5-(N,N-dimethylamino)naphthylethynylphenylacetylene in the presence of the palladium-copper catalyst system, in excellent yields. The influence of the alternating naphthylethynyl-phenylethynyl chains on the fluorescence emission radiation, in the dendron structures, has been analyzed. 相似文献
998.
Boris GuintchinStefan Bienz 《Tetrahedron》2003,59(38):7527-7533
Enantiomerically enriched (E)- and (Z)-configured α-acetoxyallylsilanes have been prepared starting from a chiral acylsilane bearing an asymmetric unit at the silicon portion. Treatment of these compounds with organocuprates afforded the respective vinylogous substitution products in high yields and high stereoselectivities. The transformations proceed essentially by complete anti attack of the nucleophiles to the allylic acetates and predominantly via transition states leading to the (E)-configured vinylsilane products. By the proper choice of the double bond geometry in the starting material, the configuration of the newly formed stereogenic center can be controlled. The method represents a new and flexible entry into chiral vinylsilanes that can be used for subsequent transformations. As an example, the α,β-unsaturated γ-chiral, naturally occurring ketone (S)-(+)-bishomomanicone was synthesized with this method, which represents the first synthetic access to this compound. 相似文献
999.
Shyh‐Jong Chen Cheng Chen Yaw‐Shun Hong 《International journal of quantum chemistry》2005,103(2):198-214
This investigation conducted reaction channels of weakly bound complexes CO2…HF, CO2…HF…NH3, CO2…HF…NH2CH3, CO2…HF…NH(CH3)2, and CO2…HF…N(CH3)3 systems, using the Gaussian 98 package at the B3LYP/6‐311++G(3df,2pd) level. The syn‐fluoroformic acid or syn‐fluoroformic acid plus NH3 or amine conformers are more stable than the related anti‐fluoroformic acid or anti‐fluoroformic acid plus NH3 or amine conformers. However, the above‐mentioned weakly bound complexes are more stable than both the related syn‐ and anti‐type fluoroformic acid or acid plus NH3 or amine conformers and their related decomposed into CO2 + HF or CO2 + NHR3F (R?H, CH3) combined molecular systems. Five reaction channels of the weakly bound complexes exist. Each channel includes weakly bound complexes and their related above‐mentioned systems. Moreover, each reaction channel contains two transition states. The transition state between the weakly bound complex and anti‐fluoroformic acid type structure (T13) is significantly higher than that of internal rotation (T23) between syn‐ and anti‐FCO2H (or FCO2H…NR3) structures. However, the above‐mentioned T13 can significantly decrease its energy by adding the third molecule NH3 or NR3 (R?H or CH3). The more CH3 that is substituted in NR3 of the reaction channel, the lower the activation energy of the transition state in the system is affected. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
1000.
Amidines can be prepared on a solid support by reducing polymer-bound amidoximes with SnCl2·2H2O. The method has proved to be straightforward and highly efficient. Amidoximes attached to the solid support are readily available by treating resin-bound nitriles with hydroxylamine. 相似文献