全文获取类型
收费全文 | 1646篇 |
免费 | 48篇 |
专业分类
化学 | 794篇 |
晶体学 | 10篇 |
力学 | 43篇 |
数学 | 102篇 |
物理学 | 474篇 |
无线电 | 271篇 |
出版年
2023年 | 15篇 |
2021年 | 25篇 |
2020年 | 25篇 |
2019年 | 25篇 |
2018年 | 15篇 |
2017年 | 13篇 |
2016年 | 39篇 |
2015年 | 27篇 |
2014年 | 29篇 |
2013年 | 63篇 |
2012年 | 66篇 |
2011年 | 74篇 |
2010年 | 52篇 |
2009年 | 45篇 |
2008年 | 78篇 |
2007年 | 86篇 |
2006年 | 80篇 |
2005年 | 61篇 |
2004年 | 63篇 |
2003年 | 46篇 |
2002年 | 41篇 |
2001年 | 41篇 |
2000年 | 30篇 |
1999年 | 16篇 |
1998年 | 15篇 |
1997年 | 25篇 |
1996年 | 22篇 |
1995年 | 29篇 |
1994年 | 34篇 |
1993年 | 43篇 |
1992年 | 21篇 |
1991年 | 14篇 |
1990年 | 22篇 |
1989年 | 22篇 |
1988年 | 18篇 |
1986年 | 15篇 |
1985年 | 15篇 |
1984年 | 24篇 |
1983年 | 19篇 |
1982年 | 24篇 |
1981年 | 18篇 |
1980年 | 18篇 |
1979年 | 16篇 |
1978年 | 28篇 |
1977年 | 16篇 |
1976年 | 29篇 |
1975年 | 17篇 |
1974年 | 24篇 |
1973年 | 14篇 |
1972年 | 18篇 |
排序方式: 共有1694条查询结果,搜索用时 250 毫秒
51.
Wang YN Topol IA Collins JR Burt SK 《Journal of the American Chemical Society》2003,125(43):13265-13273
Phosphate hydrolysis by GTPases plays an important role as a molecular switch in signal transduction and as an initiator of many other biological processes. Despite the centrality of this ubiquitous reaction, the mechanism is still poorly understood. As a first step to understand the mechanisms of this process, the nonenzymatic hydrolysis of mono-phosphate and tri-phosphate esters were systematically studied in gas phase and aqueous solution using hybrid density functional methods. The dielectric effect of the environment on the energetics of these processes was also explored. Theoretical results show that for mono-phosphate ester, the dissociative pathway is much more favorable than the associative pathway. However, the reaction barriers for the dissociative and associative pathways of tri-phosphate hydrolysis are very close in aqueous solution, though the dissociative pathway is more favorable in the gas phase. High dielectric solvents, such as water, significantly lower the activation barrier of the associative pathway due to the greater solvation energy of the associative transition states than that of the reactant complex. By contrast, the barrier of the dissociative pathway, with respect to the gas phase, is less sensitive to the surrounding dielectric. In the associative hydrolysis pathway of the tri-phosphate ester, negative charge is transferred from the gamma-phosphate to beta-phosphate through the bridging ester oxygen and results in Pgamma-O bond dissociation. No analogous charge transfer was observed in the dissociative pathway, where Pgamma-O bond dissociation resulted from proton transfer from the gamma-phosphate to the bridge oxygen. Finally, the active participation of local water molecules can significantly lower the activation energy of the dissociative pathway for both mono-phosphate and tri-phosphate. 相似文献
52.
C. B. Collins 《General Relativity and Gravitation》1991,23(3):321-334
A particular class of solutions of Einstein's field equations, in which the source is a perfect fluid and the geometry admits a two-parameter Abelian isometry group with spacelike orbits, is examined for the possible admission of higher symmetries. It is shown that in certain cases the geometry is spatially homogeneous, being either of the orthogonal Bianchi type I or of the tilted Bianchi-Behr type VIUh withh = –4, and that no other cases of higher symmetry (in the sense of isometry groups) are possible. The global behaviour of the Bianchi-Behr type VIUh, models is studied, and conformal diagrams are given. This investigation is extended to the case when additional homothetic vectors are admitted, and a parallel study of the global behaviour, complete with conformal diagrams, is provided. A brief argument also shows that, within the class considered, whenever the fluid flow-lines possess identical thermal histories, the geometry is necessarily spatially homogeneous. 相似文献
53.
54.
55.
56.
57.
58.
Summary In the determination of several perhalogenated compounds after gas chromatographic separation on an Apiezon L column, using
a flame ionization detector, all the compounds tested gave linear area-mass plots although the coefficients observed do not
lead to extrapolations which would permit quantitation of perhalogenated compounds for which no standard is available. Of
the compounds tested, dibromodichloromethane, tetrachloroethene and tetrabromoethene gave good linear correlations of area
ratio-mass ratio (using n-decane as the internal standard). Bromotrichloromethane and tetrabromomethane gave continuously
curving area ratio-mass ratio plots which were very reproducible and could be used for graphical interpolation. 相似文献
59.
Makarycheva-Mikhailova AV Bokach NA Kukushkin VY Kelly PF Gilby LM Kuznetsov ML Holmes KE Haukka M Parr J Stonehouse JM Elsegood MR Pombeiro AJ 《Inorganic chemistry》2003,42(2):301-311
Pt(IV)-mediated addition of the sulfimide Ph2S = NH and the mixed sulfide/sulfimides o- and p-[PhS(=NH)](PhS)-C6H4 by the S=NH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4[NH=C(R)N=SR'Ph]2] (R' = Ph, R = Me, Et, CH2Ph, Ph; R' = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2S=NH leads exclusively to trans-[PtCl4[NH=C(R)N=SPh2]2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4[NH=C(Me)N=SPh2]2] and the latter have been separated by column chromatography. Theoretical calculations at both HF/HF and MP2//HF levels for the cis and trans isomers of [PtCl4[NH=C(Me)N=SMe2]2] indicate a higher stability for the latter. Compounds trans-[PtCl4[E-NH=C(R)N=SPh2]2] (R = Me, Et) and cis-[PtCl4[E-NH=C(Me)N=SPh2][Z-NH=C(Me)N=SPh2]] have been characterized by X-ray crystallography. The complexes [PtCl4[NH=C(R)N=SPh2]2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4[NH=C(NH2)R]2] the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the coupling--in contrast to the Pt(IV) species--gives the chelates [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh]]. The X-ray crystal structure of [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh-o]] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum. 相似文献
60.
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
![点击此处可从《天然气化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
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