全文获取类型
收费全文 | 4725篇 |
免费 | 693篇 |
国内免费 | 283篇 |
专业分类
化学 | 4006篇 |
晶体学 | 15篇 |
力学 | 493篇 |
综合类 | 44篇 |
数学 | 358篇 |
物理学 | 785篇 |
出版年
2024年 | 2篇 |
2023年 | 47篇 |
2022年 | 63篇 |
2021年 | 242篇 |
2020年 | 233篇 |
2019年 | 145篇 |
2018年 | 171篇 |
2017年 | 154篇 |
2016年 | 263篇 |
2015年 | 256篇 |
2014年 | 278篇 |
2013年 | 510篇 |
2012年 | 311篇 |
2011年 | 298篇 |
2010年 | 212篇 |
2009年 | 283篇 |
2008年 | 263篇 |
2007年 | 279篇 |
2006年 | 251篇 |
2005年 | 254篇 |
2004年 | 222篇 |
2003年 | 214篇 |
2002年 | 145篇 |
2001年 | 67篇 |
2000年 | 62篇 |
1999年 | 49篇 |
1998年 | 49篇 |
1997年 | 65篇 |
1996年 | 52篇 |
1995年 | 39篇 |
1994年 | 33篇 |
1993年 | 24篇 |
1992年 | 36篇 |
1991年 | 21篇 |
1990年 | 17篇 |
1989年 | 8篇 |
1988年 | 16篇 |
1987年 | 9篇 |
1986年 | 10篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1982年 | 13篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 7篇 |
1978年 | 3篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有5701条查询结果,搜索用时 31 毫秒
1.
Kento Nishikibe Keisuke Nishikawa Momochika Kumagai Matsumi Doe Yoshiki Morimoto 《化学:亚洲杂志》2022,17(1):e202101137
There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis. 相似文献
2.
利用标量化方法建立对称向量拟均衡问题有效解的存在性定理。作为标量化方法的应用,利用这一方法得到向量变分不等式和拟向量变分不等式有效解的存在性定理。 相似文献
3.
Dr. Zhongyun Liu Dr. Yang Liu Dr. Wulin Qiu Prof. William J. Koros 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):14987-14993
Glassy polyimide membranes are attractive for industrial applications in sour natural gas purification. Unfortunately, the lack of fundamental understanding of relationships between polyimide chemical structures and their gas transport properties in the presence of H2S constrains the design and engineering of advanced membranes for such challenging applications. Herein, 6FDA-based polyimide membranes with engineered structures were synthesized to tune their CO2/CH4 and H2S/CH4 separation performances and plasticization properties. Under ternary mixed sour gas feeds, controlling polymer chain packing and plasticization tendency of such polyimide membranes via tuning the chemical structures were found to offer better combined H2S and CO2 removal efficiency compared to conventional polymers. Fundamental insights into structure–property relationships of 6FDA-based polyimide membranes observed in this study offer guidance for next generation membranes for sour natural gas separation. 相似文献
4.
Yulu Jiang Dr. Taro Ozaki Mei Harada Tadachika Miyasaka Dr. Hajime Sato Dr. Kazunori Miyamoto Dr. Junichiro Kanazawa Dr. Chengwei Liu Prof. Dr. Jun-ichi Maruyama Dr. Masaatsu Adachi Dr. Atsuo Nakazaki Prof. Dr. Toshio Nishikawa Prof. Dr. Masanobu Uchiyama Dr. Atsushi Minami Prof. Dr. Hideaki Oikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18152-18158
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
5.
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
6.
7.
8.
Martín Soto Dr. Raquel G. Soengas Prof. Artur M. S. Silva Prof. Vicente Gotor-Fernández Prof. Humberto Rodríguez-Solla 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(57):13104-13108
In this work, the first example of a radical stereodivergent reaction directed towards the stereoselective synthesis of both (R*,R*)- and (R*,S*)-2,2′-biflavanones promoted by samarium diiodide is reported. Control experiments showed that the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate a variety of 2,2′-biflavanones bearing different substitution patterns at the aromatic ring in good-to-quantitative yields, being both stereoisomers of the desired compounds obtained with total or high control of selectivity. A mechanism that explains both the generation of the corresponding 2,2′-biflavanones and the selectivity is also discussed. The structure and stereochemistry determination of each isomer was unequivocally elucidated by single-crystal X-ray diffraction experiments. 相似文献
9.
Natural products with a variety of pharmacological effects are important sources for commercial drugs, and it is very crucial to develop effective techniques to selectively extract and isolate bioactive natural components from the plants against the background of sustainable development. Ionic liquids (ILs) are a kind of designable material with unique physicochemical properties, including good thermal stability, negligible vapor pressure, good solvation ability, etc. ILs have already been used in pharmaceuticals for extraction, purification, drug delivery, etc. It has been reported that multi-interactions, like hydrogen bonding, hydrophobic interactions, play important roles in the extraction of bioactive components from the plants. In this review, recent progress in the understanding of scientific essence of hydrogen bonding, the special interaction, in ILs was summarized. The extraction of various natural products, one important area in pharmaceutical, by conventional and functional ILs as well as the specific roles of multi-interactions in this process were also reviewed. Moreover, problems existing in bioactive compound extraction by ILs and the future developing trends of this area are given, which might be helpful for scientists, especially beginners, in this field. 相似文献
10.
Dr. Gregory K. Pierens 《Chemphyschem》2021,22(21):2207-2214
The calculation of DFT (density functional theory) chemical shifts have become an important technique for the verification of a proposed structure. An easily calculated metric developed for proton and carbon chemical shifts of natural products and organic compounds, the calculated chemical shift index (CCSI), has been developed, which uses the deviation of each pair of calculated and experimental chemical shifts. The mean absolute deviation (MAD), which is commonly used as the goodness of fit metric for DFT calculated chemical shifts, can conceal large deviations in the calculated data. A classification strategy is also proposed for the CCSI to highlight when further assessment of the NMR data is required. 相似文献