全文获取类型
收费全文 | 1375篇 |
免费 | 31篇 |
国内免费 | 9篇 |
专业分类
化学 | 982篇 |
晶体学 | 10篇 |
力学 | 28篇 |
数学 | 205篇 |
物理学 | 190篇 |
出版年
2023年 | 18篇 |
2022年 | 30篇 |
2021年 | 50篇 |
2020年 | 27篇 |
2019年 | 41篇 |
2018年 | 32篇 |
2017年 | 35篇 |
2016年 | 55篇 |
2015年 | 41篇 |
2014年 | 41篇 |
2013年 | 86篇 |
2012年 | 79篇 |
2011年 | 90篇 |
2010年 | 49篇 |
2009年 | 50篇 |
2008年 | 98篇 |
2007年 | 91篇 |
2006年 | 87篇 |
2005年 | 68篇 |
2004年 | 59篇 |
2003年 | 27篇 |
2002年 | 37篇 |
2001年 | 14篇 |
2000年 | 21篇 |
1999年 | 8篇 |
1998年 | 15篇 |
1997年 | 14篇 |
1996年 | 13篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 8篇 |
1990年 | 7篇 |
1989年 | 7篇 |
1988年 | 11篇 |
1987年 | 7篇 |
1985年 | 4篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1980年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1924年 | 2篇 |
1912年 | 2篇 |
1911年 | 2篇 |
1910年 | 2篇 |
1858年 | 1篇 |
排序方式: 共有1415条查询结果,搜索用时 15 毫秒
1.
The linearized stability of charged thin shell wormholes under spherically symmetric perturbations is analyzed. It is shown that the presence of a large value of charge provides stabilization to the system, in the sense that the constraints onto the equation of state are less severe than for non-charged wormholes. 相似文献
2.
Maximiliano A. Burgos Paci Gustavo A. Argüello Plcido García Helge Willner 《国际化学动力学杂志》2003,35(1):15-19
Thermal decomposition of bis(trifluoromethyl) peroxydicarbonate has been studied. The mechanism of decomposition is a simple bond fission, homogeneous first‐order process when the reaction is carried out in the presence of inert gases such as N2 or CO. An activation energy of 28.5 kcal mol?1 was determined for the temperature range of 50–90°C. Decomposition is accelerated by nitric oxide because of a chemical attack on the peroxide forming substances different from those formed with N2 or CO. An interpretation on the influence of the substituents in different peroxides on the O? O bond is given. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 15–19, 2003 相似文献
3.
Fabian Buffa Gustavo A. Abraham Brian P. Grady Daniel Resasco 《Journal of Polymer Science.Polymer Physics》2007,45(4):490-501
A commercially available aliphatic thermoplastic polyurethane formulated with a methylene bis(cyclohexyl) diisocyanate hard segment and a poly(tetramethylene oxide) soft segment and chain‐extended with 1,4‐butanediol was dissolved in dimethylformamide and mixed with dispersed single‐walled carbon nanotubes. The properties of composites made with unfunctionalized nanotubes were compared with the properties of composites made with nanotubes functionalized to contain hydroxyl groups. Functionalization almost eliminated the conductivity of the tubes according to the conductivity of the composites above the percolation threshold. In most cases, functionalized and unfunctionalized tubes yielded composites with statistically identical mechanical properties. However, composites made with functionalized tubes did have a slightly higher modulus in the rubbery plateau region at higher nanotube fractions. Small‐angle X‐ray scattering patterns indicated that the dispersion reached a plateau in the unfunctionalized composites that was consistent with the plateau in the rubbery plateau region. The room‐temperature modulus and tensile strength increase was proportionally higher than almost all increases seen previously in thermoplastic polyurethanes; however, the increase was still an order of magnitude below what has been reported for the best nanotube–polymer systems. Nanotube addition increased the hard‐segment glass transition temperature slightly, whereas the soft‐segment glass transition was so diffuse that no conclusions could be drawn. Unfunctionalized tubes suppressed the crystallization of the hard segment; whereas functionalized tubes had no effect. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 490–501, 2007 相似文献
4.
Gustavo Portalone Marcello Colapietro 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):o650-o654
The asymmetric unit of the amino–oxo tautomer of 5‐formyluracil (systematic name: 2,4‐dioxo‐1,2,3,4‐tetrahydropyrimidine‐5‐carbaldehyde), C5H4N2O3, comprises one planar amino–oxo tautomer, as every atom in the structure lies on a crystallographic mirror plane. At variance with all the previously reported small‐molecule crystal structures containing the 5‐formyluracil residue, the formyl substituent in the title compound exhibits an unusual syn conformation. The molecules are linked into planar sheets parallel to the bc plane by a combination of six N—H...O and C—H...O hydrogen bonds. Four of the hydrogen bonds are utilized to stabilize the formyl group in the syn conformation. 相似文献
5.
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
6.
A method for the determination of 2-furaldehyde (F) and 5-hydroxymethyl-2-furaldehyde (HMF) in alcoholic beverages by high performance liquid chromatography (HPLC) is described. A C-18 column and an acetonitrile-water mobile phase with isocratic elution were used. UV detection at 280 nm was carried out. The method was validated according to the EURACHEM guidelines. The procedure offers a high specificity and detection limits of the order of 0.005 μg mL− 1. Recoveries of 94-103% were obtained from spiked samples at different levels with both analytes. Intermediate precision calculated for a period of 2 months was + 0.8% for HMF and + 0.4% for F. The method was applied to the analysis of alcoholic beverages like bourbon, rum, brandy, liquors and aperitif wines. 相似文献
7.
Fabio E. Malanca M. Burgos Paci Gustavo A. Argüello 《Journal of photochemistry and photobiology. A, Chemistry》2002,150(1-3):1-6
Photolyses of CF3C(O)X and C2F5C(O)X (X=Cl, F) at 254 nm in the presence of O2 yield the perfluorinated radicals C2F5O (C2) and CF3O (C1), respectively. The C2 radicals decompose to give CF3 radicals:which, in turn, react with O2 leading to the formation of C1 radicals. When in addition to O2, CO is present, the C1 radicals react with it leading to its catalytic oxidation to CO2. The trioxide CF3OC(O)O3C(O)OCF3 was observed following the photolysis of all four halides in the presence of O2 and CO.
C2F5O→CF3+CF2O
The other radical partners coming from the initial step in the photolysis (XC(O)) as well as the products of their reaction with O2 (XC(O)Oy, y=1, 2) do not react with CO but when X=F they lead to the formation of a new stable peroxy molecule with the formula CF3OC(O)O2C(O)F. Some of the properties of this new molecule, its stability and its IR features are presented in this work. 相似文献
8.
Grumelli DE Forzani ES Morales GM Miras MC Barbero CA Calvo EJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(6):2349-2355
The sulfonation of polyaniline (PANI) films by nucleophilic addition of sulfite ion has been controlled through the polymer oxidation state under electrochemical control. The process was monitored by in situ electrochemical quartz crystal microbalance (EQCM), and the polymer oxidation was accomplished by electrode potential steps in sulfite aqueous solutions. The nucleophilic addition of sulfite to PANI only takes place on the oxidized polymer. From the ratio of added mass to the injected charge, the degree of sulfonation has been obtained with a yield as high as 50%. It has been observed that the ion-exchange mechanism during the oxidation-reduction process in the resulting sulfonated polymer is analogous to the polymer produced by electrophilic sulfonation of polyaniline or by copolymerization of aniline with aminosulfonic acids, unlike the ionic exchange observed for unmodified PANI. 相似文献
9.
The Hammond postulate is a useful, qualitative tool that interrelates structural similarities between reactants, transition structures, and products with the exo- or endothermicity of reactions. It applies to most chemical reactions, although several exceptions are known. In this study the following problem is addressed: is it possible to formulate conditions for the validity of the quantitative Hammond postulate in terms of simple physical quantities characteristic to the molecules involved? A detailed analysis is given for the conditions of validity of the postulate, in terms of bounds on the internal forces and force constants of nuclear arrangements encountered along a reaction path. We have determined a broad class of constraints on barrier shapes that must be satisfied in order to obtain a critical situation that violates the Hammond postulate: a reactant-like transition structure (“transition state”) for endothermic reactions, and a product-like one for exothermic reactions. The general constraints are formulated in terms of physically meaningful quantities: (i) energy differences, (ii) restrictions on slopes (e.g., an upper bound on internal forces), and (iii) restrictions on curvatures (e.g., upper bounds on force constants) along potential curves. 相似文献
10.
In this article we present a method for the study of shapes of general, asymmetric van der Waals surfaces. The procedure is simple to apply and it consists of two steps. First, the surface is decomposed into spherical domains, according to the interpenetration of the van der Waals atomic spheres. Each domain defines a topological object that is either a 2-manifold or some truncated 2-manifold. Second, we compute the homology groups for all the objects into which the surface is divided. These groups are topological and homotopical invariants of the domains, hence they remain invariant to conformational changes that preserve the essential features of these domains of decomposition. In particular, these homology groups do not depend explicitly on the molecular symmetry. Major rearrangements of the nuclear configurations, however, do alter the decomposition into spherical domains, and the corresponding variation of the homology groups can be followed easily under conformational rearrangements. We discuss a partitioning of the metric internal configuration spaceM into shape regions of van der Waals surfaces, which allows one to identify those rearrangements which introduce an essential change in shape and to distinguish them from those which do not alter the fundamental shape of the molecular surface. The dependence of the shape group partitioning ofM on the symmetry under permutation of nuclear changes is discussed briefly, considering a simple illustrative example. 相似文献