全文获取类型
收费全文 | 878篇 |
免费 | 51篇 |
国内免费 | 11篇 |
专业分类
化学 | 588篇 |
力学 | 24篇 |
数学 | 196篇 |
物理学 | 132篇 |
出版年
2024年 | 1篇 |
2023年 | 16篇 |
2022年 | 27篇 |
2021年 | 43篇 |
2020年 | 22篇 |
2019年 | 21篇 |
2018年 | 20篇 |
2017年 | 23篇 |
2016年 | 43篇 |
2015年 | 43篇 |
2014年 | 43篇 |
2013年 | 76篇 |
2012年 | 64篇 |
2011年 | 73篇 |
2010年 | 51篇 |
2009年 | 45篇 |
2008年 | 47篇 |
2007年 | 67篇 |
2006年 | 40篇 |
2005年 | 57篇 |
2004年 | 39篇 |
2003年 | 17篇 |
2002年 | 15篇 |
2001年 | 5篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 2篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1987年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1976年 | 1篇 |
排序方式: 共有940条查询结果,搜索用时 15 毫秒
911.
Bellarosa L Díez J Gimeno J Lledós A Suárez FJ Ujaque G Vicent C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(25):7749-7765
The catalytic activity of ruthenium(IV) ([Ru(η(3):η(3)-C(10)H(16))Cl(2)L]; C(10)H(16) = 2,7-dimethylocta-2,6-diene-1,8-diyl, L = pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, 2-(1H-pyrazol-3-yl)phenol or indazole) and ruthenium(II) complexes ([Ru(η(6)-arene)Cl(2)(3,5-dimethylpyrazole)]; arene = C(6)H(6), p-cymene or C(6)Me(6)) in the redox isomerisation of allylic alcohols into carbonyl compounds in water is reported. The former show much higher catalytic activity than ruthenium(II) complexes. In particular, a variety of allylic alcohols have been quantitatively isomerised by using [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)] as a catalyst; the reactions proceeded faster in water than in THF, and in the absence of base. The isomerisations of monosubstituted alcohols take place rapidly (10-60?min, turn-over frequency = 750-3000?h(-1)) and, in some cases, at 35?°C in 60?min. The nature of the aqueous species formed in water by this complex has been analysed by ESI-MS. To analyse how an aqueous medium can influence the mechanism of the bifunctional catalytic process, DFT calculations (B3LYP) including one or two explicit water molecules and using the polarisable continuum model have been carried out and provide a valuable insight into the role of water on the activity of the bifunctional catalyst. Several mechanisms have been considered and imply the formation of aqua complexes and their deprotonated species generated from [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)]. Different competitive pathways based on outer-sphere mechanisms, which imply hydrogen-transfer processes, have been analysed. The overall isomerisation implies two hydrogen-transfer steps from the substrate to the catalyst and subsequent transfer back to the substrate. In addition to the conventional Noyori outer-sphere mechanism, which involves the pyrazolide ligand, a new mechanism with a hydroxopyrazole complex as the active species can be at work in water. The possibility of formation of an enol, which isomerises easily to the keto form in water, also contributes to the efficiency in water. 相似文献
912.
Cristian D. EneAndreea Lungu Constantin Mihailciuc Mihaela Hillebrand Catalina Ruiz-PérezMarius Andruh 《Polyhedron》2012,31(1):539-547
The crystal structures of two pentacyanido(L) ferrate(III) complexes, [P(C6H5)4]2[Fe(CN)5(prz)]·4H2O 1, [P(C6H5)4]2[Fe(CN)5(4,4′-bipy)]·3H2O 2, have been solved. Within the two complex anions the iron atoms are hexacoordinated by five cyanido ligands, the sixth position being occupied by the nitrogen atom arising from pyrazine and, respectively, 4,4′-bipyridine. The electrochemical properties of compounds 1, 2 and of the azido derivative, (Ph4As)2[Na(H2O)4][Fe(CN)5(N3)] 3, have been investigated by cyclic voltammetry. A relatively complicated redox behavior of these complexes was found, due especially to the electron transfer involving the central metallic ion that changes reversibly its oxidation state (FeIII/FeII redox site) and also to the coligand (4,4′-bipyridine, pyrazine or azide) which intervenes in a distinct electron transfer. The experimental data have been rationalized through DFT calculations. 相似文献
913.
Dr. Luca Bellarosa Dr. Josefina Díez Prof. Dr. José Gimeno Prof. Dr. Agustí Lledós Francisco J. Suárez Dr. Gregori Ujaque Dr. Cristian Vicent 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(25):7749-7765
The catalytic activity of ruthenium(IV) ([Ru(η3:η3‐C10H16)Cl2L]; C10H16=2,7‐dimethylocta‐2,6‐diene‐1,8‐diyl, L=pyrazole, 3‐methylpyrazole, 3,5‐dimethylpyrazole, 3‐methyl‐5‐phenylpyrazole, 2‐(1H‐pyrazol‐3‐yl)phenol or indazole) and ruthenium(II) complexes ([Ru(η6‐arene)Cl2(3,5‐dimethylpyrazole)]; arene=C6H6, p‐cymene or C6Me6) in the redox isomerisation of allylic alcohols into carbonyl compounds in water is reported. The former show much higher catalytic activity than ruthenium(II) complexes. In particular, a variety of allylic alcohols have been quantitatively isomerised by using [Ru(η3:η3‐C10H16)Cl2(pyrazole)] as a catalyst; the reactions proceeded faster in water than in THF, and in the absence of base. The isomerisations of monosubstituted alcohols take place rapidly (10–60 min, turn‐over frequency=750–3000 h?1) and, in some cases, at 35 °C in 60 min. The nature of the aqueous species formed in water by this complex has been analysed by ESI‐MS. To analyse how an aqueous medium can influence the mechanism of the bifunctional catalytic process, DFT calculations (B3LYP) including one or two explicit water molecules and using the polarisable continuum model have been carried out and provide a valuable insight into the role of water on the activity of the bifunctional catalyst. Several mechanisms have been considered and imply the formation of aqua complexes and their deprotonated species generated from [Ru(η3:η3‐C10H16)Cl2(pyrazole)]. Different competitive pathways based on outer‐sphere mechanisms, which imply hydrogen‐transfer processes, have been analysed. The overall isomerisation implies two hydrogen‐transfer steps from the substrate to the catalyst and subsequent transfer back to the substrate. In addition to the conventional Noyori outer‐sphere mechanism, which involves the pyrazolide ligand, a new mechanism with a hydroxopyrazole complex as the active species can be at work in water. The possibility of formation of an enol, which isomerises easily to the keto form in water, also contributes to the efficiency in water. 相似文献
914.
Latorre A López I Ramírez V Rodríguez S Izquierdo J González FV Vicent C 《The Journal of organic chemistry》2012,77(11):5191-5197
The mechanism of the dehydrosulfenylation of 2-arylsulfinyl esters was investigated. The reaction was found to follow a homolytic cleavage mechanism as verified by electrospray ionization tandem mass spectrometry and experimental work. Rearranged sulfoxides are obtained as byproduct during the elimination reaction. 相似文献
915.
The reactions of the ligands 2,6-(Me2NCH2)2C5H3N (N’NN’) (1) and 2,6-(PhSeCH2)2C5H3N (SeNSe) (4) with different coinage metal starting materials gave 1:1, 2:1 or 1:2 metal-to-ligand species, i.e. [Ag(N’NN’){O(O)CCF3}] (2), [{Ag(PPh3)}2(N’NN’)](OTf)2 (3), [Au(SeNSe)Cl]Cl2 (5), [Ag(PPh3)(SeNSe)](OTf) (6), [Cu(MeCN)(SeNSe)](PF6) (7) or [Cu(SeNSe)2](PF6) (8). The new compounds were investigated by IR, multinuclear NMR spectroscopies as well as mass spectrometry. In most cases, the ligands 1 and 4 act as pincer ligands. An attempt to grow single crystals of 2 gave an unexpected result. The crystal investigated by X-ray diffraction proved to be a polynuclear species, [Ag4(N’NN’){O(O)CCF3}4(EtOH)]n (2a), which contains an unusual, bimetallic triconnective coordination pattern of the N’NN’ ligand. Two tetranuclear [Ag4(N’NN’){O(O)CCF3}4(EtOH)] units form centrosymmetric dimers further associated into a polymer which contains four different coordination environments around silver atoms. The complex 3, in which the ligand also exhibits a bimetallic triconnective pattern, shows an intense, long-lived luminescence in the solid state with emission energies in the green region of the visible spectrum. 相似文献
916.
917.
Alina M. Simion Mitsunori Kakeda Naoyoshi Egashira Yoshiharu Mitoma Cristian Simion 《Central European Journal of Chemistry》2012,10(5):1547-1555
We report hereby the first method of direct treatment of a wet soil containing toxic polychloroderivatives. Using a system with metallic Ca and 5% Rh fixed on charcoal in methanol, soil samples artificially polluted with fly ash containing polychloro-dibenzodioxins (PCDDs), polychloro-dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (co-PCBs), and having 69.2% to 84.6% moisture content, were successfully treated and decontaminated. This treatment afforded excellent hydrodechlorination yields for the 29 most toxic congeners of PCDDs, PCDFs and PCBs (98.3% degradation yield based on toxic equivalent quotient — or TEQ) after a 24 h treatment, at room temperature. 相似文献
918.
Etienne de Klerk Dmitrii Pasechnik Renata Sotirov Cristian Dobre 《Mathematical Programming》2012,136(2):253-278
We derive a new semidefinite programming bound for the maximum $k$ -section problem. For $k=2$ (i.e. for maximum bisection), the new bound is at least as strong as a well-known bound by Poljak and Rendl (SIAM J Optim 5(3):467?C487, 1995). For $k \ge 3$ the new bound dominates a bound of Karisch and Rendl (Topics in semidefinite and interior-point methods, 1998). The new bound is derived from a recent semidefinite programming bound by De Klerk and Sotirov for the more general quadratic assignment problem, but only requires the solution of a much smaller semidefinite program. 相似文献
919.
Cristian González–Martínez 《manuscripta mathematica》2012,137(1-2):19-55
Let X be a nonsingular complex projective variety that is acted on by a reductive group G and such that ${X^{ss} \neq X_{(0)}^{s}\neq \emptyset}$ . We give formulae for the Hodge–Poincaré series of the quotient ${X_{(0)}^{s}/G}$ . We use these computations to obtain the corresponding formulae for the Hodge–Poincaré polynomial of the moduli space of properly stable vector bundles when the rank and the degree are not coprime. We compute explicitly the case in which the rank equals 2 and the degree is even. 相似文献
920.
We demonstrate an order-of-magnitude energy scaling of a white-light seeded noncollinear optical parametric amplifier in the visible. The generated pulses, tunable between 520 and 650 nm with sub-25-fs duration, had energies up to 310 microJ with 20% blue-pump-to-signal energy conversion efficiency at 540 nm. This new ultrafast source will make possible numerous extreme nonlinear optics applications. As a first application, we demonstrate the generation of tunable vacuum ultraviolet pulses. 相似文献