全文获取类型
收费全文 | 584篇 |
免费 | 14篇 |
国内免费 | 3篇 |
专业分类
化学 | 419篇 |
晶体学 | 5篇 |
力学 | 14篇 |
数学 | 59篇 |
物理学 | 104篇 |
出版年
2022年 | 8篇 |
2021年 | 23篇 |
2020年 | 9篇 |
2019年 | 6篇 |
2018年 | 8篇 |
2017年 | 3篇 |
2016年 | 11篇 |
2015年 | 7篇 |
2014年 | 13篇 |
2013年 | 27篇 |
2012年 | 34篇 |
2011年 | 32篇 |
2010年 | 13篇 |
2009年 | 23篇 |
2008年 | 43篇 |
2007年 | 37篇 |
2006年 | 44篇 |
2005年 | 30篇 |
2004年 | 31篇 |
2003年 | 21篇 |
2002年 | 18篇 |
2001年 | 9篇 |
2000年 | 3篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 9篇 |
1996年 | 12篇 |
1995年 | 5篇 |
1994年 | 7篇 |
1992年 | 3篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 10篇 |
1987年 | 9篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1972年 | 3篇 |
1970年 | 2篇 |
1888年 | 4篇 |
排序方式: 共有601条查询结果,搜索用时 31 毫秒
141.
Lucia Caporaso Leone Oliva 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):7008-7013
In this paper, the synthesis of isotactic polypropylenes (i‐PP) modified with ? OH groups in sides (iPP‐OH), by combination of polyinsertion ansa‐metallocene catalysis and ring opening of propene oxide (PO), is described. i‐PP sequences interrupted by isolated ethylene/p‐methylstyrene units forms the backbone. This enchainment is obtained by controlled copolymerization of propene with ethylene and p‐methylstyrene comonomers in the presence of rac‐ethylenebis(1‐indenyl)zirconiumdichloride/methylalumoxane system. The metallation reaction of the p‐methyl group with sec‐BuLi generates an anionic center that can be reacted with PO. The iPP‐OH is the result of the monoaddition reaction of PO followed by hydrolysis with acidified methanol. By changing experimental conditions in the backbone synthesis, a tuned number of the functionalizable sites as well as polypropylene sequence lengths can be obtained. As a consequence, iPP samples with a different number of ? OH groups for the backbone can be synthesized after the PO monoaddition reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7008–7013, 2006 相似文献
142.
Kinetic investigations on the RuIII-catalysed oxidation of glycerol by an acidified solution of KBrO3 in the presence of Hg(OAc)2 as a scavenger have been carried out in the 30–50 °C range. First order kinetics in the lower KBrO3 concentration range tended to zero order at higher concentrations. The reaction follows zero order kinetics in glycerol and [H+]; the order is one with respect to [RuIII]. An increase in [Cl–] showed a positive effect, while addition of NaClO4 has a negligible effect on the reaction rate. Hg(OAc)2 and D2O have an insignificant effect on the reaction rate. A suitable mechanism in conformity with the kinetic observations has been proposed and thermodynamic parameters computed. 相似文献
143.
An algorithm for producing identities which hold in any given finite quasigroup is described. Identities produced by the algorithm are used to prove several results concerning varieties of quasigroups. In particular varieties of quasigroups associated with various combinatorial designs are examined. 相似文献
144.
Mariaelena Ricca Vito Foderà Daniela Giacomazza Maurizio Leone Giuseppe Spadaro Clelia Dispenza 《Colloid and polymer science》2010,288(9):969-980
Poly(N-vinyl-2-pyrrolidone) (PVP) hydrogels have been synthesised from the aqueous solutions of the same linear polymer by two different
radiation sources: electron beams and UV rays. The present investigation couples conventional hydrogel characterisation techniques
with the study of the partition equilibria, fluorescence behaviour and release of two different molecular probes, 1-anilino-8-naphthalene
sulphonate (ANS) and Thioflavin T (ThT). The two probes have comparable molecular weight and different structural and optical
properties. The ‘chemical’ networks produced upon irradiation in different experimental conditions presented quite distinctive
mechanical spectra, yielded to different porous solids upon freeze-drying and showed specific rehydration ratios when ‘equilibrated’
in water. More interestingly, they offered ‘hydrophobic pockets’ to host the ANS molecules in a way that the probe is completely
occluded from water, making it fluoresce. Conversely, the generated PVP networks did not show any specific affinity towards
the hydrophilic ThT that was only barely untaken. 相似文献
145.
Giovanni Ricci Anna Sommazzi Francesco Masi Marco Ricci Aldo Boglia Giuseppe Leone 《Coordination chemistry reviews》2010,254(5-6):661-676
This article provides an overview on recent progress in the polymerization of 1,3-dienes catalyzed by transition metal complexes with phosphorus and nitrogen ligands. Polymers having different microstructures (cis-1,4; 1,2; mixed cis-1,4/1,2) and tacticity (iso- or syndiotactic) were obtained from various 1,3-dienes (1,3-butadiene, isoprene, 1,3-pentadienes, 1,3-hexadienes) depending on the catalyst used, clearly suggesting that the catalyst structure (i.e. metal nature, type of ligand) strongly affects the polymerization chemo- and stereoselectivity. However, as indicated by the results obtained in the polymerization of substituted butadienes, a fundamental role in determining the selectivity is also played by the type of monomer: polymers with different structure, some of them completely new, were obtained from different monomers with the same catalyst. All these observations permitted to confirm, and in some cases to improve, the knowledge on the diene polymerization mechanism. 相似文献
146.
Kinetic investigation in Ir(III)-catalyzed oxidation of fumaric acid (FA) and crotonic acid (CA) in an acidified solution of quinolinium fluorochromate (QFC) has been studied in the temperature range of 30–45 °C. First-order kinetics was observed in the case of catalyst Ir(III) as well as oxidant QFC. The order of reaction with respect to substrate (unsaturated acids) was found to be zero. Increase in [Cl?] showed fractional negative order. The influence of [H+] and ionic strength on the rate was found to be insignificant. The main product of oxidation of fumaric acid (FA) and crotonic acid (CA) were identified as pyruvic acid and acetone, respectively. The reaction has been studied in ten different solvents. The first-order rate constant had no effect with decrease in the dielectric constant of the medium. The values of rate constants observed at four different temperatures (30, 35, 40 and 45 °C) were utilized to calculate the activation parameters. A suitable mechanism in conformity with the kinetic observations has been proposed and the rate law has been derived on the basis of obtained data. A transient complex formed between IrIII and oxidant in a slow and rate-determining step, further reacts with substrate to give the products in a series of fast steps. 相似文献
147.
2 + 4] and [4 + 2] cycloadditions of o-thioquinones with 1,3-dienes: a computational study 总被引:1,自引:0,他引:1
Contini A Leone S Menichetti S Viglianisi C Trimarco P 《The Journal of organic chemistry》2006,71(15):5507-5514
Cycloadditions of o-thioquinones (o-TQs) with 1,3-dienes could proceed via either a [2 + 4] or a [4 + 2] mechanism. Under kinetic control and with acyclic dienes the reaction affords the spiro cycloadducts 5deriving from the [2 + 4] path as the main products. Under thermodynamic control, or with cyclic dienes, the o-TQs behave as heterodienes to give the benzoxathiin derivatives 4, in most cases with complete regioselectivity. In the present computational study, DFT calculations were performed in order to achieve a deep understanding of both [2 + 4] and [4 + 2] paths. The reactions of three o-TQs with six 1,3-dienes were thoroughly investigated at the B3LYP/TZVP//B3LYP6-31G level, and the two reaction mechanisms were then compared, evidencing that [2 + 4] cycloadditions are kinetically favored, strongly asynchronous, or even unconcerted, while [4 + 2] reactions are thermodynamically favored, quite asynchronous, but undoubtedly concerted. Moreover, the observed regioselectivity was rationalized by mean of the FMO theory and by comparison of the activation energies for different pathways. 相似文献
148.
Neutral palladium methyl chloride 2a-d [PdCH3(PˆP′)Cl] and cationic palladium methyl acetonitrile mono-triflate 3a-d [PdCH3(PˆP′)(CH3CN)](CF3SO3) complexes were synthesized and fully characterized (PˆP′ = 1a-d). All the neutral and cationic complexes containing a Cs-symmetric diphosphine exist in solution as a mixture of geometric isomers. The carbonylation at atmospheric pressure of the neutral and cationic complexes revealed that migratory insertion of carbon monoxide is not stereospecific in these systems. The neutral and cationic acyl complexes were formed in situ as mixtures of stereoisomers, which were characterized by means of NMR spectroscopy.The crystal structures of [Pd(1a)Cl]2(OTf)2 and 2d are described. 相似文献
149.
Jacobo SH Chang CT Lee GJ Lawson JA Powell WS Pratico D FitzGerald GA Rokach J 《The Journal of organic chemistry》2006,71(4):1370-1379
[reaction: see text] A new and stereoselective approach for the synthesis of all-syn isoprostanes is reported. This method, which is based on acid-catalyzed Diels-Alder reaction, allows the introduction of the side chain with a predetermined stereochemistry of the hydroxy group. The first total synthesis of an eicosapentaenoic acid (EPA)-derived iP, 8,12-iso-iPF3alpha-VI 10, was performed using this approach. 相似文献
150.
Meloni G Zou P Klippenstein SJ Ahmed M Leone SR Taatjes CA Osborn DL 《Journal of the American Chemical Society》2006,128(41):13559-13567
The photoionization of alkylperoxy radicals has been investigated using a newly developed experimental apparatus that combines the tunability of the vacuum ultraviolet radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory with time-resolved mass spectrometry. Methylperoxy (CH(3)OO) and ethylperoxy (C(2)H(5)OO) radicals are produced by the reaction of pulsed, photolytically produced alkyl radicals with molecular oxygen, and the mass spectrum of the reacting mixture is monitored in time by using synchrotron-photoionization with a double-focusing mass spectrometer. The kinetics of product formation is used to confirm the origins and assignments of ionized species. The photoionization efficiency curve for CH(3)OO has been measured, and an adiabatic ionization energy of (10.33 +/- 0.05) eV was determined with the aid of Franck-Condon spectral simulations, including ionization to the lowest triplet and singlet cation states. Using the appearance energy of CH(3)(+) from CH(3)OO, an enthalpy of formation for CH(3)OO of Delta(f) (CH(3)OO) = (22.4 +/- 5) kJ mol(-1) is derived. The enthalpy of formation of CH(3)OO(+) is derived as Delta(f) = (1019 +/- 7) kJ mol(-1) and the CH(3)(+)-OO bond energy as (CH(3)(+) - O(2)) = (80 +/- 7) kJ mol(-1). The C(2)H(5)OO(+) signal is not detectable; however, the time profile of the ethyl cation signal suggests its formation from dissociative ionization of C(2)H(5)OO. Electronic structure calculations suggest that hyperconjugation reduces the stability of the ethylperoxy cation, making the C(2)H(5)OO(+) ground state only slightly bound with respect to the ground-state products, C(2)H(5)(+) and O(2). The value of the measured appearance energy of C(2)H(5)(+) is consistent with dissociative ionization of C(2)H(5)OO via the Franck-Condon favored ionization to the ? (1)A' state of C(2)H(5)OO(+). 相似文献