全文获取类型
收费全文 | 254篇 |
免费 | 10篇 |
国内免费 | 3篇 |
专业分类
化学 | 203篇 |
晶体学 | 1篇 |
数学 | 37篇 |
物理学 | 26篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 2篇 |
2019年 | 3篇 |
2018年 | 5篇 |
2017年 | 2篇 |
2016年 | 4篇 |
2015年 | 3篇 |
2014年 | 7篇 |
2013年 | 15篇 |
2012年 | 6篇 |
2011年 | 8篇 |
2010年 | 10篇 |
2009年 | 9篇 |
2008年 | 14篇 |
2007年 | 19篇 |
2006年 | 16篇 |
2005年 | 14篇 |
2004年 | 11篇 |
2003年 | 10篇 |
2002年 | 13篇 |
2001年 | 17篇 |
2000年 | 7篇 |
1999年 | 12篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1991年 | 7篇 |
1990年 | 3篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1978年 | 3篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1938年 | 1篇 |
1928年 | 1篇 |
1923年 | 1篇 |
排序方式: 共有267条查询结果,搜索用时 140 毫秒
1.
Guillermina L. Estiú Alicia H. Jubert Jos Molina Juan Costamagna Juan Canales Juan Vargas 《Journal of Molecular Structure》1995,330(1-3):201-210
Semiempirical self-consistent field (SCF) and configuration interaction (CI) calculations of the intermediate neglect of differential overlap (INDO) type are applied to the analysis of the electronic transitions of the hexaazacyclophane base and its Ni and Cu complexes. The ground states (1Ag for the ligand and Ni complex, 2B1g for the Cu complex) are planar structures of D2h symmetry. The low-energy region of the UV-visible spectra, whose analysis may help to recognize the catalytic active sites of the complexes is associated with d → d transitions in the Ni complex, and M → L charge transfer in the Cu complex. 相似文献
2.
Gutiérrez MM Amorebieta VT Estiú GL Olabe JA 《Journal of the American Chemical Society》2002,124(35):10307-10319
The electrophilic reactivity of the pentacyanonitrosylferrate(II) ion, [Fe(CN)(5)NO](2)(-), toward hydrazine (Hz) and substituted hydrazines (MeHz, 1,1-Me(2)Hz, and 1,2-Me(2)Hz) has been studied by means of stoichiometric and kinetic experiments (pH 6-10). The reaction of Hz led to N(2)O and NH(3), with similar paths for MeHz and 1,1-Me(2)Hz, which form the corresponding amines. A parallel path has been found for MeHz, leading to N(2)O, N(2), and MeOH. The reaction of 1,2-Me(2)Hz follows a different route, characterized by azomethane formation (MeNNMe), full reduction of nitrosyl to NH(3), and intermediate detection of [Fe(CN)(5)NO](3)(-). In the above reactions, [Fe(CN)(5)H(2)O](3)(-) was always a product, allowing the system to proceed catalytically for nitrite reduction, an issue relevant in relation to the behavior of the nitrite and nitric oxide reductase enzymes. The mechanism comprises initial reversible adduct formation through the binding of the nucleophile to the N-atom of nitrosyl. The adducts decompose through OH(-) attack giving the final products, without intermediate detection. Rate constants for the adduct-formation steps (k = 0.43 M(-)(1) s(-)(1), 25 degrees C for Hz) decrease with methylation by about an order of magnitude. Among the different systems studied, one-, two-, and multielectron reductions of bound NO(+) are analyzed comparatively, with consideration of the role of NO, HNO (nitroxyl), and hydroxylamine as bound intermediates. A DFT study (B3LYP) of the reaction profile allows one to characterize intermediates in the potential hypersurface. These are the initial adducts, as well as their decomposition products, the eta(1)- and eta(2)-linkage isomers of N(2)O. 相似文献
3.
Guillermina Burillo Takeshi Ogawa Jimmy S. Hwang 《Journal of polymer science. Part A, Polymer chemistry》1992,30(10):2159-2164
A number of diacetylene containing acrylate and methacrylates have been synthesized and the interaction between their propagating radicals and the diacetylene groups was studied by ESR spectroscopy. In the case of polymerization at 70°C using AIBN as an initiator, the propagating radicals of methacrylates are temporarily trapped with the diacetylenes with rapid exchange of the electron, thus showing strong signals of the propagating radicals. Gamma irradiation of the frozen state produces a blue color in samples, and the ESR signals were found to be those of uninteracted acrylate and methacrylates. From a comparison of spectral widths, there seems to exist an intramolecular interaction between the radicals and the diacetylene group at the frozen state. © 1992 John Wiley & Sons, Inc. 相似文献
4.
A method to identify and quantify six pesticide residues - dinoseb, pirimicarb, procymidone, pyrifenox, pyrimethanil, and thiabendazole - in peaches and nectarines using capillary electrophoresis-electrospray ionization-quadrupole ion trap-tandem mass spectrometry (CE-ESI-MS/MS) is described. Separation was carried out using a buffer of 0.3 M ammonium acetate at pH 4 with 10% methanol. Pesticide residues present in peach and nectarine samples were preconcentrated by solid-phase extraction using C(18), eluted with CH(2)Cl(2), concentrated to dryness, and redissolved in buffer to obtain lower detection limits. The recoveries of the analytes ranged from 58 to 99% and the relative standard deviations were 9 to 19%. Under optimized CE-MS/MS conditions the minimum detectable levels for the six pesticides in spiked peach samples were between 0.01 mg/kg for pirimicarb and 0.05 mg/kg for procymidone with pressure injection of 50 mbar for 5 s (5 nL) at a signal-to-noise ratio of 3, which constitutes a severalfold increase in sensitivity compared to CE-MS, using a single quadrupole, and to conventional CE-UV. The potential of the method was demonstrated by analyzing different samples taken from regional agricultural cooperatives. The pesticides most often detected were thiabendazole and procymidone. 相似文献
5.
Alibés R Bayón P de March P Figueredo M Font J García-García E González-Gálvez D 《Organic letters》2005,7(22):5107-5109
[reaction: see text] A highly versatile approach to the enantioselective synthesis of securinega alkaloids is presented. Crucial steps are a palladium-catalyzed enantioselective imide alkylation, a vinylogous Mannich reaction, and a ring-closing metathesis process. Through this strategy, the synthesis of (-)-norsecurinine has been accomplished in nine steps and 11% overall yield. 相似文献
6.
Diacetylene-containing polyesters and polyurethanes were prepared by the reaction of m,m-butadiynylenedibenzyl alcohol with isophthaloyl chloride, sebacoyl chloride, hexamethylene diisocyanate and 2,4-tolylene diisocyanate. Their thermal behavior was studied by optical microscope and differential scanning calorimetry (DSC). The polyesters were crystalline. The polyurethane prepared from hexamethylene diisocyanate and polyphthalates crystallized on cooling from their melts. All turned a reddish brown color on heating at temperatures above 200°C, and prolonged heating led to a black resin, but thermal decomposition could not be avoided. Irradiation by γ-ray and UV light at room temperature deepened the color of the films, but the polymerization of the diacetylene groups was not appreciable. Simultaneous heating and irradiation was necessary to obtain transparent, amorphous, wine red colored films. 相似文献
7.
The NMR spectra of anemonin, tetrahydroanemonin and cis-bicyclo[3.3.0]octane-3,7-dione, rigid compounds with two identical functional groups, in the presence of Eu(FOD)3 are studied. The additivity of the lanthanide induced chemical shifts due to “coordination” of europium atoms at both functions is shown, while the trans configuration of the lactone rings of anemonin and the cis ring fusion in bicyclo[3.3.0]octane-3,7-dione is confirmed. 相似文献
8.
J. Muntasell M. Barrio J. Font D. O. López J. Li. Tamarit M. A. Cuevas Diarte J. Guion M. Teisseire N. B. Chanh Y. Haget 《Journal of Thermal Analysis and Calorimetry》1991,37(10):2395-2398
The paper gives some comments about the potential use of plastic crystals in energy storage. The main point deals with the possibilities of binary solid solution formation. Three binary phase diagrams in the pentaerythritol series are commented on. 相似文献
9.
10.
A History of Fischer-Tropsch Wax Upgrading at BP—— from Catalyst Screening Studies to Full Scale Demonstration in Alaska 下载免费PDF全文
John P. Collins Joep J. H. M. Font Freidet Barry Nay 《天然气化学杂志》2006,15(1):1-10
Conversion of Fischer-Tropsch wax into high quality synthetic crude or finished transportation fuels such as premium diesel has been studied over the past 15 years within BP. Catalyst screening and selection was carried out in dedicated micro-reactors and pilot plants, whose designs are critical to the performance selection. Variation in catalyst composition and defining the gas to oil feed ratios with the operating temperature are a few of the parameters studied. Product selection and maximizing diesel yield combined with stability (catalyst life) were the ultimate drivers. The selected catalyst was then tested under commercial conditions in a dedicated 300 barrel per day demonstration plant. The products were also tested in engines to assess their combustion characteristics. 相似文献