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1.
The temperature dependence of the NMR chemical shift of129Xe dissolved in liquid alkanes is examined in the context of the reaction field model. An essential feature of the theory is the inclusion of the temperature dependence of the density of thesolvent. The theory of free volume for liquids is incorporated into the reaction field model to account for this temperature dependence. Comparison of the theory with previously reported measurements indicates the sensitivity of the129Xe chemical shift to the free volume of liquids. Incorporation of free volume improves the agreement between measurement and theory for branched alkane solvents, and resolves the origin of the 62 ppm intercept in the plot of reaction field as a function of129Xe chemical shift for the n-alkanes. 相似文献
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Furton KG Hong YC Hsu YL Luo T Rose S Walton J 《Journal of chromatographic science》2002,40(3):147-155
Solid-phase microextraction (SPME) combined with gas chromatography (GC) is optimized and applied to the analysis of street-cocaine samples followed by the field-testing of isolated chemicals using certified detector dogs. SPME proves to be a very sensitive and rapid method for isolating odor chemicals from street-cocaine samples. SPME-GC and activated charcoal strip (ACS)-SPME-GC signature profile methods are developed for the detection and quantitation of cocaine-odor chemicals, including the optimization of controllable variables such as fiber chemistry, extraction time, and desorption time. The volatile odor chemicals in representative illicit cocaine samples are identified and quantitated by the ACS-SPME-GC signature profile method and direct injection. Field tests with drug detector dogs show methyl benzoate to be the dominant signature odor chemical along with cocaine on U.S. currency at a threshold level of approximately 1-10 microg when spiked or when 10 ng/s methyl benzoate is diffused from polymer bottles, which is required in order to initiate an alert. No other substance studied initiated consistent responses by the drug dogs. The results indicate that the microgram levels of cocaine that have been reported on circulated U.S. currency are insufficient to signal an alert from law-enforcement trained drug detector dogs. 相似文献
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Relative rates of solvolysis of some N-triorganosilylanilines in mixtures of ethanol and aqueous potassium hydroxide have been determined, with results as follows. (i) For XC6H4NHSiEt3 compounds in MeOH (5 vol) + aq. alkali (2 vol) at 50°: (X =) H, 1.0;p-Me, 0.80;p-OMe, 0.83;m-Me, 0.90; o-Me, 0.87; p-SMe, 1.90; p-F, 1.7; p-Cl, 2.8; o-Cl, 14; m-Cl, 4.2; m-NO2, 18; p-CN, ca. 43; p-NO2, ca. 120. (ii) For PhNHSi(C6H4Y)3 compounds in MeOH (10 vol) + aq. alkali (1 vol) at 50°: (Y =) H, 1.0; p-OMe, 0.12; p-Cl, ca. 32; m-Cl, ca. 84. (iii) For PhNHSiR3 compounds in MeOH (5 vol) + aq. alkali (2 vol) : (R3 =) Et3, 1.0; Et2Me, 18 (at 30°); Me2-i-Pr, 8 (at 30°);Me2-t-Bu, 0.012 (at 50°);i-Pr3, 0.006 (at 50°). In series (i) the relative rates correlate with σ, or where appropriate σ?-constants, with a ? value of 1.6. It is suggested that in the transition state of the rate-determining step the OSi bond is fully formed, or almost so, the SiN bond approximately 20—50% broken, and the bond between the nitrogen atom and a proton from the solvent ca. 10—30% formed. 相似文献
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All the amines studied are absorbed in excess of the exchange capacity bysulfonated polystyrene resins from aqueous solutions; the absorption is greatest with benzylamine, whose molecular structure is the closest to that of the monomer of the resin. The absorption is greater, then less the crosslinking of the resin, and it is influenced by the electrostatic field of the resin cations. There is no excess absorption from solvents such as alcohols, acetic acid or dioxane. The absorption characteristics of amines are sufficiently different that separations by elution chromatography on cation exchange resins are possible. Two such separations have been demonstrated. For quantitative analytical use, however, it would be wise to use very fine mesh resins on account of the slowness of diffusion of large amine molecules within the resins. 相似文献
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Michael I. Bruce Jennifer K. Walton Michael L. Williams Brian W. Skelton Allan H. White 《Journal of organometallic chemistry》1981,212(3):C35-C38
Contrary to some previously depicted structures, the proton in HC5(CO2Me)5 is bonded to two oxygens rather than to carbon; the lithium ion in Li[C5(CO2Me)5] (H2O) is tetrahedrally coordinated by two carbonyl oxygens from one C5 anion, one from a second anion, and a water molecule. 相似文献
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Abstract. Angiotensin is readily inactivated by ultraviolet light presumably due to the photosensitivity of its tyrosyl and phenylalanyl residues. Alkalinity promotes and acidity delays the biological decomposition. Under conditions of oxygen exclusion (i.e. under N2 or H2 ) the rate of decomposition is further depressed and when irradiation is carried out under hydrogen a biologically active product is formed. This altered angiotensin, judging from its chromatographic migration and dialysis rate, represents a polymerized form of angiotensin. Under identical irradiation conditions, angiotensin was coupled with C14 labelled pheny-lalanine which indicates that this residue might be the photoreactive species. The production of altered forms of angiotensin by ultraviolet irradiation was discussed with respect to possible utility in anti-metabolite, antigen or tracer work. 相似文献
10.
E. Holm J. Rioseco S. Ballestra A. Walton 《Journal of Radioanalytical and Nuclear Chemistry》1988,123(1):167-179
A method of99Tc determination has been developed based on sample decomposition followed by purification from interfering elements by hydroxide and oxide precipitations. Technetium is extracted by TBP and electrodeposited onto stainless steel discs from sodium hydroxide solution.99Tcm is used as yield monitor. The method has been applied to study releases from different sources and contents in different samples of atmospheric, terrestrial and marine origin. Results show enhanced99Tc/137Cs activity ratios for samples collected in recent years which are only expected to be contaminated from fallout from nuclear tests. Integrated fallout measurements did not reflect these enhanced ratios. 相似文献