全文获取类型
收费全文 | 42195篇 |
免费 | 8192篇 |
国内免费 | 6590篇 |
专业分类
化学 | 31399篇 |
晶体学 | 686篇 |
力学 | 2650篇 |
综合类 | 480篇 |
数学 | 4837篇 |
物理学 | 16925篇 |
出版年
2024年 | 96篇 |
2023年 | 819篇 |
2022年 | 1415篇 |
2021年 | 1586篇 |
2020年 | 1815篇 |
2019年 | 1851篇 |
2018年 | 1573篇 |
2017年 | 1588篇 |
2016年 | 2099篇 |
2015年 | 2265篇 |
2014年 | 2703篇 |
2013年 | 3453篇 |
2012年 | 4037篇 |
2011年 | 4164篇 |
2010年 | 3089篇 |
2009年 | 3109篇 |
2008年 | 3319篇 |
2007年 | 2773篇 |
2006年 | 2538篇 |
2005年 | 2082篇 |
2004年 | 1578篇 |
2003年 | 1323篇 |
2002年 | 1313篇 |
2001年 | 1073篇 |
2000年 | 845篇 |
1999年 | 748篇 |
1998年 | 545篇 |
1997年 | 485篇 |
1996年 | 436篇 |
1995年 | 356篇 |
1994年 | 351篇 |
1993年 | 264篇 |
1992年 | 209篇 |
1991年 | 188篇 |
1990年 | 180篇 |
1989年 | 113篇 |
1988年 | 100篇 |
1987年 | 78篇 |
1986年 | 81篇 |
1985年 | 60篇 |
1984年 | 26篇 |
1983年 | 31篇 |
1982年 | 19篇 |
1981年 | 21篇 |
1980年 | 13篇 |
1979年 | 19篇 |
1978年 | 9篇 |
1977年 | 11篇 |
1957年 | 10篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 312 毫秒
981.
Zhen‐Yu Li Ping Chen Hong‐Gui Xu Shu‐Ying Peng Yi‐Ming Yang Zhong‐Zhen Zhao Yue‐Wei Guo 《Helvetica chimica acta》2007,90(7):1353-1359
Five new polycyclic Daphniphyllum alkaloids, macropodumines F ( 1 ) and G ( 2 ), 17‐oxoyuzurimine ( 3 ), and macropodumines H ( 4 ) and I ( 5 ), were isolated from the leaves of D. macropodum Miq ., collected in Sichuan Province, China. The structures and relative configurations of the new compounds – as well as of four known, related alkaloids – were elucidated on the basis of in‐depth spectroscopic and mass‐spectrometric analyses, by chemical derivatization, and by comparison of spectroscopic data with those of known compounds. 相似文献
982.
Wang‐Ting Wu Feng‐Ying Chen Shui‐Yang He Huai‐Ming Hu Meng‐Lin Yang Yao‐Yu Wang 《中国化学》2006,24(5):711-713
The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C10H10N2O4, H2L) was prepared in H2O‐C2H5OH mixed solution, and the crystal structure of [Pr2L2(HL)2(H2O)4]·3H2O·C6H6 was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr3+ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ2‐bridging mode. 相似文献
983.
The complexes PtRu(5)(CO)(15)(PMe(2)Ph)(mu(6)-C) (2), PtRu(5)(CO)(14)(PMe(2)Ph)(2)(mu(6)-C) (3), PtRu(5)(CO)(15)(PMe(3))(mu(6)-C) (4), PtRu(5)(CO)(14)(PMe(3))(2)(mu(6)-C) (5), and PtRu(5)(CO)(15)(Me(2)S)(mu(6)-C) (6) were obtained from the reactions of PtRu(5)(CO)(16)(mu(6)-C) (1) with the appropriate ligand. As determined by NMR spectroscopy, all the new complexes exist in solution as a mixture of isomers. Compounds 2, 3, and 6 were characterized crystallographically. In all three compounds, the six metal atoms are arranged in an octahedral geometry, with a carbido carbon atom in the center. The PMe(2)Ph and Me(2)S ligands are coordinated to the Pt atom in 2 and 6, respectively. In 3, the two PMe(2)Ph ligands are coordinated to Ru atoms. In solution, all the new compounds undergo dynamical intramolecular isomerization by shifting the PMe(2)Ph or Me(2)S ligand back and forth between the Pt and Ru atoms. For compound 2, DeltaH++ = 15.1(3) kcal/mol, DeltaS++ = -7.7(9) cal/(mol.K), and DeltaG(298) = 17.4(6) kcal/mol for the transformation of the major isomer to the minor isomer; for compound 4, DeltaH++ = 14.0(1) kcal/mol, DeltaS++ = -10.7(4) cal/(mol.K), and DeltaG(298) = 17.2(2) kcal/mol for the transformation of the major isomer to the minor isomer; for compound 6, DeltaH++ = 18(1) kcal/mol, DeltaS++ = 21(5) cal/(mol.K) and DeltaG(298) = 12(2) kcal/mol. The shifts of the Me(2)S ligand in 6 are significantly more facile than the shifts for the phosphine ligand in compounds 2-5. This is attributed to a more stable ligand-bridged intermediate for the isomerizations of 6 than that for compounds 2-5. The intermediate for the isomerization of 6 involves a bridging Me(2)S ligand that can use two lone pairs of electrons for coordination to the metal atoms, whereas a tertiary phosphine ligand can use only one lone pair of electrons for bridging coordination. 相似文献
984.
The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step. 相似文献
985.
In this paper, we used bond-length equalization, aromatic stabilization energies (ASE) and nucleus-independent chemical shifts
(NICS), calculated with (density functional theory) B3LYP levels at the 6-311+G** basis set, to evaluate the aromaticity of a set of 38 five-member planar π-electron aromatic systems: sila-, aza- and phospha-
derivatives and their parent systems. The result revealed statistically significant correlations among the above three criteria,
and the order of aromaticity of the whole set was: Aza- derivatives rings > Phospha- derivatives rings > Sila- derivatives
rings > Carbon-containing rings; NICS(0.6) and NICS(0.8) had the same results in evaluating the order of aromaticity in our
case. 相似文献
986.
1—酰基—4—氯环己烷与取代芳烃的区域与立体选择性反应 总被引:2,自引:0,他引:2
从环己烯合成了1-酰基-4-氯环己烷,发现在其在AlCl3催化与苯,氯苯,溴苯等优先生成反式1-芳基-4-酰基环己烷,与联苯反应时选择性较差。 相似文献
987.
针对日益严重的砷离子污染问题,本文采用灵敏简便的原子荧光分析法,探究了凹凸棒石粘土吸附剂对砷离子的吸附性能,测定了pH、吸附时间、砷离子的初始浓度等因素对凹凸棒石粘土负载铁氧化物对砷离子吸附能力的影响,并通过SEM、EDX、FTIR对所制得的吸附剂进行了表征研究,同时进行了吸附动力学和吸附等温模型的分析。研究结果表明,改性后的凹凸棒对砷离子的吸附性能有了显著提升,在较低浓度时吸附效率可达98%,该吸附符合Langmuir等温吸附模型和准二级动力学方程。 相似文献
988.
用恒电位电流衰减法及激光扫描光电化学显微技术研究了在于PH=12.5及13.8的模拟混凝土孔溶液中钢筋钝化化膜的生长动力学及相应的破坏过程,实验结果表明,钢筋钝化膜的生长过程存在两个主要阶段,各阶段膜厚均与生长时间存在正比对数关系,但当t<30秒和t>30秒时,膜的生长表出出不同的动力学特征,在钝化发生点蚀前,钝化膜的微区光电流一定的预兆,腐蚀抑制剂NaNO2影响膜的生长过程及膜厚,能提高钢筋的抗 相似文献
989.
在前人工作的基础上, 改进了液上空间气相色谱测活度系数的方法, 实验测定了TBP. 稀释剂和水形成的多个二元系、三元系和四元系的活度系数和密度. 选用的稀释剂有n-C_6H_(14)、n-C_7H_(16)、n-C_8H_(18)、C_6H_6、cy-C_6H_(12)、CCl_4和CHCl_3. 在Pierotti理论的基础上, 采用新的硬球作用表达式和径向分布函数, 并计及分子间的排斥能、色散能、取向能和诱导能, 建立了简单的活度系数模型, 并用于TBP和稀释剂体系的计算. 从二元系回归得到的分子参数较好地预测了三元系的活度系数. 相似文献
990.
利用合成的巯基含量为2.2~2.5%的高巯基粉状巯基棉,对水中超痕量汞进行富集测定。流速可达100mL·min~(-1),检出限为0.5×10~(-12),加标回收率为90~104%。 相似文献