全文获取类型
收费全文 | 619篇 |
免费 | 4篇 |
国内免费 | 3篇 |
专业分类
化学 | 363篇 |
晶体学 | 2篇 |
力学 | 21篇 |
数学 | 146篇 |
物理学 | 94篇 |
出版年
2022年 | 8篇 |
2021年 | 15篇 |
2020年 | 10篇 |
2019年 | 8篇 |
2018年 | 8篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 16篇 |
2013年 | 40篇 |
2012年 | 40篇 |
2011年 | 32篇 |
2010年 | 24篇 |
2009年 | 29篇 |
2008年 | 22篇 |
2007年 | 18篇 |
2006年 | 18篇 |
2005年 | 14篇 |
2004年 | 29篇 |
2003年 | 23篇 |
2002年 | 22篇 |
2001年 | 10篇 |
2000年 | 19篇 |
1999年 | 13篇 |
1998年 | 6篇 |
1997年 | 12篇 |
1996年 | 9篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 14篇 |
1991年 | 7篇 |
1990年 | 3篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1983年 | 10篇 |
1982年 | 3篇 |
1981年 | 10篇 |
1980年 | 6篇 |
1979年 | 7篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 3篇 |
1971年 | 3篇 |
1970年 | 3篇 |
1906年 | 3篇 |
排序方式: 共有626条查询结果,搜索用时 15 毫秒
151.
Summary The complexes formed from cobalt(III) and dipeptides such as glycylglycine, glycylaspartic acid, glycylthreonine, glycyltyrosine and glycylproline were studied. The formation process of cobalt(III)-dipeptide species was investigated by spectrophotometry after oxidizing the cobalt(II) complexes by sodium peroxide. The formation of the cobalt(III) complexes occurs through an oxo-intermediate, as shown by the spectral behaviour, and depends on the pH of the solutions.Complex stoichiometries, molar absorptivities and concentration ratios at the equilibrium of the cobalt(III)-dipeptide complexes were determined at pH 2.2 to avoid the formation of binuclear dioxygen-cobalt complexes. 相似文献
152.
Roberto Pellicciari Benedetto Natalini A. Ricci G. Alunni-Bistocchi G. De Meo 《Journal of heterocyclic chemistry》1978,15(6):927-928
By application of the Friedlander synthesis on 2,3-dihydro-l-benzothiepin-4(5H) one (4), the corresponding [4,5-b]quinoline derivatives 5a and 5b were obtained. Starting from the ketone (4) and by application of the Fischer indole synthesis, 1-benzolhiepino[4,5-b ]indole (6) and 1-benzothiepino[4,5-b]benzo[g]indole (7) were obtained. When β-naphthylhydrazine was used in the indolisation reaction, a mixture of 1-benzothiepino[4,5-b]benzo[e]indole ( 8 ) and 1-benzothiepino[4,3-b]benzo[e] indole (9) was obtained. 相似文献
153.
Sedlácek J Pacovská M Rédrová D Balcar H Biffis A Corain B Vohlídal J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(2):366-371
The first heterogeneous catalyst which affords polymerization of substituted acetylenes into readily available high molecular weight polymers is reported. The catalyst (Rh/PBI) has been prepared by supporting di-mu-chloro-bis(eta4-cycloocta-1,5-diene)dirhodium(I), [Rh(cod)Cl]2, on commercial polybenzimidazole (PBI) porous beads by means of a simple quantitative adsorption from THF solution, and tested in polymerization of phenylacetylene, 4-fluorophenylacetylene, and 4-pentylphenylacetylene. The polymer molecules formed were found to be released from the Rh/PBI to surrounding solution during the polymerization performed in THF. Formation of high molecular weight ((M)w values up to 325,000) polymers in prevailing cis-transoid configuration has been observed with all monomers. In a comparison with free [Rh(cod)Cl]2 used as the homogeneous catalyst, the Rh/PBI can be used repeatedly, exhibits somewhat lower polymerization activity but almost no oligomerization activity, and provides polymers of higher molecular weight. 相似文献
154.
Pier Luigi Ferrarini Giuliana Biagi Oreste Livi Giampaolo Primofiore Marino Carpen 《Journal of heterocyclic chemistry》1981,18(5):1007-1010
Some 3-substituted-5,6-dihydro[1,8]naphthyrido[3,2-c][1,8]naphthyridines (V) were obtained by the condensation of 7-substituted-2,3-dihydro-1,8-naphthyridin-4-(1H)ones (IV) with 2-aminonicotinaldehyde. All of the 5,6-dihydro derivatives V were transformed into the fully aromatic compounds VI by refluxing with nitrobenzene. 相似文献
155.
Giuliana Gervasio Domenica Marabello Enrico Sappa Andrea Secco 《Journal of Cluster Science》2007,18(1):67-85
Ru3(CO)12 has been reacted with the compounds hex-1-en-3-yne [EtC≡CCH=CH2], 2-methyl-hex-1-en-3-yne [EtC≡CC(=CH2)CH3] and with 3(ethoxy-silyl)propyl isocyanate [(EtO)3Si(CH2)3NCO] and the compound tb [(EtO)3Si(CH2)3NHC(=O)OCH2C≡CCH2OC(=O)NH(CH2)3Si(OEt)3] in hydrocarbon solution. Some reactions in CH3OH/KOH solution (followed by acidification) have also been performed.
The main products of the reactions with ene-ynes are the clusters Ru3(CO)6(μ-CO)2L2 (L = C6H8, C7H10) and their demolition products, the “ferrole” Ru2(CO)6L2 complexes. One of the isomers of Ru3(CO)6(μ-CO)2L2, and Ru2(CO)6L2 (L = C7H10) have been reacted with vinyl-triethoxysilane [(EtO)3SiCH=CH2]: these reactions did not afford complexes containing new carbon–carbon bonds or triethoxy-silyl groups. Only polymerization
of vinyl-triethoxysilane occurred.
The reactions of Ru3(CO)12 with triethoxysilyl-propyl-isocyanate and tb (in the presence of Me3NO) lead to the same products, that is the isomeric complexes (μ-H)Ru3(CO)9[C=N(H)(CH2)3Si(OEt)3] with a “perpendicular” ligand (complex 3, as proposed on the basis of spectroscopic results) and (μ-H)Ru3(CO)9[HC=N(CH2)3Si(OEt)3] with a “parallel” ligand (complex 4, as confirmed by a X-ray analysis). The reaction pathways leading to these products are discussed. Complex 4 has been reacted with tetraethyl orthosilicate and the resulting material has been characterized. These reactions are part
of a study on the synthesis of inorganic-organometallic materials through sol–gel techniques.
This paper is dedicated to Prof. Gunther Schmid in the occasion of his 70th birthday. 相似文献
156.
The adsorptive interaction of 1-butyne and 1-butene with a highly dehydrated pyrogenic silica system has been studied to understand the thermodynamic behavior of the adsorption process by the application of the Langmuir model and of the Van't Hoff equation. In situ FTIR spectroscopy allowed the characterization of the adsorption phenomenon in terms of involved surface sites, gas-volumetric determinations yielded quantitative information relative to the adsorption process, and microcalorimetric results allowed the comparison between calculated and experimental data. K(eq) and Delta(ads)G degrees were obtained from Langmuir's model application; Delta(ads)H data were obtained from the Van't Hoff equation and by the isosteric heats method and were compared with experimental values. The virtual constancy of Delta(ads)H with equilibrium pressure and surface coverage (Langmuir model) allowed us to obtain the Delta(ads)H degrees values and, consequently, the Delta(ads)S degrees values for the systems of interest. 相似文献
157.
158.
159.
The objective of the research is to investigate epoxy resins where crosslinks formed in curing reactions can be cleaved and reformed without significant sacrifice in resin properties. Experimental disulfide-containing crosslinking agents have been selected for the study, including dihydrazides of dithiodicarboxylic acids (aliphatic and aromatic) and dithioaromatic diamines. Conditions for curing reactions and for subsequent cleavage of crosslinks by reduction have been determined in model systems and confirmed for a prototype epoxy resin. A comparative evaluation of cure kinetics, crosslink density, and thermal and mechanical properties has been carried out for resin cured with aromatic curing agents (dithiodianiline and methylenedianiline) and with aliphatic compounds (3, 3′-dithiopropionic acid dihydrazide and hexamethylenediamine). It has been shown that in resin fully cured with disulfide-containing crosslinking agents, crosslinks are ruptured by reduction, and re-established by oxidation under mild conditions, or by reaction of thiol groups with bifunctional alkylating agents. 相似文献
160.
Giuliana Gorrasi Liberata Guadagno Concetta D'Aniello Carlo Naddeo Gennaro Romano Vittoria Vittoria 《Macromolecular Symposia》2003,203(1):285-294
Three syndiotactic polypropylene samples were crystallized under different conditions in order to obtain different polymorphs. A first sample was crystallized at high temperature, obtaining the helical form I; a second was crystallized from the melt at 0°C for many days obtaining the trans-planar mesophase; a third sample was obtained by solvent induced crystallization followed by annaeling of the trans-planar mesophase, leading to a mixture of both the helical forms I and II. In the dynamic-mechanical analysis the helical form I showed only one peak of tan δ corresponding to the amorphous glass transition. The other polymorphs also showed this transition centered at about the same temperature. Beside the peak corresponding to the Tg, the trans-planar mesophase was characterized by a peak appearing at 70°C, and the helical form II by a peak at 100°C. These peaks, unambiguously associated to transitions of the different forms, can be considered a distinctive evidence for the polymorphs obtained in different processing conditions. 相似文献