全文获取类型
收费全文 | 642篇 |
免费 | 19篇 |
专业分类
化学 | 353篇 |
晶体学 | 8篇 |
力学 | 18篇 |
数学 | 120篇 |
物理学 | 162篇 |
出版年
2022年 | 3篇 |
2021年 | 6篇 |
2020年 | 8篇 |
2019年 | 8篇 |
2018年 | 19篇 |
2017年 | 18篇 |
2016年 | 21篇 |
2015年 | 18篇 |
2014年 | 30篇 |
2013年 | 52篇 |
2012年 | 39篇 |
2011年 | 35篇 |
2010年 | 25篇 |
2009年 | 27篇 |
2008年 | 31篇 |
2007年 | 33篇 |
2006年 | 24篇 |
2005年 | 22篇 |
2004年 | 22篇 |
2003年 | 13篇 |
2002年 | 14篇 |
2001年 | 12篇 |
2000年 | 10篇 |
1999年 | 16篇 |
1998年 | 13篇 |
1996年 | 9篇 |
1995年 | 17篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 6篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1972年 | 3篇 |
1969年 | 2篇 |
1933年 | 2篇 |
排序方式: 共有661条查询结果,搜索用时 218 毫秒
11.
Kłonkowski Andrzej M. Widernik Teresa Grobelna Beata Jóźwiak Wojciech K. Proga Henryk Szubiakiewicz Ewa 《Journal of Sol-Gel Science and Technology》2001,20(2):161-180
The sol-gel process is a useful method for preparing two series of organically and co-ordinately modified xerogels of the types [CuN
n
]·N
5–n
·5xSiO4/2 (n < 4) and [Cu(N–N)n]·(N–N)2–n
·2x SiO4/2(n 2), where N = NH2(CH2)3 SiO3/2, N–N = NH2(CH2)2NH·(CH2)3SiO3/2 and x = [SiO4/2]/[N] or [SiO4/2]/[N–N]. The amino groups in the materials are coordinately active and participate partly in the coordination sphere of Cu(II) ions. The composition of the coordination sphere can be varied with the SiO4/2 content and also as a result of the thermal decomposition of the organic residues at higher temperatures.Because the xerogel materials are considered to be catalyst precursors, this study is focused on their coordination and thermal properties. The prepared xerogels, such as silica, aminated silicates with N and N–N, as well as those entities complexed with Cu(II), were characterised by FT-IR spectroscopy. During gelation and thermal decomposition the materials were analysed by electron paramagnetic resonance (EPR) spectroscopy. The xerogels were additionally studied by UV-Vis absorption spectroscopy. The gaseous products of the thermal decomposition of these materials in an Ar atmosphere were investigated by the use of FT-IR spectroscopy coupled with TG and DTG thermal analysis. These data were complemented by temperature-programmed decomposition (TPDec) in a 2% O2 + 98% Ar stream coupled with quadrupole mass spectroscopy. 相似文献
12.
Rzeźnicka II Lee J Maksymovych P Yates JT 《The journal of physical chemistry. B》2005,109(33):15992-15996
The adsorption of methanethiol and n-propanethiol on the Au(111) surface has been studied by temperature-programmed desorption (TPD), Auger electron spectroscopy (AES), and low-temperature scanning tunneling microscopy (LT-STM). Methanethiol desorbs molecularly from the chemisorbed monolayer at temperatures below 220 K in three overlapping desorption processes. No evidence for S-H or C-S bond cleavage has been found on the basis of three types of observations: (1) A mixture of chemisorbed CH3SD and CD3SH does not yield CD3SD, (2) no sulfur remains after desorption, and (3) no residual surface species remain when the adsorbed layer is heated to 300 K as measured by STM. On the other hand, when defects are introduced on the surface by ion bombardment, the desorption temperature of CH3SH is extended to 300 K and a small amount of dimethyl disulfide is observed to desorb at 410 K, indicating that S-H bond scission occurs on defect sites on Au(111) followed by dimerization of CH3S(a) species. Propanethiol also adsorbs nondissociatively on the Au(111) surface and desorbs from the surface below 250 K. 相似文献
13.
W. Zielenkiewicz B. Golankiewicz G. L. Perlovich M. Koźbiał 《Journal of solution chemistry》1999,28(6):731-745
Solubilities of tricyclic analogs of acyclovir have been determined in water at 25, 35, and 45°C and in octanol, water-saturated octanol, and octanol-saturated water at 25°C. Octanol-water partition coefficients were determined at 25°C. Melting temperatures and molar enthalpies of fusion were measured. Activity coefficients in water, octanol, and in aqueous octanol solutions were determined and are discussed. The effect of hydrophilic and hydrophobic substituents in the tricyclic analogs on their thermodynamic properties are discussed. The standard Gibbs energy of transfer between the saturated phases were found to correlate with known values of the melting point of the solvents and the solubilities of the solute. For a number of the compounds examined, correlations between the minimum inhibitory concentration against the herpes simplex virus type 1 (HSV-1) and type 2 (HSV-2), varicella-zoster virus (VZV), thymidine kinase-deficient (TK–) strains of VZV and
were established. Detailed conclusions have been derived concerning the relationships between the structure and the thermodynamic parameters of the compounds examined. 相似文献
14.
Data on the mean multiplicity of
- produced in minimum bias proton-proton, proton-neutron and proton-nucleus interactions as well as central nucleus-nucleus collisions at momenta of 1.4–400 GeV/c per nucleon have been compiled and studied. The results for neutron-neutron and nucleon-nucleon interactions were then constructed. The dependence of the mean pion multiplicity in proton-nucleus interactions and central collisions of identical nuclei are studied as a function of the collision energy and the nucleus mass number. The number of produced pions per participant nucleon in central collisions of identical nuclei is found to be independent of the number of participants at a fixed incident momentum per nucleon. The mean multiplicity of negatively charged hadrons per participant nucleon for central nucleus-nucleus collisions is lower by about 0.12 than the corresponding multiplicity for nucleon-nucleon interactions atp
LAB
15 A·GeV/c, whereas the result at 200 A·GeV/c is above the corresponding nucleon-nucleon multiplicity. This may indicate change of the collision dynamics at high energy. 相似文献
15.
Zdzislaw Brzeźniak Marek Capiński Franco Flandoli 《Probability Theory and Related Fields》1993,95(1):87-102
Summary The asymptotic behaviour of random dynamical systems in Polish spaces is considered. Under the assumption of existence of a random compact absorbing set, assumption supposed to hold path by path, a candidate pathwise attractorA() is defined. The goal of the paper is to show that, in the case of stationary dynamical systems,A() attracts bounded sets, is measurable with respect to the -algebra of invariant sets, and is independent of when the system is ergodic. An application to a general class of Navier-Stokes type equations perturbed by a multiplicative ergodic real noise is discussed in detail. 相似文献
16.
Summary We consider the problem of optimal quadratures for integrandsf: [–1,1] which have an analytic extension
to an open diskD
r
of radiusr about the origin such that
1 on
. Ifr=1, we show that the penalty for sampling the integrand at zeros of the Legendre polynomial of degreen rather than at optimal points, tends to infinity withn. In particular there is an infinite penalty for using Gauss quadrature. On the other hand, ifr>1, Gauss quadrature is almost optimal. These results hold for both the worst-case and asymptotic settings.This research was supported in part by the National Science Foundation under Grants MCS-8203271 and MCS-8303111This research was supported in part by the National Science Foundation under Grant MCS-8923676 相似文献
17.
W. Bocian J. Jaźwiński O. Staszewska J. W. Wiench L. Stefaniak G. A. Webb 《Chemistry of Heterocyclic Compounds》1996,32(11-12):1358-1366
Multinuclear1H,13C,14N,15N, and17O NMR data are presented for some sydnones, isosydnones and isothiosydnones. The type of valence tautomerism shown in (Fig. 1) is not observed for the compounds studied. At high pH compounds2 and12 are found to undergo transformations. The more suitable NMR parameters are reported for establishing the structures of mesoionic compounds containing three heteroatoms in the five-membered conjugated ring. Someab initio GIAO calculations on a model structure of sydnones and related compounds have been performed. 相似文献
18.
Commercially available 1,4-dioxane, even of spectroscopic grade, contains various impurities that arise mostly from reaction of the solvent with oxygen. Aspects relevant to the spectroscopy and photochemistry of the dioxane/oxygen system are discussed. Methods of purification and storage of the solvent are presented. 相似文献
19.
This study presented results on reduction of alumina
supported chromium and platinum–chromium catalysts using temperature
programmed reduction method (TPR). It has been shown that catalysts after
earlier oxidation step but without calcinations one undergo reduction in lower
temperature in comparison to calcined only catalysts. Moreover, addition platinum
to Cr/Al2O3 catalysts also caused
decrease of reduction temperature. It has been observed that over the examined
catalysts oxidation CO to CO2 and reduction CO to CH4
occurs. However, on Pt–Cr catalysts both reactions proceed at lower
temperature compare to Cr catalysts. 相似文献
20.
An extraction-AAS method of determination of Co, Ni, and Mn in metallurgical copper materials containing considerable amounts ofCu, Fe, Pb, Zn, and Al has been developed. Good selectivity of group separation of Co, Ni, and Mn has been achieved by (a) the use of tetrabutylammonium bromide to improve extractability of HTTA complexes by ion-pair formation, and (b) the masking of major elements with sodium thiosulphate and sulphosalicylic acid. The extracts are stable for at least 3 weeks. 相似文献