全文获取类型
收费全文 | 19305篇 |
免费 | 3338篇 |
国内免费 | 2309篇 |
专业分类
化学 | 13630篇 |
晶体学 | 177篇 |
力学 | 1113篇 |
综合类 | 118篇 |
数学 | 2732篇 |
物理学 | 7182篇 |
出版年
2024年 | 60篇 |
2023年 | 414篇 |
2022年 | 543篇 |
2021年 | 652篇 |
2020年 | 848篇 |
2019年 | 762篇 |
2018年 | 677篇 |
2017年 | 634篇 |
2016年 | 966篇 |
2015年 | 909篇 |
2014年 | 1061篇 |
2013年 | 1434篇 |
2012年 | 1675篇 |
2011年 | 1766篇 |
2010年 | 1233篇 |
2009年 | 1105篇 |
2008年 | 1259篇 |
2007年 | 1104篇 |
2006年 | 987篇 |
2005年 | 892篇 |
2004年 | 711篇 |
2003年 | 619篇 |
2002年 | 687篇 |
2001年 | 546篇 |
2000年 | 437篇 |
1999年 | 432篇 |
1998年 | 343篇 |
1997年 | 313篇 |
1996年 | 331篇 |
1995年 | 291篇 |
1994年 | 232篇 |
1993年 | 163篇 |
1992年 | 165篇 |
1991年 | 158篇 |
1990年 | 123篇 |
1989年 | 94篇 |
1988年 | 54篇 |
1987年 | 56篇 |
1986年 | 71篇 |
1985年 | 47篇 |
1984年 | 32篇 |
1983年 | 26篇 |
1982年 | 15篇 |
1981年 | 11篇 |
1980年 | 4篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 492 毫秒
761.
Dr. Yongqi Yao Dr. Qifu Lin Dr. Wen Yang Prof. Dr. Weitao Yang Prof. Dr. Fenglong Gu Prof. Dr. Wei Guo Prof. Dr. Dingqiao Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(25):5607-5610
A cobalt(II)-catalyzed [4+2] annulation of picolinamides with alkynes via C−H bond activation has been developed. The operationally simple annulation reaction allows for the synthesis of acyl-substituted 1H-benzoquinoline bearing multiple aromatic rings (up to 96 % yield) without co-oxidant or other oxidation factors under mild conditions. Several control experiments were carried out. This practical [4+2] annulation provides an efficient route to access highly functionalized compounds. 相似文献
762.
Yujia Xu Weijing Zhang Tonglai Zhang Wei Guo Yongjun Lü 《Journal of computational chemistry》2020,41(10):1026-1033
Metal azides have attracted increasing attention as precursors for synthesizing polymeric nitrogen. In this article, we report the amorphous polymerization of nitrogen by compressing cupric azide. The ab initio molecular dynamics simulations show that crystalline cupric azide transforms into a disordered network composed of singly bonded nitrogen at a hydrostatic pressure of 40 GPa and room temperature. The transformation manifests the formation of a π delocalization along the disordered Cu-N network, thus resulting in a semiconductor–metal transition. The estimated heat of formation of the amorphous polymeric nitrogen system is comparable to conventional high-energy-density materials. The amorphization provides an alternative route to the polymerization of nitrogen under moderate conditions. 相似文献
763.
Marie-Claire Giel Dr. Christopher J. Smedley Emily R. R. Mackie Taijie Guo Prof. Dr. Jiajia Dong Dr. Tatiana P. Soares da Costa Prof. Dr. John E. Moses 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(3):1197-1202
The boom in growth of 1,4-disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the CuI-catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1-substituted-1,2,3-triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click-inspired protocol for the synthesis of 1-substituted-1,2,3-triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal-free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1-substituted-1,2,3-triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1-substituted triazolium sulfonyl fluoride salts. 相似文献
764.
Mechanics of Composite Materials - In this study, the geometry of open-cell foams is simulated using a model based on Voronoi tessellations. The fracture toughness of open-cell foams with Voronoi... 相似文献
765.
Dr. Xu Guo Xing Liu Prof. Junqing Yan Prof. Shengzhong Frank Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(69):e202202662
Solar-driven water splitting to produce clean and renewable hydrogen offers a green strategy to address the energy crisis and environmental pollution. Heterostructure catalysts are receiving increasing attention for photocatalytic hydrogen generation. ZnO/ZnS/CdS and ZnO/CdS heterostructures have been successfully designed and prepared according to two different strategies. By introducing a heterointerface layer of ZnS between ZnO and CdS, a Z scheme charge-transfer channel was promoted and achieved superior photocatalytic performance. A highest hydrogen generation rate of 156.7 μmol g−1 h−1 was achieved by precise control of the thickness of the heterointerface layer and of the CdS shell. These findings demonstrated that heterostructures are promising catalysts for solar-driven water splitting, and that heterointerface engineering is an effective way to improve the photocatalytic properties of heterostructures. 相似文献
766.
767.
Hydrogenation of acetophenone over nano‐Cu/SiO2 catalysts was investigated. The catalysts, prepared by a liquid precipitation method using various precipitating agents, were characterized using low‐temperature nitrogen adsorption, X‐ray diffraction, temperature‐programmed desorption of ammonia, hydrogen temperature‐programmed reduction, transmission electron microscopy and X‐ray photoelectron spectroscopy. It was found that the catalysts prepared by a homogeneous precipitation method had better activity and stability than those prepared by a co‐precipitation method. The catalyst prepared using urea as precipitating agent had well‐dispersed copper species, high surface area and abundant pore structure. The catalytic performance and mechanism of the Cu/SiO2 catalysts were further studied. It was found that the activity and stability of the catalysts could be improved by adjusting the proportion of Cu+/(Cu+ + Cu0). The sample prepared using urea as precipitating agent presented higher activity and selectivity. Also, the catalyst prepared using urea maintained a high catalytic performance while being continuously used for 150 h under the optimal reaction conditions. 相似文献
768.
Tianming Dai Weifan Jiang Zizheng Guo Zhenyu Wang Mingping Huang Guorui Zhong Chuxin Liang Xuzhe Pei Renke Dai 《Biomedical chromatography : BMC》2019,33(9)
Withaferin A (WA) is one of the major bioactive steroidal lactones with extensive pharmacological activities present in the plant Withania somnifera. The absolute oral bioavailability of WA remains unknown and human‐related in vitro data are not available. Therefore, in the present study, the absolute oral bioavailability of WA in male rats and the in vitro screening of absorption factors by Q‐trap and LC–MS/MS analysis were conducted to explore possible clinical properties of WA. The developed and validated analytical methods were successfully applied to the pharmacokinetic studies and in vitro measurement of WA. The oral bioavailability was determined to be 32.4 ± 4.8% based on intravenous (5 mg/kg) and oral (10 mg/kg) administrations of WA in male rats. The in vitro results showed that WA could be easily transported across Caco‐2 cells and WA did not show as a substrate for P‐glycoprotein. Moreover, the stability of WA was similar between male rat and human in simulated gastric fluid (stable), in intestinal microflora solution (slow decrease) and in liver microsomes (rapid depletion, with a half‐life of 5.6 min). As such, the first‐pass metabolism of WA was further verified by rat intestine‐liver in situ perfusion, revealing that WA rapidly decreased and 27.1% remained within 1 h, while the content of three major metabolites (M1, M4, M5) identified by Q‐trap increased. This perfusion result is consistent with the oral bioavailability results in vivo. The first‐pass metabolism of WA might be the main barrier in achieving good oral bioavailability in male rats and it is predicted to be similar in humans. This study may hold clinical significance. 相似文献
769.
Jia-Bin Han Ao Guo Prof. Xiang-Ying Tang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):2989-2994
A challenging deoxygenation of alkoxyl radicals from readily accessible alcohol derivatives was developed, affording facile synthesis of functionalized alkenes with good functional group tolerance under mild reaction conditions. Because alkoxyl radicals can easily undergo β-fragmentations or hydrogen abstractions, this new strategy for deoxygenation of alkoxyl radicals is highly valuable. Moreover, mechanistic studies revealed that the electron-neutral phosphine acts as the deoxygenation reagent. 相似文献
770.
Saikat Banerjee Waqas Rasheed Ruixi Fan Dr. Apparao Draksharapu Dr. Williamson N. Oloo Prof. Dr. Yisong Guo Prof. Dr. Lawrence Que Jr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(41):9608-9613
The [FeIV(O)(Me3NTB)]2+ (Me3NTB=tris[(1-methyl-benzimidazol-2-yl)methyl]amine) complex 1 has been shown by Mössbauer spectroscopy to have an S=1 ground state at 4 K, but is proposed to become an S=2 trigonal-bipyramidal species at higher temperatures based on a DFT model to rationalize its very high C−H bond-cleavage reactivity. In this work, 1H NMR spectroscopy was used to determine that 1 does not have C3-symmetry in solution and is not an S=2 species. Our results show that 1 is unique among nonheme FeIV=O complexes in retaining its S=1 spin state and high reactivity at 193 K, providing evidence that S=1 FeIV=O complexes can be as reactive as their S=2 counterparts. This result emphasizes the need to identify factors besides the ground spin state of the FeIV=O center to rationalize nonheme oxoiron(IV) reactivity. 相似文献