全文获取类型
收费全文 | 475篇 |
免费 | 7篇 |
国内免费 | 2篇 |
专业分类
化学 | 320篇 |
力学 | 15篇 |
数学 | 66篇 |
物理学 | 83篇 |
出版年
2022年 | 7篇 |
2021年 | 7篇 |
2020年 | 3篇 |
2019年 | 4篇 |
2018年 | 11篇 |
2017年 | 4篇 |
2016年 | 9篇 |
2015年 | 10篇 |
2014年 | 8篇 |
2013年 | 19篇 |
2012年 | 22篇 |
2011年 | 25篇 |
2010年 | 13篇 |
2009年 | 19篇 |
2008年 | 33篇 |
2007年 | 32篇 |
2006年 | 26篇 |
2005年 | 21篇 |
2004年 | 25篇 |
2003年 | 23篇 |
2002年 | 17篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 12篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1976年 | 2篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1972年 | 4篇 |
1968年 | 2篇 |
1963年 | 2篇 |
排序方式: 共有484条查询结果,搜索用时 15 毫秒
121.
Guidotti S Camurati I Focante F Angellini L Moscardi G Resconi L Leardini R Nanni D Mercandelli P Sironi A Beringhelli T Maggioni D 《The Journal of organic chemistry》2003,68(14):5445-5465
The reaction of pyrroles and indoles with B(C(6)F(5))(3) and BCl(3) produces 1:1 B-N complexes containing highly acidic sp(3) carbons, for example, N-[tris(pentafluorophenyl)borane]-5H-pyrrole (1) and N-[tris(pentafluorophenyl)borane]-3H-indole (2), that are formed by a new formal N-to-C hydrogen shift, the mechanism of which is discussed. With some derivatives, restricted rotation around the B-N bond and/or the B-C bonds was observed by NMR techniques, and some rotational barriers were calculated from experimental data. The acidity of the sp(3) carbons in these complexes is shown by their ability to protonate NEt(3), with formation of pyrrolyl- and indolyl-borate ammonium salts. The driving force for this reaction is given by the restoration of the aromaticity of the heterocycle. 相似文献
122.
Quagliotto P Viscardi G Barolo C Barni E Bellinvia S Fisicaro E Compari C 《The Journal of organic chemistry》2003,68(20):7651-7660
A new series of pyridinium cationic gemini surfactants was prepared by quaternization of the 2,2'-(alpha,omega-alkanediyl)bispyridines with N-alkylating agents, whose reactivity is briefly discussed. Particularly useful was the use of long-chain alkyl triflates (trifluoromethanesulfonates) for both overcoming the sterical hindrance in the pyridines and obtaining higher synthetic yields. Well-known 4,4'-(alpha,omega-alkanediyl)bis(1-alkylpyridinium) structures showed narrow temperature ranges for practical applications, due to their high Krafft points, while the new 2,2'-(alpha,omega-alkanediyl)bis(1-alkylpyridinium) series, accounted for good surface active properties. Due to the Krafft points below 0 degrees C, they could be exploited as solutions in water at any temperature. The characterization of the behavior of the series was performed by conductivity measurements. Some of the proposed structures exhibited unusual surface active behavior, which was interpreted in terms of particular conformational arrangements. 相似文献
123.
Greci L Castagna R Carloni P Stipa P Rizzoli C Righi L Sgarabotto P 《Organic & biomolecular chemistry》2003,1(21):3768-3771
N,N-Dimethyl-p-nitrosoaniline reacts with benzoyl chloride affording a complex salt containing a cation, a hybrid between a nitrenium ion and an iminium ion. The salt reacts with nucleophiles (indoles, indolizines) yielding compounds characterized by a new carbon-nitrogen bond, derived from the nitrenium ion form. According to the type of nucleophile, the reaction, to differing extents, is in competition with an electron transfer process which leads to the formation of the dimer of the nucleophile and of the azoxy corresponding to the N,N-dimethyl-p-nitrosoaniline. In one of the reactions studied, a chlorinated azoxy derivative was also isolated, and its structure was elucidated by X-ray analysis. 相似文献
124.
Focante F Camurati I Resconi L Guidotti S Beringhelli T D'Alfonso G Donghi D Maggioni D Mercandelli P Sironi A 《Inorganic chemistry》2006,45(4):1683-1692
Reaction between 7-azaindole and B(C6F5)3 quantitatively yields 7-(C6F5)3B-7-azaindole (4), in which B(C6F5)3 coordinates to the pyridine nitrogen of 7-azaindole, leaving the pyrrole ring unreacted even in the presence of a second equivalent of B(C6F5)3. Reaction of 7-azaindole with H2O-B(C6F5)3 initially produces [7-azaindolium]+[HOB(C6F5)3]- (5) which slowly converts to 4 releasing a H2O molecule. Pyridine removes the borane from the known complexes (C6F5)3B-pyrrole (1) and (C6F5)3B-indole (2), with formation of free pyrrole or indole, giving the more stable adduct (C6F5)3B-pyridine (3). The competition between pyridine and 7-azaindole for the coordination with B(C6F5)3 again yields 3. The molecular structures of compounds 4 and 5 have been determined both in the solid state and in solution and compared to the structures of other (C6F5)3B-N-heterocycle complexes. Two dynamic processes have been found in compound 4. Their activation parameters (DeltaH = 66 (3) kJ/mol, DeltaS = -18 (10) J/mol K and DeltaH = 76 (5) kJ/mol, DeltaS = -5 (18) J/mol K) are comparable with those of other (C6F5)3B-based adducts. The nature of the intramolecular interactions that result in such energetic barriers is discussed. 相似文献
125.
Adami G Capriglia L Barbieri P Cozzi F Lo Coco F Acquavita A Reisenhofer E 《Annali di chimica》2006,96(9-10):601-612
The following metals: Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined by inductively coupled plasma - atomic emission spectroscopy (ICP-AES) in fluvial sediments of Rosandra Creek, using two different, strong and mild sediment decomposition methods. The purpose was to obtain information about the contamination by metals and distribution paths of pollutants in the area crossed by Rosandra Creek: this little river is the unique epigeous watercourse in the Italian Karst and very few data can be found in literature. In this area, we can find a natural park, but also agricultural activities and an industrial district that was recently defined as "polluted site of national interest". By comparing the results of the strong and mild extraction we have obtained the percentage of extraction and enrichment factors for each metal in the different sediments of the sites R2 and R3 exposed to pollution, while the site R1 was considered as a pristine one because situated in the natural park. The computed enrichment factors are generally not very high, but copper, lead and zinc have factors that require attention. The principal component analysis (PCA) shows that the typically anthropogenic metals (as Cr, Pb, Cu and Zn) constitute the first factor, while the lithogenic metals, as Fe and Ni, constitute the second one; moreover the score plots permit to classify and distinguish the 3 sites: site R3, possibly the more exposed to contamination, has high scores both for anthropogenic and lithogenic metals. 相似文献
126.
Guido Viscardi Piero Savarino Pierluigi Quagliotto Ermanno Barni Mauro Botta 《Journal of heterocyclic chemistry》1996,33(4):1195-1200
Heterocyclic azodyes of the pyridylazonaphthol and pyridylazoresorcinol series containing tuned hydrophobic chains have been prepared. Due to their chelating properties, the dyes are suitable candidates for preconcentration and selective separation of transition metal ions. After a discussion on the choice of the best synthetic pathway, physical and spectral uv/visible properties are presented and correlated with the structural features. A detailed analysis of nmr spectra allowed the clarification of currently unresolved signal assignments. 相似文献
127.
Pierluigi Barbieri Gianpiero Adami Andrea Favretto E. Reisenhofer 《Fresenius' Journal of Analytical Chemistry》1998,361(4):349-352
Within research on the quality of the waters of the Gulf of Trieste, this study on patterns of trace metal contents in the
inner part of the gulf (Muggia Bay) discusses data of Cu, Pb, Cd and Zn, determined voltammetrically (DPASV), and collected
in three sites with a 10-day frequency over the period of one year. Two of the sites lie inside the dam system which protects
the harbour of Trieste, while the third one is situated outside for comparison purposes. Principal component analysis pointed
out different metal patterns inside and outside the dam system; PC scores were related to meteorological information: rain
plays a major role in conditioning the estuarine inner site: wind stirring action was detectable for the outer site. Both
univariate graphics and canonical correlation analysis suggest a diffuse source for Pb, probably atmospheric deposition.
Received: 1 August 1997 / Revised: 20 November 1997 / Accepted: 23 November 1997 相似文献
128.
Quadrelli P Scrocchi R Piccanello A Caramella P 《Journal of combinatorial chemistry》2005,7(6):887-892
The synthesis of 1,2,4-oxadiazole-4-oxides on polystyrenic solid phase docked at the position 3 of the heterocyclic ring has been performed through the cycloaddition of stable supported nitrile oxides to amidoximes. The photochemical cycloreversion of these heterocycles afforded the free nitrosocarbonyl intermediates that were trapped by suitable dienes or enes. The method is proposed as a clean and environmental friendly approach to the fleeting nitrosocarbonyl intermediates, which afford valuable adducts for various synthetic applications. The isomeric heterocycles docked at the position 5 of the ring have also been obtained by cycloaddition of nitrile oxides to supported amidoximes. Their photolysis afforded resin-bound nitrosocarbonyls that were trapped with dienes affording valuable supported adducts suitable for further elaboration on solid-phase chemistry. 相似文献
129.
Pierluigi Nordio Maria V. Pavan Giovanni Giacometti 《Theoretical chemistry accounts》1963,1(4):302-307
Hyperconjugated models are used for a m.o. calculation of proton h.f.s. constants in Ethyl and Cyclohexadienyl radicals. A slightly modified Pariser-Parr-Pople SCF method is employed including extensive configuration interaction. The calculated spin densities for the hyperconjugated protons are in good agreement with experiment.
We thank the Italian National Research Council (Chemistry Committee, Research Group IV) for financial support. One of us (P.L.N.) thanks Sicedison S.p.A. for a grant. 相似文献
Zusammenfassung Zur Berechnung von Protonenhyperfeinstrukturkonstanten von Äthyl- und Cyclohexadienyl-Radikalen werden Modelle mit Hyperkonjugation verwendet. Die Rechnung gründet sich auf eine leicht modifizierte Pariser-Parr-Pople-Methode einschließlich ausgedehnter Konfigurationswechselwirkung. Die berechneten Spin-Dichten für die hyperkonjugierten Protonen stimmen mit experimentell ermittelten Werten gut überein.
Résumé Des modèles tenant compte à la hyperconjugaison sont usés pour le calcul des constantes de structure hyperfine protonique des radicaux éthyl et Cyclohexadiényl. Le calcul se base sur une méthode Pariser-Parr-Pople un peu modifiée et comprenant une interaction de configurations extensive. Les densités de spin calculées pour les protons hyperconjugués sont en bon accord avec des valeurs expérimentales.
We thank the Italian National Research Council (Chemistry Committee, Research Group IV) for financial support. One of us (P.L.N.) thanks Sicedison S.p.A. for a grant. 相似文献
130.