全文获取类型
收费全文 | 2836篇 |
免费 | 261篇 |
国内免费 | 14篇 |
专业分类
化学 | 2118篇 |
晶体学 | 8篇 |
力学 | 60篇 |
数学 | 414篇 |
物理学 | 511篇 |
出版年
2023年 | 52篇 |
2022年 | 35篇 |
2021年 | 118篇 |
2020年 | 166篇 |
2019年 | 186篇 |
2018年 | 83篇 |
2017年 | 69篇 |
2016年 | 198篇 |
2015年 | 149篇 |
2014年 | 160篇 |
2013年 | 193篇 |
2012年 | 274篇 |
2011年 | 266篇 |
2010年 | 154篇 |
2009年 | 127篇 |
2008年 | 194篇 |
2007年 | 155篇 |
2006年 | 148篇 |
2005年 | 97篇 |
2004年 | 59篇 |
2003年 | 30篇 |
2002年 | 30篇 |
2001年 | 25篇 |
2000年 | 17篇 |
1999年 | 14篇 |
1998年 | 11篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 9篇 |
1994年 | 9篇 |
1993年 | 4篇 |
1992年 | 9篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1981年 | 6篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1971年 | 1篇 |
1957年 | 1篇 |
1936年 | 1篇 |
1932年 | 2篇 |
1928年 | 1篇 |
排序方式: 共有3111条查询结果,搜索用时 671 毫秒
991.
Prokofieva A Prikhod'ko AI Dechert S Meyer F 《Chemical communications (Cambridge, England)》2008,(8):1005-1007
A highly preorganized bioinspired dicopper complex with imidazole ligation catalyzes the selective benzylic para-C-H activation of 2,4,6-trimethylphenol under aerobic conditions, yielding either the stilbenequinone or 4-methoxymethyl-2,6-dimethylphenol depending on the solvent used. 相似文献
992.
Sinnwell S Inglis AJ Davis TP Stenzel MH Barner-Kowollik C 《Chemical communications (Cambridge, England)》2008,(17):2052-2054
The tendency of electron-deficient dithioesters to undergo hetero Diels-Alder cycloadditions is successfully used to generate polymer conjugates between a RAFT-polymerized poly(styrene) and a diene-terminated poly(epsilon-caprolactone). 相似文献
993.
Michael Dom Jiong Guo Rolf Niedermeier Sebastian Wernicke 《Journal of Discrete Algorithms》2008,6(3):393-407
Set Cover problems are of core importance in many applications. In recent research, the “red-blue variants” where blue elements all need to be covered whereas red elements add further constraints on the optimality of a covering have received considerable interest. Application scenarios range from data mining to interference reduction in cellular networks. As a rule, these problem variants are computationally at least as hard as the original set cover problem. In this work we investigate whether and how the well-known consecutive ones property, restricting the structure of the input sets, makes the red-blue covering problems feasible. We explore a sharp border between polynomial-time solvability and NP-hardness for these problems. 相似文献
994.
995.
Five recently synthesized pyridinium ionic liquids [(1-butyl-4-methylpyridinium, 1-octylpyridinium, 1-octyl-2-methylpyridinium, 1-octyl-3-methylpyridinium, and 1-octyl-4-methylpyridinium, all with anion bis(trifluoromethylsulfonyl)imide], were investigated to establish the influence of substituting a methyl group and the influence of alkyl chain length on the cation on polarity ET(N) and on three Kamlet-Taft parameters: dipolarity/polarizabilty (pi*), hydrogen-bond acidity (alpha), and hydrogen-bond basicity (beta). Experimental measurements cover the range 25 to 65 degrees C. 相似文献
996.
A practical method for the synthesis of gem-2,2-disubstituted tertiary amines from the corresponding lactams (or amides) is reported. It is based on the reaction of thioiminium ions, easily prepared from lactams and amides with organometallic reagents such allylmagnesium, benzylmagnesium, and primary alkylcerium reagents. 相似文献
997.
Asymmetric 1,4-addition of arylboronic acids to (E)-methyl 2-cyano-3-arylpropenoates proceeded in the presence of a rhodium catalyst (3 mol %) coordinated with a chiral diene ligand, (R,R)-Ph-bod*, to give high yields of the corresponding methyl 3,3-diaryl-2-cyanopropanoates with high enantioselectivity (up to 99% ee). This catalytic asymmetric transformation was applied to the asymmetric synthesis of (R)-tolterodine. 相似文献
998.
The 1,3-alternate 25,27-bis-[p-chlorobenzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase was synthesized, structurally characterized, and used as a selector in high performance liquid chromatography. Selectivity studies on that phase used aromatic positional isomers, alkylbenzenes, polynuclear aromatic hydrocarbons, sulfonamides, and non-steroidal anti-inflammatory drugs as analytes. The effects of organic modifier content and pH of the mobile phase on retention and selectivity of selected aromatic positional isomers were studied. Selectivity comparisons of the novel phase vs. 1,3-alternate 25,27-di-[benzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene phase and commercially available RP-Phenyl phases were performed. The retention mechanism was also discussed. The results indicated that the calixarene stationary phase behaves like a reversed-phase packing; however, other retention mechanisms seem to be involved in the separation process. 相似文献
999.
Dr. Zhiyu Zou Dr. Alessandro Sala Dr. Mirco Panighel Dr. Ezequiel Tosi Dr. Paolo Lacovig Dr. Silvano Lizzit Dr. Mattia Scardamaglia Dr. Esko Kokkonen Dr. Cinzia Cepek Dr. Cristina Africh Prof. Giovanni Comelli Prof. Dr. Sebastian Günther Prof. Dr. Laerte L. Patera 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202213295
The synthesis of high-value fuels and plastics starting from small hydrocarbon molecules plays a central role in the current transition towards renewable energy. However, the detailed mechanisms driving the growth of hydrocarbon chains remain to a large extent unknown. Here we investigated the formation of hydrocarbon chains resulting from acetylene polymerization on a Ni(111) model catalyst surface. Exploiting X-ray photoelectron spectroscopy up to near-ambient pressures, the intermediate species and reaction products have been identified. Complementary in situ scanning tunneling microscopy observations shed light onto the C−C coupling mechanism. While the step edges of the metal catalyst are commonly assumed to be the active sites for the C−C coupling, we showed that the polymerization occurs instead on the flat terraces of the metallic surface. 相似文献
1000.
Sebastian Jusuf Yuewei Zhan Meng Zhang Natalie J. Alexander Adam Viens Michael K. Mansour Ji-Xin Cheng 《Photochemistry and photobiology》2023,99(3):936-946
Hyphae formation is a key step for fungal penetration into epithelial cells and escaping from macrophages or neutrophils. We found that 405 nm light-induced catalase deactivation results in the inhibition of hyphae growth in Candida albicans. The treatment is capable of inhibiting hyphae growth across multiple hyphae-producing Candida species. Metabolic studies on light-treated C. albicans reveal that light treatment results in a strong reduction in both lipid and protein metabolism. A significant decrease in unsaturated and saturated fatty acids was detected through mass spectroscopy, indicating that the suppression of hyphae through light-induced catalase deactivation may occur through inhibition of lipid metabolism. Initial in vivo tests indicate that blue light treatment can suppress the hyphae forming capabilities of C. albicans within murine abrasion infections. Together, these findings open new avenues for the treatment of Candida fungal infections by targeting their dimorphism. 相似文献