全文获取类型
收费全文 | 4892篇 |
免费 | 481篇 |
国内免费 | 604篇 |
专业分类
化学 | 4429篇 |
晶体学 | 56篇 |
力学 | 153篇 |
综合类 | 103篇 |
数学 | 298篇 |
物理学 | 938篇 |
出版年
2024年 | 8篇 |
2023年 | 48篇 |
2022年 | 115篇 |
2021年 | 143篇 |
2020年 | 165篇 |
2019年 | 171篇 |
2018年 | 141篇 |
2017年 | 182篇 |
2016年 | 221篇 |
2015年 | 185篇 |
2014年 | 275篇 |
2013年 | 541篇 |
2012年 | 302篇 |
2011年 | 286篇 |
2010年 | 238篇 |
2009年 | 276篇 |
2008年 | 252篇 |
2007年 | 302篇 |
2006年 | 255篇 |
2005年 | 229篇 |
2004年 | 205篇 |
2003年 | 168篇 |
2002年 | 153篇 |
2001年 | 117篇 |
2000年 | 98篇 |
1999年 | 102篇 |
1998年 | 106篇 |
1997年 | 80篇 |
1996年 | 90篇 |
1995年 | 67篇 |
1994年 | 71篇 |
1993年 | 68篇 |
1992年 | 43篇 |
1991年 | 35篇 |
1990年 | 37篇 |
1989年 | 25篇 |
1988年 | 29篇 |
1987年 | 18篇 |
1986年 | 18篇 |
1985年 | 15篇 |
1984年 | 10篇 |
1983年 | 8篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 15篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1973年 | 3篇 |
排序方式: 共有5977条查询结果,搜索用时 125 毫秒
61.
G. A. Gavrilova M. G. Voronkov N. N. Chipanina L. I. Gubanova O. M. Trofimova Yu. L. Frolov 《Russian Chemical Bulletin》1995,44(4):667-669
The IR spectra of solutions of (=OSi)-(benzoyloxymethyl)trifluorosilane (1),-(benzoyloxymethyl)methyldifluorosilane (2), and butyl benzoate (3) are examined in the region of thev(C=O) stretching vibrations in 24 solvents. The ability of compounds1—3 to undergo specific intermolecular interactions is evaluated from the dependence ofv(C=O) on the Kamlet-Taft (*,, ) parameters, which was obtained for the carbonyl groups involved in the intramolecular coordinate (=OSi) bond and for free carbonyl groups. The corresponding values of the coefficients in the Kamlet-Taft equations are indicative of a weak ability of pentacoordinate silicon compounds1 and2 to undergo acid-base interactions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 689–692, April, 1995. 相似文献
62.
Jin-Woong?Kim Jin-Gyu?Park Jee-Hyun?Ryu Ih-Seop?Chang Kyung-Do?SuhEmail author 《Colloid and polymer science》2005,283(11):1233-1240
This study presents a method to produce monodisperse chloromethyl-functionalized macroporous poly(styrene-co-divinylbenzene) polymer particles by seeded polymerization in aqueous media. We observed that the molecular structure of
polystyrene seed particles, the composition of the secondary monomer mixtures, and the type of solvents were very important
factors that determine the morphology and porosity of the final particles. This study proposes that the molecular chemistry
of polystyrene seed polymers, increasing molecular weight or crosslinking, is another factor that can control the porosity
of the final particles. Also, the selection of a poor solvent was effective in forming the larger surface area. In this study,
it was confirmed that the chloromethyl groups introduced on the surface of porous particles were quantified chemically and
their effective incorporation had a close relationship with the surface area. 相似文献
63.
The absorption spectra of isoquinoline-iodine or 2,4-lutidine-iodine solutions in organic solventsn-hexane,n-heptane, cyclohexane, carbon tetrachloride, benzene, toluene, chlorobenzene, ando-dichlorobenzene have been measured and interpreted in terms of the D+I2=DI2 equilibrium, where D is isoquinoline or 2,4-lutidine. Values ofK (288–320°K), ΔHo, and ΔSo for the reaction were calculated. A correlation between theK values and the solubility parameter of the solvent (Buchowski's relation) has been found. 相似文献
64.
Bhattacharya S Schiavone M Nayak A Bhattacharya SK 《Applied biochemistry and biotechnology》2005,120(3):159-167
Our laboratory has recently developed a device employing immobilized F0F1 adenosine triphosphatase (ATPase) that allows synthesis of adenosine triphosphate (ATP) from adenosine 5′-diphosphate and
inorganic phosphate using solar energy. We present estimates of total solar energy received by Earth’s land area and demonstrate
that its efficient capture may allow conversion of solar energy and storage into bonds of biochemicals using devices harboring
either immobilized ATPase or NADH dehydrogenase. Capture and storage of solar energy into biochemicals may also enable fixation
of CO2 emanating from polluting units. The cofactors ATP and NADH synthesized using solar energy could be used for regeneration
of acceptor d-ribulose-1,5-bisphosphate from 3-phosphoglycerate formed during CO2 fixation. 相似文献
65.
在过去二十年间,高分子的单链弹性已经得到了广泛的研究.然而由于环境和高分子之间往往有着复杂的相互作用,实验中很难得到高分子在严格无扰状态下的单链弹性(即本征弹性).为此,利用单分子力谱技术研究了高真空条件下聚乙二醇(PEG)的单链弹性.结果表明,由于高真空条件下溶剂分子的干扰被消除,PEG在这一准无扰状态下呈现其本征弹性.在非极性有机溶剂中,由于溶剂分子和PEG之间只有微弱的范德华力作用,PEG表现出和高真空中基本一致的弹性.然而,在不同环境中,力曲线的低力区(F<100 pN)存在着细微的差异.这一现象可归因于不同条件下基底与PEG链之间的吸附力不同.采用的高真空力谱可用于研究其他高分子单链在准无扰状态下的本征弹性. 相似文献
66.
When crystallized from appropriate solvents, the complex aqua-bis(dimethylglyoximato)nitrocobalt (III) may incorporate solvent molecules, thus forming a variety of mixed crystals. In the resulting host-guest crystals, the space groupP2l/m and the packing motif of the pure host compound are retained. Lattice constantsa andb remain essentially unaltered upon intercalation, whereasc and the monoclinic angle depend largely on the clathrated guest. Space filling and intermolecular contacts are discussed.Dedicated to Professor Peter Paetzold at the occasion of his 60th birthday. A preliminary account of this work has been given at the Spring Meeting of the British Crystallographic Association, Newcastle upon Tyne, 1994. 相似文献
67.
Langlet J. Claverie P. Pullman B. Piazzola D. Daudey J. P. 《Theoretical chemistry accounts》1977,46(2):105-116
The effect of water on the conformational preferences of acetylcholine has been studied within the discrete, the continuum and the combined discrete-continuum models described in parts I and II of this series. All the models lead to the conclusion that the trans-gauche form which is, following refined quantum-mechanical computations, the intrinsically preferred one and the one observed in the crystal of acetylcholine and of a number of analogues should remain also the preferred conformation in water. This result agrees with NMR studies. The results of the empirical discrete model used here compare favorably to those obtained by an ab initio super-molecule treatment. The continuum model utilized here represents a net improvement above such models utilized in other works. 相似文献
68.
Ogbonnaya Ofor 《Journal of colloid and interface science》1996,180(2):323
Using “pure” natural hematite selected from a high silica Nigerian hematitic ore, oleate adsorption densities at the hematite–water interface were determined in the presence of various inorganic ions (anions and cations) of different charges and at varying concentrations. Adsorption density was determined using electrical conductivity measurements. The specific surface area of the hematite particles was determined using the method of adsorption of paranitrophenol in aqueous solution. Inorganic ions in solution depressed oleate adsorption at the aqueous hematite surface. The charge of the ion proved to be the dominant factor determining the depression of oleate adsorption. Ionic strength also was an influence, up to a limiting value at which monolayer oleate coverage of the hematite surface occurred. The inorganic ions in solution are considered to function through nonspecific adsorption in the diffuse region of the electric double layer. 相似文献
69.
The generalized (reductive) criterion of solvent polarity was obtained by the method of multiparametric optimization of the Snyder index P", Hildebrand parameter
T
, permittivity
r
, and solvatochromism parameter E
T
(30). Possibilities of employing this criterion for estimation of the elution power of normal and reversed mobile phases used in high-performance liquid chromatography were considered. 相似文献
70.
The low vapor pressure and the versatility of the physico-chemical properties of ionic liquids make them really attractive as an alternative for conventional molecular solvents. The knowledge of their physico-chemical properties (viscosity, conductivity, miscibility with organic solvents and anion-cation interactions) has appeared mandatory for better targeting their applications, although it is generally still lacking or incomplete.This work promotes capillary electrophoresis instrumentation as an integrated apparatus for measurement of viscosity, conductivity and absorbance of pure ionic liquids and ionic liquid-molecular solvent mixtures. Compared to current conventional techniques, the assets of this instrumentation for this purpose are the combined availability of a pressure delivery system, power supply, diode array absorbance detector and thermoregulation device, allowing unattended, automatic and easy operation, involving minimum sample handling. Most importantly, the required sample volume can be reduced to about 50 μL, making this protocol very cost-effective. A protocol was optimized with respect to time, sample consumption and data reliability for the determination of these physico-chemical parameters. Ionic liquids selected for method development and validation differed in the nature of their cation (butyl- and ethyl-methylimidazolium) and anion (trifluoromethanesulfonate and bis(trifluoromethanesulfonyl)imide). Various molecular solvents were mixed with these ionic liquids (acetonitrile, methanol, dimethylformamide and trifluoroethanol) and the same physico-chemical properties were determined by optimized methods. The knowledge of these data should be of great support in various application areas, including the development of new separation media for capillary electrophoresis and chromatographic techniques. 相似文献