全文获取类型
收费全文 | 3936篇 |
免费 | 119篇 |
国内免费 | 22篇 |
专业分类
化学 | 2378篇 |
晶体学 | 25篇 |
力学 | 80篇 |
数学 | 572篇 |
物理学 | 1022篇 |
出版年
2023年 | 24篇 |
2022年 | 35篇 |
2021年 | 48篇 |
2020年 | 58篇 |
2019年 | 59篇 |
2018年 | 62篇 |
2017年 | 86篇 |
2016年 | 124篇 |
2015年 | 113篇 |
2014年 | 122篇 |
2013年 | 214篇 |
2012年 | 191篇 |
2011年 | 270篇 |
2010年 | 148篇 |
2009年 | 113篇 |
2008年 | 234篇 |
2007年 | 205篇 |
2006年 | 205篇 |
2005年 | 134篇 |
2004年 | 139篇 |
2003年 | 100篇 |
2002年 | 96篇 |
2001年 | 59篇 |
2000年 | 61篇 |
1999年 | 50篇 |
1998年 | 29篇 |
1997年 | 26篇 |
1996年 | 41篇 |
1995年 | 33篇 |
1994年 | 28篇 |
1993年 | 36篇 |
1992年 | 29篇 |
1990年 | 24篇 |
1989年 | 35篇 |
1987年 | 30篇 |
1986年 | 38篇 |
1985年 | 47篇 |
1984年 | 36篇 |
1983年 | 37篇 |
1982年 | 31篇 |
1980年 | 29篇 |
1979年 | 24篇 |
1978年 | 36篇 |
1977年 | 26篇 |
1976年 | 32篇 |
1975年 | 28篇 |
1972年 | 27篇 |
1969年 | 23篇 |
1968年 | 29篇 |
1966年 | 29篇 |
排序方式: 共有4077条查询结果,搜索用时 500 毫秒
51.
Infrared laser ablation study of pressed soil pellets with inductively coupled plasma atomic emission spectrometry 总被引:1,自引:0,他引:1
Mikolás J Musil P Stuchliková V Novotný K Otruba V Kanický V 《Analytical and bioanalytical chemistry》2002,374(2):244-250
Potential of infrared laser ablation (LA) coupled with ICP-AES as a technique suitable for the determination of trace elements (Zn, Cu, Ni, Cr, and V) in agricultural soils was studied. Operating parameters such as laser beam energy, laser beam focusing with respect to the sample surface, and velocity of the sample translation in the plane perpendicular to the laser beam were optimized. Soil samples were mixed with powdered Ag as a binder, and an internal standard (GeO(2)), and pressed into pellets. Calibration samples were prepared by adding known amounts of oxides of elements of interest into soils of known elemental composition and then processed in the same way as the analyzed samples. Calibration curves were found to be linear at least up to several hundreds of mg kg(-1) for the elements of interest. The elemental contents obtained by using LA-ICP-AES were compared with those obtained by analysis using wet chemistry followed by ICP-AES with pneumatic nebulization (PN). The results were in good agreement. Accuracy was also tested using certified reference soils with a bias not exceeding 10% relative. 相似文献
52.
Two simple modification methods for ordered mesoporous silicas were examined and compared. MCM-41 molecular sieve was physically coated with 4-cyano-4-biphenyl [4(4-pentenyloxy)]benzoate (CBPB) and chemically modified using trimethylethoxysilane. The structural and surface properties of the obtained materials were characterized using elemental analysis, thermogravimetry and nitrogen adsorption over a wide pressure range.It was shown that the pore size of the MCM-41 material was not decreased significantly after the coating procedure, even for high loadings of CBPB. Moreover, low pressure adsorption measurements indicated that significant fractions of the MCM-41 surface were not covered by CBPB, even for high CBPB loadings, which suggests that the attained coverage may be very nonuniform. The chemical bonding procedure led to a marked decrease in the pore size and change of surface properties.It was demonstrated that nitrogen adsorption measurements provide a means of a thorough characterization of modified MCM-41 materials, allowing to estimate the surface area, pore volume and pore size distribution. Moreover, low pressure adsorption data can be used to qualitatively or semiquantitatively assess the surface coverage of the coated/bonded organic groups, which may be used to estimate the uniformity of the coverage and therefore, the usefulness of the modification procedure. 相似文献
53.
The sorption of solvent vapours onto dried cellulose has been investigated. The time-dependence and the effect of the solvent-water ratio is discussed. The studies concerned the properties of methanol, ethanol, propanol and butanol. 相似文献
54.
Jaroslav Koutecký 《Theoretical chemistry accounts》1967,8(3):244-248
Approximate pairing properties are proved for the Hartree-Fock solutions for highly symmetric heteroatomic molecules. These molecules have an alternant topology and are built from two kinds of atoms in such a way that by an operation the atoms of one kind go over into the atoms of the second kind and vice versa.
Supported in part by a grant to The Johns Hopkins University from the Petroleum Research Fund of the American Chemical Society. 相似文献
Zusammenfassung Es werden genäherte alternierende Eigenschaften für Hartree-Fock-Lösungen hochsymmetrischer heterocyclischer Moleküle abgeleitet. Diese Moleküle haben eine alternierende Topologie, sie sind aus zwei Sorten von Atomen in solcher Weise aufgebaut, daß die Atome der ersten Sorte in die Atome der zweiten Sorte — und umgekehrt — transformiert werden können.
Résumé Des propriétés d'accouplement orbital approché sont prouvées pour les solutions de type Hartree-Fock des molécules hétéroatomiques hautement symétriques. Ces molécules ont une topologie alternante et sont formées de deux classes d'atomes de telle sorte qu'il existe une opération interchangeant les atomes des deux classes.
Supported in part by a grant to The Johns Hopkins University from the Petroleum Research Fund of the American Chemical Society. 相似文献
55.
Suspensions of lignite in a solution of a high molecular weight carboxymethylcellulose show peculiar rheological behaviour.
Unless the lignite concentration is sufficiently high, apparent viscosity and viscoelastic moduli of the suspension are lower
than those of the pure solution. This effect is not suppressed by changing pH and seems to be common for low-concentrated
suspensions in solutions of high molecular weight (bio)polymer. It is explained by specific structuring of the suspensions.
Lignite particles at lower concentration separate long cellulose chains and facilitate their movement under shear flow. The
particles loosen inter-chain contacts, disturb and release elastic gel-like structure formed by the long cellulose chains,
which results in the low strain oscillatory deformation, the decrease in the moduli and the increase in the loss angle. If
the amount of lignite particles is sufficiently high, suspension stiffening occurs as usual. No such effect was observed for
suspensions prepared from the low molecular weight derivative.
Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users. 相似文献
56.
The solubility products for some rare earth hydroxides and their temperature dependence have been shown. Greater solubility is shown for larger atomic radii and for lower temperature. 相似文献
57.
Maprotiline determination in blood serum samples was investigated by the use of both capillary isotachophoresis and spectrofluorimetric techniques. The analyte had to be enriched before determination and extraction with n-heptane was used for this purpose. The preliminary separation enabled the determination of maprotiline in blood serum at therapeutic concentration levels. 相似文献
58.
Teplý F Stará IG Starý I Kollárovic A Saman D Vyskocil S Fiedler P 《The Journal of organic chemistry》2003,68(13):5193-5197
A nonphotochemical synthetic route to 3-hexahelicenol is reported. It involves a key [2+2+2] cycloisomerization of CH(3)O-substituted triyne that is readily available from 1-methoxy-3-methylbenzene and 1-bromo-2-(bromomethyl)naphthalene. Further functional group transformations led to 3-CO(2)CH(3), 3-NH(2), 3-PPh(2), and 3-SC(O)N(CH(3))(2) substituted hexahelicenes. 相似文献
59.
Ludvík Beneš Klára Melánová Vítězslav Zima Jaroslava Kalousová Jiří Votinský 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(3):275-286
Recent knowledge of the kinetics and intercalation mechanisms are summarized and accompanied by examples of intercalation reactions of water and ethanol into anhydrous vanadyl phosphate and redox intercalation of alkali metal cations into vanadyl phosphate dihydrate. Three possible mechanisms of intercalation are presented which are based on: (i) a concept of exfoliation of layers; (ii) the formation of stages and randomly stacked layers; (iii) co-existence of intercalated and non-intercalated parts of crystals of the host separated by an advancing phase boundary. The corresponding kinetic curves are ascribed to mechanisms (ii) and (iii). 相似文献
60.
Stará IG Alexandrová Z Teplý F Sehnal P Starý I Saman D Budesínský M Cvacka J 《Organic letters》2005,7(13):2547-2550
[reaction: see text] A new approach to nonracemic [7]helicene-like molecules has been developed. Stereoselective Co(I)-mediated [2 + 2 + 2] cycloisomerization of aromatic triynes containing an asymmetric carbon atom produces [7]helicene-like scaffolds in diastereomeric ratios up to 100:0. This central-to-helical chirality transfer can be controlled by the absolute configuration at the asymmetric center and by the presence of carbon substituents. 相似文献