全文获取类型
收费全文 | 2919篇 |
免费 | 161篇 |
国内免费 | 15篇 |
专业分类
化学 | 2184篇 |
晶体学 | 5篇 |
力学 | 46篇 |
数学 | 325篇 |
物理学 | 535篇 |
出版年
2023年 | 30篇 |
2022年 | 27篇 |
2021年 | 40篇 |
2020年 | 70篇 |
2019年 | 76篇 |
2018年 | 43篇 |
2017年 | 41篇 |
2016年 | 94篇 |
2015年 | 112篇 |
2014年 | 84篇 |
2013年 | 127篇 |
2012年 | 163篇 |
2011年 | 178篇 |
2010年 | 122篇 |
2009年 | 91篇 |
2008年 | 169篇 |
2007年 | 149篇 |
2006年 | 142篇 |
2005年 | 165篇 |
2004年 | 129篇 |
2003年 | 97篇 |
2002年 | 121篇 |
2001年 | 55篇 |
2000年 | 48篇 |
1999年 | 41篇 |
1998年 | 45篇 |
1997年 | 64篇 |
1996年 | 48篇 |
1995年 | 51篇 |
1994年 | 50篇 |
1993年 | 36篇 |
1992年 | 34篇 |
1991年 | 22篇 |
1990年 | 28篇 |
1989年 | 17篇 |
1988年 | 10篇 |
1987年 | 21篇 |
1986年 | 23篇 |
1985年 | 22篇 |
1984年 | 25篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 13篇 |
1979年 | 11篇 |
1977年 | 16篇 |
1975年 | 8篇 |
1974年 | 9篇 |
1973年 | 7篇 |
1971年 | 11篇 |
排序方式: 共有3095条查询结果,搜索用时 62 毫秒
61.
R. Ott 《Monatshefte für Chemie / Chemical Monthly》1955,86(4):622-636
Zusammenfassung Durch weitere Untersuchungen und Abbaureaktionen an dem bisher als o-Chinon formulierten Oxydationsprodukt des 1,2-4,5-Dibenzpyrens wird es als ein Pyren-3,7-chinon erkannt. Obwohl es somit ein amphi-Chinon ist, reagiert es mit o-Phenylendiamin unter Phenazinbildung. Die Tautomerieerscheinungen am Oxydibenzpyrenchinon und Oxy-dibenzpyrenophenazin werden erörtert und Vergleiche mit dem amphi-Chrysenchinon und den entsprechenden Derivaten gezogen. Die Farbreaktion der beiden amphi-Chinone, ähnlich derBambergerschen für o-Chinone, zeigt, daß eine solche nicht unbedingt beweisend für o-Stellung der Carbonyle ist. Der auffallende Oxydationsverlauf am 1,2-4,5-Dibenzpyren, der zu keinem 3,8- bzw. 3,10-Chinon führt, wird besprochen. Die Verseifung des Benzoylderivats des Oxyphenazins beim Chromatographieren an Al2O3 wurde beobachtet. 相似文献
62.
The influence of a xenobiotic compound on an organism is usually summarized by the expression biological activity. If a controlled, therapeutically relevant, and regulatory action is observed the compound has potential as a drug, otherwise its toxicity on the biological system is of interest. However, what do we understand by the biological activity? In principle, the overall effect on an organism has to be considered. However, because of the complexity of the interrelated processes involved, as a simplification primarily the "main action" on the organism is taken into consideration. On the molecular level, biological activity corresponds to the binding of a (low-molecular weight) compound to a macromolecular receptor, usually a protein. Enzymatic reactions or signal-transduction cascades are thereby influenced with respect to their function for the organism. We regard this binding as a process under equilibrium conditions; thus, binding can be described as an association or dissociation process. Accordingly, biological activity is expressed as the affinity of both partners for each other, as a thermodynamic equilibrium quantity. How well do we understand these terms and how well are they theoretically predictable today? The holy grail of rational drug design is the prediction of the biological activity of a compound. The processes involving ligand binding are extremely complicated, both ligand and protein are flexible molecules, and the energy inventory between the bound and unbound states must be considered in aqueous solution. How sophisticated and reliable are our experimental approaches to obtaining the necessary insight? The present review summarizes our current understanding of the binding affinity of a small-molecule ligand to a protein. Both theoretical and empirical approaches for predicting binding affinity, starting from the three-dimensional structure of a protein-ligand complex, will be described and compared. Experimental methods, primarily microcalorimetry, will be discussed. As a perspective, our own knowledge-based approach towards affinity prediction and experimental data on factorizing binding contributions to protein-ligand binding will be presented. 相似文献
63.
The difference in steric strain between the oxidized and the reduced forms of tetraaminecopper complexes is correlated with the corresponding reduction potentials. The experimentally determined data considered range from ?0.54 to ?0.04 V (vs. NHE) in aqueous solution and from ?0.35 to ?0.08 V (vs. NHE) in MeCN. The observed and/or computed geometries of the tetraaminecopper(II) complexes are distorted octahedral or square-pyramidal (4 + 2 or 4+1) with (distorted) square-planar CuN4 chromophores (CuII? N = 1.99–2.06 Å; Cu? O ≈ 2.5 Å; Cu? O ≈ 2.3 Å), those of the tetraaminecopper(I) complexes are (distorted) tetrahedral (four-coordinate; CuI? N = 2.12–2.26 Å; tetrahedral twist angle ?? = 30–90°). The reduction potentials of CuII/I couples with primary-amine ligands and those with macrocyclic secondary-amine ligands were correlated separately with the corresponding strain energies, leading to slopes of 70 and 61 kJ mol?1 V?1, with correlation coefficients of 0.89 and 0.91, respectively. The approximations of the model (entropy, solvation, electronic factors) and the limits of applicability are discussed in detail and in relation to other approaches to compute reduction potentials of transition-metal compounds. 相似文献
64.
[reaction: see text] Fmoc-protected amino acid fluorides were found to be excellent reagents for the acylation of sulfonamide safety-catch linkers (SCL) suitable for the subsequent preparation of peptide C-terminal thioesters. High loadings were obtained on different types of resins with low levels of epimerization. 相似文献
65.
Susanne Bredendiek-Kämper Holger Jenett 《Fresenius' Journal of Analytical Chemistry》1993,346(1-3):315-317
Summary The system of plasma sprayed Al2O3 on Ni substrates is investigated by means of AES/depth profiling. The influence of two process parameters — preoxidation procedure and spraying temperature — is examined. Rupture between substrate and ceramic layer occurs between a residual — or, in the case of excessive preoxidation, a superfluous — NiO layer on Ni, the thickness of the former depending on preoxidation conditions and the Al2O3 layer, the back side of which being partially covered with NiO. The thickness of this NiO layer increases up to about 1 m with the thickness of the initial NiO layer on the substrate, until this layer is about 1.3 m thick, and remains constant thereafter. The same dependence is observed for the width (0.1–1 m range) of the mixed oxide interface between the sprayed Al2O3 layer and the NiO layer below. These results represent the chemical contribution to adherence. Contrary to excessive preoxidation, an increase of the spraying temperature from 300°C to 500°C effects broader interfaces.This poster was awarded the First Prize in Poster Section C by the Deutscher Arbeitskreis für Spektroskopie (DASp) 相似文献
66.
The Au-.CO2 ion-molecule complex has been studied by gas phase infrared photodissociation spectroscopy. Several sharp transitions can be identified as combination bands involving the asymmetric stretch vibrational mode of the CO2 ligand. Their frequencies are redshifted by several hundred cm(-1) from the frequencies of free CO2. We discuss our findings in the framework of ab initio and density-functional theory calculations, using anharmonic corrections to predict vibrational transition energies. The infrared spectrum is consistent with the formation of an aurylcarboxylate anion with a strongly bent CO2 subunit. 相似文献
67.
68.
The protected 2-formyl-L-arabinal 2 reacted with thiourea and cyanamide in the presence of sodium hydride to afford via ring transformations the 5-[1R,2S-1,2- bis(benzyloxy)-3-hydroxypropyl]-1,2-dihydropyrimidines 3 and 4, respectively. Similarly, treatment of 2 with 3-amino-2H-1,2,4-triazole yielded 6-[1R,2S-1,2- bis(benzyloxy)-3-hydroxypropyl][1,2,4]-triazolo[1,5-a]pyrimidine (5). 相似文献
69.
The stability of gold phosphine complexes of the form [Au(PH(3))(n)()](+) (n = 1-4) and [AuCl(PH(3))(n)()] (n = 1-3) is analyzed in detail by applying quantum theoretical methods and compared to the coordination behavior of the lighter group 11 elements copper and silver. It is shown that, once [M(PH(3))(2)](+) or [MClPH(3)] (M = Cu, Ag, and Au) is formed, further coordination by PH(3) ligands is relatively weak; i.e., the energy gain to form [M(PH(3))(3)](+) from [M(PH(3))(2)](+) is less than 60 kJ mol(-)(1), and less than 100 kJ mol(-)(1) to form [MCl(PH(3))(2)] from [MClPH(3)]. Relativistic effects in gold significantly influence these factors and reduce the tendency for phosphine coordination beyond two-coordination. This implies that the most favored coordination number for gold is two with either a linear P-Au-P or P-Au-X arrangement (X = a strongly coordinating ligand like Cl(-)). Instead, X-Au-PH(3) units prefer to interact via close Au-Au contacts (aurophilic interactions) keeping the linear structure approximately intact, while the corresponding copper and silver compounds prefer PH(3) coordination to strongly bound M(2)Cl(2) units (M = Cu or Ag) where two chlorine atoms bridge the two metal atoms thus having the formal coordination number of three for copper or silver. 相似文献
70.
Single crystal structure determinations prove the two pyridine substituents in di(2-pyridyl)ketone (H4C4NC)2C=O to be twisted out of the carbonyl skeleton plane by torsion angles (OCCN) of 41° and –163°, in contrast to their planar arrangement in azo-di(2-pyridine) H4C4NC)-N=N-(CNC4H4). In order to rationalize the surprising difference between the two isoelectronic molecules, approximate PM3 enthalpy of formation hypersurfaces have been calculated for each of the two ring torsions, which are assumed to be the dominant ones among the 3N – 6 = 60 degrees of freedom. For both the ketone and the azo derivative, global minima are calculated, the torsion angles of which deviate from the crystal structure results, and, therefore, support the assumption that both the experimentally determined twisting of di(2-pyridyl)ketone as well as the flattening of azo-di(2-pyridine) might be affected by the crystal packing. 相似文献