全文获取类型
收费全文 | 9003篇 |
免费 | 413篇 |
国内免费 | 22篇 |
专业分类
化学 | 7187篇 |
晶体学 | 58篇 |
力学 | 139篇 |
数学 | 896篇 |
物理学 | 1158篇 |
出版年
2023年 | 75篇 |
2022年 | 159篇 |
2021年 | 273篇 |
2020年 | 216篇 |
2019年 | 199篇 |
2018年 | 153篇 |
2017年 | 150篇 |
2016年 | 321篇 |
2015年 | 284篇 |
2014年 | 299篇 |
2013年 | 565篇 |
2012年 | 695篇 |
2011年 | 770篇 |
2010年 | 482篇 |
2009年 | 415篇 |
2008年 | 590篇 |
2007年 | 607篇 |
2006年 | 501篇 |
2005年 | 494篇 |
2004年 | 394篇 |
2003年 | 308篇 |
2002年 | 287篇 |
2001年 | 150篇 |
2000年 | 139篇 |
1999年 | 107篇 |
1998年 | 72篇 |
1997年 | 59篇 |
1996年 | 71篇 |
1995年 | 56篇 |
1994年 | 53篇 |
1993年 | 53篇 |
1992年 | 47篇 |
1991年 | 38篇 |
1990年 | 34篇 |
1989年 | 28篇 |
1988年 | 32篇 |
1987年 | 25篇 |
1986年 | 26篇 |
1985年 | 37篇 |
1984年 | 35篇 |
1983年 | 28篇 |
1982年 | 18篇 |
1981年 | 18篇 |
1980年 | 16篇 |
1979年 | 11篇 |
1978年 | 10篇 |
1977年 | 11篇 |
1975年 | 7篇 |
1973年 | 4篇 |
1970年 | 4篇 |
排序方式: 共有9438条查询结果,搜索用时 31 毫秒
51.
Ana Bellomo 《Tetrahedron letters》2007,48(17):3047-3051
Diasterodivergent episulfides were chemoenzymatically derived from bromobenzene by sequential toluene dioxygenase dihydroxylation, followed by chemical epoxidation and thiolysis. The epoxide ring-opening by thiocyanate ion under literature conditions rendered the corresponding hydroxy thiocyanates and not the thiiranes as usually observed. Ring closing under carefully optimized conditions allowed the preparation of optically pure thiiranes that are key precursors for the preparation of thioconduritols and pseudodisaccharides. 相似文献
52.
Asymmetry and magnetism in bis(oximato)-bridged heterobimetallic compounds: a computational approach
Cano J Rodríguez-Fortea A Alemany P Alvarez S Ruiz E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(2):327-333
A density functional study of exchange coupling was carried out for a series of heterobinuclear oximato-bridged transition metal complexes. Model calculations were used to examine the influence of the electronic configuration of the metal atoms on the coupling constants. This analysis was complemented by a study of the variation of the coupling constant with the most usual structural distortions within this family of compounds. The influence of the nature of the terminal ligands as well as that of the symmetry on the bridge were also investigated. 相似文献
53.
Ana M. Piloto 《Tetrahedron》2006,62(51):11955-11962
The properties of three oxobenzo[f]benzopyrans as new fluorogenic photolabile protecting groups for the carboxylic function of amino acids were studied. Fluorescent amino acid conjugates were efficiently prepared and characterised. Photodeprotection of these compounds was carried out by irradiation at 300, 350 and 419 nm, the most suitable wavelength being 350 nm, on account of short irradiation times and good deprotection yields. 相似文献
54.
Pilar Alonso Isabel de Frutos Teresa Gutiérrez Antonio Doadrio López 《Transition Metal Chemistry》1987,12(2):133-136
Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO2(LL)2], [Mo2O5(LL)2], [Mo2O4(LL)2], [MoOCl(LL)2], [MoCl2(LL)] and [MoO(OH)(LL)2)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring. 相似文献
55.
R. Zitzumbo F.J. Ornelas-Rodriguez S. Alonso F. Avalos A. Zizumbo 《European Polymer Journal》2006,42(6):1298-1304
The elastic deformation-recovery and mechanical properties of semi-crystalline polymers (HDPE, LDPE and their blends) were investigated. An optoelectronic technique based on a laser beam was used to analyze the behavior of the samples under radial stress. The laser technology showed that the recovery process develops in two stages. The first one is governed by the elastic component and the second and slower one is controlled by the inelastic component of the material. At low deformation, the overall recovery is attributed to the development of structural micro-domains generated when shearing the amorphous segments of the polymer. The radial Young modulus was also determined and compared to unidirectional measurements. At low deformation both techniques provide very similar values; nevertheless, the radial Young modulus departs significantly from the unidirectional one when increasing the number of cycles of deformation-recovery. 相似文献
56.
F. Garcias J. A. Alonso M. Barranco J. M. López A. Mañanes J. Németh 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1994,31(4):275-277
The competition experimentally observed between asymmetric fission and neutral monomer evaporation as dissociation channels of excited doubly charged sodium clusters has been investigated by means of an axially symmetric, fully selfconsistent Kohn-Sham method. Ellipsoidal equilibrium configurations for parent and daughter clusters have been considered using a deformed jellium model.This paper was originally submitted in connection with the 2nd. Int. Conference on Atomic and Nuclear Clusters held in Santorini from 28. June–2. July 1993 and is published here as a regular article after an independent refereeing procedure according to the standards of Z. Phys. D 相似文献
57.
Margarita Valero Silvia M. B. Costa José R. Ascenso M. Mercedes Velázquez Licesio J. Rodríguez 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(4):663-677
The inclusion of the anti-inflammatory drug, Nabumetone, in -, - and hydroxypropyl--cyclodextrin (CDs) is studied using UV-VIS absorption and steady-state fluorescence emission. Binding constants and thermodynamic parameters of complex formation are determined by spectrofluorimetry. The inclusion phenomena of Nabumetone with the three cyclodextrins is compared with that of the well known similar anti-inflammatory drug Naproxen. In the case of Nabumetone pronounced differences are observed in the complexation process with each cyclodextrin whereas the respective Naproxen complexes are nearly identical. 1H-NMR experiments show that the inclusion process in Nabumetone can occur either through the substituents in the -2 (butanone) or -6 (methoxy) positions in the naphthalene ring. 相似文献
58.
Optimization of a microwave-assisted extraction method for the analysis of polychlorinated biphenyls in ash samples 总被引:2,自引:0,他引:2
Ramil Criado M Rodríguez Pereiro I Cela Torrijos R 《Journal of chromatography. A》2003,985(1-2):137-145
An alternative method for the extraction of polychlorinated biphenyls (PCBs) in ash samples, which is less time and solvent consuming than Soxhlet extraction, is presented. A study was carried out to evaluate the possibilities of microwave-assisted extraction (MAE) to determine exactly which parameters affect the efficiency of the process, since direct extrapolation of extraction conditions for PCBs in other solid matrices, failed when applied to coplanar congeners in ash samples. Influence of the organic solvent on the yield of the extraction was first evaluated using two ash samples with different percentages of carbon. Once the extraction solvent was fixed, the effects of solvent volume, extraction temperature and extraction time were investigated using an experimental design. It was found that the volume of organic solvent played a more important role in the extraction efficiency than the other factors. In the optimal conditions microwave extractions were performed at 110 degrees C. for 10 min and using 30 ml of toluene. Recoveries higher than 80% were obtained for all the highly chlorinated congeners. including coplanar species, in a spiked ash sample containing a relatively high concentration of carbon. The proposed method was also applied to the determination of PCBs in a reference material of urban dust. Recoveries were similar to those obtained for spiked ash samples. 相似文献
59.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7161-7169
Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model. 相似文献
60.
Ruiz E Rodríguez-Fortea A Cano J Alvarez S Alemany P 《Journal of computational chemistry》2003,24(8):982-989
The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data. 相似文献