全文获取类型
收费全文 | 15440篇 |
免费 | 1497篇 |
国内免费 | 4845篇 |
专业分类
化学 | 15966篇 |
晶体学 | 488篇 |
力学 | 526篇 |
综合类 | 162篇 |
数学 | 1674篇 |
物理学 | 2966篇 |
出版年
2024年 | 20篇 |
2023年 | 167篇 |
2022年 | 196篇 |
2021年 | 385篇 |
2020年 | 460篇 |
2019年 | 377篇 |
2018年 | 422篇 |
2017年 | 512篇 |
2016年 | 569篇 |
2015年 | 479篇 |
2014年 | 711篇 |
2013年 | 1241篇 |
2012年 | 1635篇 |
2011年 | 900篇 |
2010年 | 734篇 |
2009年 | 975篇 |
2008年 | 1080篇 |
2007年 | 1191篇 |
2006年 | 1105篇 |
2005年 | 1047篇 |
2004年 | 970篇 |
2003年 | 781篇 |
2002年 | 717篇 |
2001年 | 577篇 |
2000年 | 568篇 |
1999年 | 528篇 |
1998年 | 459篇 |
1997年 | 407篇 |
1996年 | 402篇 |
1995年 | 386篇 |
1994年 | 333篇 |
1993年 | 240篇 |
1992年 | 292篇 |
1991年 | 211篇 |
1990年 | 167篇 |
1989年 | 121篇 |
1988年 | 97篇 |
1987年 | 67篇 |
1986年 | 70篇 |
1985年 | 54篇 |
1984年 | 36篇 |
1983年 | 18篇 |
1982年 | 24篇 |
1981年 | 14篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1973年 | 4篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 703 毫秒
991.
Solid-stateSynthesisatLow-heatingTemperatureandCrystalStructureofaDinuclearMolybdenumComplexwithOxalateLigand[Bu_4N]_2[Mo_2O_2(... 相似文献
992.
Steric structures of dysprosium(III) aminobenzoate complexes with the 11 and 12 molar ratio in aqueous solutions were determined on the basis of pH-metric and paramagnetic birefringence data. An increase in conjugation observed for the series of the acids,viz., benzoic,meta-, ortho-, andpara-aminobenzoic acids, results in the increased stability of the complexes with the 11 and 12 composition. In the case ofpara-aminobenzoic acid, the polyhedra [DyL(H2O)6]2+ and [DyL2(H2O)4]+ are cubes with the ligands coordinated to one and two edges, respectively. In the case ofmeta-aminobenzoic acid, the polyhedra [DyL(H2O)6]2+ and [DyL2(H2O)4]+ are a dodecahedron with the ligand coordinated to one edge and a square anti-prism with the ligands coordinated to two edges, respectively. In the case ofortho-aminobenzoic acid, both the 11 and 12 complexes have structures that are intermediate between the structures ofmeta- andpara-aminobenzoic acids.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1767–1770, October, 1994. 相似文献
993.
Two polyether bridged dihydroxamic acids and their mono-and binuclear manganese(Ⅱ), zinc(Ⅱ) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono-and binuclear metal, the pseudo-macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dthydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo-macrocyclic polyether might synergetically activate H20 coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP. 相似文献
994.
A structure and kinetic stability study on some complexes with the general formula MN5, where M are the alkali-metal atoms, Li, Na, K, and Rb, has been carried by using hybrid density functional methods. Complex B (C2v) with two points of attachment to the N5 ring is the most energetically favored for all metals considered here. Pyramidal structures A (C5v) are kinetically unstable and they rapidly rearrange to the most stable planar structures B. At the QCISD(T)/6-311 + G*//B3LYP/6-311 + G* + ZPE (B3LYP/6-311 + G*) level, the decomposition barrier heights of LiN5-B, NaN5–B, KN5-B, and RbN5-B are predicted to be 19.9, 22.0, 22.5, and 23.0 kcal/mol, respectively. In addition, the rate constants of the decomposition reaction MN5-B MN3 + N2 (M + Li, Na, K, and Rb) are also predicted using conventional transition state theory and canonical variational transition state theory, respectively. 相似文献
995.
通过分子模拟方法研究了手性金属配合物[Rh(bpy)2Chrysi]^3+(bpy=2,2’-bipyridineChrysi=5,6-chrysenequinonediimine)对包含C:T错配碱基对的B-DNA序列的识别作用.结合类似的针对含G:A错配的和正常的B-DNA序列的识别作用研究,发现配合物I-Rh(bpy)zChrysi]^3+可以对错配B-DNA序列进行序列特异性的识别.能量对比计算结果表明,该经典插入识别作用倾向于在错配碱基对附近进行,其中△-[Rh(bpy)2chrysi]^3+比其手性异构体更占优势.这同Barton教授工作组的实验结果是一致的.另外插入作用倾向于在错配序列中的正常双碱基对C3A4/G3T4(错配碱基对附近)中从小沟进行.与该配合物对含G:A错配的和正常的B-DNA序列的识别作用不同的是,对包含C:T错配碱基对的B-DNA序列的识别作用倾向于从小沟进行.这一点可能源于C:T碱基对结构的不同. 相似文献
996.
1INTRODUCTION Over the past decades,olefin oligomerization and polymerization based on late transition metal catalysts have been the most exciting developments in the area of organometallic chemistry and polymer science[1~3].In this broad context,neutral nickel(II)complexes have attracted much attention for their less sensitivity to protonic solvents and polar mon-mers.The most typical one is the SHOP-type cata-lyst[4~6],which contains an anionic[P,O]chelate ring and shows high activ… 相似文献
997.
ZHOU Yin-Zhuang② LI Jin-Fang TU Shu-Jie ZHANG Min 《结构化学》2005,24(10):1193-1197
1 INTRODUCTION The chemistry of copper compounds has been extensively investigated and the relationship be- tween structure and reactivity, ranging from indus- trial catalysis to biochemistry activity, is of major importance. For binuclear copper(II) complexes equa- torially bridged by pair of hydroxide[1] or alkoxide[2, 3] groups, satisfactory linear correlation is found be- tween the Cu–O–Cu bridging angle and spin coupling between the metal centers. However, for binuclear copper(I… 相似文献
998.
Junko Fukutomi Yuko Adachi Akari Kaneko Atsuomi Kimura Hideaki Fujiwara 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):115-122
The inclusion complex formation of 4-sulfothiacalix[4]arene sodium salt (STCAS) and Xe has been investigated by using hyperpolarized
129Xe NMR spectroscopy. Our new continuous-flow type hyperpolarizing system has advantageous capabilities that can supply hyperpolarized
gases continuously and directly to a sample solution in a NMR tube. Consequently saturated Xe concentration in the aqueous
solution of STCAS is maintained during the NMR experiment, and 129Xe NMR spectra can be obtained in remarkably short time. STCAS concentration dependence of 129Xe chemical shift has been analyzed in an elaborated way by a computer method as well as a simple graphic method that we have
proposed. The association constant K:13.6±0.8 M−1 at 25 °C was obtained, and further analysis of the temperature dependence has successfully given thermodynamic parameters
of enthalpy (ΔH) and entropy (ΔS) for the inclusion complex formation: ΔH = −11.9±1.9 kJ mol−1 and ΔS = −17.4±5.8 JK−1 mol−1. The energetic aspects of complex formation are discussed from the size effect and from the molecular theory of standard
entropy, and a release of definite number of water molecules from STCAS cavity is suggested in the inclusion complex formation
with Xe. 相似文献
999.
本文用~(13)C-NMR研究了异戊二烯(IP)在均相催化剂(CF_3CO_2)_2LnCl·EtOH—(i-Bu)AlH—o-C_6D_4Cl_2作用下的聚合过程。单体首先被活化同稀土配位生成η~4-IP稀土配合物(反式和顺式),然后η~4-IP的C-3和C-4插入Ln-H键生成η~3-烯丙基稀土配合物——η~3-(2-甲基)丁烯基稀土配合物(同式和对式)。二维~(13)C-NMR交换谱表明η~4-IP和0η~3-烯丙基的每对异构体在常温下分别进行慢交换反应(互变异构),这一过程使插入反应在常温下得以进行。 相似文献
1000.
Reactions among Cu(ClO4)2 · 6H2O, Cu(acac)2/VO(acac)2 and 3-methoxysalicylaldehyde Picoloylhydrazone in different solvents give three complexes, [Cu2L(acac)(H2O)2]ClO4 (1), [Cu4L2(acac)2(py)2](ClO4)2 (2) and (VO2)2L2Cu2(acac)2 (3) (acac = acetyl acetonate and py = pyridine). There is an extended 2D structure in complex 1 constructed by hydrogen bonds between the binuclear complex cation and the ClO4− anion, and an extended 1D structure in complex 2 constructed by weak ππ stacking interactions between neighboring cyclic tetranuclear complex molecules. Complex 3 is the first oxovanadium–copper complex with a bridging oxo oxygen atom between the V atom and the Cu atom. The solid-state photoluminescent properties of the three title complexes have been studied. There is an antiferromagnetic interaction in 1. 相似文献