全文获取类型
收费全文 | 4237篇 |
免费 | 696篇 |
国内免费 | 584篇 |
专业分类
化学 | 2889篇 |
晶体学 | 74篇 |
力学 | 280篇 |
综合类 | 26篇 |
数学 | 619篇 |
物理学 | 1629篇 |
出版年
2024年 | 4篇 |
2023年 | 94篇 |
2022年 | 166篇 |
2021年 | 163篇 |
2020年 | 204篇 |
2019年 | 159篇 |
2018年 | 171篇 |
2017年 | 187篇 |
2016年 | 202篇 |
2015年 | 188篇 |
2014年 | 248篇 |
2013年 | 308篇 |
2012年 | 375篇 |
2011年 | 393篇 |
2010年 | 250篇 |
2009年 | 292篇 |
2008年 | 290篇 |
2007年 | 250篇 |
2006年 | 285篇 |
2005年 | 194篇 |
2004年 | 125篇 |
2003年 | 113篇 |
2002年 | 113篇 |
2001年 | 91篇 |
2000年 | 80篇 |
1999年 | 85篇 |
1998年 | 73篇 |
1997年 | 53篇 |
1996年 | 66篇 |
1995年 | 43篇 |
1994年 | 41篇 |
1993年 | 33篇 |
1992年 | 29篇 |
1991年 | 31篇 |
1990年 | 28篇 |
1989年 | 12篇 |
1988年 | 11篇 |
1987年 | 14篇 |
1986年 | 9篇 |
1985年 | 5篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1973年 | 2篇 |
1957年 | 2篇 |
1929年 | 2篇 |
1926年 | 2篇 |
排序方式: 共有5517条查询结果,搜索用时 31 毫秒
151.
Ping Lv Xin Shen Zhiliyu Cui Bo Li Qiangqiang Xu Zhuo Yu Weijie Lu Haonan Shao Yan Ge Zhenhui Qi 《Journal of polymer science. Part A, Polymer chemistry》2021,59(23):3001-3008
Fiber-reinforced-concrete (FRC) mechanism refers short discrete fibers that are uniformly distributed and randomly oriented, which offers an effective way to improve the mechanical performance of concrete. In the design of supramolecular polymers, an analogous concept of FRC appears to have been considered very rarely-although fibrous structure has been frequently observed/generated during the supramolecular polymerization. In this work, we apply the alkane thermosets, octadecane (C18H38) and tetracosane (C24H50), taking the role of “concrete”, and the low-molecular-weight monomer with long alkyl chains as the essential “fiber” component, to fabricate the “fiber reinforced supramolecular polymer”. Very much like FRC mechanism in material science, the resulting fiber reinforced supramolecular polymer thus exhibit unusually high mechanical strength and stiffness, which is unprecedented in the conventional supramolecular strategy. 相似文献
152.
Xinming Zhang Tianzhan Zhang Shuanli Guo Yang Zhang Rongtian Sheng Ruimeng Sun Lixia Chen Ruijuan Lv Yanfei Qi 《Molecules (Basel, Switzerland)》2020,25(24)
Fungal infections pose a serious threat to human health. Polyoxometalates (POMs) are metal–oxygen clusters with potential application in the control of microbial infections. Herein, the Ag3PW12O40 composites have been synthesized and verified by Fourier transform infrared (FT-IR) spectrum, transmission electron microscopy (TEM), scanning electron microscope (SEM), elemental analysis, and X-ray diffraction (XRD). The antifungal activities of Ag3PW12O40 were screened in 19 Candida species strains through the determination of minimum inhibitory concentration (MIC) by the microdilution checkerboard technique. The minimum inhibitory concentration (MIC50) values of Ag3PW12O40 are 2~32 μg/mL to the Candida species. The MIC80 value of Ag3PW12O40 to resistant clinical isolates C. albicans HL963 is 8 μg/mL, which is lower than the positive control, fluconazole (FLC). The mechanism against C. albicans HL963 results show that Ag3PW12O40 can decrease the ergosterol content. The expressions of ERG1, ERG7, and ERG11, which impact on the synthesis of ergosterol, are all prominently upregulated by Ag3PW12O40. It indicates that Ag3PW12O40 is a candidate in the development of new antifungal agents. 相似文献
153.
Xingxing Ge Xicheng Liu Zhenzhen Tian Shujiao Chen Xinyu Liu Lihua Guo Peiwei Gong Baoping Ling Xiang‐Ai Yuan Zhe Liu 《应用有机金属化学》2019,33(11)
Four half‐sandwich rutheniumII (RuII) complexes with triphenylamine‐modifed dipyridine frameworks were synthesized and characterized. The cytotoxicity of target complexes toward A549 (lung cancer cells), HeLa (cervical cancer cells) and HepG2 (hepatoma cells) were obtained by the MTT assay, which were superior to cisplatin with the IC50 values changed from 2.4 ± 0.1 μM to 9.2 ± 2.7 μM. Meanwhile, complexes possess the ability of antimetastasis to cancer cells. RuII complexes could be transported by serum albumin, catalyze the conversion of NADH (the reduced state of nicotinamide‐adenine dinucleotide) to NAD+ and induce the accumulation of reactive oxygen species, which confirmed the antineoplastic mechanism of oxidation. RuII complexes could enter A549 cells followed by a non‐energy dependent cellular uptake mechanism, target lysosomes with the Pearson's colocalization coefficient of 0.75, lead to lysosomal damage, disturb the cell cycle (S phase), and eventually induce apoptosis. The results demonstrate that these RuII complexes are potential anticancer agents with dual functions, including metastasis inhibition and lysosomal damage. 相似文献
154.
Mengyuan Ge Guangwen Li Zibo Ni Ning Liu Yushan Liu Yuzhou Liu 《Journal of polymer science. Part A, Polymer chemistry》2020,58(21):3009-3017
Utilizing collective forces between reactant and multiple catalyst molecules has been unprecedented due to the difficulty in realizing high order catalysis. Inspired by the power of collective forces in enzymes and organic catalysts, herein we report a rare example of high order catalysis for ring opening reaction (ROR) of strained rings by methanol. ROR is an important way to produce various polysiloxanes, but usually suffers from serious side reactions especially at high conversion, and currently there is a need to design new reaction pathway to achieve low molecular dispersity. In our study, the judiciously designed strained spiral cyclosiloxanes enable a high order catalysis by methanol, and this new methodology leads to a cyclic polysiloxane with high molecular weight and low dispersity even at full conversion of reactants. Kinetic study indicates an extremely unusual high-order reaction involving multiple methanol molecules per reaction, also confirmed by quantum calculation which reveals the presence of zwitterionic ions stabilized by collecting force of hydrogen bonds by methanol molecules. The inherent driving force for this unusual phenomenon is dominated by enthalpy stabilization of the reactive intermediates through hydrogen bonding. The selective formation of Si O Si bonds, instead of silanol products, reflects the power of scientific design. 相似文献
155.
Copper‐Catalyzed Reaction Cascade of Thiophenol Hydroxylation and S‐Arylation through Disulfide‐Directed C−H Activation 下载免费PDF全文
Prof. Dr. Dawei Wang Xin Yu Wei Yao Wenkang Hu Chenyang Ge Prof. Dr. Xiaodong Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5543-5546
Copper‐catalyzed thiophenol C?H activation is described. Through an initial attempt to conduct C‐arylation with arylboronic acid, a rather surprising sequential C?H activation and S‐arylation was discovered. Mechanistic investigation revealed the disulfide intermediate as the key component in directing C?H oxidation. The overall reaction proceeded under mild conditions with molecular oxygen as the oxidant. Discovery of disulfide as the directing group provides a potential new direction for catalytic C?H functionalization under mild conditions. 相似文献
156.
157.
Jian-Ming Zhang Shang-Ru Zhai Bin Zhai Qing-Da An Ge Tian 《Journal of Sol-Gel Science and Technology》2012,64(2):347-357
Multifunctional nanomaterials with task-specific physicochemical properties, especially core?Cshell nanostructures with Fe3O4 core and NH2-functional shells (Fe3O4@SiO2?CNH2), have been extensively investigated as high-performance adsorbents, catalysts and catalyst supports; and in most cases the controllable sol?Cgel technique is the choice for fabrication of this kind of widely applied materials. Herein, we demonstrated that mono-dispersed and spherical Fe3O4@SiO2?CNH2 nanomaterials with magnetic response core, NH2-functional shell structure can be facilely prepared by co-condensation of TEOS with APTMS using a versatile sol?Cgel process. It was shown that the proper usage of APTMS and appropriate pre-hydrolysis time of TEOS were crucial and key steps for formation of highly uniform and desirable amino loading Fe3O4@SiO2?CNH2 materials. The TEOS pre-hydrolysis and the critical time (around 90?min) before the addition of APTMS prove to be vital for uniform structure evolution, while the appropriate concentration of APTMS (~2.28?mmol?L?1 in our system) leads to well-dispersed materials with relatively high loading of amino functionality. The as-prepared Fe3O4@SiO2?CNH2 magnetic nanoparticles prepared under optimum conditions possessing superparamagnetic behavior, uniform core?Cshell structure (~200?nm in diameter), relatively large BET surface area (~138?m2/g) and high incorporation of amino-functionality (~2.90?wt?%). 相似文献
158.
159.
160.
For the synthesis of 2-substituted 4H-4-chromenones, 2-methylsulfonyl-4H-4-chromenones as common intermediate were reacted with nucleophiles such as amines and thiophenol to afford the corresponding 2-substituted adducts in very high yields. 相似文献