全文获取类型
收费全文 | 1048篇 |
免费 | 21篇 |
国内免费 | 3篇 |
专业分类
化学 | 774篇 |
晶体学 | 11篇 |
力学 | 4篇 |
数学 | 191篇 |
物理学 | 92篇 |
出版年
2022年 | 14篇 |
2021年 | 21篇 |
2020年 | 18篇 |
2019年 | 18篇 |
2018年 | 13篇 |
2017年 | 13篇 |
2016年 | 21篇 |
2015年 | 32篇 |
2014年 | 35篇 |
2013年 | 54篇 |
2012年 | 51篇 |
2011年 | 46篇 |
2010年 | 36篇 |
2009年 | 48篇 |
2008年 | 75篇 |
2007年 | 67篇 |
2006年 | 56篇 |
2005年 | 67篇 |
2004年 | 48篇 |
2003年 | 50篇 |
2002年 | 34篇 |
2001年 | 19篇 |
2000年 | 11篇 |
1998年 | 14篇 |
1997年 | 11篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 11篇 |
1993年 | 9篇 |
1992年 | 11篇 |
1991年 | 4篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 10篇 |
1987年 | 5篇 |
1985年 | 4篇 |
1984年 | 12篇 |
1983年 | 7篇 |
1982年 | 9篇 |
1980年 | 6篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 8篇 |
1975年 | 9篇 |
1974年 | 3篇 |
1973年 | 8篇 |
1943年 | 4篇 |
1939年 | 3篇 |
1938年 | 4篇 |
1937年 | 3篇 |
排序方式: 共有1072条查询结果,搜索用时 15 毫秒
1.
Imre Csiszár 《Bulletin of the Brazilian Mathematical Society》2006,37(4):453-459
A simple self-contained proof of Sanov's theorem in τ-topology is given, well suited for a first course on large deviations.
*This work was supported by the Hungarian National Foundation for Scientific Research under Grant T046376 相似文献
2.
Angla Schwartz Lszl Szab Katalin Pusztay-Szab Istvn Hermecz Zoltn Mszros 《Journal of heterocyclic chemistry》1987,24(3):655-660
Ultraviolet-visible spectra of 4-oxo 1 and 4-imino 2 quinolizines or their monocyclic tautomers 3, 4 have been studied in neutral, acidic and basic ethanolic solution as well as in dimethyl sulfoxide and chloroform. Ring B of 4-oxo and 6-unsubstituted 4-imino compounds can be cleaved by sodium ethanolate more or less easily. Ring B of 6-methyl-4-iminoquinolizines is very unstable and they are present mainly in the monocyclic form which are partly dissociated in ethanol and dimethyl sulfoxide especially in higher dilution or in the presence of sodium ethanolate. In dilute acidic ethanol or chloroform, the dissociation is suppressed and in the latter solvent and in some cases, absorption bands can be observed due to a small amount of the 4-imino-6-methylquinolizines. In acidic solution of compounds 3B=C, 3D, 4E, 4F=G having simultaneously cyano and ethoxycarbonyl groups in 1 and 3 position, not simple reprotonation occurs but irreversible changes can be observed. 相似文献
3.
Aiming at a simultaneous extension of Khintchine(X,X,m,T)(X,\mathcal{X},\mu,T)
and a set
A ? XA\in\mathcal{X}
of positive measure, the set of integers n such that
A T^2nA T^knA)(A)^k+1-\mu(A{\cap} T^{n}A{\cap} T^{2n}A{\cap} \ldots{\cap} T^{kn}A)>\mu(A)^{k+1}-\epsilon
is syndetic. The size of this set, surprisingly enough, depends on the length (k+1) of the arithmetic progression under consideration. In an ergodic system, for k=2 and k=3, this set is syndetic, while for kòf(x)f(Tnx)f(T2nx)? f(Tknx) dm(x)\int{f(x)f(T^{n}x)f(T^{2n}x){\ldots} f(T^{kn}x) \,d\mu(x)}
, where k and n are positive integers and f is a bounded measurable function. We also derive combinatorial consequences of these results, for example showing that for a set of integers E with upper Banach density d*(E)>0 and for all
{n ? \mathbbZ\colon d*(E?(E+n)?(E+2n)?(E+3n)) > d*(E)4-e}\big\{n\in\mathbb{Z}{\colon} d^*\big(E\cap(E+n)\cap(E+2n)\cap(E+3n)\big) > d^*(E)^4-\epsilon\big\} 相似文献
4.
The aim of the paper is to investigate the limit behaviour of the least squares estimator of the shift parameter of nearly unstable, nearly stable, and nearly explosive AR(1) models. Both zero start and stationary cases are treated. Connection with the maximum likelihood estimator of the shift parameter of continuous time AR(1) processes is also discussed. 相似文献
5.
István Szilágyi László. Horváth Imre Labádi Klara Hernadi István Pálinkó Tamás Kiss 《Central European Journal of Chemistry》2006,4(1):118-134
An imidazolate-bridged copper(II)-zinc(II) complex (Cu(II)-diethylenetriamino-μ-imidazolato-Zn(II)-tris(2-aminoethyl)amine perchlorate (denoted as “Cu,Zn complex”) and a simple copper(II) complex (Cu(II)-tris(2-aminoethyl)
amine chloride (“Cu-tren”) were prepared and immobilised on silica gel (by hydrogen or covalent bonds) and montmorillonite
(by ion exchange). The immobilised substances were characterised by FT-IR spectroscopy and their thermal characteristics were
also studied. The obtained materials were tested in two probe reactions: catalytic oxidation of 3,5-di-tert-butyl catechol (DTBC) (catecholase activity) and the decomposition of hydrogen peroxide (catalase activity). It was found
that the catecholase activity of the Cu,Zn complex increased considerably upon immobilization on silica gel via hydrogen bonds and intercalation by ion exchange among the layers of montmorillonite. The imidazolate-bridged copper(II)-zinc(II)
complex and its immobilised versions were inactive in hydrogen peroxide decomposition. The Cu(II)-tris(2-aminoethyl)amine
chloride complex displayed good catalase activity; however, immobilisation could not improve it. 相似文献
6.
Katalin E. Kövér Dušan Uhr?&#x;n Victor J. Hruby 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1998,130(2):162-168
A pulsed field gradient version of the sensitivity-enhanced 2D TOCSY experiment is proposed which yields high-quality spectra with improved sensitivity and a minimum of two scans pert1increment. For rapid acquisition of 1D TOCSY spectra, the 1D DPFGSE–TOCSY experiment was modified to include phase-encoded multiple-selective excitation followed by a simple spectral editing. Combination of these two building blocks is used in a sensitivity-enhanced 2D analog of the 3D TOCSY–TOCSY experiment which provides an efficient tool for resolving severely overlapped signals of oligomers in short experimental time. 相似文献
7.
The aim of this research work was to clarify the role of the mixed emulsifier in the structure formation and water binding
mode in the case of o/w creams prepared with different surfactants. The swelling behavior of mixed emulsifiers was examined
by means of direct investigation methods such as transmission electron microscopy (TEM) and X-ray diffraction. The detailed
structure image of the creams was created with the help of the latter. The influence of the structure of the hydrophilic gel
phase, and the structural changes during storage were studied with rheological methods. On the basis of the results, it can
be stated that the investigated creams had different structures from those mentioned in the literature: surfactant did not
create a mixed bilayer with the structure to furnish fatty amphiphile; instead, micelles were formed. These results correlated
well with the results of the rheological tests. 相似文献
8.
Valentina Domenici Carlo Alberto Veracini Katalin Fodor-Csorba Giacomo Prampolini Ivo Cacelli Andrjia Lebar Bostjan Zalar 《Chemphyschem》2007,8(16):2321-2330
The orientational properties of the banana-shaped liquid crystal 4-chloro-1,3-phenylenebis{4-[4'-(10-undecenyloxy)]benzoyloxy} benzoate (ClPbis11BB) are reported in the nematic phase under the effect of an external magnetic field. A new hypothesis, which states that the central ring of the aromatic core is oriented perpendicularly to the external magnetic field, is proposed. In support of this hypothesis, a series of studies based on (2)H NMR spectroscopy, both in the bulk and in solution, are discussed. (2)H NMR measurements on three selectively deuterium-labelled isotopomers are presented, together with DFT results from B3LYP/cc-pvDz calculations performed on the aromatic core. The rather flat shape of the investigated intramolecular energy surface allows for several different conformations to be populated, the computed magnetic susceptibilities of which are consistent with the proposed hypothesis of peculiar orientation of banana-shaped molecules. Moreover, the orientation of the magnetic susceptibility tensor is shown to be strongly dependent on the internal conformation of the banana-shaped molecules. 相似文献
9.
Szöllosi G Bucsi I Cserényi S Bartók M 《Rapid communications in mass spectrometry : RCM》2005,19(24):3743-3748
We have studied the adsorption on a platinum (Pt) catalyst of two compounds utilizable as a chiral basic catalyst and a chiral modifier, dihydrocinchonidine (DHCD), and a new cinchona alkaloid derivative containing a bulky group, the Ph3SiO-DHCD molecule. The method of choice was the detection by electrospray ionization (ESI) ion-trap tandem mass spectrometry (MS/MS) of hydrogen/deuterium (H/D) exchange at room temperature, in tetrahydrofuran, at a D2 pressure of 1 bar. Based on the ESI-MS/MS spectrum of the new compound, we propose a mechanism for the formation of the silatropylium cation containing a Si-O bond. From the fragmentation pattern of Ph3SiO-DHCD it was confirmed that ESI-ion-trap MS/MS can be used to study the adsorption processes of complicated carbon compounds by investigating their H/D exchange reactions. In the case of Ph3SiO-DHCD, the results demonstrate that H/D exchange takes place mainly on the quinoline skeleton. However, the strong pi-bonded adsorption of the quinoline skeleton parallel with the imaginary plane of Pt is not preferred because the bulky Ph3Si group inhibits the multiple pi-bonded adsorption of the Ph3SiO-DHCD. Because of this hindrance the molecule was adsorbed tilted via the nonbonding electron pair of the N atom and C2' atom of the quinoline skeleton; consequently, mainly alkaloid-d1 and alkaloid-d2 are formed. 相似文献
10.
Perczel A Jákli I McAllister MA Csizmadia IG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(11):2551-2566
Folding properties of small globular proteins are determined by their amino acid sequence (primary structure). This holds both for local (secondary structure) and for global conformational features of linear polypeptides and proteins composed from natural amino acid derivatives. It thus provides the rational basis of structure prediction algorithms. The shortest secondary structure element, the beta-turn, most typically adopts either a type I or a type II form, depending on the amino acid composition. Herein we investigate the sequence-dependent folding stability of both major types of beta-turns using simple dipeptide models (-Xxx-Yyy-). Gas-phase ab initio properties of 16 carefully selected and suitably protected dipeptide models (for example Val-Ser, Ala-Gly, Ser-Ser) were studied. For each backbone fold most probable side-chain conformers were considered. Fully optimized 321G RHF molecular structures were employed in medium level [B3LYP/6-311++G(d,p)//RHF/3-21G] energy calculations to estimate relative populations of the different backbone conformers. Our results show that the preference for beta-turn forms as calculated by quantum mechanics and observed in Xray determined proteins correlates significantly. 相似文献