全文获取类型
收费全文 | 59281篇 |
免费 | 5288篇 |
国内免费 | 6170篇 |
专业分类
化学 | 38905篇 |
晶体学 | 2761篇 |
力学 | 3811篇 |
综合类 | 743篇 |
数学 | 7465篇 |
物理学 | 17054篇 |
出版年
2023年 | 444篇 |
2022年 | 830篇 |
2021年 | 1874篇 |
2020年 | 1435篇 |
2019年 | 1538篇 |
2018年 | 1291篇 |
2017年 | 1578篇 |
2016年 | 1935篇 |
2015年 | 1808篇 |
2014年 | 2438篇 |
2013年 | 4482篇 |
2012年 | 2839篇 |
2011年 | 2977篇 |
2010年 | 2693篇 |
2009年 | 3270篇 |
2008年 | 3475篇 |
2007年 | 3797篇 |
2006年 | 3303篇 |
2005年 | 2611篇 |
2004年 | 2531篇 |
2003年 | 2282篇 |
2002年 | 4535篇 |
2001年 | 1926篇 |
2000年 | 1466篇 |
1999年 | 1335篇 |
1998年 | 993篇 |
1997年 | 860篇 |
1996年 | 990篇 |
1995年 | 861篇 |
1994年 | 826篇 |
1993年 | 797篇 |
1992年 | 774篇 |
1991年 | 561篇 |
1990年 | 381篇 |
1989年 | 314篇 |
1988年 | 314篇 |
1987年 | 256篇 |
1986年 | 241篇 |
1985年 | 367篇 |
1984年 | 266篇 |
1983年 | 167篇 |
1982年 | 320篇 |
1981年 | 485篇 |
1980年 | 431篇 |
1979年 | 474篇 |
1978年 | 373篇 |
1977年 | 286篇 |
1976年 | 244篇 |
1975年 | 75篇 |
1973年 | 150篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
R.?R.?NazmutdinovEmail author T.?T.?Zinkicheva 《Russian Journal of Electrochemistry》2005,41(2):206-212
The fluoride ion adsorption from a gas phase on various faces of a single crystal of silver is studied by a density functional method within a cluster model for metal. The adsorption bond energy is found to increase in the series Ag(100) < Ag(111) < Ag(311) < Ag(110). A substantial structural and energetic heterogeneity of various adsorption sites is revealed. The results are utilized to simulate the electrochemical interface between individual faces of a single crystal of silver and aqueous solutions containing the fluoride ion. It is assumed that the adsorption potential may be represented as the sum of two contributions, one of which describes the metal–ion interaction and the other, the ion solvation energy. The plotted adsorption terms take into account partial degradation of the fluoride ion when adsorbed from an aqueous solution. Estimates of discreteness of the electrical double layer are presented. A conclusion on the maximum manifestation of specific adsorption of the fluoride ion for the Ag(100) face is made.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 232–238.Original Russian Text Copyright © 2005 by Nazmutdinov, Zinkicheva.This revised version was published online in April 2005 with corrections to the article note and article title and cover date. 相似文献
992.
993.
This review covers our extensive research activities in the area of fluorine containing phospha- and arsaalkenes as well as selenocarbonyls, which differ considerably in their properties and reactivities from their alkyl and aryl counterparts and thus contribute in a gratifying manner to the still growing field of unsaturated element-carbon compounds of 3rd and 4th row main group elements E. Of particular interest is the influence of the fluorine substituents and other small groups (OR, NR2) with either inductive and/or mesomeric effects on the polarity and reactivity of the EC bond. Addition reactions of proton acidic and hydridic polar HX reactants as well as [2+2], [3+2] and [4+2] cycloadditions have been thoroughly studied. The results obtained allow a classification of the EC systems within five different types, A to E, and prove a change from “normal” to “inverse” heteroalkenes in this sequence. The ligand properties of some derivatives have also been investigated in some detail. 相似文献
994.
Afarin Moezzi Marylin M. Olmstead Doris C. Pestana Philip P. Power 《无机化学与普通化学杂志》1995,621(11):1933-1938
The reaction of either Li2PPh or Li2AsPh with the diborane(4) derivative B2(NMe2)2Br2 affords the compounds [PhP(BNMe2)2]2 ( 1 ) or [PhAs(BNMe2)2]2 ( 2 ) in good yield. Both 1 and 2 have cyclic structures featuring non-planar P2B4 or As2B4 six-membered rings which have chair configurations. Although all four borons in each ring have planar coordination, the two phosphorus or arsenic centers have different degrees of pyramidalization. Bond distances within the rings indicate that the B? B, B? P or B? As bonds are single, whereas the exo-B? N bond lengths are consistent with significant π-bonding. The ring structures of 1 and 2 are in sharp contrast to the related boron-nitrogen species (t-BuN)2N4Me4 which has a nido-N2B4 framework. The attempted synthesis of the nitrogen analogue of 1 or 2 by using a similar approach did not result in the isolation of [PhN(BNMe2)2]2, instead the tetramino diborane(4) species [B(NMe2)NHPh]2 ( 3 ), which has a structure similar to other tetramine diborane(4) compounds, was isolated. 相似文献
995.
Elena Laukhina Vladislava Tkacheva Salavat Khasanov Leokadia Zorina Jordi Gómez-Segura Angel Pérez del Pino Jaume Veciana Vladimir Laukhin Concepció Rovira 《Chemphyschem》2006,7(4):920-923
Temperature has great impact on the structure and size of the linked crystallites of the conducting topmost layer formed at the surface of a polycarbonate film via the reaction BEDT-TTF+IBr [BEDT-TTF=bis(ethylenedithio)tetrathiafulvalene]. We show that fine temperature control permits formation of a semiconducting topmost layer of alpha'-(BEDT-TTF)(2)(I(x)Br(1-x))(3) crystallites with either micro- or nanometre size, a result that opens a route to miniaturized conducting plastic materials. 相似文献
996.
A. S. Golubev N. D. Chkanikov M. Yu. Antipin Yu. T. Struchkov A. F. Kolomiets A. V. Fokin 《Russian Chemical Bulletin》1992,41(8):1425-1429
Condensation of methyl trifluoropyruvate with 2-(3,4-dimethoxyphenyl)ethylamine, tryptamine, and (D, L)-tryptophan yielded 1-methoxycarbonyl-1-trifluoromethyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline, 1-methoxycarbonyl-1-trifluoromethyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole, and Z-1-methoxycarbonyl-1-trifluoromethyl-3-carboxy-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole, respectively. The Z configuration of the latter was determined by x-ray structural analysis.A. N. Nesmayanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow, Russia. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1831–1836, August, 1992. 相似文献
997.
V. I. Sokol L. V. Baikalova E. S. Domnina M. A. Porai-Koshits 《Russian Chemical Bulletin》1992,41(6):1076-1079
The crystal and molecular structures of 1,1-divinyl-2,2-biimidazolyl (L) were determined by x-ray crystallographic analysis. It was established that the molecule of L has crystallographic symmetry 2 and a cisoid conformation with an angle of rotation of 128° between the imidazole rings. The length of the C2-C2 bond is increased to 1.485(11) Å compared with the length of the analogous bond in unsubstituted 2,2-biimidazolyl (1.423 Å). Localization of the N=C multiple bond is observed [1.297(9) Å]. The other N-C bonds of the ring are almost equalized (1.374 Å) and are close to the standard values for bonds of the C
sp
2-N type in imidazoles. The angle between the plane of the heterocycle and the plane passing through the atoms of the vinyl group amounts to 7°.N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 117907 Moscow. Irkutsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1376–1380, June, 1992. 相似文献
998.
环戊二烯基希土氯化物是一类合成希土有机配合物的重要前身。尽管在1980年前没能成功地合成含轻希土元素的这类配合物,但目前已发现,采用具有较大体积的取代环戊二烯做配体,如C_5Me_5H,C_5H_3〔Si(CH_3)_3〕_2H,C_5Me_4C_3H_7H和桥联的配体(C_5H_4)_2(CH_2)_3H_2都可得到相应的取代环戊二烯基轻希土氯化物。控制LnCl_3和CpNa的反应摩尔比也可以成功地得到这类轻希土的环戊二烯基氯化物。 相似文献
999.
原子簇化合物的合成方法,由于条件限制,只有B、C、St等非金属元素与过渡金属袈基化合物等较为成熟.贵金属原子簇的合成则较困难.然而,应用激光等离子体反应,可使周期表内几乎所有元素都生成原子簇,为原子簇的生成与研究提供了一条新途径.该方法生成的原子簇在飞行时间质谱仪上可记录到一系列信号,某些信号呈现区域极大(或被称为‘匈数’吵].郑兰芬等用纯化的红磷粉分别与金粉、银粉混合,在激光等离子作源飞行时间质谱仪上得到一系列谱图【2]:ig与P作用只得到单核xg与P形成的lgy:iE离子簇.谱图较简单,*沪X最大可达叱叱… 相似文献
1000.
Eckhard Herrmann Moein Nouaman Zdirad
k Gisbert Großmann Gisela Ohms 《无机化学与普通化学杂志》1994,620(11):1879-1888
Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by 1H, 13C, and 31P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the 2JP? N? P coupling constants were determined by 13C{1H, 31P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group. 相似文献