全文获取类型
收费全文 | 1967篇 |
免费 | 122篇 |
国内免费 | 6篇 |
专业分类
化学 | 1751篇 |
晶体学 | 13篇 |
力学 | 23篇 |
数学 | 129篇 |
物理学 | 179篇 |
出版年
2024年 | 3篇 |
2023年 | 28篇 |
2022年 | 53篇 |
2021年 | 105篇 |
2020年 | 80篇 |
2019年 | 59篇 |
2018年 | 37篇 |
2017年 | 40篇 |
2016年 | 78篇 |
2015年 | 75篇 |
2014年 | 91篇 |
2013年 | 122篇 |
2012年 | 198篇 |
2011年 | 142篇 |
2010年 | 90篇 |
2009年 | 72篇 |
2008年 | 111篇 |
2007年 | 119篇 |
2006年 | 94篇 |
2005年 | 89篇 |
2004年 | 79篇 |
2003年 | 61篇 |
2002年 | 53篇 |
2001年 | 15篇 |
2000年 | 7篇 |
1999年 | 10篇 |
1998年 | 12篇 |
1997年 | 11篇 |
1996年 | 18篇 |
1995年 | 8篇 |
1994年 | 6篇 |
1993年 | 6篇 |
1992年 | 12篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 11篇 |
1987年 | 13篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 9篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1968年 | 2篇 |
1961年 | 2篇 |
排序方式: 共有2095条查询结果,搜索用时 600 毫秒
51.
Changho Yoo Henry M. Dodge Alexandra H. Farquhar Kristen E. Gardner Alexander J. M. Miller 《Chemical science》2020,11(44):12130
A unique chain-rupturing transformation that converts an ether functionality into two hydrocarbyl units and carbon monoxide is reported, mediated by iridium(i) complexes supported by aminophenylphosphinite (NCOP) pincer ligands. The decarbonylation, which involves the cleavage of one C–C bond, one C–O bond, and two C–H bonds, along with formation of two new C–H bonds, was serendipitously discovered upon dehydrochlorination of an iridium(iii) complex containing an aza-18-crown-6 ether macrocycle. Intramolecular cleavage of macrocyclic and acyclic ethers was also found in analogous complexes featuring aza-15-crown-5 ether or bis(2-methoxyethyl)amino groups. Intermolecular decarbonylation of cyclic and linear ethers was observed when diethylaminophenylphosphinite iridium(i) dinitrogen or norbornene complexes were employed. Mechanistic studies reveal the nature of key intermediates along a pathway involving initial iridium(i)-mediated double C–H bond activation.A unique chain-rupturing transformation that converts an ether functionality into two hydrocarbyl units and carbon monoxide is reported. 相似文献
52.
Dirhodium(II)-catalyzed reaction of 3-indolyl alpha-diazo-beta-ketoester 25 in the presence of hexanamide results in competing metal carbene N-H insertion and Wolff rearrangement. The corresponding phenyl diazoketoester 32, on the other hand, gives only the product of N-H insertion, suggesting that the indole moiety is more prone to 1,2-rearrangement. The competing processes were investigated in a range of 3-indolyl alpha-diazo-beta-ketoesters (36, 38, 40, 44); these studies established that the Wolff rearrangement could be effectively suppressed by the presence of a strong electron-withdrawing group on the indole nitrogen. Dirhodium(II) catalysts were also more effective than copper or Lewis acid catalysts in favoring the insertion process. The products of N-H insertion, the ketoamides (26, 47, 49, 51, 53), were readily cyclodehydrated to the corresponding 5-(3-indolyl)oxazoles. The N-H insertion/cyclodehydration methodology was used in a formal synthesis of the marine natural product martefragin A. Thus the N-Boc homoisoleucine amide 23, prepared by asymmetric hydrogenation of a dehydro amino acid, underwent N-H insertion with the rhodium carbene derived from the N-nosyl indolyl diazoester 40, followed by cyclodehydration and deprotection to give the 5-(3-indolyl)oxazole martefragin A precursor 75. 相似文献
53.
N.E. Schore B.E. La Belle M.J. Knudsen H. Hope X-J. Xu 《Journal of organometallic chemistry》1984,272(3):435-446
Dicobalt octacarbonyl is shown to react with acetylene and carbon monoxide under mild conditions in dimethoxyethane or benzene to produce, in low yields, bicyclo[3.3.0]octa-3,7-diene-2,6-dione, benzoquinone, and the cyclopentadienone-derived products 3a,4,7,7a-tetrahydro-2,7-methanoindene-1,10-dione, 1-indanone, tetracyclo[5.5.2.02,608,12]tetradeca-4,10,13-triene-3,9-dione, and tetracyclo[5.5.2.02,608,12]tetradeca-4,9,13-triene-3,11-dione. Possible mechanisms for the formation of these products are discussed. 相似文献
54.
Leyla Bitiş Sevda Süzgeç Ulaş Sözer Hasan Özçelik Josef Zapp Alexandra K. Kiemer Filiz Meriçli Ali H. Meriçli 《Helvetica chimica acta》2007,90(11):2217-2221
From the aerial parts of Delphinium buschianum Grossh ., collected in Turkey, a new diterpenoid alkaloid 1 , named budelphine, was isolated along with the known diterpenoid alkaloids karakoline ( 2 ), 18‐hydroxy‐14‐O‐methylgadesine ( 3 ), delsoline ( 4 ), lapaconidine ( 5 ), columbianine ( 6 ), 14‐benzoylneoline ( 7 ), and hetisine ( 9 ). The structure of 1 was established on the basis of 1H‐, 13C‐, DEPT, 1H,1H‐COSY, NOESY, HSQC, and HMBC NMR studies. 相似文献
55.
Bingham RJ Findlay JB Hsieh SY Kalverda AP Kjellberg A Perazzolo C Phillips SE Seshadri K Trinh CH Turnbull WB Bodenhausen G Homans SW 《Journal of the American Chemical Society》2004,126(6):1675-1681
In the present study we examine the thermodynamics of binding of two related pyrazine-derived ligands to the major urinary protein, MUP-I, using a combination of isothermal titration calorimetry (ITC), X-ray crystallography, and NMR backbone (15)N and methyl side-chain (2)H relaxation measurements. Global thermodynamics data derived from ITC indicate that binding is driven by favorable enthalpic contributions, rather than the classical entropy-driven hydrophobic effect. Unfavorable entropic contributions from the protein backbone and side-chain residues in the vicinity of the binding pocket are partially offset by favorable entropic contributions at adjacent positions, suggesting a "conformational relay" mechanism whereby increased rigidity of residues on ligand binding are accompanied by increased conformational freedom of side chains in adjacent positions. The principal driving force governing ligand affinity and specificity can be attributed to solvent-driven enthalpic effects from desolvation of the protein binding pocket. 相似文献
56.
57.
Eduard E. Karslyan Andrew I. Konovalov Alexandra O. Borissova Pavel V. Petrovskii Alexander R. Kudinov 《Mendeleev Communications》2012,22(4):189-191
The [2 + 2] photodimerization of the complex [(C5Me4CH2OMe)Ru(η6-C12H8)]+ under visible-light irradiation leads to a mixture of the head-to-head heptacyclene products [(μ-η6: η6-C24H16)Ru2(C5Me4CH2OMe)2]2+ (syn- and anti-) with the predominant formation of the syn-isomer; the structures of both isomers were established by X-ray diffraction analysis. 相似文献
58.
Pharmacokinetics (PK) is a branch of pharmacology dedicated to the study of the time course of drug concentrations, from absorption to excretion from the body. PK dynamic models are often based on homogeneous, multi-compartment assumptions, which allow to identify the PK parameters and further predict the time evolution of drug concentration for a given subject. One key characteristic of these time series is their high variability among patients, which may hamper their correct stratification. In the present work, we address this variability by estimating the PK parameters and simultaneously clustering the corresponding subjects using the time series. We propose an expectation maximization algorithm that clusters subjects based on their PK drug responses, in an unsupervised way, collapsing clusters that are closer than a given threshold. Experimental results show that the proposed algorithm converges fast and leads to meaningful results in synthetic and real scenarios. 相似文献
59.
60.