全文获取类型
收费全文 | 15460篇 |
免费 | 2522篇 |
国内免费 | 2798篇 |
专业分类
化学 | 12574篇 |
晶体学 | 282篇 |
力学 | 809篇 |
综合类 | 184篇 |
数学 | 1480篇 |
物理学 | 5451篇 |
出版年
2024年 | 69篇 |
2023年 | 348篇 |
2022年 | 652篇 |
2021年 | 685篇 |
2020年 | 728篇 |
2019年 | 782篇 |
2018年 | 635篇 |
2017年 | 638篇 |
2016年 | 773篇 |
2015年 | 793篇 |
2014年 | 985篇 |
2013年 | 1209篇 |
2012年 | 1309篇 |
2011年 | 1344篇 |
2010年 | 1060篇 |
2009年 | 947篇 |
2008年 | 980篇 |
2007年 | 834篇 |
2006年 | 827篇 |
2005年 | 773篇 |
2004年 | 655篇 |
2003年 | 547篇 |
2002年 | 581篇 |
2001年 | 537篇 |
2000年 | 381篇 |
1999年 | 319篇 |
1998年 | 228篇 |
1997年 | 148篇 |
1996年 | 176篇 |
1995年 | 125篇 |
1994年 | 136篇 |
1993年 | 115篇 |
1992年 | 96篇 |
1991年 | 85篇 |
1990年 | 64篇 |
1989年 | 44篇 |
1988年 | 31篇 |
1987年 | 23篇 |
1986年 | 31篇 |
1985年 | 24篇 |
1984年 | 21篇 |
1983年 | 18篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1971年 | 1篇 |
1959年 | 3篇 |
1957年 | 2篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
101.
手性配体的空间结构与产物对映选择性的关系 总被引:2,自引:0,他引:2
首次采用4-烷氧羰基噻唑烷、E唑烷作为手性配体,诱导烷基锌对醛类的亲核加成反应,获得产物是烷基化的醛,最高达90%ee,产率98%的(S)-二级醇。系统地考察了该类手性配体三维空间结构变化与产物对映选择性的关系,当配体4-位烷氧羰基上的R、2-位R′基和环体上原子X发生变化时都会引起产物(S)-二 级醇的对映选择性发生规律性变化。对五种不同结构的底物醛在同一手性配体催化下,诱导烷基锌对醛类的亲核加成反应,底物结构变化也会引起(S)-二级醇对映选择性变化。 相似文献
102.
富氧条件下乙炔选择催化还原NOx 总被引:1,自引:0,他引:1
Acetylene as a reducing agent of metal exchanged HY catalysts, for selective catalytic reduction of NO in the reaction system of 0.16% NO, 0 (C2H2-SCR) was investigated over a series 08% C2H2, and 9.95% O2 (volume percent) in He. 75% of NO conversion to N2 with hydrocarbon efficiency about 1.5 was achieved over a Ce-HY catalyst around 300 ℃. The NO removal level was comparable with that of selective catalytic reduction of NOx by C3H6 reported in literatures, although only one third of the reducing agent in carbon moles was used in the C2H2-SCR of NO. The protons in zeolite were crucial to the C2H2-SCR of NO, and the performance of HY in the reaction was significantly promoted by cerium incorporation into the zeolite. NO2 was proposed to be the intermediate of NO reduction to N2, and the oxidation of NO to NO2 was rate-determining step of the C2H2-SCR of NO over Ce-HY. The suggestion was well supported by the results of the NO oxidation with O2, and the C2H2 consumption under the conditions in the presence or absence of NO. 相似文献
103.
Shu Jiang ZHANG Yan Feng LI Xiao Long WANG Da Xue YIN Yu SHAO Xin ZHAO 《中国化学快报》2005,16(9):1165-1168
A new aromatic diamine monomer containing pyridine unit, 2,6-bis (4-aminophenoxy- 4'-benzoyl)pyridine(BABP), was synthesized in three steps, starting from 2,6-pyridinedicarboxyl chloride. A series of novel pyridine-containing polyimides were prepared v/a the polycondensation of BABP with various aromatic dianhydrides through poly(amic acid) precursors, and thermal or chemical imidization of the precursors. The polyimides exhibit desirable properties, e.g., good solubility in N-methyl-2-pyrrolidone and m-cresol, excellent thermal stability and film-forming capability, as well as high inherent viscosity, indicating high molecular weight. 相似文献
104.
Three new alkaloids, longistylumphyllines A–C (1–3), together with the six known alkaloids deoxycalyciphylline B, deoxyisocalyciphylline B, methyl homosecodaphniphyllate, daphnicyclidin A, daphnicyclidin B, and daphnicyclidin F, were isolated from the stems and leaves of Daphniphyllum longistylum. Their structures and relative configuration were elucidated on the basis of spectroscopic data, especially 1D and 2D NMR techniques. 相似文献
105.
Xin‐Zhou Yang Li‐Gen Lin Chun‐Ping Tang Yong‐Qiang Liu Yang Ye 《Helvetica chimica acta》2007,90(2):318-325
Five new nonalkaloid constituents, a neolignan, japonin A ( 1 ), a macrocyclic lactone, japonin B ( 2 ), a (phenylethyl)benzoquinone, japonin C ( 3 ), a phenanthraquinone, japonin D ( 4 ), as well as a dihydrostilbene, stilbostemin M ( 5 ), were isolated from the roots of Stemona japonica, together with eight known compounds. Their structures were established by spectroscopic analyses. 相似文献
106.
107.
108.
Two new coordination polymers of PbII complexes with bridging 4,4′‐[(1E)‐ethane‐1,2‐diyl]bis[pyridine] (ebp), thiocyanato, and acetato ligands, [Pb(μ‐SCN)2(μ‐ebp)1.5]n ( 1 ) and {[Pb(μ‐OAc)(μ‐ebp)](ClO4)}n ( 2 ), were synthesized and characterized by elemental analysis, FT‐IR, 1H‐ and 13C‐NMR, thermal analysis, and single‐crystal X‐ray diffraction. In 1 , the Pb2+ ions are doubly bridged by both the ebp and the SCN− ligands into a two‐dimensional polymeric network. The seven‐coordinate geometry around the Pb2+ ion in 1 is a distorted monocapped trigonal prism, in which the Pb2+ ions have a less‐common holodirected geometry. In 2 , the Pb2+ ions are bridged by AcO− ligands forming linear chains, which are also further bridged by the neutral ebp ligands into a two‐dimensional polymeric framework. The Pb2+ ions have a five‐coordinate geometry with two N‐atoms from two ebp ligands and three O‐atoms of AcO−. Although ClO acts as a counter‐ion, it also makes weak interactions with the Pb2+ center. The arrangement of the ligands in 2 exhibits hemidirected geometry, and the coordination gap around the Pb2+ ion is possibly occupied by a configurationally active lone pair of electrons. 相似文献
109.
建立了处理双原子分子-表面相互作用的推广的LEPS势.借助推广的LEPS势,系统研究了一氧化碳分子在铂低指数表面吸附的动力学特性,重现了低指数表面的分子吸附热、吸附几何及本征振动等实验数据;鉴定了某些不合理的文献信息,预测了实验尚未探测到的重要信息:预测到Pt(100)表面四重洞位的C-O伸缩振动频率为1 962.60 cm-1;预测到Pt(110)表面吸附态的C-O及C-Pt键长分别为115.1、147 pm. 相似文献
110.
两种含锌化合物对慢性染铅大鼠海马NADPH-d阳性神经元影响的比较 总被引:1,自引:0,他引:1
为探讨硫酸锌(ZnSO4)和牛磺酸锌(TZC)拮抗铅对学习记忆的损害的不同,采用NADPH-黄递酶(NADPH-d)组化,观察了饮用含0.2g/L醋酸铅(PbAc)饮水和含不同剂量(5.0,15.0g/kg)ZnSO4、(5.9、17.7g/kg)TZC饲料喂养的大鼠海马一氧化氮合酶(NOS)活性的变化。结果表明,各补锌组均不同程度地缓解铅致NOS活力减低,铅 低TZC组、铅 高ZnSO4组和铅 低ZnSO4组大鼠海马神经元的NOS活性明显高于染铅组,其中铅 低TZC组的保护作用最显著,而铅 高TZC组的NOS活性明显低于对照组,而接近染铅组水平。结论是锌对抗铅的毒性作用与锌的化学结合形式、锌的剂量密切相关。 相似文献