全文获取类型
收费全文 | 5297篇 |
免费 | 461篇 |
国内免费 | 674篇 |
学科分类
数理化 | 6432篇 |
出版年
2024年 | 9篇 |
2023年 | 46篇 |
2022年 | 109篇 |
2021年 | 141篇 |
2020年 | 226篇 |
2019年 | 177篇 |
2018年 | 154篇 |
2017年 | 173篇 |
2016年 | 203篇 |
2015年 | 198篇 |
2014年 | 241篇 |
2013年 | 479篇 |
2012年 | 285篇 |
2011年 | 291篇 |
2010年 | 263篇 |
2009年 | 289篇 |
2008年 | 303篇 |
2007年 | 281篇 |
2006年 | 284篇 |
2005年 | 273篇 |
2004年 | 296篇 |
2003年 | 280篇 |
2002年 | 214篇 |
2001年 | 118篇 |
2000年 | 125篇 |
1999年 | 110篇 |
1998年 | 113篇 |
1997年 | 83篇 |
1996年 | 111篇 |
1995年 | 83篇 |
1994年 | 75篇 |
1993年 | 75篇 |
1992年 | 69篇 |
1991年 | 38篇 |
1990年 | 36篇 |
1989年 | 30篇 |
1988年 | 26篇 |
1987年 | 17篇 |
1986年 | 23篇 |
1985年 | 14篇 |
1984年 | 18篇 |
1983年 | 7篇 |
1982年 | 17篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有6432条查询结果,搜索用时 328 毫秒
21.
A new type of phosphino-phosphonium ylide ligand bearing a chiral sulfinyl center affords a P,C-chelated palladium(II) complex with a resolved asymmetric ylidic carbon atom. According to 31P NMR analysis of the crude material, the diastereoselectivity of the complexation at room temperature is ca. 7:1. In the crystal state, an X-ray diffraction analysis of one epimer reveals a quasi C2-symmetric chloro-bridged dinuclear structure, where the (S) configuration of the sulfur atom induces a (S) configuration of the ylidic carbon atom. A in situ Pd(0) catalyst generated from the phosphino-ylide and Pd(PPh3)4 promotes allylic substitution of 3-acetoxy-1,3-diphenylpropene by sodium malonate in 70% yield and 5% e.e. 相似文献
22.
本文利用比较原理以及一种特殊变换研究了一类非线性退化方程的混合问题,得到了这类复杂问题解的渐进性质。 相似文献
23.
Yoshiro Masuyama Takanori SugaAkiko Watabe Yasuhiko Kurusu 《Tetrahedron letters》2003,44(14):2845-2847
2-Propenyl tin species, prepared from 3-halopropenes or 2-propenyl mesylate with tin(IV) chloride and tetrabutylammonium iodide in dichloromethane, causes nucleophilic addition to aldehydes to produce the corresponding homoallylic alcohols. 相似文献
24.
Shahla Yekta 《Journal of fluorine chemistry》2004,125(4):517-525
New partially fluorinated binaphthols were obtained using a copper-catalyzed oxidative coupling. The corresponding enantiomerically pure compounds were prepared by fractional crystallization of the corresponding bis(menthyl)carbamates. Nucleophilic aromatic substitution using oxygen- and carbon-based nucleophiles resulted in functionalized derivatives without concomitant racemization. The titanium(IV) complexes of these ligands are catalytically active in the asymmetric oxidation of sulfides. 相似文献
25.
Homogeneously prepared tosylcelluloses (TC) with degrees of substitution (DS) of DSTos 0.1–1.8 were used as intermediates for the synthesis of methylaminocelluloses (MAC) by nucleophilic substitution with methylamine. TC with DSTos up to 1.1 were shown to be valuable intermediates for selective synthesis of MAC with DSMA varying from 0.1 to approximately 1. No nucleophilic substitution was observed at higher DSTos. At the chosen reaction conditions (60 °C, 48 h) residual tosyl moieties remained unchanged and little hydrolysis took place. The samples obtained were characterized by means of elemental analysis, FTIR and 13C CP/MAS NMR spectroscopy. 13C CP/MAS NMR spectroscopy was found to be an efficient tool for quantification of DSMA. Furthermore, the swelling behaviour in water was investigated and preliminary tests concerning the bilirubin adsorption capacity of MAC were carried out. 相似文献
26.
Sheng‐Huei Hsiao Chien‐Wei Chen Guey‐Sheng Liou 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3302-3313
Two new diamines, 2,4‐diaminotriphenylamine ( 3 ) and N‐(2,4‐diaminophenyl)carbazole ( 4 ), were synthesized via the cesium fluoride‐mediated aromatic substitution reactions of 1‐fluoro‐2,4‐dinitrobenzene with diphenylamine and carbazole, followed by palladium‐catalyzed hydrazine reduction. Amorphous and soluble aramids having pendent diphenylamino and carbazolyl groups were prepared by the phosphorylation polycondensation of aromatic dicarboxylic acids with diamines 3 and 4 , respectively. The aramids derived from diamine 3 had sufficiently high molecular weights to permit the casting of flexible and tough films. They exhibited excellent mechanical properties and moderately high softening temperatures in the 221–298 °C range. However, the reactions of diamine 4 with aromatic diacids gave relatively lower molecular weights products that could not afford flexible films. For a comparative purpose, the parent aramids derived from m‐phenylenediamine and aromatic diacids were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3302–3313, 2004 相似文献
27.
Praveen K. Tandon Gayatri Sumita Sahgal Manish Srivastava Santosh B. Singh 《应用有机金属化学》2007,21(3):135-138
Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H2O2. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
28.
The 57Fe Mössbauer technique has been used to investigate the effect of zinc oxide substitution in (25???x)MnO–xZnO–15Fe2O3–60B2O3 glass system (x?=?0, 5, 10, 15 and 20 mol% of ZnO ). Mössbauer absorption spectra for all the samples recorded at room temperature suggest the existence of the two paramagnetic quadrupole doublets. The observed variations in hyperfine parameters have been explained on the basis of cations distribution and exchange interaction at the lattice sites and it is concluded that B–B interaction increases while the metal–metal interaction decreases due to replacement of manganese oxide by zinc oxide. These results suggest that the present glass system exhibits a paramagnetic behaviour that changes towards the weak paramagnetic when manganese oxide was replaced with zinc oxide. 相似文献
29.
In market, excess demands for many products can be met by reorder even during one period, and retailers usually adopt substitution strategy for more benefit. Under the retailer's substitution strategy and permission of reorder, we develop the profits maximization model for the two-substitutable-product inventory problem with stochastic demands and proportional costs and revenues. We show that the objective function is concave and submodular, and therefore the optimal policy exists. We present the optimal conditions for order quantity and provide some properties of the optimal order quantities. Comparing our model with Netessine and Rudi's, we prove that reorder and adoption of the substitution strategy can raise the general profits and adjust down the general stock level. 相似文献
30.