全文获取类型
收费全文 | 29121篇 |
免费 | 4678篇 |
国内免费 | 4808篇 |
专业分类
化学 | 22327篇 |
晶体学 | 483篇 |
力学 | 1471篇 |
综合类 | 414篇 |
数学 | 3276篇 |
物理学 | 10636篇 |
出版年
2024年 | 46篇 |
2023年 | 377篇 |
2022年 | 584篇 |
2021年 | 836篇 |
2020年 | 1035篇 |
2019年 | 1058篇 |
2018年 | 924篇 |
2017年 | 848篇 |
2016年 | 1320篇 |
2015年 | 1369篇 |
2014年 | 1626篇 |
2013年 | 2210篇 |
2012年 | 2652篇 |
2011年 | 2690篇 |
2010年 | 2023篇 |
2009年 | 1960篇 |
2008年 | 2321篇 |
2007年 | 2067篇 |
2006年 | 1817篇 |
2005年 | 1526篇 |
2004年 | 1337篇 |
2003年 | 1152篇 |
2002年 | 1255篇 |
2001年 | 1019篇 |
2000年 | 799篇 |
1999年 | 640篇 |
1998年 | 417篇 |
1997年 | 394篇 |
1996年 | 346篇 |
1995年 | 292篇 |
1994年 | 274篇 |
1993年 | 236篇 |
1992年 | 226篇 |
1991年 | 169篇 |
1990年 | 160篇 |
1989年 | 124篇 |
1988年 | 78篇 |
1987年 | 69篇 |
1986年 | 61篇 |
1985年 | 61篇 |
1984年 | 45篇 |
1983年 | 31篇 |
1982年 | 23篇 |
1981年 | 22篇 |
1980年 | 10篇 |
1978年 | 12篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1974年 | 9篇 |
1973年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
991.
Seven chiral thiazolidines bound rhodium complexes were synthesized and their catalytic asymmetric hydrosilation properties were investigated It was found through investigation that the configuration of newly formed chiral centre C2 of substituted chiral thiazolidines prepared from L-cysteine or its esters has no effect on the final results of catalytic asymmetric hydrosilation.The direct reason for causing this phenomenon is reported by the present quantitative results for the first time:the rapid racemation of chiral center C2 of chiral thiazolidine ligands takes place under the catalysis of rhodium(Ⅰ) complex [Rh(COD)CI]2 相似文献
992.
N,N''''-硝基苯酰基取代苯酰氨基硫脲的合成与生物活性 总被引:6,自引:0,他引:6
酰氨基硫脲类化合物不仅具有广谱抗菌性能 ,还具有极好的杀虫和植物生长调节活性 [1~ 3] ,因而引起许多国内外学者对硫脲类化合物的合成及其化学结构与生物活性关系方面的研究 [4~ 8] .为了进一步研究不同的取代基团对此类化合物生物活性的影响 ,作者用硝基苯酰基异硫氰酸酯与芳基酰肼加成制得相应的 N ,N -硝基苯酰基取代苯酰氨基硫脲 ( ) ,并初步测定了它们抑制大肠杆菌和枯草杆菌生长的生物活性 .这些化合物尚未见文献报道 .Ar— COCl KSCN Ar—CONCS a~ cAr CONHNH2 ( 1 ~ 7) Ar—CONHC( S) NHNHCOAr Ar:a.o-N… 相似文献
993.
配体的空间构型及疏水性对钌(Ⅱ)多吡啶配合物与DNA作用的影响 总被引:19,自引:2,他引:19
合成了4-氰基苯基咪唑并[5,6-f]邻菲咯啉(CYIP)和2-羧基苯基咪唑并[5, 6-f]邻菲咯啉(COIP)两种新配体及它们的钌混配配合物[Ru(bpy)2CYIP](ClO4)2 ·H2O(Rul)(bpy=2,2′-联吡啶),[Ru(phen)2CYIP](ClO4)2·H2O(Ru2) (phen=1,10-邻菲咯啉),[Ru(bpy)2COIP](ClO4)2·3H2O(Ru3)和[Ru(phen)2COIP] (ClO4)2·H2O(Ru4),并用红外光谱、紫外光谱、核磁和质谱对它们进行了表征。 通过循环伏安法研究了这些配合物的电化学性质。采用电子吸收光谱、稳态荧光、 圆二色谱和粘度测定研究了配合物与小牛胸腺DNA的相互作用。结果表明配合物 Rul和Ru2通过CYIP配体以插入的方式与DNA结合,而配合物Ru3和Ru4则通过COIP配 体以部分插入的方式与DNA结合。 相似文献
994.
Theoretical study of the unimolecular decomposition mechanisms of energetic TNAD and TNAZ explosives
Min‐Hsien Liu Cheng Chen Yaw‐Shun Hong 《International journal of quantum chemistry》2005,102(4):398-408
Calculation methods based on hybrid Density Functional Theory (DFT) with the basis sets of the B3LYP/6‐31+G(d)//B3LYP/4‐31G(d) method and the differential overlap (INDO) program were used to derive reasonable decomposition mechanisms of 1,4,5,8‐tetranitro‐1,4,5,8‐tetraazadecalin (TNAD) and 1,3,3‐trinitroazetidine (TNAZ) explosives. All possible decomposition species and transition states, including intermediates and products, were identified and their corresponding enthalpy of formation and Gibbs free energy of formation were obtained using polyparametric modification equations. INDO bond energy calculation results reveal the weakest bonding site for reference and determine where cleavage can occur easily. This work is concerned mainly with eliminating HONO (cis or trans form). The activation energy for trans‐form HONO elimination is lower than that of cis‐form HONO elimination in the initial steps of both TNAD and TNAZ decomposition, being 18.5 kJ/mol and 33.3 kJ/mol, respectively. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
995.
996.
997.
以苯重氮硼氟酸盐与亚铁盐在微量铜离子存在时能引发丙烯腈聚合,聚合速率服从:R∝[φN_2~+]~(1/2)[Fe~(++)]~(1/4)[Cu~(++)]~(1/4),氧化还原引发历程为: Fe~(++)+Cu~(++) Fe~(+++)+Cu~+ φN_2~++Cu~+→φ·+N_2+Cu~(++) φ·+M→φM·→φMM·…该历程符合上述动力学关系。但使用对硝基苯重氮硼氟酸盐时,微量铜离子对聚合反应速率影响不大,与亚铁盐浓度在一定范围呈R∝[Fe~(++)]~(1/2)的关系,因此例的引发历程为: φN_2~++Fe~(++)→φ·+N_2+Fe~(+++) φ·+M→φM·→φMM·…苯环上推电子取代基降低了重氮基的氧化势,如对位取代甲氧基、甲基或没有取代基都不能用纯亚铁盐引发丙烯腈聚合,需有微量铜盐存在才能聚合。而拉电子取代基如对位取代硝基、羧基可用纯亚铁盐引发聚合。 相似文献
998.
999.
Zhen‐Yu Li Ping Chen Hong‐Gui Xu Shu‐Ying Peng Yi‐Ming Yang Zhong‐Zhen Zhao Yue‐Wei Guo 《Helvetica chimica acta》2007,90(7):1353-1359
Five new polycyclic Daphniphyllum alkaloids, macropodumines F ( 1 ) and G ( 2 ), 17‐oxoyuzurimine ( 3 ), and macropodumines H ( 4 ) and I ( 5 ), were isolated from the leaves of D. macropodum Miq ., collected in Sichuan Province, China. The structures and relative configurations of the new compounds – as well as of four known, related alkaloids – were elucidated on the basis of in‐depth spectroscopic and mass‐spectrometric analyses, by chemical derivatization, and by comparison of spectroscopic data with those of known compounds. 相似文献
1000.
Gao H Petzold CJ Leavell MD Leary JA 《Journal of the American Society for Mass Spectrometry》2003,14(8):916-924
A rapid and accurate method of quantifying positional isomeric mixtures of phosphorylated hexose and N-acetylhexosamine monosacchrides by using gas-phase ion/molecule reactions coupled with FT-ICR mass spectrometry is described. Trimethyl borate, the reagent gas, reacts readily with the singly charged negative ions of phosphorylated monosaccharides to form two stable product ions corresponding to the loss of one or two neutral molecules of methanol from the original adduct. Product distribution in the ion/molecule reaction spectra differs significantly for isomers phosphorylated in either the 1- or the 6-position. As a result, the percents of total ion current of these product ions for a mixture of the two isomers vary with its composition. In order to determine the percentage of each isomer in an unknown mixture, a multicomponent quantification method is utilized in which the percents of total ion current of the two product ions for each pure monosaccharide phosphate and the mixture are used in a two-equation, two-unknown system. The applicability of this method is demonstrated by successfully quantifying mock mixtures of four different isomeric pairs: Glucose-1-phosphate and glucose-6-phosphate; mannose-1-phosphate and mannose-6-phosphate; galactose-1-phosphate and galactose-6-phosphate; N-acetylglucosamine-1-phosphate and N-acetylglucosamine-6-phosphate. The effects of mixture concentrations and ion/molecule reaction conditions on the quantification are also discussed. Our results demonstrate that this assay is a fast, sensitive, and robust method to quantify isomeric mixtures of phosphorylated monosaccharides. 相似文献