全文获取类型
收费全文 | 5639篇 |
免费 | 780篇 |
国内免费 | 282篇 |
专业分类
化学 | 3790篇 |
晶体学 | 43篇 |
力学 | 1199篇 |
综合类 | 47篇 |
数学 | 618篇 |
物理学 | 1004篇 |
出版年
2024年 | 3篇 |
2023年 | 55篇 |
2022年 | 76篇 |
2021年 | 238篇 |
2020年 | 247篇 |
2019年 | 160篇 |
2018年 | 198篇 |
2017年 | 175篇 |
2016年 | 280篇 |
2015年 | 283篇 |
2014年 | 308篇 |
2013年 | 561篇 |
2012年 | 345篇 |
2011年 | 373篇 |
2010年 | 252篇 |
2009年 | 359篇 |
2008年 | 334篇 |
2007年 | 351篇 |
2006年 | 318篇 |
2005年 | 305篇 |
2004年 | 272篇 |
2003年 | 262篇 |
2002年 | 124篇 |
2001年 | 86篇 |
2000年 | 79篇 |
1999年 | 65篇 |
1998年 | 61篇 |
1997年 | 75篇 |
1996年 | 72篇 |
1995年 | 49篇 |
1994年 | 39篇 |
1993年 | 40篇 |
1992年 | 48篇 |
1991年 | 37篇 |
1990年 | 32篇 |
1989年 | 16篇 |
1988年 | 33篇 |
1987年 | 13篇 |
1986年 | 14篇 |
1985年 | 14篇 |
1984年 | 13篇 |
1983年 | 2篇 |
1982年 | 14篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 8篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有6701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.
Combustion processes in porous media have been used by the petroleum engineering industry to extract heavy oil from reservoirs. This study focuses on a one-dimensional nonlinear hybrid system consisting of reaction–diffusion–convection equations coupled with ordinary differential equations, which models a combustion front moving through a porous medium with parallel layers. The state variables are the temperature and fuel concentration in each layer. Coupling occurs in both the reaction function and differential operator coefficients. We prove the existence of a classical solution, first locally and then globally over time, to an initial and boundary value problem for the corresponding system. The proof uses a new approach for combustion problems in porous media. The local solution is obtained by defining an operator in a set of Hölder continuous functions and using Schauder’s fixed-point theorem to find a fixed point as the desired solution. Using Zorn’s lemma, we extend the local solution to a global solution, proving that the first-order spatial derivative of the temperature in each layer is a bounded function. 相似文献
3.
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
4.
Yifeng Xiang Xi Tang Changjun Min Guanghao Rui Yan Kuai Fengya Lu Pei Wang Hai Ming Qiwen Zhan Xiaocong Yuan Joseph R. Lakowicz Douguo Zhang 《Annalen der Physik》2020,532(4):1900497
Near-field optical trapping can be realized with focused evanescent waves that are excited at the water–glass interface due to the total internal reflection, or with focused plasmonic waves excited on the water–gold interface. Herein, the performance of these two kinds of near-field optical trapping techniques is compared using the same optical microscope configuration. Experimental results show that only a single-micron polystyrene bead can be trapped by the focused evanescent waves, whereas many beads are simultaneously attracted to the center of the excited region by focused plasmonic waves. This difference in trapping behavior is analyzed from the electric field intensity distributions of these two kinds of focused surface waves and the difference in trapping behavior is attributed to photothermal effects due to the light absorption by the gold film. 相似文献
5.
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
6.
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
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.
9.
10.
在无扰动、随机式扰动以及正弦式扰动下,通过对竖直恒温面处状态Ra为1.328×10^9、Pr为6.24的自然对流进行模拟,探索了热边界层的不稳定性和共振强化自然对流换热。结果表明:(1)竖直自然对流边界层上游位置的随机式扰动对热边界层的影响主要体现在稳定阶段;(2)该状态下的竖直自然对流边界层的特征频率为15 067,且相比于无扰动状态,频率为15 067的正弦式扰动能在竖直恒温面处提高5.15%的换热量;(3)在竖直自然对流边界层上游位置加入特征频率的正弦式扰动,竖直恒温面处的局部努塞尔数Nu均出现明显波动,且波动随着边界层高度的增加而增大。 相似文献