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71.
Mary E. R. McHale Ann-Sofi M. Kauppila Joyce R. Powell Pablo Otero Jr. Melani Jayasekera William E. Acree Jr. 《Journal of solution chemistry》1996,25(3):295-302
Experimental solubilities are reported for benzil dissolved in six binary mixtures containing dibutyl ether with hexane, heptane, octane, cyclohexane, methylcyclohexane, and 2,2,4-trimethylpentane at 25°C. Results of these measurements are compared to the predictions of equations developed previously for solubility in systems of nonspecific interactions. The most successful equation in terms of goodness of fit involved a volume fraction average of the excess Gibbs energies relative to the Flory-Huggins model, and predicted the experimental solubilities in the six systems studied to within an overall average absolute deviation of 3.4% and with a maximum deviation of 6.0%. 相似文献
72.
Moroney C Lehane M Braña-Magdalena A Furey A James KJ 《Journal of chromatography. A》2002,963(1-2):353-361
Azaspiracids have been identified as the cause of a new toxic syndrome called azaspiracid poisoning (AZP) that has led to incidents of human intoxications throughout Europe following the consumption of mussels. Although five AZP toxins have been structurally elucidated to-date, azaspiracid (AZA1), 8-methylazaspiracid (AZA2) and 22-demethylazaspiracid (AZA3) are the predominant toxins. Separation of the three main AZP toxins was achieved using reversed-phase liquid chromatography (LC) and coupled to an electrospray ionisation source of an ion-trap mass spectrometer. Five reversed-phase (C18) and three diol solid-phase extraction (SPE) cartridges were compared for their efficacy in the cleanup of shellfish matrix. The comparison was based on the optimum recoveries of AZA1, AZA2 and AZA3 from extracts of mussel tissues. LC-electrospray MS3 analysis was used to quantify the AZP toxins in wash and eluate fractions in the SPE studies. Good recovery and reproducibility data were obtained for one diol SPE cartridge and two C18 SPE cartridge types. 相似文献
73.
Huang Y Triscari JM Pasa-Tolic L Anderson GA Lipton MS Smith RD Wysocki VH 《Journal of the American Chemical Society》2004,126(10):3034-3035
Analysis of fragmentation patterns from 5654 unique doubly charged tryptic peptides is obtained. Great variability of average relative abundance of bond cleavage is found between different amino acid combinations. There exist similarities as well as differences between b and y ions. Strong enhancement or suppression of cleavage gives insight into possible chemical interactions at reactive conformations formed by preferred phi-psi angles. 相似文献
74.
Li I Bandara J Shultz MJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(24):10474-10480
Many interfacial studies on solid surfaces, for example, quartz/water, assume that a standard cleaning procedure regenerates the surface reproducibly. In the reported work, the results of two surface specific techniques, sum frequency generation (SFG) spectroscopy and atomic force microscopy, show that the effects of prolonged exposure to Nanopure water and to pH 10 NaOH are distinctly different. In conjunction with the experimental data, molecular mechanics is used to correlate the SFG spectral frequencies to the hydrogen stretching vibrations of the surface-bound water molecules. It is found that after 17 days of soaking in water, water molecules penetrate into the SiO2 matrix to produce a swollen and amorphous layer; it is likely that broken Si-O bonds from the polishing process serve as nucleation sites for hydration and swelling. Disorder introduced in the interfacial water layer is detected by the rising intensity of the weakly hydrogen-bonded SFG peak at 3450 cm(-1). Dominance of the 3450 cm(-1) is absent in a pH 10, NaOH-soaked quartz disk, indicating that the strong hydrogen-bonded network in water remains intact. 相似文献
75.
Mills NS Tirla C Benish MA Rakowitz AJ Bebell LM Hurd CM Bria AL 《The Journal of organic chemistry》2005,70(26):10709-10716
[reaction: see text] Electrochemical oxidation of meta-substituted diphenylmethylidenefluorenes (3a-g) results in the formation of fluorenylidene dications that are shown to be antiaromatic through calculation of the nucleus independent chemical shift (NICS) for the 5- and 6-membered rings of the fluorenyl system. There is a strong linear correlation between the redox potential for the dication and both the calculated NICS and sigma(m). Redox potentials for formation of dications of analogously substituted tetraphenylethylenes shows that, with the exception of the p-methyl derivative, the redox potentials for these dications are less positive than for formation of the dications of 3a-g and for dications of p-substituted diphenylmethylidenefluorenes, 2a-g. The greater instability of dications of 2a-g and 3a-g compared to the reference system implies their antiaromaticity, which is supported by the positive NICS values. The redox potentials for formation of the dications of meta-substituted diphenylmethylidenes (3a-g) are more positive than for the formation of dications of para-substituted diphenylmethylidenes (2a-g), indicating their greater thermodynamic instability. The NICS values for dications of 3a-g are more antiaromatic than for dications of 2a-g, which is consistent with their greater instability of the dications of 3a-g. Although the substituted diphenylmethyl systems are not able to interact with the fluorenyl system through resonance because of their geometry, they are able to moderate the antiaromaticity of the fluorenyl cationic system. Two models have been suggested for this interaction, sigma to p donation and the ability of the charge on the substituted ring system to affect delocalization. Examination of bond lengths shows very limited variation, which argues against sigma to p donation in these systems. A strong correlation between NICS and sigma constants suggests that factors that affect the magnitude of the charge on the benzylic (alpha) carbon of the diphenylmethyl cation affect the antiaromaticity of the fluorenyl cation. Calculated atomic charges on carbons 1-8 and 10-13 show an increase in positive charge, and therefore greater delocalization of charge in the fluorenyl system, with increasing electronegativity of the substituent. The change in the amount of positive charge correlated strongly with NICS, supporting the model in which the amount of delocalization of charge is related to the antiaromaticity of the species. Thus, both aromatic and antiaromatic species are characterized by extensive delocalization of electron density. 相似文献
76.
Salts of pentadecafluorooctanoic acid (PFOA) are polymerization aids used in the manufacture of fluoropolymers; one of the applications of fluoropolymers is the coating of metal cookware products. A method was developed to determine if PFOA might be present in and extracted from the surface of commercial frying pans coated with a DuPont fluoropolymer under simulated cooking conditions. Commercial grade cookware was obtained, then extracted with water and ethanol/water mixtures at 100 and 125 degrees C, and the resulting extracts were analyzed by liquid chromatography tandem mass spectrometry (LC/MS/MS). Detection and quantification limits as low as 100 pg cm(-2) were demonstrated. None of the fluoropolymer treated cookware samples analyzed showed detectable levels of PFOA when extracted under simulated cooking conditions. 相似文献
77.
Lisa A. Marzilli David Wang William R. Kobertz John M. Essigmann Paul Vouros 《Journal of the American Society for Mass Spectrometry》1998,9(7):676-682
The biological consequences of a carcinogen—DNA adduct are defined by the structure of the lesion and its position within the genome. Electrospray ionization ion trap mass spectrometry (ESI-ITMS) is shown here to be a sensitive and rapid approach capable of defining both of these parameters. Three isomeric oligonucleotides of the sequence 5′-CCGGAGGCC modified by the potent human carcinogen aflatoxin B1 (AFB1) at different guanines were analyzed by ESI-ITMS. All three samples possessed the same molecular ion confirming the presence of an intact aflatoxin moiety in each oligonucleotide. In addition, each sample displayed a characteristic fragmentation pattern that permitted unambiguous identification of the site of modification within the sequence. Furthermore, an AFB1-modified oligonucleotide was converted under alkaline conditions to its more stable formamidopyrimidine (FAPY) derivative. Analysis of this sample revealed the presence of a molecular ion corresponding to the presence of the FAPY adduct and a distinctive fragmentation pattern that paralleled the known chemical stability of the FAPY metabolite. This approach should be of general use in the determination of not only the nature and site of covalent modifications, but also the chemical stability of DNA adducts. 相似文献
78.
Ion-selective electrodes based on the neutral carrier, 12-crown-4, in a poly(vinyl chloride) matrix were found to respond ideally, or almost ideally, to potassium, sodium, barium, strontium, magnesium, cobalt(II), nickel(II) and aluminum ions. The electrode showed good selectivity for Al3+ over Co2+ and Mg2+, and for Co2+ over Mg2+. Little selectivity was found for the other ions tested. 相似文献
79.
The tumor-associated carbohydrate antigens Globo-H, SSEA-3, and Gb3 were synthesized in a linear fashion using glycosyl phosphate monosaccharide building blocks. All of the building blocks were prepared from readily available common precursors. The difficult alpha-(1-->4-cis)-galactosidic linkage was installed using a galactosyl phosphate donor with high selectivity. Introduction of the beta-galactosamine unit required the screening a variety of amine protecting groups to ensure good donor reactivity and protecting group compatibility. An N-trichloroacetyl-protected galactosamine donor performed best for the installation of the beta-glycosidic linkage. Conversion of the trichloroacetyl group to the N-acetyl group was achieved under mild conditions, fully compatible with the presence of multiple glycosidic bonds. This synthetic strategy is expected to be amenable to the synthesis of the globo-series of tumor antigens on solid-support. 相似文献
80.
Straightforward analysis for components in a single certified reference sediment is of limited use for assessing the accuracy of environmental determinations. A systematic approach requires mixing of certified sediments, one with another and with environmental samples, and the preparation of secondary reference material by the laboratory. Use of Youden pairs, reference material embedded in samples and linear models should enable valid accuracy statements to be made based on well known statistical concepts. For assessing accuracy, reference sediments which are matched in particle size, and are end-members for components or sediment types are most useful. 相似文献