全文获取类型
收费全文 | 20686篇 |
免费 | 3407篇 |
国内免费 | 2290篇 |
专业分类
化学 | 14706篇 |
晶体学 | 260篇 |
力学 | 1251篇 |
综合类 | 188篇 |
数学 | 2057篇 |
物理学 | 7921篇 |
出版年
2024年 | 75篇 |
2023年 | 467篇 |
2022年 | 669篇 |
2021年 | 760篇 |
2020年 | 818篇 |
2019年 | 788篇 |
2018年 | 661篇 |
2017年 | 626篇 |
2016年 | 972篇 |
2015年 | 978篇 |
2014年 | 1105篇 |
2013年 | 1443篇 |
2012年 | 1859篇 |
2011年 | 1890篇 |
2010年 | 1247篇 |
2009年 | 1106篇 |
2008年 | 1294篇 |
2007年 | 1283篇 |
2006年 | 1130篇 |
2005年 | 1009篇 |
2004年 | 724篇 |
2003年 | 628篇 |
2002年 | 569篇 |
2001年 | 431篇 |
2000年 | 411篇 |
1999年 | 470篇 |
1998年 | 355篇 |
1997年 | 369篇 |
1996年 | 309篇 |
1995年 | 296篇 |
1994年 | 302篇 |
1993年 | 246篇 |
1992年 | 196篇 |
1991年 | 198篇 |
1990年 | 177篇 |
1989年 | 112篇 |
1988年 | 86篇 |
1987年 | 89篇 |
1986年 | 60篇 |
1985年 | 44篇 |
1984年 | 43篇 |
1983年 | 24篇 |
1982年 | 25篇 |
1981年 | 18篇 |
1980年 | 14篇 |
1975年 | 2篇 |
1957年 | 4篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
121.
122.
An enantioselective total synthesis of hamacanthin B (1) is described. This synthesis is based on the asymmetric synthesis of (S)-2-azido-(indol-3-yl)ethylamine 7, which is coupled with the 3-indolyl-alpha-oxoacetyl chloride 8 and subsequently used in a successful intramolecular Staudinger-aza Wittig cyclization to form the central dihydropyrazinone ring. The stereochemistry of naturally isolated hamacanthin B is revealed as the (S)-configuration. 相似文献
123.
C.L. Liu X.Y. Wang Z.M. Wang S.S. Li C.T. Xin H.F. Wang B. Li L. Jiang 《Journal of Radioanalytical and Nuclear Chemistry》2001,250(3):587-591
The migration of 99Tc in a weak loess aquifer was investigated in-situ with undisturbed aquifer medium columns. The columns were obtained horizontally at a depth of 3236 m in an Underground Research Facility (URF). Quartz containing 3H (HTO) and 99Tc (in the form of 99TcO4
-) was introduced into one end of the columns and the columns were covered tightly. Aquifer water was introduced into the columns directly from an experimental shaft in the UFR. Effluents from the columns were collected and the activity of 3H and 99Tc were determined with a liquid scintillation analyzer. The breakthrough curves of 3H and 99Tc indicate that 99Tc migrates a little faster than that 3H does in the aquifer. 相似文献
124.
Jiang J Renshaw JC Sarsfield MJ Livens FR Collison D Charnock JM Eccles H 《Inorganic chemistry》2003,42(4):1233-1240
The solution chemistry of uranyl ion with iminodiacetate (IDA) and oxydiacetate (ODA) was investigated using NMR and EXAFS spectroscopies, potentiometry, and calorimetry. From the NMR and EXAFS data and depending on stoichiometry and pH, three types of metal:ligand complex were identified in solution in the pH range 3-7: 1:1 and 1:2 monomers; a 2:2 dimer. From NMR and EXAFS data for the IDA system and previous studies, we propose the three complex types are [UO(2)(IDA)(H(2)O)(2)], [UO(2)(IDA)(2)](2)(-), and [(UO(2))(2)(IDA)(2)(mu-OH)(2)](2)(-). From EXAFS spectroscopy, similar 1:1, 2:2, and 1:2 complexes are found for the ODA system, although (13)C NMR spectroscopy was not a useful probe in this system. For the 1:1 and 1:2 complexes in solution, EXAFS spectroscopy is ambiguous because the data can be fitted with either a long U-N/O(ether) value (ca. 2.9 A) suggesting 1,7-coordination of the ligand or a U-C interaction at a similar distance, consistent with terminal bidentate coordination. However, the NMR data of the IDA system suggest that 1,7-coordination is the more likely. The stability constants of the three complexes were determined by potentiometric titrations; the log beta values are 9.90 +/-, 16.42 +/-, and 10.80 +/- for the 1:1, 1:2, and 2:2 uranyl-IDA complexes, respectively, and 5.77 +/-, 7.84 +/-, and 4.29 +/- for the 1:1, 1:2, and 2:2 uranyl-ODA complexes, respectively. The thermodynamic constants for the complexes were calculated from calorimetric titrations; the enthalpy changes (kJ mol(-)(1)) and entropy changes (J K(-)(1) mol(-)(1)) of complexation for the 1:1, 1:2, and 2:2 complexes respectively are the following. IDA: 12 +/- 2, 230 +/- 8; 8 +/- 2, 151 +/- 9; -33 +/- 3, -283 +/- 11. ODA: 26 +/- 2, 198 +/- 12; 20 +/- 2, 106 +/- 8; -24 +/- 2; -219 +/- 8. 相似文献
125.
Summary The method for the contraction and expansion of graphs is used to treat the subspectrality of benzenoid hydrocarbons in relation to eigenvalues ±1. Counts of benzenoid hydrocarbons together with degeneracies of eigenvalues have been carried out for all species having h 7 hexagons. In addition, twelve homologous series are evaluated, and the closed results for the distribution of eigenvalues ± 1 and degeneracies in terms of the number of repeated units are tabulated. This method is universal and applicable to cases sharing other eigenvalues and to nonbenzenoid systems.Also known as Yuan-sun Kiang 相似文献
126.
A sensitive and selective method is described for the determination of neodymium in mixed rare earths using fourth-derivative spectrophotometry. The method is based on the absorption spectra of 4f electron transitions of the complex of neodymium with methyl thymol blue and cetylpyridinium chloride. The influence of various instrumental parameters and reaction conditions for maximum colour development are investigated. The calibration curve is linear over the range 0–3.5 g ml–1 neodymium. The relative standard deviation for determination of 1.4 g ml–1 neodymium (n = 7) is 1.6%. The detection limit (signal-to-noise ratio = 3) is 0.2 g ml–1. 相似文献
127.
128.
The anodic reaction of Ni in an alkaline solution was studied by the tip–substrate voltammetry mode of scanning electrochemical microscopy (SECM) and cyclic voltammetry (CV). A platinum microdisc electrode was selected as the tip electrode, which functioned as a pH sensor with transient response capability. The pH value of the solution near the Ni electrode surface varied while the Ni substrate oxidation reaction occurred, and the pH variation could be detected by the tip faradic current. The cyclic voltammogram results showed that two types of hydroxides: i.e. α‐Ni(OH)2 and β‐Ni(OH)2 were formed during Ni oxidation in the lower potential region. In the proceedings of α‐Ni(OH)2 → γ‐NiOOH and β‐Ni(OH)2 → β‐NiOOH, the process of OH? concentration decrease in the solution was ahead and behind of electron transfer in the solid phase, respectively. These results indicate that the OH? adsorption process occurs as an elementary step in the former reaction and the H+ diffusion process from the inner to the outer layer of the solid phase occurs as a subsequent step in the latter reaction. The results also revealed that the oxide film on the Ni surface has a two‐layer structure. The real potential of the oxygen evolution reaction (OER) on the Ni surface with different cycles is also analyzed in the paper. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
129.
A new method for constructing nonorthogonal localized molecular orbitals (NOLMOs) is presented. The set of highly localized NOLMOs is obtained by minimization of the spread functional starting from an initial set of canonical orthogonal molecular orbitals. To enhance the stability and efficiency, the centroids of the NOLMOs are constrained to be those of the corresponding orthogonal localized molecular orbitals (OLMOs), which are obtained with the Boys criterion in advance. In particular, these centroid constraints make the optimization for each NOLMO independent of the others, which is an attractive feature for application to large systems. The minimization with the constraints incorporated through the multiplier-penalty function method is stable and efficient in convergence. While exhibiting the classical bonding pattern in chemistry and sharing a spatial distribution similar to that of the corresponding OLMOs, the obtained NOLMOs are more compact than the corresponding OLMOs with about 10%-28% reduction in the value of the spread functional and devoid of the troublesome "orthogonalization tails." 相似文献
130.