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排序方式: 共有102条查询结果,搜索用时 15 毫秒
1.
Adcock W Baran Y Filippi A Speranza M Trout NA 《The Journal of organic chemistry》2005,70(3):1029-1034
Experimental gas-phase acidities are reported for a series of 3-substituted (X) bicyclo [1.1.1]pent-1-yl carboxylic acids (1, Y = COOH). A comparison with available calculated data (MP2/6-311++G**// B3LYP/6-311+G**) reveals good agreement. The relative substituent effects are shown to be adequately described by a much lower level of theory (B3LYP/6-31+G*). Various correlations are presented which clearly point to polar field effects as being the origin of the relative acidities. 相似文献
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The oxidation of selected clinically important neurotransmitter metabolites with acidic potassium permanganate in the presence of polyphosphates evokes chemiluminescence of sufficient intensity to enable the sensitive determination of these species. Limits of detection for 5-hydroxyindole-3-acetic acid (5-HIAA), vanilmandelic acid (VMA; α,4-dihydroxy-3-methoxybenzeneacetic acid), 4-hydroxy-3-methoxyphenylglycol (MHPG), homovanillic acid (HVA, 4-hydroxy-3-methoxyphenylacetic acid) and 3,4-dihydroxyphenylacetic acid (DOPAC) were between 5 × 10−9 and 4 × 10−8 M, using flow-injection analysis methodology. In addition, we demonstrate the rapid determination of homovanillic acid and 5-hydroxyindole-3-acetic acid in human urine - without the need for extraction procedures - using monolithic column chromatography with chemiluminescence detection. 相似文献
5.
1,2‐N‐Migration in a Gold‐Catalysed Synthesis of Functionalised Indenes by the 1,1‐Carboalkoxylation of Ynamides
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Holly V. Adcock Dr. Thomas Langer Dr. Paul W. Davies 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7262-7266
Unique α‐hemiaminal ether gold carbene intermediates were accessed by a gold‐catalysed 1,1‐carboalkoxylation strategy and evolved through a highly selective 1,2‐N‐migration. This skeletal rearrangement gave functionalised indenes, and isotopic labelling confirmed the rare C?N bond cleavage of the ynamide moiety. The effect of substituents on the migration has been explored, and a model is proposed to rationalise the observed selectivity. 相似文献
6.
π‐Facial selectivity data for the reduction and methylation of some 4ax‐substituted (X) 2‐adamantanones ( 3 , Y = O) as well as the nucleophilic trapping of secondary and tertiary 4ax‐substituted (X)‐2‐adamantyl cations ( 4 ; R = H and CH3, respectively) and the 4‐methylene‐2‐adamantyl radical ( 8 ) are presented. The pronounced anti‐face selectivities observed for ( 3 , Y = O and 4 , R = CH3) emphasize the importance of the steric factor as expected for systems with a strong steric bias. However, the dominant syn‐face capture of 4 (R = H) was completely unexpected and highlights a subtle interplay between steric and electronic effects. Finally, the very high anti‐face stereoselectivity for the trapping of ( 8 ) with the trimethylstannyl anion (Me3Sn?) is rationalized in terms of an electrostatic effect overwhelming the steric factor. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
7.
Graeme Butt N. Pirzada Ronald D. Topsom William Adcock Anil N. Abeywickrema 《Tetrahedron letters》1982,23(21):2161-2162
The carbon-13 substituent chemical shifts of 4-substituted bicyclo[2.2.2]oct-1-yl cyanides are a linear function of the substituent inductive parameters. 相似文献
8.
Holly V. Adcock Elli Chatzopoulou Paul W. Davies 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(51):15745-15749
Gold carbene reactivity patterns were accessed by ynamide insertion into a C(sp3) H bond. A substantial increase in molecular complexity occurred through the cascade polycyclization of N‐allyl ynamides to form fused nitrogen‐heterocycle scaffolds. Exquisite selectivity was observed despite several competing pathways in an efficient gold‐catalyzed synthesis of densely functionalized C(sp3)‐rich polycycles and a copper‐catalyzed synthesis of fused pyridine derivatives. The respective gold–keteniminium and ketenimine activation pathways have been explored through a structure–reactivity study, and isotopic labeling identified turnover‐limiting C H bond‐cleavage in both processes. 相似文献
9.
Brendan J. Holland Jacqui L. Adcock Pavel N. Nesterenko Anton Peristyy Paul G. Stevenson Neil W. Barnett Xavier A. Conlan Paul S. Francis 《Analytica chimica acta》2014
Sodium polyphosphate is commonly used to enhance chemiluminescence reactions with acidic potassium permanganate through a dual enhancement mechanism, but commercially available polyphosphates vary greatly in composition. We have examined the influence of polyphosphate composition and concentration on both the dual enhancement mechanism of chemiluminescence intensity and the stability of the reagent under analytically useful conditions. The average chain length (n) provides a convenient characterisation, but materials with similar values can exhibit markedly different distributions of phosphate oligomers. There is a minimum polyphosphate chain length (∼6) required for a large enhancement of the emission intensity, but no further advantage was obtained using polyphosphate materials with much longer average chain lengths. Providing there is a sufficient average chain length, the optimum concentration of polyphosphate is dependent on the analyte and in some cases, may be lower than the quantities previously used in routine detection. However, the concentration of polyphosphate should not be lowered in permanganate reagents that have been partially reduced to form high concentrations of the key manganese(III) co-reactant, as this intermediate needs to be stabilised to prevent formation of insoluble manganese(IV). 相似文献
10.
13C and 19F chemical shift studies of a series of CH2M(CH3)3 and CH2M(C6H5)3 (M Si, Ge, Sn, Pb) - substituted aryl derivatives (phenyl; 1-naphthyl; 2-naphthyl) have established unambiguously that the order of hyperconjugative electron release in the neutral ground state is Pb>Sn>Ge>Si. This order is clearly at variance with the commonly accepted order(Pb>Sn>Ge>Si) based on studies of electron deficient substrates. The phenomenon is discussed in terms of current theories on σ-π interactions. In addition, substituent parameters (σI and σRo) for the PB(CH3)3 group have been derived utilizing new data from the fluorophenyl tag. These new constants are compared with those previously reported. 相似文献