全文获取类型
收费全文 | 1056篇 |
免费 | 42篇 |
国内免费 | 3篇 |
专业分类
化学 | 785篇 |
晶体学 | 9篇 |
力学 | 22篇 |
数学 | 134篇 |
物理学 | 151篇 |
出版年
2023年 | 9篇 |
2022年 | 14篇 |
2021年 | 28篇 |
2020年 | 18篇 |
2019年 | 15篇 |
2018年 | 16篇 |
2017年 | 19篇 |
2016年 | 38篇 |
2015年 | 34篇 |
2014年 | 32篇 |
2013年 | 58篇 |
2012年 | 65篇 |
2011年 | 63篇 |
2010年 | 46篇 |
2009年 | 30篇 |
2008年 | 60篇 |
2007年 | 60篇 |
2006年 | 67篇 |
2005年 | 55篇 |
2004年 | 27篇 |
2003年 | 33篇 |
2002年 | 26篇 |
2001年 | 12篇 |
2000年 | 11篇 |
1999年 | 14篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 12篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 14篇 |
1992年 | 12篇 |
1991年 | 10篇 |
1990年 | 15篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1986年 | 10篇 |
1985年 | 18篇 |
1984年 | 13篇 |
1983年 | 7篇 |
1982年 | 13篇 |
1981年 | 10篇 |
1980年 | 9篇 |
1979年 | 8篇 |
1978年 | 7篇 |
1977年 | 11篇 |
1976年 | 6篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1969年 | 3篇 |
排序方式: 共有1101条查询结果,搜索用时 62 毫秒
21.
Efforts to develop a quantitative understanding of molecular recognition rely on the additivity of individual intermolecular interactions, and cooperativity represents one of the major potential stumbling blocks. A chemical double-mutant cycle has been used to experimentally measure cooperativity between functional group interactions within a complex framework. The interaction between two aromatic groups varies by 0.2 +/- 0.4 kJ mol(-1) in synthetic H-bonded complexes that differ by 8-13 kJ mol(-1) in overall stability. In these systems, the free energies associated with individual intermolecular interactions can therefore be reliably treated in an additive fashion. The results suggest that alternative explanations should be considered for cooperative phenomena observed in other systems, and a rationale based on the population of partially bound states in flexible molecules is proposed to account for the enthalpic chelate effect and enthalpy-entropy compensation. 相似文献
22.
Karim Adil Gilles Dujardin Marc Leblanc Vincent Maisonneuve 《Journal of fluorine chemistry》2004,125(11):1709-1714
Tren amine cations and carbonate anions adopt a ternary symmetry while tetra amine cations are tetrahedral. The symmetry of these constitutive ions influences strongly the nature of the solids which crystallise from solutions. Large fluorinated aluminate polyanions with tetrahedral symmetry appear in the presence of tren amine, while infinite chains of AlF6 octahedra are observed with tetra amine and that noncentrosymmetric structures are frequently encountered in rare earth fluoride carbonates. 相似文献
23.
24.
25.
26.
Carrillo-Marquez T Caggiano L Jackson RF Grabowska U Rae A Tozer MJ 《Organic & biomolecular chemistry》2005,3(22):4117-4123
Two distinct routes to beta-cycloalkylalanine derivatives have been developed. The first route employs the reaction of the iodoalanine-derived zinc-copper reagent 2 with cycloalk-1-en-3-yl phosphates, and the second uses the palladium-catalysed coupling of the iodoalanine-derived zinc reagent 1 with cycloalkenyl triflates; in each case, catalytic hydrogenation of the unsaturated product leads to the protected beta-cycloalkylalanine. The latter route allows access to a range of cycloalkyl derivatives, with ring sizes of 5-8. beta-(1-Methyl-1-cyclohexyl)alanine may be prepared using reaction of the zinc-copper reagent 2 with 3-methyl-2-cyclohexenyl chloride, followed by hydrogenation. The corresponding cyclopentyl derivative may be prepared by reaction of the same zinc-copper reagent 2 with diethyl geranylphosphate, followed by ring-closing metathesis and hydrogenation. 相似文献
27.
Chemosensors for the marine toxin saxitoxin 总被引:1,自引:0,他引:1
Gawley RE Pinet S Cardona CM Datta PK Ren T Guida WC Nydick J Leblanc RM 《Journal of the American Chemical Society》2002,124(45):13448-13453
Eleven anthracylmethyl crown ethers have been synthesized and evaluated as fluorescence sensors for the marine toxin saxitoxin. Fluorescence enhancement data are consistent with a 1:1 binding complex for all crowns. The binding constants are in the range of 10(4) M(-)(1) in ammonium phosphate buffer (pH 7.1) in 80% ethanol solvent. Selectivity for sensing saxitoxin versus several organic analytes has been demonstrated for the first time. Possible modes of binding are presented, and relevance to saxitoxin monitoring programs are discussed. 相似文献
28.
D. Frackowiak L. G. Erokhina G. Picard R. M. Leblanc 《Photochemistry and photobiology》1987,46(2):277-285
Polarized absorption, photoacoustic, fluorescence excitation and fluorescence emission spectra of phycobilisomes were measured when embedded in polyvinyl alcohol films. The phycobilisomes were isolated from the following organisms: Anabaena cylindrica, Nostoc punctiforma and Synechococcus elongatus. The ratio of photoacoustic spectra to absorption was taken as a measure of thermal dissipation of excitation energy. The isotropic samples and those oriented by the film stretching were investigated. The stretching of the sample strongly influences the efficiency of excitation energy transfer occurring among biliproteins in phycobilisomes, as is seen from the dramatic changes in the fluorescence and thermal dissipation spectra. The effect of stretching the film depends on the shape of phycobilisomes and on the strength of interactions between biliproteins in phycobilisomes. 相似文献
29.
Energy selected trimethyl phosphine ions were prepared by threshold photoelectron photoion coincidence (TPEPICO) spectroscopy. This ion dissociates via H, CH(3), and CH(4) loss, the latter two involving hydrogen transfer steps. The ion time-of-flight distribution and the breakdown diagram are analyzed in terms of the statistical RRKM theory, which includes tunneling. Ab initio and DFT calculations provide the vibrational frequencies required for the RRKM modeling. CH(3) loss could produce both the P(CH(3))(2)(+) by a simple bond dissociation step, and the more stable HP(CH(2))CH(3)(+) ion by a hydrogen transfer step. Quantum chemical calculations are extensively used to uncover the reaction scheme, and they strongly suggest that the latter product is exclusively formed via an isomerization step in the energy range of the experiment. The data analysis, which includes modeling with the trimethyl phosphine thermal energy distribution, provides accurate onset energies for both H (E(0K) = 1024.1 +/- 3.5 kJ/mol) and CH(3) (E(0K) = 1024.8 +/- 3.5 kJ/mol) loss reactions. From this analysis, we conclude that the Delta(f)H(298K) degrees [HP(CH(2))(CH(3))(+)] = 783 +/- 8 kJ/mol and Delta(f)H(298K) degrees [P(CH(2))(CH(3))(2)(+)] = 711 +/- 8 kJ/mol. 相似文献
30.
Roberto Martínez Manuel F. Rubio Ramírez G. Guillermo Tomas Camacho Linzaga E. Irma Claudia Mancera 《Journal of heterocyclic chemistry》1995,32(3):827-830
Oximation of ortho-substituted phenylbenz[a]acridinones using hydroxylamine hydrochloride, sodium hydroxide and ethanol as the solvent gave always the benzoquinacridine N-oxide 2 . Oximation of para-substituted phenylbenz[a]acridinones, however, gave only the corresponding oximes. The structure of all products was corroborated by ir, 1H and 13C-nmr and mass spectral data. Theoretical calculations support the experimental findings. 相似文献