全文获取类型
收费全文 | 3639篇 |
免费 | 447篇 |
国内免费 | 379篇 |
专业分类
化学 | 2478篇 |
晶体学 | 47篇 |
力学 | 149篇 |
综合类 | 25篇 |
数学 | 348篇 |
物理学 | 1418篇 |
出版年
2024年 | 5篇 |
2023年 | 25篇 |
2022年 | 78篇 |
2021年 | 67篇 |
2020年 | 111篇 |
2019年 | 94篇 |
2018年 | 106篇 |
2017年 | 117篇 |
2016年 | 177篇 |
2015年 | 143篇 |
2014年 | 252篇 |
2013年 | 299篇 |
2012年 | 190篇 |
2011年 | 231篇 |
2010年 | 208篇 |
2009年 | 230篇 |
2008年 | 237篇 |
2007年 | 220篇 |
2006年 | 245篇 |
2005年 | 183篇 |
2004年 | 183篇 |
2003年 | 155篇 |
2002年 | 122篇 |
2001年 | 94篇 |
2000年 | 66篇 |
1999年 | 101篇 |
1998年 | 55篇 |
1997年 | 75篇 |
1996年 | 49篇 |
1995年 | 53篇 |
1994年 | 46篇 |
1993年 | 27篇 |
1992年 | 30篇 |
1991年 | 24篇 |
1990年 | 17篇 |
1989年 | 15篇 |
1988年 | 23篇 |
1987年 | 24篇 |
1986年 | 12篇 |
1985年 | 15篇 |
1984年 | 24篇 |
1983年 | 5篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 9篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 1篇 |
排序方式: 共有4465条查询结果,搜索用时 109 毫秒
101.
V. V. Dunina M. Yu. Kazakova Yu. K. Grishin O. R. Malyshev E. I. Kazakova 《Russian Chemical Bulletin》1997,46(7):1321-1330
A new homochiral dimericortho-palladated complex bearing a bulkytert-butyl substituent at the carbon stereocenter was synthesized from optically activeN,N-dimethyl-α-tert-butylbenzylamine. Regioselective activation of only the aromatic C−H bond was shown to occur during the cyclometallation
process proceeding under very mild conditions due to steric effects. Spectral characteristics of mononuclear derivatives of
the new dimeric complex indicate that the five-membered palladacycle exists predominantly in one of two possible chiral conformations
with the axial position of thetert-butyl substituent.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1375–1384, July, 1997. 相似文献
102.
In contrast to the high precision with which masses of atoms and molecules can be specified, their external dimensions remain intrinsically fuzzy. Attention is directed to the difference between measurements of interatomic separations within molecules, that in many instances are cited with error bars of +/– 0.002 Å, and the available approximate magnitudes of over-all sizes, needed for estimating packing densities (in solids or liquids). The following account, is a critical examination of the underlying concepts and of the diversity of data in the literature, regarding internal dimensions (bond lengths), overall extensions, cross-sectional areas, and volumes of molecules that may be derived from a variety of experiments. Historical markers of the evolution of the underlying theories and experiments are included. 相似文献
103.
J.S. Yadav B.V.Subba Reddy B. Padmavani Ch. Venugopal A.Bhaskar Rao 《Tetrahedron letters》2007,48(26):4631-4633
Enzymatic kinetic resolution of (±)-hydroxytetrahydropyrans has been achieved for the first time by means of lipase-mediated transesterification to afford optically active (2S,4R)-tetrahydropyranyl acetates and (2R,4S)-tetrahydropyranols in excellent yields with high enantioselectivity. Absolute configurations of the tetrahydropyranyl acetates were assigned as (S) by chemical correlation. 相似文献
104.
Jian-binSong Min-qiaoRen Qing-yongChen Shu-yunWang Qing-xiangZhao Hong-fangZhang 莫志深 《高分子科学》2004,(5):491-496
Based on the X-ray scattering intensity theory and using the approximate expression for the atomic scattering factor, the correction factors for three crystalline peaks and an amorphous peak of Nylon 1212 were calculated and the formula of degree of crystallinity of Nylon 1212 was derived by a graphic multipeak resolution method. The degree of crystallinity calculated from the WAXD method is compatible with those obtained by density and calorimetry methods. 相似文献
105.
Benjamin Esquivel Lawrence Nicholson Linda Peerey Michael Fazio 《Journal of separation science》1991,14(12):816-823
Factors influencing the stereoisomeric resolution of underivatized dipeptides and a representative tripeptide on Crownpak (CR) columns have been investigated. The elution order and relative retention suggest that a combination of chiral, steric, and hydrophobic interactions effects the extent of chiral recognition and the retention achieved during separations. Some dipeptides whose amine terminus is located three atoms from the asymmetric center (such as dipeptides of D ,L -glycine) were resolved, but the elution order was the opposite of that expected for the type of Crownpak column used (CR(+)). Peptides containing hydrophobic substituents were strongly retained, but their retention times could be significantly reduced, and detectability improved, by use of gradient elution. Analysis of a commercial sample of D ,L -leucine-D ,L -alanine revealed the stereoisomers to be present in an unexpected quantitative ratio and demonstrated the utility of these separations for quality assurance and quantitative analyses. 相似文献
106.
Jue Xiao CAI Zheng Hong ZHOU Kang Ying LI Chi Hung YEUNG Chu Chi TANG* State Key Laboratory of Elemento-Organic Chemistry Institute of Elemento-Organic Chemistry Nankai University Tianjin Open Laboratory of Chirotechnology D 《中国化学快报》2002,13(7)
Optically active 1,1-binaphthalene-2, 2-diol has become a quite important chiral source in different fields of chirotechnology, especially in asymmetric synthesis1. Its synthesis and resolution has been extensively studied and various resolution methods have been reported2. Among the reported resolution methods, the following three, namely, via the formation of phosphoric acid derivatives3, boric acid derivatives4 and inclusion complexes5, are the most important. OHOH+_( )-1(-)-(S)-1(+)-(R)… 相似文献
107.
Shigeru?ArimotoEmail author Mark?Spivakovsky Keith?F.?Taylor Paul?G.?Mezey 《Journal of mathematical chemistry》2005,37(2):171-189
The present article is a direct continuation of the first part of this series. We reduce a proof of the Fukui conjecture (concerning the additivity problem of the zero-point vibrational energies of hydrocarbons) to that of a proposition related to the theory of algebraic curves, so that we can focus on the key mechanism of the additivity phenomena. Namely, by establishing what is called the Basic Piecewise Monotone Theorem (BPMT), we reduce a proof of the Fukui conjecture to that of a proposition, called the Local Analyticity Proposition, Version 1 (LAP1), which admits a proof via resolution of singularities. By LAP1, the essential part of the mechanism of the asymptotic linearity phenomena is extracted and is elucidated by using tools from the mathematical theory of algebraic curves, whose language is of vital importance in analyzing the crux of the additivity mechanism.
Dedicated to the memory of Prof. Kenichi Fukui (1918–1998). 相似文献
108.
Yu-Ping Zhang Kwang-Pill Lee Hyun-Joo Noh Ali Md Showkat Seong-Ho Choi 《Microchemical Journal》2004,78(2):99-106
An appropriate optimization strategy should be used to find a desired resolution or selectivity with a minimum number of experiments in a limited time, which could assure the baseline separation of all target compounds. It was usually realized by means of a specialized computer program. In this paper, mapping optimization method and overlapping resolution mapping were compared for the optimization of a reversed-phase high-performance liquid chromatography (HPLC) isocratic separation of neutral compounds. The calculated resolutions and separation time of 7 to 10 experiments are fitted by different equations, which were used to build a contour plot with a minimum effective resolution and maximum retention time as a function of a mobile phase composition. The balance between resolution and analysis time could be easily realized by the overlapping of the final overlapping resolution mapping and analysis time mapping. The validity of the two methods was confirmed by some typical experiments. The models are simple, visual, and common without theoretical arithmetic. 相似文献
109.
The lipase-catalyzed transesterifications of various substituted diphenyl 1,2-ketals of glycerol have been investigated. Efficient modification of the substrate structure with bis(4-bromophenyl) ketal was found to enhance the enantioselectivity up to E=57 at 0 °C. 相似文献
110.
Summary Capillary electrophoresis has been used for the chiral analysis of two -amino alcohol pharmaceutical compounds. Capillary zone electrophoresis conditions were used with -cyclodextrin as a chiral mobile phase additive. The effects of variation of -cyclodextrin concentration, temperature, pH, background electrolyte composition and concentration have been investigated. Optimum separations were achieved for clenbuterol using -cyclodextrin at its solubility limit (16mM), the lowest practicable temperature (19°C), pH 4.0 and an electrolyte solution with a high ionic strength prepared from 0.1 M citric acid and 0.3 M Na2HPO4. For the development compound picumeterol and its (S)-enationmer, the optimum pH 4.0 buffer was prepared from 0.1 M citric acid and 0.2 M sodium acetate. Baseline separation with resolution greater than 2 was achieved for both compounds.This work was presented in part at the 2nd International Symposium on Chiral Discrimination, Rome, May 27–31, 1991. 相似文献