全文获取类型
收费全文 | 4038篇 |
免费 | 96篇 |
国内免费 | 16篇 |
专业分类
化学 | 3206篇 |
晶体学 | 37篇 |
力学 | 54篇 |
数学 | 397篇 |
物理学 | 456篇 |
出版年
2023年 | 20篇 |
2022年 | 93篇 |
2021年 | 96篇 |
2020年 | 60篇 |
2019年 | 59篇 |
2018年 | 46篇 |
2017年 | 48篇 |
2016年 | 114篇 |
2015年 | 96篇 |
2014年 | 125篇 |
2013年 | 218篇 |
2012年 | 221篇 |
2011年 | 254篇 |
2010年 | 146篇 |
2009年 | 152篇 |
2008年 | 267篇 |
2007年 | 213篇 |
2006年 | 229篇 |
2005年 | 211篇 |
2004年 | 169篇 |
2003年 | 144篇 |
2002年 | 136篇 |
2001年 | 63篇 |
2000年 | 43篇 |
1999年 | 53篇 |
1998年 | 40篇 |
1997年 | 44篇 |
1996年 | 49篇 |
1995年 | 46篇 |
1994年 | 41篇 |
1993年 | 34篇 |
1992年 | 33篇 |
1991年 | 30篇 |
1990年 | 16篇 |
1989年 | 25篇 |
1988年 | 22篇 |
1987年 | 18篇 |
1985年 | 27篇 |
1984年 | 23篇 |
1983年 | 23篇 |
1982年 | 33篇 |
1981年 | 32篇 |
1980年 | 32篇 |
1979年 | 22篇 |
1978年 | 19篇 |
1977年 | 17篇 |
1975年 | 16篇 |
1956年 | 19篇 |
1955年 | 39篇 |
1954年 | 57篇 |
排序方式: 共有4150条查询结果,搜索用时 0 毫秒
171.
172.
Ashton PR Balzani V Clemente-León M Colonna B Credi A Jayaraman N Raymo FM Stoddart JF Venturi M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(3):673-684
Aliphatic amines, incorporating one or three (branched) acylated beta-D-glucopyranosyl residues, were coupled with the acid chloride of ferrocenecarboxylic acid and with the diacid chloride of 1,1'-ferrocenedicarboxylic acid to afford four dendrimer-type, carbohydrate-coated ferrocene derivatives in good yields (54-92%). Deprotection of the peracylated beta-D-glucopyranosyl residues was achieved quantitatively by using Zemplén conditions, affording four water-soluble ferrocene derivatives. When only one of the two cyclopentadienyl rings of the ferrocene unit is substituted, strong complexes are formed with beta-cyclodextrin in H2O, as demonstrated by liquid secondary ion mass spectrometry (LSIMS), 1H NMR spectroscopy, electrochemical measurements, and circular dichroism spectroscopy. Molecular dynamics calculations showed that the unsubstituted cyclopentadienyl ring is inserted through the cavity of the toroidal host in these complexes. The electrochemical behavior of the protected and deprotected ferrocene-containing dendrimers was investigated in acetonitrile and water, respectively. The diffusion coefficient decreases with increasing molecular weight of the compound. The potential for oxidation of the ferrocene core, the rate constant of heterogeneous electron transfer, and the rate constant for the energy-transfer reaction with the luminescent excited state of the [Ru(bpy)3]2+ complex (bpy = 2,2'-bipyridine) are strongly affected by the number (one or two) of substituents and by the number (one or three) of carbohydrate branches present in the substituents. These effects are assigned to shielding of the ferrocene core by the dendritic branches. Electrochemical evidence for the existence of different conformers for one of the dendrimers in aqueous solution was obtained. 相似文献
173.
Zbigniew GrobelnyAndrzej Stolarzewicz Barbara Morejko-Bu?Adalbert Maercker 《Journal of organometallic chemistry》2002,660(1):6-13
The linear ether bond was exclusively cleaved in benzyl glycidyl ether and triphenylmethyl glycidyl ether under the influence of K−, K+(15-crown-5)2 (1), whereas the strongly strained three-membered oxacyclic ring remained undisturbed. Potassium glycidoxide and benzylpotassium were found as the primary reaction products of benzyl glycidyl ether with 1. Subsequently, benzylpotassium reacted with benzyl glycidyl ether giving the next potassium glycidoxide molecule and bibenzyl. Benzyl phenyl ether was used as a model compound to explain the mechanism of bibenzyl formation. The reaction of triphenylmethyl glycidyl ether with 1 resulted in potassium glycidoxide and stable triphenylmethylpotassium. After treating with a quenching agent a new glycidyl ether or glycidyl ester was obtained from potassium glycidoxide. These results were found when the reaction occurred at the excess of glycidyl ether. In another case, i.e. at the excess of 1 further reactions took place with the participation of potassium anions and various new compounds were observed in the reaction mixture after benzylation or methylation. Thus, the method of substrates delivery influences the course of studied processes in a decisive way. 相似文献
174.
175.
The lipophilicity of some antiarrhythmic and antihypertensive active 1-[2-hydroxy- or 1-[2-acetoxy-3-(4-aryl-1-piperazinyl)propyl]pyrrolidin-2-one derivatives (1-12) has been investigated. Their lipophilicity (R(MO) and log k') was determined by reversed-phase thin-layer chromatography and reversed-phase high-performance liquid chromatography with mixtures of acetonitrile and Tris buffer as mobile phases. The partition coefficients of compounds 1-12 (log P(ScilogP)) were also calculated with the ScilogP program. Comparison of R(MO), log k' and calculated log D(7.0 ScilogP) values enabled calculation of clog D(7.0 TLC) and clog D(7.0 HPLC) values. Preliminary quantitative structure-activity relationship studies indicated that for active compounds there is a dependence between affinity for alpha(2)-adrenoceptors and their clog D(7.0 HPLC) values. 相似文献
176.
A prototype calix[4]arene-based receptor for carbohydrate recognition containing peptide and phosphate binding groups 总被引:2,自引:0,他引:2
Segura M Bricoli B Casnati A Muñoz EM Sansone F Ungaro R Vicent C 《The Journal of organic chemistry》2003,68(16):6296-6303
A novel class of macrobicyclic receptors for carbohydrate recognition based on upper rim, peptide-bridged calix[4]arenes has been designed and synthesized. Receptor 12, in which a charged phosphate group cooperates with peptide hydrogen-bonding donor and acceptor groups in the binding process, is the most efficient and selective in the complexation of simple carbohydrate derivatives. The selectivity observed is toward beta-glucoside 13a, which is better bound (DeltaG degrees = 19.6 kJ mol(-)(1)) compared to the corresponding alpha anomer 13b (DeltaG degrees = 17.0 kJ mol(-)(1)) and to the beta-galactoside 13c (DeltaG degrees = 17.7 kJ mol(-)(1)) in CDCl(3). A substantial drop in the stability constant is observed by esterification of the phosphate group in the host 12 or by alkylation of the OH groups in the 2 and 3 positions in the beta-glucoside and beta-galactoside derivatives. On the basis of a careful analysis of the (1)H NMR data available, a binding mode of the beta-octylglucoside 13a to receptor 12 is proposed. 相似文献
177.
Sobolevsky TG Chernetsova ES Revelsky AI Revelsky IA Starostin AB Miller B Oriedo V 《European journal of mass spectrometry (Chichester, England)》2003,9(5):487-495
Mass spectra of trialkylsilyl derivatives of fatty acids, dicarboxylic acids, hydroxyacids, oxoacids, sugars, amino acids and alcohols were obtained. Amino acids were analyzed as tert-butyldimethylsilyl derivatives; all other model compounds were analyzed as trimethylsilyl derivatives. Reproducibility of the electron ionization (EI) mass spectra for the derivatives obtained was discussed. It was shown that, for many investigated derivatives, composition of the respective mass spectra depended greatly on ion source contamination. The trimethylsilylated alpha-tocopherol mass spectrum composition was most significantly influenced by ion source contamination. This compound can be used to test ion source contamination. 相似文献
178.
179.
Wieslaw Wojnowski Barbara Becker Karl Peters Eva-Maria Peters Hans Georg von Schnering 《无机化学与普通化学杂志》1987,553(10):287-292
Structure of Pentaphenyldisilane For the first time Pentaphenyldisilane was prepared by Gilman and Goodman. It is produced by the reaction of Ph3SiLi with Ph2ClSiH. The crystal structure presents an ideally staggered conformation. The distance d(Si? Si) = 235.7 pm corresponds to a normal single bond length. This emphasizes the complete relief of the central Si? Si bond by the insertion of only one hydrogen atom. 相似文献
180.