全文获取类型
收费全文 | 375篇 |
免费 | 50篇 |
国内免费 | 46篇 |
专业分类
化学 | 242篇 |
晶体学 | 4篇 |
力学 | 21篇 |
综合类 | 11篇 |
数学 | 122篇 |
物理学 | 71篇 |
出版年
2023年 | 5篇 |
2022年 | 7篇 |
2021年 | 7篇 |
2020年 | 13篇 |
2019年 | 18篇 |
2018年 | 21篇 |
2017年 | 22篇 |
2016年 | 18篇 |
2015年 | 17篇 |
2014年 | 27篇 |
2013年 | 61篇 |
2012年 | 20篇 |
2011年 | 16篇 |
2010年 | 17篇 |
2009年 | 11篇 |
2008年 | 21篇 |
2007年 | 20篇 |
2006年 | 11篇 |
2005年 | 15篇 |
2004年 | 15篇 |
2003年 | 15篇 |
2002年 | 8篇 |
2001年 | 11篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 3篇 |
排序方式: 共有471条查询结果,搜索用时 15 毫秒
41.
42.
43.
Liang Song Chunlai Tu Yunfeng Shi Feng Qiu Lin He Yi Jiang Qi Zhu Bangshang Zhu Deyue Yan Xinyuan Zhu 《Macromolecular rapid communications》2010,31(5):443-448
A simple approach to tune the optical properties of the hyperbranched conjugated polymers by only adjusting the terminal‐backbone interactions has been reported in this article. Hyperbranched conjugated polyazomethines have been successfully prepared by the reaction of tetramine and dialdehyde. Not only varying the monomer feed ratio to change the quantity of terminal amino groups, but also adopting protonation or complexion with proper dopants (SnCl2 and β‐cyclodextrin), can alter the interactions between amino terminals and imine bonds in the backbone. Correspondingly, the optical properties of the resulting hyperbranched polymers are controlled.
44.
45.
We have synthesized a homologous series of azoesters consisting of a coumaryl moiety as the end group. Eleven derivatives of this series exhibit mesomorphism. The nematic mesophase is exhibited from ethyl homologue onward, while the smectic phase commences at the pentyl derivative and is exhibited along with the nematic phase up to the hexadecyl derivative. The N-I transition temperatures curves show the usual odd-even effect. All the compounds in this series are thermally stable and exhibit a wide mesomorphic range of nearly 120°C. Their thermal stabilities and other characteristics are discussed. 相似文献
46.
作为有机强碱,胍类化合物可用于催化多种反应[1 5],并且反应可以在均相、无水条件下进行,不需要相转移催化剂。本文探讨用胍催化邻苯二甲酰亚胺对环氧化合物进行开环。用三光气将二乙胺转变为四乙基脲1,后者用五氯化磷和叔丁胺处理得到1,1,3,3 四乙基 2 叔丁基胍2。用2催化邻苯二甲酰亚胺与末端环氧化合物的反应,实现了环氧化合物的区域选择性开环。合成路线如下:1 实验部分1 1仪器与试剂WC 1型显微熔点仪(四川大学科仪厂),温度计未校正;Carlo ErbaModel1110自动元素分析仪,Varian400MHz核磁共振仪。溶剂和试剂经干燥、重蒸后使用… 相似文献
47.
Dr. Caroline M. Storey Dr. Matthew R. Gyton Dr. Rhiann E. Andrew Dr. Adrian B. Chaplin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14715-14723
Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC-based pincer ligands—which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC-n)(C2H4)][BArF4] (n=12, 14, 16; ArF=3,5-(CF3)2C6H3)—have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr’ (Ar’=3,5-tBu2C6H3) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3-enynes by C−C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E-alkenyl complexes derived from HC≡CtBu and gem-alkenyl complexes derived from HC≡CAr’, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E-tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E-alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar'C≡CC(=CH2)Ar’ is encumbered relative to head-to-head coupling of HC≡CAr’ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC-Me)(C2H4)][BArF4] and solvent effects. 相似文献
48.
49.
50.
以有机高价碘杂环化合物1,2为底物,在Pd(PPh3)2Cl2-CuCl催化剂存在下与末端炔烃进行交叉偶联反应,实验发现该反应为--化学选择性反应,控制反应体系的物料比、温度及反应时间可以分别得到单偶联或双偶联产物,从而证实了有机高价碘杂环化合物的碘盐在进行交叉偶联反应时的反应活性比sp2的碘化物高. 相似文献