全文获取类型
收费全文 | 82003篇 |
免费 | 7059篇 |
国内免费 | 8115篇 |
专业分类
化学 | 32727篇 |
晶体学 | 373篇 |
力学 | 8640篇 |
综合类 | 1301篇 |
数学 | 26863篇 |
物理学 | 27273篇 |
出版年
2024年 | 126篇 |
2023年 | 771篇 |
2022年 | 1720篇 |
2021年 | 1824篇 |
2020年 | 1895篇 |
2019年 | 2157篇 |
2018年 | 1724篇 |
2017年 | 2019篇 |
2016年 | 2389篇 |
2015年 | 2163篇 |
2014年 | 3025篇 |
2013年 | 5677篇 |
2012年 | 3394篇 |
2011年 | 3809篇 |
2010年 | 3309篇 |
2009年 | 4548篇 |
2008年 | 5017篇 |
2007年 | 5208篇 |
2006年 | 4863篇 |
2005年 | 4066篇 |
2004年 | 3660篇 |
2003年 | 3674篇 |
2002年 | 3374篇 |
2001年 | 2860篇 |
2000年 | 2806篇 |
1999年 | 2520篇 |
1998年 | 2360篇 |
1997年 | 1906篇 |
1996年 | 1698篇 |
1995年 | 1534篇 |
1994年 | 1429篇 |
1993年 | 1203篇 |
1992年 | 1146篇 |
1991年 | 906篇 |
1990年 | 740篇 |
1989年 | 637篇 |
1988年 | 582篇 |
1987年 | 475篇 |
1986年 | 393篇 |
1985年 | 463篇 |
1984年 | 451篇 |
1983年 | 229篇 |
1982年 | 364篇 |
1981年 | 413篇 |
1980年 | 306篇 |
1979年 | 304篇 |
1978年 | 230篇 |
1977年 | 210篇 |
1976年 | 162篇 |
1974年 | 110篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Josinira A. Amorim Osvaldo Chiavone-Filho Márcio L.L. Paredes Krishnaswamy Rajagopal 《Fluid Phase Equilibria》2007
High-pressure density data for cyclohexane + n-hexadecane mixtures at a wide temperature range was modeled with several classical equations of state (EOS) and correlative models. A modification for softening the co-volume and another for a volume scaling of the Peng–Robinson EOS (VS-PR) were proposed. The VS-PR model is able to correlate the pure component experimental data employing only five adjustable parameters, with root-mean-square deviation (RMSD) between calculated and experimental densities essentially within the experimental error. This result is superior to widely used approaches, i.e., a six parameter Tait model and six parameter volume translations (temperature and pressure dependent) for Peng–Robinson and Patel–Teja EOS. The VS-PR model also represents well the isobaric thermal expansion and the isothermal compressibility coefficients of the pure cyclohexane, a small naphthenic substance as well as a long chain n-alkane hydrocarbon, n-hexadecane. When modeling the mixture data, the use of VS-PR model of pure components along with the Redlich–Kister expansion, truncated at the first term, the density was correlated within a RMSD only 60% greater than the experimental error. The proposed model is able to accurately represent all the tested mixture data with a relatively small number of parameters. 相似文献
942.
The molecular orientation distribution function of a stable radical 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl in magnetic-field oriented 4-cyano-4’-n-pentylbiphenyl was determined from the angular dependence of the ESR spectra. The preferred molecular orientation of radical species in the liquid crystal matrix was determined. The temperature evolution of the orientation distribution function was studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 2005. 相似文献
943.
Warunee Klinklai Tomonobu Mizumo Jitladda Tangpakdee Sakdapipanich Hiroyuki Ohno 《European Polymer Journal》2003,39(8):1707-1712
Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (Tg) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH4)2S2O8 in the presence of propanal. The resulting liquid epoxidized rubber (Mn≈104) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li+ as an ionic conducting medium, that is, solid polymer electrolyte. 相似文献
944.
I. Gascón S. Martín P. Cea M. C. López F. M. Royo 《Journal of solution chemistry》2002,31(11):905-915
Densities and speeds of sound of the binary mixtures 1,3-dioxolane + 1-butanol, 1,3-dioxolane + 2-butanol, 1,4-dioxane + 1-butanol, and 1,4-dioxane + 2-butanol have been measured at 25 and 40°C. The excess molar volumes and excess isentropic compressibility coefficients were calculated from experimental data and fitted to a Redlich–Kister polynomial function. Results were analyzed in terms of molecular interactions and compared with literature data. 相似文献
945.
The solubility of argon in pure liquid water was measured at ca. 100 kPa and from 2 to 40°C using an analytical method characterized by an imprecision of about ±0.05%. From the experimental results, Henry fugacities H
2,1
(T,P
s,1
) (also known as Henry's Law constants or Henry coefficients) at the vapor pressure P
s,1
of water as well as Ostwald coefficients L
2,1
at infinite dilution were obtained. Measurements were made at roughly 0.5°C and/or 1° intervals between 2 and 8°C (region I), and at 5°C intervals above 10°C (region II). A difference plot lnH
2,1
/T suggests an unusual temperature dependence in region I, i.e., between 2 and 8°C. Because of this, the data were treated separately in two parts corresponding to these two regions. Our results are compared with the recent high-precision data of Krause and Benson (Henry fugacities), and with calorimetrically determined quantities (enthalpies and heat capacities of solution). Finally, experimental results are compared with values calculated via scaled particle theory.Communicated in part at the 2nd International Symposium on Solubility Phenomena in Newark, New Jersey, August 12–15, 1986, and at the 4th ISSP in Troy, New York, July 20–August 3, 1990. 相似文献
946.
Enthalpies of dissolution of benzo-15-crown-5 ether (B15C5) in mixtures of acetonitrile with water and in solutions of NaI and NaBPh4 (I=0.05 mol dm–3) in these mixtures were measured at 298.15 K. From the obtained results and appropriate literature data, the thermodynamic functions of B15C5/Na+ complex formation in acetonitrile-water mixtures were determined. The enthalpies of transfer of the complex B15C5/Na+ from pure acetonitrile to the examined mixtures were calculated and are discussed. 相似文献
947.
Designing peptide inhibitors of the p53-MDM2 interaction against cancer is of wide interest. Computational modeling and virtual screening are a well established step in the rational design of small molecules. But they face challenges for binding flexible peptide molecules that fold upon binding. We look at the ability of five different peptides, three of which are intrinsically disordered, to bind to MDM2 with a new Bayesian inference approach (MELD × MD). The method is able to capture the folding upon binding mechanism and differentiate binding preferences between the five peptides. Processing the ensembles with statistical mechanics tools depicts the most likely bound conformations and hints at differences in the binding mechanism. Finally, the study shows the importance of capturing two driving forces to binding in this system: the ability of peptides to adopt bound conformations () and the interaction between interface residues (). 相似文献
948.
Gálvez-Ruano E Iriepa-Canalda I Morreale A Lipkowitz KB 《Journal of computer-aided molecular design》1999,13(1):57-68
We have derived a model of the nicotinic acetylcholine binding site. This was accomplished by using three known agonists (acetylcholine, nicotine and epibatidine) as templates around which polypeptide side chains, found to be part of the receptor cavity from published molecular biology studies, are allowed to flow freely in molecular dynamics simulations and mold themselves around these templates. The resulting supramolecular complex should thus be a complement, both in terms of steric effects as well as electronic effects, to the agonists and it should be a good estimation of the true receptor cavity structure. The shapes of those minireceptor cavities equilibrated rapidly on the simulation time scale and their structural congruence is very high, implying that a satisfactory model of the nicotinic acetylcholine binding site has been achieved. The computational methodology was internally tested against two rigid and specific antagonists (dihydro--erytroidine and erysoidine), that are expected to give rise to a somewhat differently shaped binding site compared to that derived from the agonists. Using these antagonists as templates there were structural reorganizations of the initial receptor cavities leading to distinctly different cavities compared to agonists. This indicates that adequate times and temperatures were used in our computational protocols to achieve equilibrium structures for the agonists. Overall, both minireceptor geometries for agonists and antagonists are similar with the exception of one amino acid (ARG209). 相似文献
949.
Lizhuang Zou Buxing Han Haike Yan K.L. Kasperski Yuming Xu L.G. Hepler 《Journal of colloid and interface science》1997,190(2):472
The enthalpies of adsorption and the isotherms for adsorption of naphthenic acid onto Na-montmorillonite, Na-kaolinite, and Na-illite were studied by means of calorimetry and the static method at 298.15 K. The results show that the enthalpies of adsorption and saturated adsorption amounts of naphthenic acid on different clays change in the order Na-montmorillonite > Na-illite > Na-kaolinite. The interaction between naphthenic acid and clays is discussed. 相似文献
950.
制备了一系列V,Ag,Ni原子比不同的三元氧化物,应用TPD-MS技术研究了样品表面氧的性质,并测定了甲苯选择性氧化生成苯甲醛的催化活性。实验结果表明,样品表面存在有多种吸附的氧物种。在脱附温度<900℃:当Ni含量对Ag(或V)的原子比为0.25或0.50时,仅在低温处出现有表面的O^-和O^2^-两种氧物种的脱附峰;当Ni含量对Ag(或V)的原子比增高到>0.75时,除有表面的O^-和O^2^ 相似文献