全文获取类型
收费全文 | 2991篇 |
免费 | 103篇 |
国内免费 | 4篇 |
专业分类
化学 | 2153篇 |
晶体学 | 6篇 |
力学 | 38篇 |
数学 | 582篇 |
物理学 | 319篇 |
出版年
2021年 | 30篇 |
2020年 | 41篇 |
2019年 | 36篇 |
2018年 | 25篇 |
2016年 | 81篇 |
2015年 | 65篇 |
2014年 | 74篇 |
2013年 | 93篇 |
2012年 | 120篇 |
2011年 | 142篇 |
2010年 | 81篇 |
2009年 | 89篇 |
2008年 | 108篇 |
2007年 | 103篇 |
2006年 | 104篇 |
2005年 | 72篇 |
2004年 | 97篇 |
2003年 | 62篇 |
2002年 | 73篇 |
2001年 | 43篇 |
2000年 | 47篇 |
1999年 | 43篇 |
1998年 | 47篇 |
1997年 | 32篇 |
1996年 | 28篇 |
1995年 | 44篇 |
1994年 | 35篇 |
1993年 | 38篇 |
1992年 | 35篇 |
1991年 | 40篇 |
1990年 | 30篇 |
1989年 | 46篇 |
1988年 | 38篇 |
1987年 | 34篇 |
1986年 | 29篇 |
1985年 | 47篇 |
1984年 | 35篇 |
1983年 | 41篇 |
1982年 | 30篇 |
1981年 | 22篇 |
1980年 | 36篇 |
1979年 | 30篇 |
1978年 | 27篇 |
1977年 | 36篇 |
1976年 | 23篇 |
1975年 | 19篇 |
1973年 | 17篇 |
1971年 | 21篇 |
1934年 | 27篇 |
1933年 | 17篇 |
排序方式: 共有3098条查询结果,搜索用时 250 毫秒
81.
82.
Zusammenfassung Acenaphthylen wurde durch Anpolymerisation und zweifache Hochvakuumsublimation gereinigt. Die Reinigungsmethode wird ausführlich beschrieben.Bei verschiedenen Temperaturen wurde mit einer dilatometrischen Methode die thermische Bruttogeschwindigkeit gemessen. Zwischen 95 und 105 °C giltk
br=7,08·1010 exp (– 30,9 kcal/RT).Die beträchtliche Aktivierungsenergie der Bruttoreaktion ist sowohl auf eine große Aktivierungsenergie der thermischen Startreaktion als auch auf eine relativ hohe Wachstumsaktivierungsenergie zurückzuführen.Das Polymerisationsverhalten von Acenaphthylen kann vermutlich aufgrund seiner sterischen Eigenschaften erklärt werden.
Summary Acenaphthylene was purified by partial polymerisation, followed by double stage high vacuum sublimation. The method of purification is described in detail.The thermal overall rate was measured at different temperatures by a dilatometric method. Between 95 and 105 °C the following relation holds:k th=7,08 · 1010 exp (– 30,9 kcal/RT).The considerable energy of activation of the overall reaction depends on a relatively high energy of activation of both the thermal initiation and the propagation reaction.It is supposed, that the polymerisation behaviour of acenaphthylene depends mainly on its steric properties.相似文献
83.
Pericet-Camara R Papastavrou G Borkovec M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(8):3264-3270
The adsorption behavior of poly(amidoamine) dendrimers to mica surfaces was investigated as a function of ionic strength and pH. The conformation and lateral distribution of the adsorbed dendrimers of generations G8 and G10 were obtained ex situ by tapping mode atomic force microscopy (AFM). The deposition kinetics of the dendrimers was found to follow a diffusion-limited process. Fractional surface coverage and pair correlation functions of the adsorbed dendrimers were obtained from the AFM images. The data are interpreted in terms of the random sequential adsorption (RSA) model, where electrostatic repulsion due to overlapping double layers is considered. Although the general trends typical for an RSA-determined process are well-reproduced, quantitative agreement is lacking at low ionic strengths. 相似文献
84.
The rhodium(I) complexes trans‐[Rh(diphos)(CO)Cl] 7 (diphos=pbpb), 8 (diphos=nbpb), and 9 (diphos=cbpb) were synthesized (Scheme 4) and used as catalysts for the carbonylation of MeOH to AcOH (Scheme 1). The trans coordination imposed by the rigid C‐spacer framework of the diphos ligands pbpb, nbpb, and cbpb, demonstrated by 31P‐NMR and IR spectroscopy of 7 – 9 and unambiguously confirmed by single‐crystal X‐ray structure analysis of 7 , improved the thermal stability of the rhodium(I) system under carbonylation conditions and, hence, the catalytic performance of the complexes. For the catalytic carbonylation of MeOH, the active catalyst could be prepared in situ from the mixture of [Rh(CO)2Cl]2 and the corresponding diphos ligand pbpb, nbpb, or cbpb, giving the same results as carbonylation in the presence of the isolated complexes 7, 8 or 9 (see Table). The highest activity was observed for complex 7 (or the mixture [Rh(CO)2Cl]2/pbpb, the catalytic turnover number (TON) being 950 after 15 min (170°, 22 bar). 相似文献
85.
Sem DS Bertolaet B Baker B Chang E Costache AD Coutts S Dong Q Hansen M Hong V Huang X Jack RM Kho R Lang H Ma CT Meininger D Pellecchia M Pierre F Villar H Yu L 《Chemistry & biology》2004,11(2):185-194
Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases. 相似文献
86.
Werner Georg Nowak 《manuscripta mathematica》1982,39(2-3):277-285
Let G (R) denote the number of lattice points (,) **Z2 in the domain B(R) bounded by the lemniscate (x2+y2)2=2R2 (x2–y2) and put P(R)=G(R)-R2(R2 being the area of B(R)). The purpose of this paper is to determine the order of magnitude of P(R) for large R by proving the asymptotic relation (3). An analogous result is given for the eight curve x4=R2 (x2–y2). 相似文献
87.
Bismuth Monoiodide, a Compound with Bi(O) and Bi(II) Bismuth monoiodide was synthesized in closed tubes from the elements as well as from Bi and HgI2 as a black coloured crystalline compound. With increasing temperature BiI passes two transitions. α-BiI is stable below 370 K and changes to β-BiI by a martensitic transition. γ-BiI is the stable modification above 564 K and decomposes at 585 K peritectically to BiI3 and a lower iodide. All three modification crystallize in the monoclinic space group C2/m. The structures (single crystal studies) of α-BiI and β-BiI are characterized by onedimensional infinite chains [Bi4I4] with covalent bonds but only weak interactions in between. The [Bi4I4]-chains are built up by two completely different Bi atoms. Bi(A) is only bonded to three Bi whereas Bi(B) has bonds to one Bi and four I. The average bond lengths are Bi? Bi = 304.5 pm and Bi? I = 313.7 pm respectively. The configuration of the Bi(A) atoms is typical for BiO and that one of the Bi(B) atoms is characteristic for Bi2+ with the electron configuration s2p1. Therefore, α-BiI and β-BiI are mixed valence compounds [BiOBi2+I4]. The structures are variants of the simple cubic polonium type of structure and differ in the stacking of connected units. The structures and their transitions, the possible configurations for monohalides BiX on principle as well as the energy balances of the disproportionation of Bi+ are discussed together in detail. 相似文献
88.
[reaction: see text] The combination of diethyl phosphite and DMAP as ligands for nickel in an 8:1 THF-N-ethylpyrrolidinone (NEP) mixture allows a very efficient cross-coupling reaction to be performed between various functionalized arylzinc halides and aryl bromides, triflates and activated chlorides. The reaction proceeds at 25 degrees C within 1-48 h and requires only 0.05 mol % of the nickel catalyst. 相似文献
89.
We present the results of relativistic and non-relativistic self-consistent field and configuration interaction calculations for the gold atom, using the spin-free no-pair Hamiltonian in a basis set expansion. A new basis set for the gold atom is discussed and its results in relativistic and non-relativistic self-consistent field calculations are compared to those of numerical Dirac-Hartree-Focic and Hartree-Fock calculations, respectively. Excitation energies, electron affinities and ionization potentials were calculated using a multi-reference configuration interaction technique and are in reasonable agreement with experiment in the relativistic case. 相似文献
90.