全文获取类型
收费全文 | 2431篇 |
免费 | 88篇 |
国内免费 | 8篇 |
专业分类
化学 | 1864篇 |
晶体学 | 34篇 |
力学 | 22篇 |
数学 | 137篇 |
物理学 | 470篇 |
出版年
2023年 | 14篇 |
2021年 | 25篇 |
2020年 | 39篇 |
2019年 | 37篇 |
2018年 | 33篇 |
2017年 | 16篇 |
2016年 | 48篇 |
2015年 | 66篇 |
2014年 | 55篇 |
2013年 | 98篇 |
2012年 | 129篇 |
2011年 | 157篇 |
2010年 | 86篇 |
2009年 | 81篇 |
2008年 | 157篇 |
2007年 | 167篇 |
2006年 | 145篇 |
2005年 | 132篇 |
2004年 | 142篇 |
2003年 | 118篇 |
2002年 | 88篇 |
2001年 | 48篇 |
2000年 | 44篇 |
1999年 | 18篇 |
1998年 | 18篇 |
1997年 | 10篇 |
1996年 | 25篇 |
1995年 | 24篇 |
1994年 | 24篇 |
1993年 | 19篇 |
1992年 | 24篇 |
1991年 | 30篇 |
1990年 | 28篇 |
1989年 | 20篇 |
1988年 | 20篇 |
1987年 | 12篇 |
1986年 | 26篇 |
1985年 | 24篇 |
1984年 | 29篇 |
1983年 | 18篇 |
1982年 | 23篇 |
1981年 | 23篇 |
1980年 | 25篇 |
1979年 | 15篇 |
1978年 | 17篇 |
1977年 | 24篇 |
1976年 | 12篇 |
1975年 | 13篇 |
1974年 | 11篇 |
1973年 | 15篇 |
排序方式: 共有2527条查询结果,搜索用时 93 毫秒
1.
2.
3.
4.
5.
Prof. Isao Fujii Dr. Makoto Hashimoto Kaori Konishi Akiko Unezawa Haruka Sakuraba Kenta Suzuki Harue Tsushima Miho Iwasaki Satsuki Yoshida Akane Kudo Rina Fujita Aika Hichiwa Koharu Saito Dr. Takashi Asano Dr. Jun Ishikawa Dr. Daigo Wakana Dr. Yukihiro Goda Ayumi Watanabe Mamoru Watanabe Yui Masumoto Dr. Junichiro Kanazawa Dr. Hajime Sato Prof. Masanobu Uchiyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8542-8548
Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark. 相似文献
6.
Ami Saito Dr. Tomohisa Sawada Prof. Dr. Makoto Fujita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20547-20550
Porous metal complexes enable single-crystal X-ray crystallographic observation of included guests or reaction intermediates through simple soaking with the guests/substrates. Previous studies on this technique have often encountered difficulties in the observation of chiral structures because the host frameworks had no chirality. We synthesized a new metal–peptide porous complex through a folding-and-assembly strategy and utilized the chiral pore for trapping chiral guests. Chiral alcohols and ketones were successfully included within the pore. Crystallographic analyses clearly revealed not only their chemical structures but also chiral transformation events within the pore such as fixed conformations or an unstable hemiacetal formation. 相似文献
7.
Haruka Takeuchi Prof. Dr. Shinsuke Inuki Kohei Nakagawa Takaaki Kawabe Dr. Atsuhiko Ichimura Prof. Dr. Shinya Oishi Prof. Dr. Hiroaki Ohno 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21396-21401
We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radical ipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses. 相似文献
8.
Dr. Yasuyuki Yamada Hayato Iida Shinya Shibano Dr. Nozomi Mihara Prof. Tatsuhisa Kato Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(37):e202200819
Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linkage. We found that closely stacking two π systems requires bridging alkyl chains above a certain length, and the shorter bridges hinder stacking because of their lower flexibility. The stacking distance between porphyrin and phthalocyanine in the conjugate with decyl (C10) chains was estimated to be 4.03 Å and showed a unique physical character arising from short-distance interactions. The longer alkyl chains minimized steric restriction inside the fourfold rotaxane and allowed efficient communication between the porphyrin and phthalocyanine units. This is due to the flexibility of the side chains. 相似文献
9.
Dr. Hua Zhang Prof. Dr. Shinya Hagihara Prof. Dr. Kenichiro Itami 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(47):16796-16800
The dimethylamino (Me2N) group is arguably the most versatile functional group capable of highly efficient and site‐selective directed aromatic functionalizations at the ortho‐, meta‐, and para‐positions depending on reaction conditions. While the repertoire of Me2N‐directed reactions is growing at a rapid pace, the lack of a general method to transform this group to other functionalities hampers its wider application in organic synthesis. Here we report nickel‐catalyzed C?N borylations of aryl‐ and benzyl‐dimethylamines that permit the conversion of a huge library of largely underutilized Me2N‐containing organic molecules into various functional molecules by taking advantage of the wealth of existing C?B functionalization methods. 相似文献
10.
High Catalytic Activity of Nitrogen and Sulfur Co‐Doped Nanoporous Graphene in the Hydrogen Evolution Reaction 下载免费PDF全文
Dr. Yoshikazu Ito Weitao Cong Dr. Takeshi Fujita Prof. Zheng Tang Prof. Mingwei Chen 《Angewandte Chemie (International ed. in English)》2015,54(7):2131-2136
Chemical doping has been demonstrated to be an effective way to realize new functions of graphene as metal‐free catalyst in energy‐related electrochemical reactions. Although efficient catalysis for the oxygen reduction reaction (ORR) has been achieved with doped graphene, its performance in the hydrogen evolution reaction (HER) is rather poor. In this study we report that nitrogen and sulfur co‐doping leads to high catalytic activity of nanoporous graphene in HER at low operating potential, comparable to the best Pt‐free HER catalyst, 2D MoS2. The interplay between the chemical dopants and geometric lattice defects of the nanoporous graphene plays the fundamental role in the superior HER catalysis. 相似文献