全文获取类型
收费全文 | 13045篇 |
免费 | 2647篇 |
国内免费 | 439篇 |
专业分类
化学 | 4172篇 |
晶体学 | 26篇 |
力学 | 701篇 |
综合类 | 105篇 |
数学 | 408篇 |
物理学 | 1721篇 |
无线电 | 8998篇 |
出版年
2024年 | 57篇 |
2023年 | 210篇 |
2022年 | 334篇 |
2021年 | 366篇 |
2020年 | 484篇 |
2019年 | 435篇 |
2018年 | 426篇 |
2017年 | 385篇 |
2016年 | 685篇 |
2015年 | 776篇 |
2014年 | 973篇 |
2013年 | 1063篇 |
2012年 | 1181篇 |
2011年 | 1041篇 |
2010年 | 740篇 |
2009年 | 705篇 |
2008年 | 729篇 |
2007年 | 834篇 |
2006年 | 783篇 |
2005年 | 697篇 |
2004年 | 579篇 |
2003年 | 517篇 |
2002年 | 354篇 |
2001年 | 361篇 |
2000年 | 286篇 |
1999年 | 191篇 |
1998年 | 186篇 |
1997年 | 123篇 |
1996年 | 135篇 |
1995年 | 94篇 |
1994年 | 86篇 |
1993年 | 71篇 |
1992年 | 41篇 |
1991年 | 45篇 |
1990年 | 30篇 |
1989年 | 26篇 |
1988年 | 25篇 |
1987年 | 17篇 |
1986年 | 10篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1974年 | 2篇 |
1970年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
901.
Hitzbleck J O'Brien AY Forsyth CM Deacon GB Ruhlandt-Senge K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(13):3315-3323
Two series of heavy alkaline earth metal pyrazolates, [M(Ph(2)pz)(2)(thf)(4)] 1 a-c (Ph(2)pz=3,5-diphenylpyrazolate, M=Ca, Sr, Ba; THF=tetrahydrofuran) and [M(Ph(2)pz)(2)(dme)(n)] (M=Ca, 2 a, Sr, 2 b, n=2; M=Ba, 2 c, n=3; DME=1,2-dimethoxyethane) have been prepared by redox transmetallation/ligand exchange utilizing Hg(C(6)F(5))(2). Compounds 1 a and 2 b were also obtained by redox transmetallation with Tl(Ph(2)pz). Alternatively, direct reaction of the alkaline earth metals with 3,5-diphenylpyrazole at elevated temperatures under solventless conditions yielded compounds 1 a-c and 2 a-c upon extraction with THF or DME. By contrast, [M(Me(2)pz)(2)(Me(2)pzH)(4)] 3 a-c (M=Ca, Sr, Ba; Me(2)pzH=3,5-dimethylpyrazole) were prepared by protolysis of [M[N(SiMe(3))(2)](2)(thf)(2)] (M=Ca, Sr, Ba) with Me(2)pzH in THF and by direct metallation with Me(2)pzH in liquid NH(3)/THF. Compounds 1 a-c and 2 a-c display eta(2)-bonded pyrazolate ligands, while 3 a,b exhibit eta(1)-coordination. Complexes 1 a-c have transoid Ph(2)pz ligands and an overall coordination number of eight with a switch from mutually coplanar Ph(2)pz ligands in 1 a,b to perpendicular in 1 c. In eight coordinate 2 a,b the pyrazolate ligands are cisoid, whilst 2 c has an additional DME ligand and a metal coordination number of ten. By contrast, 3 a,b have octahedral geometry with four eta(1)-Me(2)pzH donors, which are hydrogen-bonded to the uncoordinated nitrogen atoms of the two trans Me(2)pz ligands. The application of synthetic routes initially developed for the preparation of lanthanoid pyrazolates provides detailed insight into the similarities and differences between the two groups of metals and structures of their complexes. 相似文献
902.
Panchaud P Chabaud L Landais Y Ollivier C Renaud P Zigmantas S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3606-3614
A novel reaction for the introduction of an azide moiety by means of a mild radical process is currently under development. Sulfonyl azides are suitable azidating agents for nucleophilic radicals, such as secondary and tertiary alkyl radicals. More electrophilic radicals, such as enolate radicals, do not react with sulfonyl azides. This feature allowed the development of efficient intra- and intermolecular carboazidations of olefins. Due to the versatility of the azido group, this reaction has an important synthetic potential, as already demonstrated by the preparation of the core of several alkaloids, particularly those containing an amino-substituted quaternary carbon center, such as FR901483. 相似文献
903.
Stoikov I. I. Gafiullina L. I. Ibragimova D. Sh. Antipin I. S. Konovalov A. I. 《Russian Chemical Bulletin》2004,53(6):1172-1180
New calix[4]arenes, di- and tetrasubstituted at the lower rim, with different functional groups were synthesized. They were studied as carriers of a series of dicarboxylic and -hydroxycarboxylic acids through a liquid impregnated membrane. The calix[4]arenes under study are capable of molecular recognition of oxalic acid in the series of structurally similar dicarboxylic and -hydroxycarboxylic acids. The regularities found make it possible to change purposefully the receptor ability of 1,3-disubstituted calix[4]arenes by variation of the nature of substituents. 相似文献
904.
Vadim G. Kessler 《Journal of Sol-Gel Science and Technology》2004,32(1-3):11-17
The article describes the principles of the Single Source Precursor approach to inorganic materials and introduces the Geometrical Molecular Structure Design Concept (MSDC) based on the choice of a proper molecular structure type for the desired precursor and completing it with ligands providing both the necessary number of donor atoms and the sterical protection of the chosen core. Application of MSDC is illustrated with examples taken from development of new approaches in the synthesis of oxide and sulfide catalysts and ferroelectric oxide materials. 相似文献
905.
906.
907.
Neonatal exposure to synthetic estrogen endocrine disruptors or estrogen-receptor inhibitors induces developmental abnormalities in the male reproductive system. To investigate whether neonatal exposure affects spermatogenesis in juvenile and pubertal testis, Sprague-Dawley rat pups were given synthetic estrogen endocrine disruptors or estrogen-receptor inhibitors by a single injection on the day of birth at concentrations ranging between 2 to 40 mm, and sacrificed on day 21 (juvenile), 35 (prepuberty) or 50 (puberty). The testes were weighed and examined histologically at each stage. Further, the metabolites of steroidogenesis were analyzed using normal-phase high performance liquid chromatography. Neonatal exposure significantly reduced testis weights and steroidogenesis to one- fifth to one-half of that of the juvenile control, and further suppressed irreversible steroidogenesis and spermatogenesis during puberty. 相似文献
908.
909.
A series of 12‐ to 22‐membered macrocycles, with druglike functionality and properties, have been generated by using a simple and efficient copper‐catalyzed azide–acetylene cycloaddition reaction, conducted in flow in high‐temperature copper tubing, under environmentally friendly conditions. The triazole‐containing macrocycles have been generated in up to 90 % yield in a 5 min reaction, without resorting to the high‐dilution conditions typical of macrocyclization reactions. This approach represents a very efficient method for constructing this important class of molecules, in terms of yield, concentration, and environmental considerations. 相似文献
910.
Minjuan Xu Dr. Torsten Bruhn Dr. Barbara Hertlein Reto Brun Prof. Dr. August Stich Dr. Jun Wu Dr. Gerhard Bringmann Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(14):4206-4216
Five novel dimeric naphthylisoquinoline alkaloids, shuangancistrotectorines A ( 3 a ), B ( 3 b ), C ( 4 ), D ( 5 a ), and E ( 5 b ), have been isolated from the twigs of the Chinese plant Ancistrocladus tectorius. Their absolute stereostructures were determined by spectroscopic and chiroptical methods in combination with quantum chemical CD calculations. In contrast to all other known dimeric naphthylisoquinoline alkaloids, in which the central binaphthalene axis is 6′,6′′‐coupled and thus not rotationally hindered, the dimers described here are linked via the sterically more hindered 3′,3′′‐ or 1′,1′′‐positions of the naphthalene units. They are thus the first such dimers—and even the very first natural products at all—that have three consecutive stereogenic axes. Hence, including the stereogenic centers, they have up to seven stereogenic units in total. Some of the compounds, in particular shuangancistrotectorines A, B, and D ( 3 a , 3 b , and 5 a ) exhibit very good, and specific, antiplasmodial activities. 相似文献