全文获取类型
收费全文 | 360篇 |
免费 | 0篇 |
国内免费 | 1篇 |
专业分类
化学 | 329篇 |
力学 | 5篇 |
数学 | 16篇 |
物理学 | 11篇 |
出版年
2023年 | 2篇 |
2022年 | 2篇 |
2021年 | 2篇 |
2013年 | 6篇 |
2012年 | 9篇 |
2011年 | 13篇 |
2010年 | 2篇 |
2009年 | 2篇 |
2008年 | 15篇 |
2007年 | 17篇 |
2006年 | 8篇 |
2005年 | 14篇 |
2004年 | 11篇 |
2003年 | 6篇 |
2002年 | 6篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1998年 | 2篇 |
1997年 | 7篇 |
1996年 | 11篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 8篇 |
1992年 | 10篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 17篇 |
1984年 | 6篇 |
1983年 | 11篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 12篇 |
1978年 | 18篇 |
1977年 | 14篇 |
1976年 | 10篇 |
1975年 | 13篇 |
1974年 | 5篇 |
1973年 | 6篇 |
1972年 | 8篇 |
1971年 | 4篇 |
1970年 | 5篇 |
1957年 | 2篇 |
1906年 | 1篇 |
1902年 | 1篇 |
1901年 | 1篇 |
排序方式: 共有361条查询结果,搜索用时 0 毫秒
1.
2.
L. Moens F. De Corte A. Simonits Lin Xilei A. De Wispelaere J. De Donder J. Hoste 《Journal of Radioanalytical and Nuclear Chemistry》1982,70(1-2):539-550
A new method is presented to calculate with improved accuracy the absolute peak efficiency of cylindrical Ge and Ge(Li) detectors
for point, disk and cylinder sources, positioned at any source-detector distance. Moreover attention was paid to true-coincidence
effects. The method is extensively tested and applied for the analysis of reference materials. The accuracy turned out to
be 3% or better.
Research associate of the “Nationaal Fonds voor Wetenschappelijk Onderzoek”. 相似文献
3.
4.
5.
Klaus Rakus Sergej P. Verevkin Hans-Dieter Beckhaus Christoph Rüchardt 《欧洲无机化学杂志》1994,127(11):2225-2234
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献
6.
7.
Renáta Oriňáková Hans-Dieter Wiemhöfer Jürgen Paulsdorf Veronika Barinková Anna Bednáriková Roger M. Smith 《Journal of Solid State Electrochemistry》2006,10(7):458-464
The electrochemical impedance method was applied during the electrochemical deposition of a binary Ni–Co coating on iron powder in a fluidised bed electrode system. The influence of the suspension density on the charge transfer in the course of the electro-deposition process was studied. At a potential of −900 mV (vs. Ag/AgCl/3 M KCl), when the binary Ni–Co layer was formed, the impedance data were characterised by two semicircles with the semicircle at high frequencies being larger in magnitude. A contribution of the diffusion process to the overall current was observed. The optimal suspension density for the charge transfer in the bed was 10×10−3–15×10−3 (i.e., 4–6 g of iron powder in 50 ml of electrolyte). The most probable mechanism of the charge transfer for the studied concentrations of powder particles is the convective mechanism. The iron particles dispersed in the electrolyte were considered to act as either a depolariser or an additional working electrode depending on the applied electrode potential and on the suspension density. 相似文献
8.
Summary Using the X-ray crystal structure of the human topoisomerase I (top1) – DNA cleavable complex and the Sybyl software package, we have developed a general model for the ternary cleavable complex formed with four protoberberine alkaloids differing in the substitution on the terminal phenyl rings and covering a broad range of the top1-poisoning activities. This model has the drug intercalated with its planar chromophore between the −1 and +1 base pairs flanking the cleavage site, with the nonplanar portion pointing into the minor groove. The ternary complexes were geometry-optimized and relative interaction energies, computed by using the Tripos force field, were found to rank in correct order the biological potency of the compounds; in addition, the model is also consistent with the top1-poisoning inactivity of berberine, a major prototype of the protoberberine alkaloids. The model might serve as a rational basis for elaboration of the most active compound as a lead structure, in order to develop more potent top1 poisons as next generation anti-cancer drugs. 相似文献
9.
10.
de Meijere A Kozhushkov SI Rauch K Schill H Verevkin SP Kümmerlin M Beckhaus HD Rüchardt C Yufit DS 《Journal of the American Chemical Society》2003,125(49):15110-15113
The enthalpies of formation [Delta(g)] of tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),10(14),11-heptaene (2, 1,2-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1-ene) and tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),8,10(14),11-octaene (3, 1,2,9,10-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1,9-diene) have been determined by measuring their heats of combustion in a microcalorimeter and their heats of sublimation by the transpiration method. Values of the strain energies (SE) [SE(2) = 34.7 kcal mol(-)(1), SE(3) = 42.0 kcal mol(-)(1)] have been derived from the gas-phase heats of formation and are compared with those from MM3 and PM3 calculations and with the corresponding value SE(1) = 30.1 kcal mol(-)(1) for the parent tricyclo[8.2.2.2(4,7)]hexadeca-1(13),4(16),5,7(15),10(14),11-hexaene (1, [2.2]paracyclophane). The higher strain energies of 2 and 3 (by 4.6 and 11.9 kcal mol(-)(1)) are in accord with the well-known increased reactivities of their aromatic rings as a consequence of their increased bending. As revealed by an X-ray crystal structure analysis, the bending in the monoene 2 corresponds to that of 1 and 3 at one of two bridging corners. 相似文献