全文获取类型
收费全文 | 4949篇 |
免费 | 224篇 |
国内免费 | 32篇 |
专业分类
化学 | 3544篇 |
晶体学 | 22篇 |
力学 | 113篇 |
数学 | 701篇 |
物理学 | 825篇 |
出版年
2023年 | 36篇 |
2022年 | 83篇 |
2021年 | 111篇 |
2020年 | 104篇 |
2019年 | 102篇 |
2018年 | 66篇 |
2017年 | 57篇 |
2016年 | 158篇 |
2015年 | 136篇 |
2014年 | 160篇 |
2013年 | 312篇 |
2012年 | 347篇 |
2011年 | 370篇 |
2010年 | 237篇 |
2009年 | 239篇 |
2008年 | 369篇 |
2007年 | 332篇 |
2006年 | 272篇 |
2005年 | 293篇 |
2004年 | 238篇 |
2003年 | 175篇 |
2002年 | 179篇 |
2001年 | 75篇 |
2000年 | 71篇 |
1999年 | 46篇 |
1998年 | 43篇 |
1997年 | 46篇 |
1996年 | 47篇 |
1995年 | 46篇 |
1994年 | 39篇 |
1993年 | 27篇 |
1992年 | 31篇 |
1991年 | 33篇 |
1990年 | 43篇 |
1989年 | 26篇 |
1988年 | 29篇 |
1987年 | 20篇 |
1986年 | 19篇 |
1985年 | 33篇 |
1984年 | 25篇 |
1983年 | 7篇 |
1982年 | 18篇 |
1981年 | 17篇 |
1980年 | 12篇 |
1979年 | 16篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 6篇 |
1975年 | 6篇 |
1973年 | 5篇 |
排序方式: 共有5205条查询结果,搜索用时 46 毫秒
111.
Moreno M. M. Torres Santos R. H. A. Gambardella M. T. P. Camargo A. J. da Silva A. B. F. Trsic M. 《Structural chemistry》1998,9(5):365-373
The crystal and molecular structures of the following molecules have been determined: 1-acetyl-indoline, 1-acetyl-5-nitro-indoline, l-acetyl-5-nitro-7-bromo-indoline, 1-acetyl-5-bromo-7-nitroindoline, and l-acetyl-5-bromo-7-nitro-indol. Molecular orbital calculations are performed for these compounds and two related species. 相似文献
112.
Fátima Nunes Serralha José Madeira Lopes Francisco Lemos Duarte Prazeres Maria Aires-Barros Joo Rocha Joaquim Cabral Fernando Ramôa Ribeiro 《Reaction Kinetics and Catalysis Letters》2000,69(2):217-222
Novel [CrIII(amp)(bipy)(Cl)] (1) (H2amp = N-(hydroxyphenyl)salicyldimine; bipy = 2,2-bipyridyl) and [CrIII(app)(bipy)(Cl)]+ (2) (H2app = N-(hydroxyphenyl)pyridine-2-carboxaldimine; bipy = 2,2-bipyridyl) complexes have been synthesized and characterized by physico-chemical methods. Complexes 1 and 2 have been employed as catalysts in the oxidation of both saturated and unsaturated hydrocarbons using tert-butylhydroperoxide (t-BuOOH). The significance of the results with respect to oxo-functionalization of C-H bonds both in unsaturated and saturated hydrocarbons is noted. 相似文献
113.
Fernando Bernardi H.Bernhard Schlegel Glauco Tonachini 《Journal of Molecular Structure》1978,48(2):243-248
Techniques to improve the computational efficiency of the force relaxation method are discussed. Force constants for fragments in previously computed smaller molecules can be transferred to construct a guess force constant matrix. Additional force constants that may be needed can be computed by a procedure which uses only one additional force calculation per diagonal force constant required. A scaling technique to improve convergence on the optimized geometry is discussed. 相似文献
114.
Jung SY Lim SM Albertorio F Kim G Gurau MC Yang RD Holden MA Cremer PS 《Journal of the American Chemical Society》2003,125(42):12782-12786
The molecular level details of the displacement of surface adsorbed fibrinogen from silica substrates were studied by atomic force microscopy, immunochemical assays, fluorescence microscopy, and vibrational sum frequency spectroscopy. The results showed that human plasma fibrinogen (HPF) can be readily displaced from the interface by other plasma proteins near neutral pH because the positively charged alpha C domains on HPF sit between the rest of the macromolecule and the underlying surface. The alpha C domains make weak electrostatic contact with the substrate, which is manifest by a high degree of alignment of Lys and Arg residues. Upon cycling through acidic pH, however, the alpha C domains are irreversibly removed from this position and the rest of the macromolecule is free to engage in stronger hydrogen bonding, van der Waals, and hydrophobic interactions with the surface. This results in a 170-fold decrease in the rate at which HPF can be displaced from the interface by other proteins in human plasma. 相似文献
115.
Pérez Pavón JL Guerrero Peña A García Pinto C Moreno Cordero B 《Journal of chromatography. A》2004,1047(1):101-109
The direct coupling of a headspace sampler with a mass spectrometer is proposed as a screening tool for the rapid detection of soil pollution by hydrocarbons from petroleum and derivatives. The samples are subjected to the headspace generation process, with no prior treatment, and the volatiles generated are introduced directly into the mass spectrometer, thereby obtaining a fingerprint of the sample analysed. Suitable treatment of the signal by chemometric techniques allows unequivocal characterisation of the different types of sample. The use of fast gas chromatography with a mass spectrometer detector coupled to the headspace sampler allows identification of the major hydrocarbons present in the mineral and organic polluted samples, interpretation of the results obtained, and demonstrates the analytical potential of headspace-mass spectrometry coupling. 相似文献
116.
Luís J. Moreno López Manuel Callejón Mochón Juán C. Jiménez Sánchez Alfonso Guiraúm Pérez 《Mikrochimica acta》1996,124(3-4):187-194
A method for the determination of salicylaldehyde (2 × 10–6–10–4
M) by differential-pulse polarography, based on the in situ formation of its Girard-P derivative in aqueous solution at pH 2.5, is proposed. The relative standard deviation was 1.5% (ten determinations of 4 × 10–5
M level). The applicability of this method was checked in synthetic samples containing salicyl alcohol,o-aminophenol, 2-methylphenol, salicylic acid and 4-aminobenzoic acid. 相似文献
117.
We report molecular dynamics computer simulations of the surface tension and interfacial thickness of ionic liquid-vapor interfaces modeled with a soft core primitive model potential. We find that the surface tension shows an anomalous oscillatory behavior with interfacial area. This observation is discussed in terms of finite size effects introduced by the periodic boundary conditions employed in computer simulations. Otherwise we show that the thickness of the liquid-vapor interface increases with surface area as predicted by the capillary wave theory. Data on the surface tension of size-asymmetric ionic liquids are reported and compared with experimental data of molten salts. Our data suggest that the surface tensions of size-asymmetric ionic liquids do not follow a corresponding states law. 相似文献
118.
The solution conformation of bicyclo [3.1.0] hexan-3-one has been obtained by the use of the shifts induced in its 1H and 13C NMR by Yb(fod)3. Refinement of the angle of pucker, ∝, of the 5-membered ring indicates that the molecule adopts a flattened boat conformation with ∝ = 195°. This prediction is supported by ab initio, STO-3G, calculations on the isolated molecule. Use of a two- or four-site model for lanthanide-substrate complexing adequately reproduces the experimental data whereas a one-site binding model is unsatisfactory. The importance of multi-site binding is further emphasised by results for the C2v-symmetric ketone, adamantanone, where only a four-site model gives satisfactory agreement between observed and calculated lanthanide-induced shifts. 相似文献
119.
Barluenga J Fernández MA Aznar F Valdés C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2276-2283
A novel approach for the synthesis of the important indole ring is described. Indoles are obtained from o-bromoanilines and alkenyl halides in a Pd-catalyzed cascade process that involves an alkenyl amination followed by an intramolecular Heck reaction. The overall process represents the first example of the participation of alkenyl amination reactions in Pd-catalyzed cascade reactions. Initially, the relative reactivity of aryl and alkenyl bromides and chlorides towards Pd-catalyzed amination was investigated. Competition experiments were carried out in the presence of primary and secondary amines, and these revealed the reactivity order alkenyl bromides > aryl bromides > alkenyl chlorides > aryl chlorides, as well as very high chemoselectivity; the more reactive halide was always favored. Thereafter, optimized reaction conditions for the sequential alkenyl amination/Heck cyclization to give indoles were investigated with the model reaction of o-bromoaniline with alpha-bromostyrene. An extensive screening of ligands, bases, and reaction conditions revealed that the [Pd2(dba)3]/DavePhos, NaOtBu, toluene combination at 100 degrees C were the optimized reaction conditions to carry out the cascade process (dba=dibenzylideneacetone, DavePhos=2-dicyclohexylphosphino-2'-N,N-dimethylaminobiphenyl). The reaction proceeds with aryl, alkyl, and functionalized substitutents in both starting reactants. The cyclization was also studied with N-substituted o-bromoanilines (which would give rise to N-substituted indoles); however, in this case, indole formation occurred only with 1-substituted-2-bromoalkenes. Finally, the application of this methodology to o-chloroanilines required further optimization. Although the catalyst based on DavePhos failed to promote the cascade process, a catalytic combination based on [Pd2(dba)3]/X-Phos promoted the formation of the indole ring also from the less reactive chloroanilines. 相似文献
120.
Kean H. Khoo K. Rodney Fernando Richard J. Fereday Chee-Yan Chan 《Journal of solution chemistry》1995,24(10):1039-1048
The solubility of thallium(I) chloride has been determined in aqueous solutions of strontium chloride and barium chloride at concentrations up to 1.5 mol kg–1. The data were analyzed using Pitzer's equations without making explicit assumption of association to ion pairs by assuming =3 instead of =2, with the (1) term for TlCl being equivalent to the (2) term for 2-2 electrolytes. Best values of (0) and (1) for TlCl are recommended together with K
s
, the activity solubility product. These were used to fit the present solubility data and derive the Pitzer model mixture parameters relevant to the systems, fTIN and fTINCl (N=Sr, Ba). Mixture parameters for TlCl+MCl+H2O systems are also derived to complete the parameter base. The fit of the experimental data was found to be worse when higher-order terms for asymmetrical mixing were included in the analysis. Activity coefficients for thallium(I) chloride in the mixtures are derived. 相似文献