全文获取类型
收费全文 | 70994篇 |
免费 | 10290篇 |
国内免费 | 6639篇 |
专业分类
化学 | 47651篇 |
晶体学 | 662篇 |
力学 | 4688篇 |
综合类 | 515篇 |
数学 | 8588篇 |
物理学 | 25819篇 |
出版年
2024年 | 228篇 |
2023年 | 1401篇 |
2022年 | 2298篇 |
2021年 | 2363篇 |
2020年 | 2543篇 |
2019年 | 2439篇 |
2018年 | 2203篇 |
2017年 | 1952篇 |
2016年 | 2984篇 |
2015年 | 3090篇 |
2014年 | 3676篇 |
2013年 | 4907篇 |
2012年 | 5935篇 |
2011年 | 6081篇 |
2010年 | 4110篇 |
2009年 | 4039篇 |
2008年 | 4235篇 |
2007年 | 3858篇 |
2006年 | 3637篇 |
2005年 | 3143篇 |
2004年 | 2528篇 |
2003年 | 1944篇 |
2002年 | 1706篇 |
2001年 | 1542篇 |
2000年 | 1432篇 |
1999年 | 1574篇 |
1998年 | 1339篇 |
1997年 | 1188篇 |
1996年 | 1247篇 |
1995年 | 1083篇 |
1994年 | 1013篇 |
1993年 | 873篇 |
1992年 | 778篇 |
1991年 | 675篇 |
1990年 | 570篇 |
1989年 | 487篇 |
1988年 | 378篇 |
1987年 | 357篇 |
1986年 | 307篇 |
1985年 | 312篇 |
1984年 | 215篇 |
1983年 | 188篇 |
1982年 | 162篇 |
1981年 | 120篇 |
1980年 | 93篇 |
1978年 | 65篇 |
1977年 | 70篇 |
1976年 | 69篇 |
1975年 | 83篇 |
1973年 | 66篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
31.
Pengjin Qin Li-An Wang Prof. Joseph M. O'Connor Prof. Kim K. Baldridge Yifan Li Burak Tufekci Jiyue Chen Prof. Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18114-18121
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5H5)Ru(NCMe)3]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations. 相似文献
32.
Lei Chen Hui-Qing Yang Cheng-Yu Jin Zhao-Xu Chen 《International journal of quantum chemistry》2020,120(22):e26366
We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH− group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH− group and the Fukui function condensed on the OH− group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts. 相似文献
33.
Nanocomposite hydrogel consisting of Na‐montmorillonite with enhanced mechanical properties 下载免费PDF全文
Ting Li Shuangfei Xiang Piming Ma Huiyu Bai Weifu Dong Mingqing Chen 《Journal of Polymer Science.Polymer Physics》2015,53(14):1020-1026
A new kind of nanocomposite (NC) hydrogel with Na‐montmorillonite (MMT) is presented in this article. The NC hydrogels were synthesized by free radical copolymerization of acrylamide and (3‐acrylamidopropyl) trimethylammonium chloride (ATC) in the presence of MMT and N,N′‐methylene‐bis‐acrylamide used as chemical cross‐linker. Due to the cation‐exchange reaction between MMT and ATC (cationic monomer) during the synthesis of NC hydrogels, MMT platelets were considered chemical “plane” cross‐linkers, different from “point” cross‐linkers. With increasing amount of MMT, the crosslinking degree enhanced, causing a decrease of the swelling degree at equilibrium. Investigations of mechanical properties indicated that NC hydrogels exhibited enhanced strength and toughness, which resulted from chemical interaction between exfoliated MMT platelets and polymer chains in hydrogels. Dynamic shear measurements showed that both storage modulus and loss modulus increased with increasing MMT content. The idea described here provided a new route to prepare hydrogels with high mechanical properties by using alternative natural Na‐MMT. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1020–1026 相似文献
34.
35.
36.
37.
Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis,Structure, and Properties 下载免费PDF全文
Houhe Pan Chao Chen Kang Wang Prof. Dr. Wenjun Li Prof. Dr. Jianzhuang Jiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(8):3168-3173
Novel pyrene‐fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17‐hexakis(2,6‐dimethylphenoxy)‐22,25‐diaza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz‐pyrene)(OC8H9)6] ( 1 ) and 2,3,9,10‐tra(2,6‐dimethylphenoxy)‐15,18,22,25‐traza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz‐pyrene)2(OC8H9)4] ( 2 ) were isolated for the first time. These unsymmetrical pyrene‐fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene‐fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X‐ray diffraction analysis of 1 , representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene. 相似文献
38.
39.
Richiro Ushimaru Zhang Chen Houyuan Zhao Po-hsun Fan Prof. Dr. Hung-wen Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(9):3586-3590
Albomycin δ2 is a sulfur-containing sideromycin natural product that shows potent antibacterial activity against clinically important pathogens. The l -serine-thioheptose dipeptide partial structure, known as SB-217452, has been found to be the active seryl-tRNA synthetase inhibitor component of albomycin δ2. Herein, it is demonstrated that AbmF catalyzes condensation between the 6′-amino-4′-thionucleoside with the d -ribo configuration and seryl-adenylate supplied by the serine adenylation activity of AbmK. Formation of the dipeptide is followed by C3′-epimerization to produce SB-217452 with the d -xylo configuration, which is catalyzed by the radical S-adenosyl-l -methionine enzyme AbmJ. Gene deletion suggests that AbmC is involved in peptide assembly linking SB-217452 with the siderophore moiety. This study establishes how the albomycin biosynthetic machinery generates its antimicrobial component SB-217452. 相似文献
40.
Hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have been deemed as clean and sustainable strategies to solve the energy crisis and environmental problems. Various catalysts have been developed to promote the process of HER and OER. Among them, two-dimensional covalent organic frameworks (2D COFs) have received great attention due to their diverse and designable structure. In this minireview, we mainly summarize the diverse linkages of 2D COFs and strategies for enhancing the catalytic performance of 2D COFs for HER and OER, such as introducing active building blocks, metal ions and tailored linkages. Furthermore, a brief outlook for the development directions of COFs in the field of HER and OER is provided, expecting to stimulate new opportunities in future research. 相似文献