全文获取类型
收费全文 | 2513篇 |
免费 | 254篇 |
国内免费 | 364篇 |
专业分类
化学 | 1548篇 |
晶体学 | 24篇 |
力学 | 31篇 |
综合类 | 21篇 |
数学 | 21篇 |
物理学 | 154篇 |
综合类 | 1332篇 |
出版年
2024年 | 5篇 |
2023年 | 27篇 |
2022年 | 41篇 |
2021年 | 45篇 |
2020年 | 72篇 |
2019年 | 72篇 |
2018年 | 55篇 |
2017年 | 64篇 |
2016年 | 93篇 |
2015年 | 100篇 |
2014年 | 125篇 |
2013年 | 154篇 |
2012年 | 161篇 |
2011年 | 138篇 |
2010年 | 90篇 |
2009年 | 98篇 |
2008年 | 103篇 |
2007年 | 109篇 |
2006年 | 101篇 |
2005年 | 134篇 |
2004年 | 121篇 |
2003年 | 130篇 |
2002年 | 132篇 |
2001年 | 79篇 |
2000年 | 89篇 |
1999年 | 127篇 |
1998年 | 76篇 |
1997年 | 75篇 |
1996年 | 83篇 |
1995年 | 72篇 |
1994年 | 50篇 |
1993年 | 43篇 |
1992年 | 51篇 |
1991年 | 49篇 |
1990年 | 39篇 |
1989年 | 47篇 |
1988年 | 31篇 |
1987年 | 21篇 |
1986年 | 9篇 |
1985年 | 6篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1979年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有3131条查询结果,搜索用时 15 毫秒
81.
82.
A 4, 4'-bipyridine bridging dumbbell-like dimeric pentamolybdate [4, 4'-H2bipy]3[4,4'-Hbipy]2[(Mo5O17)2(4,4'-bipy)] has been synthesized by hydrothermal synthesis and characterized by elemental analysis, IR spectrum, UV spectrum, TG and X-ray crystallography. The title compound crystallizes in triclinic, space group P(-1) with a = 10.578(2), b = 11.047(2), c = 16.576(3) (A), α = 79.86(3), β = 75.34(3), γ = 79.40(3)°, C60H58Mo1oN12O34, Mr = 2450.58, V = 1824.8(6) (A)3, Z = 1, Dc = 2.230 g/cm3, F(000) = 1194, μ = 1.757 mm-1, the final R = 0.0252 and wR = 0.0559 for 5506 observed reflections with I > 2σ(Ⅰ). The structural analysis indicates that the title compound contains a novel polyanion [(Mo5O17)2(4,4'-bipy)]8-, in which two identical (Mo5O17)4- anions are buttressed by a 4,4'-bipyridine molecule through Mo-N bond. 相似文献
83.
Michelini Mdel C Russo N Alikhani ME Silvi B 《Journal of computational chemistry》2005,26(12):1284-1293
The interaction between molybdenum, atom, and dimer, with nitrous oxide has been investigated using density functional theory. The analysis of the potential energy surfaces for both reactions has revealed that a single molybdenum atom can activate the N--O bond of N2O requiring a small activation energy. However, the presence of several intersystem crossings between three different spin states, namely, septet, quintet and triplet states, seems to be the major constraint to the Mo + N2O reaction. Contrarily, the low-lying excited states (triplet and quintet) do not participate in the reaction between the molybdenum dimer and N2O. The latter reaction fully evolves on the singlet spin surface. Three different regions have been distinguished along the pathway: formation of an adduct complex, formation of an inserted compound, and the N2 detachment. The connection between the two first regions has been characterized by the formation of a special complex in which the N--O bond is so weakened that it could be considered as a first step in the insertion process. It has been shown that the topological changes along the pathways provide a clear explanation for the geometrical changes that occur along the reaction pathway. In summary, the detachment of the N2 molecule is found to be kinetically an effective process for both reactions, owing to the high exothermicity and consequently to the high internal energy of the insertion intermediates. However, in the case of Mo atom, the reaction should be a slow process due to the presence of spin-forbidden transitions. These results fully agree with previous experimental works. 相似文献
84.
Penicillamine Complexes of Nickel, Chromium, and Molybdenum — Structural Particularity and Biological/Medical Relevance The compounds Tl2[NiII(H2O)6][NiII(D-pen)(L-pen)]2[NiII(SCN)2(H2O)4] 1 , Tl[NiII(D-pen)2H] · H2O 2 , Tl[CrIII(D-pen)2] 3 , and Na2[MoO4(pen)2] · 3 CH3OH · 3 H2O 4 have been prepared by the reaction of nickel nitrate (for 1 ), nickel acetate (for 2 ), potassium chromate (for 3 ), and sodium molybdate (for 4 ) with D- and D, L-penicillamine, respectively. They were characterized by single-crystal X-ray structure analysis and other physical methods. Whereas penicillamine acts as a bidentate (N, S)-ligand in 1 and 2 , CrIII (in 3 ), and MoV (in 4 ) are coordinated to the three ligand atoms N, O, and S. The presence of three different types of NiII-complexes a cationic, a neutral, and an anionic one in 1 is remarkable. For crystal data see Inhaltsübersicht. 相似文献
85.
19F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo6Br Cl )F ]2?, n = 0 – 8 The complete system of the innersphere mixed clusters (Mo6BrCl)4+ is formed by exchange of innersphere bound Cli against outersphere bound Bra on tempering the solid [(Mo6Cl)Br] at 500°C for 16 h. After conversion with conc. HCl into (H3O)2[(Mo6BrCl)Cl] and precipitation of the outer Cla with AgBF4 in ethanol, treatment with tetrabutylammonium(TBA)fluoride yields (TBA)2 [(Mo6BrCl)F], a mixture of 22 different species. According to the sets of chemical equivalent fluorine atoms in total 55 19F nmr signals are expected, which are really observed in the high resolution 1D-19F-nmr spectrum. Using increments of chemical shifts, peak intensities and multiplet structures as well as the 2D-19F/19F-COSY spectrum the complete and unambiguous assignment of all resonances is achieved. From the measured integral intensities the distribution of the different compounds is determined, revealing statistical formation of the geometrical isomers. 相似文献
86.
Nunes CD Valente AA Pillinger M Rocha J Gonçalves IS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4380-4390
Mo K-edge XAFS spectra have been measured for ordered mesoporous silica MCM-41 grafted with the complexes [MoO2X2(thf)2] (X=Cl, Br). For grafting reactions in the absence of triethylamine, materials with 1 wt. % Mo are obtained; the Mo K-edge EXAFS results indicate the co-existence of isolated surface-fixed monomeric species [MoO2[(-O)3SiO]2(thf)(n)] and [MoO2[(-O)3SiO]X(thf)(n)]. When Et3N is used in the grafting reactions, materials with 4 wt. % Mo are obtained. The EXAFS data for the material prepared using [MoO2Cl2(thf)2] and Et3N indicate the presence of dinuclear species with two Mo(VI) centres, each with two Mo=O groups and each linked by one or two oxo bridges (Mo...Mo 3.27 A). The molybdenum centres in the material prepared using the dibromo complex comprise mainly isolated four-coordinate dioxomolybdenum(VI) and trioxomolybdenum(VI) monomeric species, with a small contribution from dimeric species. All materials were further characterised in the solid state by powder X-ray diffraction, N2 adsorption analysis, MAS NMR (13C, 29Si) and FTIR spectroscopy. The derivatised MCMs perform differently as catalysts in the liquid-phase oxidation of various olefins and alcohols with tert-butyl hydroperoxide. The highest alkene epoxidation activity was recorded for the catalysts with low metal loading, whereas the material containing oxo-bridged dimers had the highest activity for oxidation of alcohols. The recyclability of all the catalysts was tested: the catalytic activity of the derivatised materials tended to stabilize with ageing. 相似文献
87.
Cuesta L Gerbino DC Hevia E Morales D Navarro Clemente ME Pérez J Riera L Riera V Miguel D del Río I García-Granda S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1765-1777
The hydroxo compounds [Re(OH)(CO)(3)(N-N)] (N-N=bipy, 2 a; Me(2)-bipy, 2 b) were prepared in a biphasic H(2)O/CH(2)Cl(2) medium by reaction of [Re(OTf)(CO)(3)(N-N)] with KOH. In contrast, when anhydrous CH(2)Cl(2) was used, the binuclear hydroxo-bridged compound [[Re(CO)(3)(bipy)](2)(mu-OH)]OTf (3-OTf) was obtained. Compound [Re(OH)(CO)(3)(Me(2)-bipy)] (2 b) reacted with phenyl acetate or vinyl acetate to afford [Re(OAc)(CO)(3)(Me(2)-bipy)] (4) and phenol or acetaldehyde, respectively. The reactions of [Mo(OH)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1), 2 a, and 2 b toward several unsaturated organic electrophiles were studied. The reaction of 1 with (p-tolyl)isocyanate afforded an adduct of N,N'-di(p-tolyl)urea and the carbonato-bridged compound [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(mu-eta(1)(O),eta(1)(O)-CO(3))] (5). In contrast, the reaction of 2 a with phenylisocyanate afforded [Re(OC(O)NHPh)(CO)(3)(bipy)] (6); this results from formal PhNCO insertion into the O-H bond. On the other hand, compounds [Mo[SC(O)NH(p-tolyl)](eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (7), [Re[SC(O)NH(p-tolyl)](CO)(3)(Me(2)-bipy)] (8 a), and [Re[SC(O)NHEt](CO)(3)(Me(2)-bipy)] (8 b) were obtained by reaction of 1 or 2 b with the corresponding alkyl or aryl isothiocyanates. In those cases, RNCS was inserted into the M-O bond. The reactions of 1, 2 a, and 2 b with dimethylacetylenedicarboxylate (DMAD) gave the complexes [Mo[C(OH)-C(CO(2)Me)C(CO(2)Me)-O](eta(3)-C(3)H(4)-Me-2)(CO)(phen)] (9) and [Re[C(OH)C(CO(2)Me)C(CO(2)Me)O](CO)(2)(N-N)] (N-N=bipy, 10 a; Me(2)-bipy, 10 b). The molecules of these compounds contain five-membered metallacycles that are the result of coupling between the hydroxo ligand, DMAD, and one of the CO ligands. The new compounds were characterized by a combination of IR and NMR spectroscopy, and for [[Re(CO)(3)(bipy)(2)(mu-OH)]BF(4) (3-BF(4)), 4, 5, 6, 7, 8 b, 9, and 10 b, also by means of single-crystal X-ray diffraction. 相似文献
88.
作者根据对新疆东天山典型金矿床的沉淀成矿环境、地球化学特征、稳定同位素特征等的系统分析和研究,论证了形成金矿床的硅质流体最初是一种以水为主要溶剂,以溶解态、胶体态氧化硅为主要溶质的高温高压(超临界态)溶液,其来源于地幔,是一种溶解了大量SiO2的地幔流体。而成矿元素主要来源于硅质流体上升运移过程中所经围岩,以致成矿物质来源具异源性。这对研究内生金矿床的成矿机制和成因有着十分重要的意义。 相似文献
89.
渐新统沙二段是济阳坳陷车西地区的主力油层,为了弄清其油气分布和控制因素,综合利用大量的地质和地球物理资料,首次在该段识别出漫湖洪水—风暴重力流沉积.该沉积具有明显的重力流沉积特征,砂岩的成分和结构成熟度均较低,粒度概率图多由悬浮次总体组成,沉积序列可用Bouma序列来描述.在明确了砂体的沉积层位和沉积边界的基础上,描述了漫湖洪水—风暴的沉积特征并建立了沉积模式,系统分析了这个环境下储集性砂体的分布及其油气聚集特征,为车西洼陷的进一步勘探指明了方向. 相似文献
90.