全文获取类型
收费全文 | 82022篇 |
免费 | 413篇 |
国内免费 | 421篇 |
专业分类
化学 | 26938篇 |
晶体学 | 811篇 |
力学 | 6777篇 |
数学 | 32690篇 |
物理学 | 15640篇 |
出版年
2021年 | 42篇 |
2019年 | 50篇 |
2018年 | 10445篇 |
2017年 | 10283篇 |
2016年 | 6127篇 |
2015年 | 893篇 |
2014年 | 357篇 |
2013年 | 532篇 |
2012年 | 3945篇 |
2011年 | 10691篇 |
2010年 | 5719篇 |
2009年 | 6101篇 |
2008年 | 6842篇 |
2007年 | 9005篇 |
2006年 | 506篇 |
2005年 | 1581篇 |
2004年 | 1738篇 |
2003年 | 2123篇 |
2002年 | 1154篇 |
2001年 | 313篇 |
2000年 | 351篇 |
1999年 | 211篇 |
1998年 | 236篇 |
1997年 | 197篇 |
1996年 | 280篇 |
1995年 | 171篇 |
1994年 | 131篇 |
1993年 | 133篇 |
1992年 | 100篇 |
1991年 | 95篇 |
1990年 | 94篇 |
1989年 | 90篇 |
1988年 | 94篇 |
1987年 | 98篇 |
1986年 | 105篇 |
1985年 | 116篇 |
1984年 | 111篇 |
1983年 | 92篇 |
1982年 | 91篇 |
1981年 | 89篇 |
1980年 | 105篇 |
1979年 | 83篇 |
1978年 | 91篇 |
1977年 | 66篇 |
1976年 | 55篇 |
1975年 | 48篇 |
1973年 | 63篇 |
1914年 | 45篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
951.
Ab initio calculations using both pseudopotential and double and triple-ζ all-electron basis sets, with and without electron correlation (MP2, QCISD), have been performed on the λ4-sulfanyl (SH3), λ4-selanyl (SeH3), and λ4-tellanyl (TeH3) radicals. All-electron basis sets of double-ζ quality predict that SH3 and SeH3 correspond to transition states on their respective potential energy surfaces. In contrast, the pseudopotentials of Hay and Wadt predict that SH3 and SeH3 correspond to local minima at the QCISD level of theory while the pseudopotentials of Christiansen and Stevens predict transition states. By comparison, TeH3 proved to be a local minimum at all levels of theory. Interestingly, when a very large (triple-ζ) all-electron basis set was used, SH3 proved to be a transition state; however, in this instance the potential energy surface was found to be much flatter than in the case for which a double-ζ basis set was used, suggesting that further improvements in the basis set may lead to a local minimum. Further improvements in the all-electron selenium basis also led to a local minimum for SeH3 at the QCISD level of theory. © 1995 by John Wiley & Sons, Inc. 相似文献
952.
Hans König 《Analytical and bioanalytical chemistry》1973,266(2):119-124
The separation of a mixture of 22 bactericides has been achieved by gas chromatography on columns with silicone rubber W-982 as stationary phase with temperatures between 100° and 300°C. The unchanged compounds as well as their silylation products have been used. The latter are more conveniently used especially for the quantitative determination. To be able to calculate the retention indices after Kovats gas chromatography has been performed isothermally at 180°C for the more volatile compounds and at 250°C for all other bactericides.The retention indices obtained under these conditions are tabulated together with the limits of detection. 相似文献
953.
Valérie Chevalier-Billosta Jean-Paul Joseleau Alain Cochaux Katia Ruel 《Cellulose (London, England)》2007,14(2):141-152
The composition and ultrastructural arrangement of cell wall polymers in wood fibres have determining influence on the properties
of wood derived materials. It is therefore important to improve our understanding of the relationship between fibres organisation,
the modifications induced by pulping treatments, and the resulting paper sheet mechanical properties. The different treatments
to which fibres are subjected during the manufacturing of pulps and papers induce morphological and micro-structural alterations
due to the removal of wall constituents and of microfibrillar elements. The impact of pulping processes on fibres was investigated
at the ultrastructural scale of transmission electron microscopy. Particular attention was given to the effects of beating
in refiners at various intensities on the ultrastructure of fibres. The most characteristic effects consisted of delaminations,
microfibril disorganisation, and even fractures, of varying importance depending on the intensity of the mechanical refining.
The consequences of internal alterations and surface modifications of the fibres were examined in relation to the paper sheet
mechanical properties. Correlations between the type of alteration observed in the fibres and its possible impact on a given
paper mechanical property are suggested. With similar approaches, the effects of drying and recycling were studied. 相似文献
954.
Stereoselectivity of reductive amination of (R)-1-hydroxy-1-phenylpropan-2-one by methylamine was studied. From the four isomers possible, only two are produced by this
reaction. These are marked as (−)-(1R,2S)-ephedrine (desired product) and (+)-(1S,2R)-ephedrine. The reaction stereoselectivity depends both on the type of the catalyst and reaction conditions. The most suitable
type is the supported platinum. However, this catalyst rapidly deactivates. With a decreasing activity of Pt catalyst, the
stereoselectivity decreases. It is also decreased during the production of the second liquid phase (water) in the reaction
mixture. 相似文献
955.
Gabriela Flores-Ramírez Manuel Rivera Alfredo Morales-Pablos Joel Osuna Xavier Soberón Paul Gaytán 《BMC chemical biology》2007,7(1):1
Background
The effect of single and multiple amino acid substitutions in the green fluorescent protein (GFP) from Aequorea victoria has been extensively explored, yielding several proteins of diverse spectral properties. However, the role of amino acid deletions in this protein -as with most proteins- is still unknown, due to the technical difficulties involved in generating combinatorial in-phase amino acid deletions on a target region. 相似文献956.
Nucleophilic vinylic substitutions of 4H-pyran-4-one and 2-methyl-4H-pyran-4-one with ammonia were calculated by the B3LYP method using the 6-31G(d,p) basis set. Bulk solvent effects of aqueous
solution were estimated by the polarized continuum and Poisson–Boltzmann self-consistent reaction field models using the 6-311+G(d,p)
basis set. In the gas phase different mechanisms were found for the two reaction systems calculated. The reaction of 4H-pyran-4-one proceeds through enol, whereas a feasible path for the less reactive 2-methyl-4H-pyran-4-one is the mechanism through a keto intermediate. Addition of ammonia in concert with proton transfer is the rate-determining
step ofthe reaction. The mechanism proceeding either by a bimolecular nucleophilic substitution (SN2) or by one involving a tetrahedral zwitterionic intermediate is shown to be unlikely in the gas phase or nonpolar solution.
The effects of bulk solvent not only consist in a reduction of the various activation barriers by about 25–40 kJ mol−1 but also in a change in the reaction mechanism.
Received 26 May 2002 / Accepted 26 July 2002 /
Published online: 14 February 2003 相似文献
957.
This study utilizes photoelectron spectroscopy (PES) combined with theoretical methods to determine the electronic structure contributions to the large reduction potential difference between [FeCl(4)](2)(-)(,1)(-) and [Fe(SR)(4)](2)(-)(,1)(-) (DeltaE(0) approximately 1 V). Valence PES data confirm that this effect results from electronic structure differences because there is a similarly large shift in the onset of valence ionization between the two reduced species (DeltaI(vert) = 1.4 +/- 0.3 eV). Specific electronic contributions to DeltaI(vert) have been investigated and defined. Ligand field effects, which are often considered to be of great importance, contribute very little to DeltaI(vert) (DeltaE(LF) < -0.05 eV). By contrast, electronic relaxation, a factor that is often neglected in the analysis of chemical reactivity, strongly affects the valence ionization energies of both species. The larger electronic relaxation in the tetrathiolate allows it to more effectively stabilize the oxidized state and lowers its I(vert) relative to that of the chloride (DeltaE(rlx) = 0.2 eV). The largest contribution to the difference in redox potentials is the much lower effective charge () of the tetrathiolate in the reduced state, which results in a large difference in the energy of the Fe 3d manifold between the two redox couples (DeltaE(Fe)( )(3d) = 1.2 eV). This difference derives from the significantly higher covalency of the iron-thiolate bond, which decreases and significantly lowers its redox potential. 相似文献
958.
In cetyltrimethylammonium/n-pentanol/H2O W/O (W/O = water in oil microemulsion) mixtures and bi-continuous microemulsions, phenothiazine (PTZ) molecules exist in
the membrane phase of the dispersion either with the N atom or with the S atom pointed toward the polar head of cetyltrimethylammonium
(CTAB). Cyclic voltammetry has been used to investigate the effects of the compositions and structures of the microemulsions,
pH, and the salt on the location distribution of PTZ in the membrane phase of the dispersion in CTAB/n-C5H11OH/H2O W/O and bi-continuous microemulsions. The results show that the location distribution of PTZ in the membrane phase of the
dispersion in microemulsions is mainly dependent on the hydrogen bond between PTZ and n-C5H11OH (or the counterion), and on the electrostatic attractive interaction between the N atom in PTZ and the polar head of CTAB. 相似文献
959.
The thermodynamic properties of the mixed aqueous electrolyte of ammonium and alkaline earth metal nitrates have been studied using the hygrometric method at 25?°C. The water activities of these {yNH4NO3+(1?y)Y(NO3)2}(aq) systems with Y ≡ Ba2+, Mg2+ and Ca2+ were measured at total molalities ranging from 0.10 mol?kg?1 to saturation for different NH4NO3 ionic-strength fractions of y=0.20, 0.50 and 0.80. These data allow the calculation of osmotic coefficients. From these measurements, the ionic mixing parameters are determined and used to calculate the solute activity coefficients in the mixtures at different ionic-strength fractions. The results of these ternary solution measurements are compared with those for binary solutions of the alkaline earth nitrates of magnesium, calcium and barium with ammonium nitrates. The behavior of the aqueous electrolyte solutions containing mixtures of barium or calcium or magnesium with ammonium nitrates are correlated and show that ionic interactions are more important for the system containing Mg2+ than for Ca2+ or Ba2+. The trends are mainly due to the effects of the ionic size, polarizability and the hydration of the ions in these solutions. 相似文献
960.
Michael I. Bruce Michael Schulz Brian W. Skelton Allan H. White 《Journal of Cluster Science》2000,11(1):79-86
Addition of aqueous HCl to Ru5(
3-C=CH2)(-SMe)2(-PPh2)2(CO)10 afforded the structurally characterized carbyne complex Ru5(
3-SMe)(
3-CMe)(-Cl)(-SMe)(-PPh2)2(CO)9, formed by addition of H to the vinylidene ligand; a Cl atom bridges an Ru–Ru bond. 相似文献