全文获取类型
收费全文 | 1225篇 |
免费 | 50篇 |
国内免费 | 5篇 |
专业分类
化学 | 974篇 |
晶体学 | 10篇 |
力学 | 6篇 |
数学 | 66篇 |
物理学 | 224篇 |
出版年
2023年 | 10篇 |
2022年 | 9篇 |
2021年 | 15篇 |
2020年 | 15篇 |
2019年 | 24篇 |
2018年 | 15篇 |
2017年 | 19篇 |
2016年 | 26篇 |
2015年 | 25篇 |
2014年 | 33篇 |
2013年 | 78篇 |
2012年 | 64篇 |
2011年 | 97篇 |
2010年 | 44篇 |
2009年 | 38篇 |
2008年 | 88篇 |
2007年 | 76篇 |
2006年 | 72篇 |
2005年 | 77篇 |
2004年 | 78篇 |
2003年 | 70篇 |
2002年 | 74篇 |
2001年 | 14篇 |
2000年 | 17篇 |
1999年 | 13篇 |
1998年 | 14篇 |
1997年 | 11篇 |
1996年 | 15篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 6篇 |
1988年 | 7篇 |
1986年 | 3篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1982年 | 6篇 |
1981年 | 13篇 |
1980年 | 10篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1964年 | 3篇 |
1961年 | 2篇 |
排序方式: 共有1280条查询结果,搜索用时 31 毫秒
151.
Masato Saito Dr. Yusuke Kobayashi Prof. Dr. Yoshiji Takemoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(44):10314-10318
The reactions of thioamides with ortho-nitro-substituted iodonium ylides proceeded under mild conditions to give enaminones or thiazoles, depending on the iodonium ylide used. This protocol allowed the use of protic solvents, including aqueous solutions, and therefore coupling reactions with complex molecules such as peptides or steroids were possible. A mild and efficient method for the synthesis of various iodonium ylides was established. DFT calculations suggested that the halogen bonding between a thioamide and iodonium ylide was important in this chemoselective coupling reaction. The potential use of enaminones conjugated with pharmaceuticals as prodrugs was also demonstrated. 相似文献
152.
Mika Sakai Masayoshi Mori Dr. Masato Hirai Dr. Naoki Ando Prof. Dr. Shigehiro Yamaguchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(38):e202200728
Two kinds of planarized phenyldithienylboranes, which contain (CH3)2C- or CH2-bridging moieties, were synthesized. The difference of the bridging moieties affects their packing structures and photophysical properties. In particular, the (CH3)2C-bridged derivative exhibits a large Stokes shift, unusual for such planarized compounds, that results from a large structural relaxation in the excited state. A series of π-extended derivatives was synthesized, among which a p-(diphenylamino)phenyl-substituted derivative shows large solvatochromism in the fluorescence spectra, while maintaining high quantum yields even in polar solvents. The Lewis acidity of the phenyldithienylborane derivatives was also assessed by titration with pyridine. The Lewis acidity of the boron center is affected not only by the difference in the steric bulk of the bridging moieties, but also by the electronic effect of the substituents introduced at remote positions relative to the boron atom. These results demonstrate the characteristic features of planarized phenyldithienylboranes as building blocks for boron-based π-electron materials. 相似文献
153.
Masato Kawamoto Yasuyuki Mori Akihiko Tsuge Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2022,60(8):1416-1421
Anionic ring-opening polymerization (ROP) behavior of trans-cyclohexene carbonate (CHC) using metal alkoxides as initiators was investigated. As a result, lithium tert-butoxide-initiated ROP of CHC with a high-monomer concentration (10 M) at low temperature (−15 to −10°C) proceeded to afford a poly(trans-cyclohexene carbonate) (PCHC) without undesired side reactions such as mainly backbiting. The suppression of side reactions enables the control of the molecular weight (Mn = 2400–6100) of PCHC with low molar-mass dispersity values (Mw/Mn = 1.16–1.22). Furthermore, by increasing the feed ratio of the monomer to the initiator, the molecular weight increases proportionally, indicating a controllable polymerization. The results of a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis, a kinetic study, and a chain extension experiment suggested a living nature of this ROP using lithium tert-butoxide. 相似文献
154.
Kazuki Inaba Masato Endo Naoto Iibuchi Prof. Dr. Daisuke Takahashi Prof. Dr. Kazunobu Toshima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10222-10225
The first total synthesis of terpioside B ( 1 ) has been accomplished. Key steps include the stereoselective installments of a set of challenging 1,2-cis-glycosidic linkages. Thus, α(1,4)-linked d -galactoside was effectively constructed from a 1,2-anhydrogalactose donor and an unprotected 1,6-anhydrogalactose acceptor by using a boron-mediated aglycon delivery (BMAD) method. In addition, α-l -fucofuranosides were stereoselectively and simultaneously constructed by remote group-assisted 1,2-cis-α-stereoselective glycosylations. 相似文献
155.
Prof. Dr. Shigehisa Akine Masato Miyashita Prof. Dr. Tatsuya Nabeshima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1432-1435
A closed metallomolecular cage based on the tris(saloph) framework, in which its aperture can be opened by disulfide exchange, was designed. At the apertures of the molecular cage, bridging diamine ligands having a disulfide bond were introduced to close the cage structure. These bridging ligands efficiently blocked the uptake of a guest, Cs+, but the presence of a thiolate anion significantly accelerated the guest uptake. This clearly means that this cage complex became open by the addition of the thiolate anion, because the cage closure becomes more dynamic due to the disulfide exchange reaction. 相似文献
156.
Fluorinated Vinylsilanes from the Copper‐Catalyzed Defluorosilylation of Fluoroalkene Feedstocks
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Hironobu Sakaguchi Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2018,57(1):328-332
Herein, a copper‐catalyzed C?F bond defluorosilylation reaction of tetrafluoroethylene and other polyfluoroalkenes is described. Mechanistic studies, based on a series of stoichiometric reactions with copper complexes, revealed that the key steps of this defluorosilylation reaction are 1) the 1,2‐addition of a silylcopper intermediate to the polyfluoroalkene and 2) a subsequent selective β‐fluorine elimination, which generates a Cu?F species. The β‐fluorine elimination is facilitated by Lewis acidic F?Bpin, which is generated in situ during the defluorosilylation. 相似文献
157.
The synthesis of a protected dephosphofostriecin, and thereby a formal synthesis of fostriecin, has been accomplished. Two of the four chiral centers are controlled by an external chiral auxiliary and the other two are synthesized stereoselectively, one by a novel 1,4-asymmetric induction using cobalt-alkyne complex, and the other by 1,3-asymmetric induction. 相似文献
158.
The base-mediated intramolecular cyclization reaction of 2-alkynylphenylphosphine oxides affords benzo[ b]phosphole oxides, which show intense blue-green fluorescence. Benzo[ b]phospholes are also prepared by the reduction of benzo[ b]phosphole oxides. 相似文献
159.
Soga S Shirai H Kobori M Hirayama N 《Journal of chemical information and modeling》2008,48(8):1679-1685
The idea that there should be a specific site on a protein for a particular functional small molecule is widespread. It is, however, usually not so easy to understand what characteristics of the site determine the binding ability of the functional small molecule. We have focused on the concurrence rate of the 20 standard amino acids at such binding sites. In order to correlate the concurrence rate and the specific binding site, we have analyzed high-quality X-ray structures of complexes between proteins and small molecules. A novel index characterizing the binding site based on the concurrency rate has been introduced. Using this index we have identified that there is a specific concavity designated as a chemocavity where a specific group of small molecules, i.e., canonical molecular group, is highly inclined to be bound. This study has demonstrated that a chemocavity is reserved for a specific canonical molecular group, and the prevalent idea has been confirmed. 相似文献
160.
Ogoshi S Arai T Ohashi M Kurosawa H 《Chemical communications (Cambridge, England)》2008,(11):1347-1349
The formation of a nickeladihydrofuran by oxidative cyclization of an alkyne and an aldehyde with nickel(0) has been demonstrated; the transformation of the nickeladihydrofuran into an enone by decomposition, a lactone by carbonylation and an allylic alcohol by treatment with ZnMe(2) suggests that nickeladihydrofuran is an important key intermediate in a variety of catalytic reactions. 相似文献