全文获取类型
收费全文 | 7488篇 |
免费 | 318篇 |
国内免费 | 28篇 |
专业分类
化学 | 5384篇 |
晶体学 | 59篇 |
力学 | 154篇 |
数学 | 1004篇 |
物理学 | 1233篇 |
出版年
2023年 | 51篇 |
2022年 | 84篇 |
2021年 | 135篇 |
2020年 | 127篇 |
2019年 | 145篇 |
2018年 | 128篇 |
2017年 | 109篇 |
2016年 | 277篇 |
2015年 | 231篇 |
2014年 | 243篇 |
2013年 | 423篇 |
2012年 | 572篇 |
2011年 | 596篇 |
2010年 | 336篇 |
2009年 | 263篇 |
2008年 | 539篇 |
2007年 | 542篇 |
2006年 | 468篇 |
2005年 | 453篇 |
2004年 | 345篇 |
2003年 | 298篇 |
2002年 | 218篇 |
2001年 | 184篇 |
2000年 | 153篇 |
1999年 | 77篇 |
1998年 | 58篇 |
1997年 | 46篇 |
1996年 | 93篇 |
1995年 | 69篇 |
1994年 | 57篇 |
1993年 | 78篇 |
1992年 | 52篇 |
1991年 | 38篇 |
1990年 | 41篇 |
1989年 | 20篇 |
1988年 | 27篇 |
1987年 | 25篇 |
1986年 | 24篇 |
1985年 | 37篇 |
1984年 | 28篇 |
1983年 | 26篇 |
1982年 | 19篇 |
1981年 | 13篇 |
1980年 | 14篇 |
1979年 | 9篇 |
1978年 | 11篇 |
1977年 | 13篇 |
1976年 | 7篇 |
1975年 | 6篇 |
1973年 | 8篇 |
排序方式: 共有7834条查询结果,搜索用时 0 毫秒
21.
Daniel Fernndez Daniel Vega Javier A. Ellena Gustavo Echeverría 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m418-m420
In the title compound, potassium 2‐butyl‐4‐chloro‐1‐{[2′‐(5‐tetrazolido)biphenyl‐4‐yl]methyl}‐1H‐imidazol‐5‐ylmethanol, K+·C22H22ClN6O?, the imidazole and tetrazole rings are at angles of 85.0 (2) and 51.8 (1)°, respectively, to the phenyl rings to which they are attached, while the dihedral angle between the latter two rings is 46.7 (1)°. The coordination sphere of the metal cation consists of six tetrazoyl N atoms, the methanol O atom and the π cloud of one of the phenyl rings. These interactions determine the formation of columns of molecular anions that lie parallel to the b axis, while hydrogen bonding contributes to intercolumnar cohesion. Far from the centre of the columns, the hydrocarbon chain is immersed in a hydrophobic environment. 相似文献
22.
Alvaro M Corma A Das D Fornés V García H 《Chemical communications (Cambridge, England)》2004,(8):956-957
Preparation of hybrid organic-inorganic MCM-41 and SBA-15 silicas functionalized with perfluoroalkylsulfonic acid groups has been achieved in a single step by reacting the mesoporous silicas with 1,2,2-trifluoro-2-hydroxy-1-trifluoromethylethane sulfonic acid beta-sultone; the catalysts showed higher activity than commercial Nafion-silica composite for the esterification of long chain fatty acids with ethanol. 相似文献
23.
Elías Molins Amílcar Labarta Javier Tejada Amparo Caubet Santiago Alvarez 《Transition Metal Chemistry》1983,8(6):377-380
Summary Magnetic moments and57Fe Mössbauer spectra at room temperature and at liquid nitrogen temperature of polynuclear ligand-bridged iron phthalocyanines, FePcL (L = pyrazine and 4,4-bipyridyl), are reported. The experimental data are in agreement with a pseudo-octahedral environment around the iron(II) cation. Partially oxidized derivatives, FePc(pz)I0.26 and FePc(bipy)I1.06 have been synthesized and their57Fe Mössbauer spectra and magnetic moments within the same temperature range obtained. Oxidation is shown to be metal centred and the iodine is found to be in I– form for FePc(pz)0.26 and as both I– and I
3
–
species for FePc(bipy)I1.06. While the magnetic moment of FePc(pz) increases upon oxidation, the opposite occurs for FePc(bipy). 相似文献
24.
After carrying out a systematic basis set convergence study, we evaluate several ground state potential energy surfaces of the Ar-N(2) van der Waals complex at the coupled cluster singles and doubles model including connected triples corrections. We use the aug-cc-pVXZ (X=5,Q,D) and the daug-cc-pVQZ basis sets augmented with a set of 3s3p2d1f1g (denoted 33211) and 3s3p2d2f1g (denoted 33221) midbond functions, respectively. aug-cc-pVTZ-33211 results were available in the literature. The aug-cc-pV5Z-33211 (daug-cc-pVQZ-33221) surface is characterized by a T-shaped minimum at R(e)=3.709 (3.701) A and of 99.01 (102.50) cm(-1), and a linear saddle point at 4.260 (4.257) A and D(e)=75.28 (79.73) cm(-1). These results are compared with the values provided by the semiempirical potentials available, and those of previous theoretical studies. The basis set convergence of the intermolecular potentials is also analyzed. From the potentials the rovibronic spectroscopic properties are determined. We study the basis set convergence of the rotational frequencies. The binding parameters that characterized the aug-cc-pVTZ-33211 surface are reasonable, but the surface is not good enough to evaluate the microwave spectra. The aug-cc-pVQZ-33211 basis set results considerably improve the triple zeta and are close to the aug-cc-pV5Z-33211. Considering the small differences between the quadruple and the quintuple zeta surfaces, the latter results can be expected to be close to convergence. At this level the differences with respect to the accurate experimental frequencies are in the order of 0.7%. In the case of the daug-cc-pVXZ-33211,33221 (X=5,Q,T,D) series, the convergence of the interaction energies with respect to basis set improvement is not so smooth. The errors in the frequencies obtained with the daug-cc-pVQZ-33221 basis set with respect to experiment are in the order of 0.4%. 相似文献
25.
Quantum mechanical and quantum mechanical/molecular mechanical calculations in conjunction with continuum solvation models have been used to analyze CH-pi interactions in model systems of aryl- and alkyl-aromatic interactions, as well as in a model folding system designed to study those interactions. High level calculations reproduced accurately the interaction of CH-pi interactions in both alkyl- and aryl-based model systems. Dispersion effects dominate the interaction, but the electrostatics term is also relevant for aryl CH-pi interactions. Theoretical calculations were also used to examine the influence of CH-pi interactions in determining the conformational flexibility of folding models. Finally, a critical comparison of the results obtained from high level calculations on model systems and the experimental data derived for folding models in apolar solvents was carried out, which allowed us to reconcile the apparent discrepancy found between both data. 相似文献
26.
Moraes ML Bonardi C Mendonça CR Campana PT Lottersberger J Tonarelli G Oliveira ON Beltramini LM 《Colloids and surfaces. B, Biointerfaces》2005,41(1):15-20
The study of interactions between biological molecules and model membranes is essential for the understanding of a number of physiological mechanisms involved in viral infections and dissemination. In this paper, the analysis of the interaction between a peptide from the p24 protein of Human Immunodeficiency Virus type 1 (HIV-1) and a phospholipid monolayer has pointed to a cooperative response in which very small amounts of peptide p24-1 (e.g. 0.05 mol%) can lead to measurable effects. Monolayer surface pressure and surface potential isotherms were affected for peptide concentrations as low as 0.05 mol%, with saturation at 0.5 mol%. The expansion effect from p24-1 is confirmed by changes in morphology of the monolayers using Brewster angle microscopy. Even though p24-1 is disordered in aqueous solutions, the interaction with dipalmitoyl phosphatidylcholine (DPPC) causes it to adopt an alpha-helix structure, as shown by circular dichroism (CD) data for multilamellar vesicles (MLV). The expansion of the phospholipid monolayer in a cooperative way may imply that p24-1 has potential antiviral activity, by participating in the cell rupture, with no need of specific receptors in the membrane. 相似文献
27.
Castro-Rubio A Castro-Rubio F García MC Marina ML 《Journal of separation science》2005,28(9-10):996-1004
A perfusion reversed-phase HPLC method enabling the simultaneous separation of soybean and cereal (wheat, corn, and rice) proteins in commercial bakery products has been proposed for the first time. The method utilises an acetonitrile-water gradient containing an ion-pairing agent. Different ion-pairing agents were tried, 0.3% (v/v) acetic acid being observed to enable the separation of soybean from wheat, rice, and corn proteins while with 0.1% (v/v) trifluoroacetic acid only the separation of soybean and corn proteins was possible. Optimisation of the solubilisation conditions for proteins was achieved by testing different acetonitrile concentrations for the simultaneous extraction of soybean and cereal proteins: best recoveries were found with 25% (v/v) acetonitrile + 0.3% (v/v) acetic acid and with 40% (v/v) acetonitrile + 0.1% (v/v) trifluoroacetic acid. Chromatographic conditions such as gradient, temperature, and wavelength detection were also optimised. The method enabled the separation of soybean and cereal proteins in binary mixtures (soybean and wheat, soybean and corn, or soybean and rice proteins) in less than 5 minutes in a total analysis time of 20 min. 相似文献
28.
Francisco García-Montelongo María J. Sánchez Miguel A. Rodríguez 《Mikrochimica acta》1989,98(4-6):259-265
A spectrophotometric method for cyanide based on its inhibition of the colour formation reaction between nickel(II) and 3-(4,5-dimethyl-2-thiazolylazo)-2,6-dihydroxybenzoic acid has been developed, and allows the determination of down to 0.1 g of cyanide. Most of the interferences can be avoided by displacement of the hydrogen cyanide using an arsine generator. 相似文献
29.
Pablo Ríos Javier Borge Francisco Fernndez de Crdova Giuseppe Sciortino Agustí Lleds Amor Rodríguez 《Chemical science》2021,12(7):2540
The concept of metal–ligand cooperation opens new avenues for the design of catalytic systems that may offer alternative reactivity patterns to the existing ones. Investigations of this concept with ligands bearing a boron center in their skeleton established mechanistic pathways for the activation of small molecules in which the boron atom usually performs as an electrophile. Here, we show how this electrophilic behavior can be modified by the ligand trans to the boron center, evincing its ambiphilic nature. Treatment of diphosphinoboryl (PBP) nickel–methyl complex 1 with bis(catecholato)diboron (B2Cat2) allows for the synthesis of nickel(ii) bis-boryl complex 3 that promotes the clean and reversible heterolytic cleavage of dihydrogen leading to the formation of dihydroborate nickel complex 4. Density functional theory analysis of this reaction revealed that the heterolytic activation of H2 is facilitated by the cooperation of both boryl moieties and the metal atom in a concerted mechanism that involves a Ni(ii)/Ni(0)/Ni(ii) process. Contrary to 1, the boron atom from the PBP ligand in 3 behaves as a nucleophile, accepting a formally protic hydrogen, whereas the catecholboryl moiety acts as an electrophile, receiving the attack from the hydride-like fragment. This manifests the dramatic change in the electronic properties of a ligand by tuning the substituent trans to it and constitutes an unprecedented cooperative mechanism that involves two boryl ligands in the same molecule operating differently, one as a Lewis acid and the other one as a Lewis base, in cooperation with the metal. In addition, reactivity towards different nucleophiles such as amines or ammonia confirmed the electrophilic nature of the Bcat moiety, allowing the formation of aminoboranes.A bis(boryl)nickel complex promotes the facile and reversible activation of H2 through a cooperative mechanism that involves the metal and both boryl moieties in a concerted five-center process. 相似文献
30.
Demetrio De Calle García M. Reichenbächer Klaus Danzer Christian Hurlbeck Christine Bartzsch Karl-Heinz Feller 《Analytical and bioanalytical chemistry》1998,360(7-8):784-787
The extraction of wine aroma compounds was studied by direct-SPME (DI/SPME), headspace-SPME (HS/SPME) and multiple-headspace-extraction-SPME
(MHE/SPME). The aromagrams obtained by HS/SPME-CGC were evaluated with chemometrical methods for the varietal classification
of wines.
Received: 25 July 1997 / Revised: 24 September 1997 / Accepted: 7 October 1997 相似文献