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91.
92.
Bintinger D Kees KH Masek GE Miller ES Thompson JR Vernon W White JT Eisner AM Palmer DA Sullivan MK Armitage JC Buijs A Van Driel MA Erné FC Langeveld WG Paar HP Sens JC Timmer J Van Uitert B Cain MP Ko W Lander RL Maeshima K McNeil RR Pellett DE Smith JR Williams MC Caldwell DO Joshi UP Lu A Schwitkis KA Yellin SJ 《Physical review letters》1985,54(8):763-766
93.
94.
Potentiometric analyses indicate that previous investigations have overestimated the stability of ferric borate complexes.
The FeB(OH)
4
2+
formation constant result obtained in the present work isBβ
1
*
= [FeB(OH)
4
2+
][H+][Fe3+]-1[B(OH)3]-1 = (5.4±0.3) x 10-3 at 25.0°C and 0.7 molal ionic strength. Our result indicates that solution concentrations of FeOH2+ and FeB(OH)
4
2+
are approximately equal in aqueous solution for boric acid concentrations on the order of 0.3 molal. Fe(B(OH)4)
2
+
is a minor species in solution compared to FeB(OH)4
2+ for conditions such that [B(OH)3][H+]-1≤ 350, and ferric borate complexation is insignificant in solutions such as seawater where [B(OH)3] ≤ 4× 10-4 molal. 相似文献
95.
96.
Certain antibiotics such as amphotericin B and nystatin are known to interact selectively with cholesterol in bilayer lipid membranes, resulting in changes in the transmembrane electrical properties. The possibilities for use of this effect in selective trace organic analysis are demonstrated by experiments performed with a simple electrical circuit incorporating a conventional research pH meter. Transmembrane resistance-based responses correlate with aqueous antibiotic concentration and are rapid and reversible. The limit of detection of the technique is approximately 10-9 M of stimulant. 相似文献
97.
Thompson H Wasse JC Skipper NT Hayama S Bowron DT Soper AK 《Journal of the American Chemical Society》2003,125(9):2572-2581
The technique of hydrogen/deuterium isotopic substitution has been used to extract detailed information concerning the solvent structure in pure ammonia and metallic lithium-ammonia solutions. In pure ammonia we find evidence for approximately 2.0 hydrogen bonds around each central nitrogen atom, with an average N-H distance of 2.4 A. On addition of alkali metal, we observe directly significant disruption of this hydrogen bonding. At 8 mol % metal there remains only around 0.7 hydrogen bond per nitrogen atom. This value decreases to 0.0 for the saturated solution of 21 mol % metal, as all ammonia molecules have then become incorporated into the tetrahedral first solvation spheres of the lithium cations. In conjunction with a classical three-dimensional computer modeling technique, we are now able to identify a well-defined second cationic solvation shell. In this secondary shell the nitrogen atoms tend to reside above the faces and edges of the primary tetrahedral shell. Furthermore, the computer-generated models reveal that on addition of alkali metal the solvent molecules form voids of approximate radius 2.5-3.0 A. Our data therefore provide new insight into the structure of the polaronic cavities and tunnels, which have been theoretically predicted for lithium-ammonia solutions. 相似文献
98.
E. J. Land A. Thompson T. G. Truscott K. V. Subbarao M. R. Chedekel 《Photochemistry and photobiology》1986,44(6):697-702
The photochemistries of the melanin precursors dopa, 5-S-cysteinyldopa (5-SCD) and 2.5-S,S'-dicysteinyldopa (2.5-SCD) were investigated by 265-nm laser flash photolysis. The quantum yield of hydrated electron following flash photolysis of dopa (9.1%) was half the yield of dopasemiquinone (19.6%), implying that dopasemiquinone is formed via two primary photochemical mechanisms: photionisation (giving e) or photohomolysis (giving H˙ ). Dopasemiquinone rapidly disproportionates to form dopaquinone and re-form dopa. Dopaquinone in turn decays via a base-catalysed unimolecular cyclisation eventually to form dopachrome. Assignment of the transient species was confirmed by previous pulse radiolysis studies of the one-electron oxidation of dopa. In contrast, flash photolysis of the cysteinyldopas, 5-SCD and 2,5-SCD results in lower photoionisation quantum yields and the production of initial transient species whose absorption spectra were markedly different from their semiquinone absorption spectra previously determined pulse radiolytically. These observations indicate that the primary cysteinyldopa photochemical species is not such a semiquinone, but rather results from S-CH2 bond photohomolysis. Absorption spectra and rate constants for the formation and decay of various transient species are reported. 相似文献
99.
Indium and palladium are determined polarographically with a dropping mercury electrode in a toluene phase, following extraction as the acetylacetonates from aqueous solutions containing 2-10 ppm of the metals (or 0.1-0.5 ppm with a greater ratio of sample volume to solvent volume). Of 31 elements examined, only Co(III), Cr(III), Cu(II), Fe(III), In, Mo(VI), Pd and Ti(IV) gave extractable complexes with reduction waves in the available potential range. Specificity for palladium is obtained by extraction at pH 0.5, and for indium at pH 9 m the presence of cyanide and ascorbic acid as masking agents. 相似文献
100.
Corley M. Thompson Sue G. Taylor William W. McGee 《Journal of polymer science. Part A, Polymer chemistry》1994,32(1):113-120
The kinetics of formation of polyurethane prepolymers is studied by an analytical technique which involves reactive quenching of the isocyanate, separation of the oligomeric species by GPC, and measurement by UV absorbance of the quenched moieties. The precision of the kinetic parameters and the ratios of the oligomers are determined. The effect of changes in reactant stoichiometry on the ratio of oligomers is measured and compared to the value predicted by an equation from Flory. Toluene diisocyanate is shown to give fewer high oligomers than predicted, while methylene diphenylene diisocyanate gives nearly the predicted values. Tetramethylxylene diisocyanate gives more high oligomers than predicted, an unexpected but possibly important result. Catalyst is shown to increase the reaction rate of the last by more than 200 times. © 1994 John Wiley & Sons, Inc. 相似文献