全文获取类型
收费全文 | 353篇 |
免费 | 2篇 |
国内免费 | 1篇 |
专业分类
化学 | 321篇 |
数学 | 6篇 |
物理学 | 29篇 |
出版年
2015年 | 2篇 |
2013年 | 6篇 |
2012年 | 3篇 |
2011年 | 2篇 |
2010年 | 3篇 |
2009年 | 4篇 |
2008年 | 3篇 |
2007年 | 2篇 |
2006年 | 3篇 |
2005年 | 4篇 |
2004年 | 3篇 |
2002年 | 2篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 5篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 8篇 |
1992年 | 12篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 12篇 |
1987年 | 5篇 |
1986年 | 9篇 |
1985年 | 10篇 |
1984年 | 17篇 |
1983年 | 16篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 19篇 |
1979年 | 16篇 |
1978年 | 19篇 |
1977年 | 9篇 |
1976年 | 10篇 |
1975年 | 5篇 |
1974年 | 8篇 |
1973年 | 11篇 |
1972年 | 7篇 |
1971年 | 4篇 |
1970年 | 5篇 |
1969年 | 3篇 |
1968年 | 6篇 |
1967年 | 12篇 |
1966年 | 9篇 |
1956年 | 1篇 |
1926年 | 1篇 |
1914年 | 2篇 |
排序方式: 共有356条查询结果,搜索用时 281 毫秒
11.
12.
13.
Walter Fischer Cyril A. Grob Reinhard Hanreich Georg von Sprecher Adrian Waldner 《Helvetica chimica acta》1981,64(7):2298-2311
The solvolysis rates and products of the 6-exo-substituted 2-exo- 1a - 1u , and 2-endo-norbornyl p-toluenesulfonates 2a - 2u , have been determined. In general, the rate constants for 1 and 2 (log k) correlate well with the inductive constants σ of the substitutents at C(6); however, their sensitivity to σ is much larger in the 2-exo-series 1 than in the 2-endo-series 2 . This differential transmission of polar effects is the cause of decreasing 2-exo/2-endo rate ratios from 2388 for R = t-C4H9 to 0.37 for R = Br, i. e. with increasing electron attraction by the substituent. The high sensitivity of the rate constants for the 2-exo-p-toluenesulfonates 1 to σ indicates an unusually strong inductive interaction between C(6) and the incipient cationic center at C(2). This interaction is ascribed to the participation of the pentacoordinate C(6)-atom, i. e. to 1,3-bridging, a consequence of steric hindrance of nucleophilic solvent participation in norbornanes. Donor substituents enhance 1,3-bridging, lead to faster reactions and to the formation of 2-exo substitution products. Conversely, acceptor substituents reduce 1,3-bridging, decrease rates and facilitate the formation of 2-endo substitution products. Graded 1,3-bridging is discussed in the light of Winstein's nonclassical ion concept. 相似文献
14.
Thermodynamic pKa-values have been determined for 38 4-substituted quinuclidinium perchlorates. They are remarkably sensitive to the polar effect of the substituent and cover a range of 3.63 pKa units. Furthermore, they vary linearly and almost equally with temperature since the contribution of the TΔS° term to the free energy of ionization is relatively small and constant. The magnitude of the polar effect of the 4-cyano group varies with the solvent and appears to depend on its ability to form hydrogen bonds to the substituent rather than its dielectric constant. New inductive substituent constants σIq are derived from the pKa values. Their correlation with known inductive constants is only fair or unsatisfactory, especially as regards the relative order of hydrogen and the alkyl groups. The discrepancies can be ascribed mainly to the different models used to derive the substituent constants. 相似文献
15.
When the Hammett-Taft equation log (k/ko)=ρq · σ is applied to the solvolysis of the 3-substituted propyl bromides 6a-6i in ethanol/water 4:1 (v/v) log k correlates linearly with σ except in cases where R exerts an anchimeric effect. The reaction constant ρq for 6 is ? 0.12 and is typical for a nucleophilic solvent-assisted ks process at a primary C-atom. The tertiary halides 1 and 3 , however, which react with little or no nucleophilic solvent assistance, i.e. by kc processes, lead to larger ρq values of ?0.71 and ?1.14, respectively. The reaction constant pq is therefore a sensitive gauge for charge development in the transition state for solvolysis of saturated compounds. 相似文献
16.
cis-10-Chloro-N-methyl-decahydro-isoquinoline ( 5 ) and its trans-isomer 6 undergo heterolytic fragmentation in 80% ethanol by different mechanisms. As predictable on stereo-chemical grounds the cis-isomer 5 reacts by the accelerated synchronous mechanism, the trans-isomer 6 , however, by the two-step carbonium ion mechanism. Synchronous fragmentation therefore dominates over the two-step process even when the latter would lead to a relatively stable tertiary carbonium ion. In both cases the more highly substituted and thermochemically more stable olefinic fragment 8 is formed. 相似文献
17.
Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and dodecanoic acid are components of the trail pheromone of the ant species Lasius fuliginosus. The acids were extracted from the contents of the rectal ampullae and identified by the mass spectra and gas chromatographic retention times of the corresponding methyl esters. 相似文献
18.
Konrad Grob 《Journal of separation science》1992,15(3):190-194
During sample evaporation in conventional vaporizing injection, the supply of heat to the evaporating liquid is a problem, first because the amounts of heat consumed are relatively large and, secondly, because the heat must be transferred to the sample within a very short time. Times available for evaporation, required amounts of heat, possible sources of heat, and the time required to transfer the heat to the sample liquid are discussed. It is shown that mixing with carrier gas contributes little heat to the evaporation process, but also that packings with glass wool have too low a heat capacity to deliver the required amount of heat to the evaporating sample. Transfer of heat from the insert wall to the sample easily requires several seconds, even if cooling of the vaporizing zone by 20° is accepted. Thus “flash evaporation” is usually impossible and most liquids must be held in the vaporizing chamber to allow full evaporation. 相似文献
19.
As most sample liquids tend to pass through an empty injector insert at a speed which is too high to enable complete evaporation, movement of the liquid must be arrested before it reaches the column entrance. Stopping the liquid means deposition on to a surface; this, however, is possible only after the temperature of the surface has been cooled to (or below) the boiling point of the liquid (solvent). The performance of different means of stopping the liquid has been tested visually (by the method described in Part 2). Baffles on the wall of the injector insert had hardly any effect on evaporation: the band of liquid leaving the syringe needle performed a perfect slalorn around them. The inverted cup proved more efficient, but the best performance was obtained from a light plug of glass wool: owing to its low thermal mass, the first fibers to be met by the liquid are immediately cooled to the solvent boiling point, allowing the liquid to wet it. The sample liquid is sucked up by the glass wool, from where the sample evaporates relatively slowly, often over a period of several seconds. 相似文献
20.
R. Stuck E. Fogarassy J. J. Grob P. Siffert 《Applied Physics A: Materials Science & Processing》1980,23(1):15-19
The solubility of several dopants (Sb, Ga, Bi, In) in laser treated silicon has been investigated. The dopants were introduced by vacuum deposition followed by ruby laser irradiation. Their solubility was determined by Rutherford backscattering spectroscopy measurements in channelling and random conditions. In all cases, a maximum solubilityC S * , much higher than the equilibrium solubility limitC S 0 and independent of the pulsed laser energy density, was found. The values obtained are in good agreement with those calculated from a simple model based on phase diagram considerations, using the relationship: $$C_S^* = \frac{{C_S^0 }}{{k_0 }}k^* ,$$ wherek 0 andk * are the equilibrium and effective distribution coefficients. Finally, the existence of a new solubility limit for a laser treatment is discussed. 相似文献