全文获取类型
收费全文 | 10143篇 |
免费 | 1901篇 |
国内免费 | 1244篇 |
专业分类
化学 | 7439篇 |
晶体学 | 62篇 |
力学 | 646篇 |
综合类 | 78篇 |
数学 | 1064篇 |
物理学 | 3999篇 |
出版年
2024年 | 11篇 |
2023年 | 273篇 |
2022年 | 232篇 |
2021年 | 344篇 |
2020年 | 479篇 |
2019年 | 416篇 |
2018年 | 339篇 |
2017年 | 291篇 |
2016年 | 491篇 |
2015年 | 431篇 |
2014年 | 526篇 |
2013年 | 756篇 |
2012年 | 956篇 |
2011年 | 973篇 |
2010年 | 640篇 |
2009年 | 631篇 |
2008年 | 707篇 |
2007年 | 625篇 |
2006年 | 553篇 |
2005年 | 478篇 |
2004年 | 366篇 |
2003年 | 319篇 |
2002年 | 255篇 |
2001年 | 208篇 |
2000年 | 206篇 |
1999年 | 240篇 |
1998年 | 207篇 |
1997年 | 188篇 |
1996年 | 197篇 |
1995年 | 175篇 |
1994年 | 142篇 |
1993年 | 121篇 |
1992年 | 101篇 |
1991年 | 74篇 |
1990年 | 83篇 |
1989年 | 55篇 |
1988年 | 47篇 |
1987年 | 44篇 |
1986年 | 29篇 |
1985年 | 27篇 |
1984年 | 14篇 |
1983年 | 9篇 |
1982年 | 13篇 |
1981年 | 8篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1957年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
31.
32.
Niklas Rinn Dr. Jens P. Eußner Willy Kaschuba Dr. Xiulan Xie Prof. Dr. Stefanie Dehnen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(9):3094-3104
Reactions of R1SnCl3 (R1=CMe2CH2C(O)Me) with (SiMe3)2Se yield a series of organo‐functionalized tin selenide clusters, [(SnR1)2SeCl4] ( 1 ), [(SnR1)2Se2Cl2] ( 2 ), [(SnR1)3Se4Cl] ( 3 ), and [(SnR1)4Se6] ( 4 ), depending on the solvent and ratio of the reactants used. NMR experiments clearly suggest a stepwise formation of 1 through 4 by subsequent condensation steps with the concomitant release of Me3SiCl. Furthermore, addition of hydrazines to the keto‐functionalized clusters leads to the formation of hydrazone derivatives, [(Sn2(μ‐R3)(μ‐Se)Cl4] ( 5 , R3=[CMe2CH2CMe(NH)]2), [(SnR2)3Se4Cl] ( 6 , R2=CMe2CH2C(NNH2)Me), [(SnR4)3Se4][SnCl3] ( 7 , R4=CMe2CH2C(NNHPh)Me), [(SnR2)4Se6] ( 8 ), and [(SnR4)4Se6] ( 9 ). Upon treatment of 4 with [Cu(PPh3)3Cl] and excess (SiMe3)2Se, the cluster fragments to form [(R1Sn)2Se2(CuPPh3)2Se2] ( 10 ), the first discrete Sn/Se/Cu cluster compound reported in the literature. The derivatization reactions indicate fundamental differences between organotin sulfide and organotin selenide chemistry. 相似文献
33.
34.
Ultrathin Co3S4 Nanosheets that Synergistically Engineer Spin States and Exposed Polyhedra that Promote Water Oxidation under Neutral Conditions 下载免费PDF全文
Youwen Liu Dr. Chong Xiao Mengjie Lyu Dr. Yue Lin Weizheng Cai Pengcheng Huang Prof. Wei Tong Prof. Youming Zou Prof. Yi Xie 《Angewandte Chemie (International ed. in English)》2015,54(38):11231-11235
Development of efficient and affordable electrocatalysts in neutral solutions is paramount importance for the renewable energy. Herein, we report that the oxygen evolution reaction (OER) performance of Co3S4 under neutral conditions can be enhanced by exposed octahedral planes and self‐adapted spin states in atomically thin nanosheets. A HAADF image clearly confirmed that the active octahedra with Jahn–Teller distortions were exposed exclusively. Most importantly, in the atomically thin nanosheets, the spin states of Co3+ in the octahedral self‐adapt from low‐spin to high‐spin states. As a result, the synergistic effect endow the Co3S4 nanosheets with superior OER performance, with exceptional low onset overpotentials of circa 0.31 V in neutral solutions, which is state‐of‐the‐art among inorganic non‐noble metal compounds. 相似文献
35.
36.
37.
In‐Depth Understanding of the Chemical Properties of Rarely Explored Carbide Cluster Metallofullerenes: A Case Study of Sc2C2@C3v(8)‐C82 that Reveals a General Rule 下载免费PDF全文
Wenting Cai Muqing Chen Lipiao Bao Dr. Yunpeng Xie Prof. Dr. Takeshi Akasaka Prof. Dr. Xing Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(8):3449-3454
The chemical properties of carbide‐cluster metallofullerenes (CCMFs) remain largely unexplored, although several new members of CCMFs have been discovered recently. Herein, we report the reaction between Sc2C2@C3v(8)‐C82, which is viewed as a prototypical CCMF because of its high abundance, and 3‐triphenylmethyl‐5‐oxazolidinone ( 1 ) to afford the corresponding pyrrolidino derivative Sc2C2@C3v(8)‐C82(CH2)2NTrt ( 2 ; Trt=triphenylmethyl). Single‐crystal X‐ray crystallography studies of 2 revealed that the reaction takes place at a [6,6]‐bond junction, which is directly over the encapsulated C2 unit and is far from either of the two scandium atoms. On the basis of theoretical calculations and by considering previously reports, we have found that a hexagonal carbon ring on the cage of Sc2C2@C3v(8)‐C82 is highly reactive toward different reagents due to the overlap of high p‐orbital axis vector (POAV) angles and large LUMO coefficients. We propose that this highly concentrated area of reactivity is generated by the encapsulation of the Sc2C2 cluster because this region is absent from the empty fullerene C3v(8)‐C82. Moreover, the absorption and electrochemical results confirm that derivative 2 is more stable than pristine Sc2C2@C3v(8)‐C82, thus illuminating its potential applications. 相似文献
38.
39.
40.
Dawei Chen Ridao Chen Ruishan Wang Jianhua Li Kebo Xie Chuancai Bian Lili Sun Xiaolin Zhang Jimei Liu Lin Yang Fei Ye Xiaoming Yu Jungui Dai 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(43):12869-12873
The catalytic promiscuity of the novel benzophenone C‐glycosyltransferase, MiCGT, which is involved in the biosynthesis of mangiferin from Mangifera indica, was explored. MiCGT exhibited a robust capability to regio‐ and stereospecific C‐glycosylation of 35 structurally diverse druglike scaffolds and simple phenolics with UDP‐glucose, and also formed O‐ and N‐glycosides. Moreover, MiCGT was able to generate C‐xylosides with UDP‐xylose. The OGT‐reversibility of MiCGT was also exploited to generate C‐glucosides with simple sugar donor. Three aryl‐C‐glycosides exhibited potent SGLT2 inhibitory activities with IC50 values of 2.6×, 7.6×, and 7.6×10−7 M , respectively. These findings demonstrate for the first time the significant potential of an enzymatic approach to diversification through C‐glycosidation of bioactive natural and unnatural products in drug discovery. 相似文献