全文获取类型
收费全文 | 209187篇 |
免费 | 1447篇 |
国内免费 | 484篇 |
专业分类
化学 | 108344篇 |
晶体学 | 3436篇 |
力学 | 10379篇 |
综合类 | 10篇 |
数学 | 23153篇 |
物理学 | 65796篇 |
出版年
2021年 | 2117篇 |
2020年 | 2112篇 |
2019年 | 2721篇 |
2018年 | 3814篇 |
2017年 | 3819篇 |
2016年 | 5031篇 |
2015年 | 2523篇 |
2014年 | 4498篇 |
2013年 | 9029篇 |
2012年 | 7208篇 |
2011年 | 8539篇 |
2010年 | 6801篇 |
2009年 | 6926篇 |
2008年 | 8018篇 |
2007年 | 7975篇 |
2006年 | 7032篇 |
2005年 | 6230篇 |
2004年 | 5916篇 |
2003年 | 5390篇 |
2002年 | 5338篇 |
2001年 | 5684篇 |
2000年 | 4217篇 |
1999年 | 3235篇 |
1998年 | 2771篇 |
1997年 | 2812篇 |
1996年 | 2619篇 |
1995年 | 2256篇 |
1994年 | 2369篇 |
1993年 | 2272篇 |
1992年 | 2556篇 |
1991年 | 2671篇 |
1990年 | 2566篇 |
1989年 | 2637篇 |
1988年 | 2542篇 |
1987年 | 2561篇 |
1986年 | 2421篇 |
1985年 | 3045篇 |
1984年 | 3113篇 |
1983年 | 2614篇 |
1982年 | 2576篇 |
1981年 | 2540篇 |
1980年 | 2339篇 |
1979年 | 2716篇 |
1978年 | 2681篇 |
1977年 | 2882篇 |
1976年 | 2878篇 |
1975年 | 2673篇 |
1974年 | 2605篇 |
1973年 | 2716篇 |
1972年 | 2089篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
921.
A systematic study of the adsorption and interfacial behaviour of the adenine mono-nucleotides (5′-AMP, 3′-AMP, cyclic 3′,5′-AMP, 5′-ADP and 5′-ATP) and adenosine for comparison at the HMDE has been carried out at pH 3.4 to 3.5. Thus, the N(1) of the adenine moiety is protonated to a major extent.The adsorption was followed by single sweep voltammetry (measurement of the time integral of the reduction peak of the adsorbed adenine moiety) and by a.c. voltammetry (out-of-phase component of the a.c. response being proportional to the differential double layer capacity). In this paper the situation corresponding to a “dilute” adsorption layer existing at low bulk concentrations is studied for various degrees of coverage. The potential dependence of the coverage is of bell shaped type with an extended maximum region around the potential of electrocapillary maximum (Eecm) of the blank. For the same bulk concentration the coverage decreases in the series AMP, ADP, ATP, i.e. with increasing negative charge of the nucleotide, and at the same time the potential range of adsorption narrows. Among the monophosphates the coverage decreases in the series 3′-AMP, 5′-AMP, cyclic 3′,5′-AMP. The variations are connected with the varying charge of the mononucleotides and with the possibilities for interactions with adjacent molecules in the adsorption layer.At elevated bulk concentrations above a threshold value a substantial increase in coverage occurs around Eecm as due to strong interactions between the adsorbed base moieties a rather compact film is formed. 相似文献
922.
Fischer indolization of ethyl pyruvate 2-methoxyphenylhydrazone (1) with p-toluene-sulfonic acid in benzene in the presence of an enolizable dicarbonyl or an indolic compound gave either an indole product having an active methine group at C6 or a novel type of 3,6′-biindole compound. Structures of the products were established by NMR spectra and chemical evidence. 相似文献
923.
Collective characteristics of the venoms belonging to various taxons of Central Asian snakes, demonstrating levels of toxicity and efficiency of hemorrhagic action, together with proteolytic, esterase, and phospholipase activities, have been obtained. A comparative analysis of the collective characteristics (“portraits”) of the venoms and their changes on degradative treatment has shown that the hemorrhagic action of the venoms of viperine and crotalid snakes is connected with metalloproteins. In contrast to the venoms of the elapids (cobras) the toxicity of the venoms of the viperine and crotalid snakes exhibits a dependence on the hemmorhagic effect and the activity of the metalloproteins causing it. 相似文献
924.
N. S. Prostakov A. V. Varlamov T. N. Borisova 《Chemistry of Heterocyclic Compounds》1984,20(5):519-521
The catalytic dehydrocyclization of 3-isopropyl-2,6-diphenylpyridine proceeds in two directions: conversion to 10-methyl-3-phenyl-4-azaphenanthrene and conversion to 9,9-dimethyl-4-azafluorene. C(9)-Unsubstituted 4-azafluorenes were obtained in the dehydrocyclization of pyridine bases that contain a phenyl group in the position and an n-propyl group in the position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 648–650, May, 1984. 相似文献
925.
O. A. Kruglaya L. I. Belousova N. P. Aktaev G. A. Sokol'skii N. S. Vyazankin 《Russian Chemical Bulletin》1977,26(12):2590-2592
Conclusions The exchange reaction of the radicals between bis(triethylgermyl)mercury and mercury derivatives R2Hg (R=C(Me2)CN, C(CF3)2CN, CH(CN)2) leads to the formation of unstable Et3GeHgR compounds. The composition of the decomposition products of these compounds depends on the nature of R.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2800–2802, December, 1977. 相似文献
926.
V. A. Zamureenko N. A. Klyuev B. V. Bocharov V. S. Kabanov A. M. Zakharov 《Chemistry of Natural Compounds》1990,25(5):549-551
The composition of the essential oil of wild bergamot bee balm introduced into the Krasnodarsk Krai has been analyzed by chromatomass spectrometry. The essential oil contains 34 components of which the main ones are -pinene (3.5%), -pinene (2.9%), -terpinene (1.7%), p-cymene (32.5), an aliphatic aldehyde (6.3%), sabinene hydrate (1.9%), -caryophyllene (1.1%), the methyl ether of carvacrol (5.5%), citronellyl acetate (1.6%), thymol (12.6%), and carvacrol (24.0%). The compounds were identified on the basis of their mass-spectrometric characteristics and arithmetical retention indices.A. N. Severtsov Institute of Animal Evolutionary Morphology and Ecology, Academy of Sciences of the USSR, Moscow. All-Union Scientific-Research Institute of Drugs, Moscow. Translated from Khimiya Prirodnykh Soedinenii, Vol. 5, pp. 646–649, September–October, 1989. 相似文献
927.
1. | The reaction of 3,3-disubstituted cyclopropene hydrocarbons with norbornadiene in the presence of 1–3 mole % CuCl or (PhO)3P·CuCl at 0–40C takes place according to the scheme of both [2 + 2]- and [1 + 2]- cycloaddition with the formation of the corresponding exo,trans-tetracyclo[5.2.1.02, 6.03, 5]-8-decenes and 3-vinykltricyclo[3.2.1.02, 4]-6-octenes with a total yield of 70–90%, and the yield of the latter increased with an increase in the temperature in going from (PhO)3P·CuCl to CuCl. |
2. | The reaction of 3-methyl-3-cyclopropylcyclopropene with more complex polycyclic hydrocarbons containing a bicyclo[2.2.1]heptene fragment takes place less efficiently and less selectively than with norbornene, and yields a mixture of products of [1+2]- and [2+2]-cycloaddition with a yield of 30–65% and significant dimerization of the starting cyclopropene in the presence of (PhO)3P·CuCl even at –20C. |
928.
Turevskaya E.P. Berdyev D.V. Turova N.Ya. 《Journal of Sol-Gel Science and Technology》1997,8(1-3):111-115
Complex formation in solutions of barium and zirconium alkoxides in ROH (R=i-Pr, Et) was studied. A number of bimetallic complexes were isolated, and their structure and properties were studied. The
sol-gel method yields a single-phase BaZrO3 powder only wheni-PrOH solutions of the alkoxides are used. In this case, the oxocomplex, BaZrO(OPr-i)4.(1–2)i-PrOH, is the precursor of the mixed oxide. 相似文献
929.
The kinetics of spontaneous hydrolysis of monoalkylsubstituted ketenes has been studied. The influence of inductive and steric effects of substituents upon the rate has been quantitatively estimated in terms of -analysis. Increasing length and branching of alkyl substiuents decrease the rate of ketene hydrolysis. 相似文献
930.
Isobutane and methane chemical ionization (CI) mass spectra of C-17a-epimeric, 17a-substituted 3-methoxyestra-1,3,5(10),8-tetraen-17a-ols and at C-17-epimeric 17-substituted 3-methoxyestra-1,3,5(10)-trien-17-ols, as well as of some their derivatives, have been studied. In each epimeric pair, the peak intensity ratio [MH-H(2)O](+) / [MH](+) is greater for stereoisomers having an axial (or quasi-axial) hydroxyl group. The same regularity in the peak intensity ratio [MH-CH(3)COOH](+) / [MH](+) is valid for acetates in the D-homo series. The observed quantitative differences in CI mass spectra of epimers are explained by steric hindrance of the attack of the proton-donating cation caused by the angular 18-methyl group. No differences in the ease of elimination of the silanol molecule were observed in CI mass spectra of epimeric silyl ethers. 相似文献