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101.
102.
Sarkar B Kaim W Klein A Schwederski B Fiedler J Duboc-Toia C Lahiri GK 《Inorganic chemistry》2003,42(20):6172-6174
The Ru(2)(III,II) mixed-valent state is strongly stabilized in [(bpy)(2)Ru(mu-bttz)Ru(bpy)(2)](5+) (3(5+), bttz = 3,6-bis(2-thienyl)-1,2,4,5-tetrazine, as evident from lowered oxidation potentials and isolability, a strongly increased comproportionation constant K(c) = 10(16.6), and a high-energy intervalence charge transfer band at 10100 cm(-1). Curiously, no such effects were observed for the diosmium(III,II) analogue, whereas the related systems [(bpy)(2)M(mu-bmptz)M(bpy)(2)](5+), bmptz = 3,6-bis(4-methyl-2-pyridyl)-1,2,4,5-tetrazine, exhibit conventional behavior, i.e., a slightly higher K(c) value of the Os(2)(III,II) analogue. EPR signals were observed at 4 K for 3(5+) but not for the other mixed-valent species, and high-frequency (285 GHz) EPR was employed to study the diruthenium(II) radical complexes 2(3+) and 3(3+). 相似文献
103.
Vapor pressure measurements and small angle scattering (SANS) experiments are reported and discussed for bispiperidinium (BP) bromide and n-tetrapentylammonium bromide solutions in methanol at 25°C. The BP+ ion which may be considered as a tetraalkylammonium (TAA) ion with pairwise connected alkyl chains, is used for the study of the effects due to flexible TAA alkyl chains. SANS intensities are calibrated with the help of the precise osmotic coefficients from the vapor pressure measurements. 相似文献
104.
105.
van de Coevering R Kuil M Gebbink RJ van Koten G 《Chemical communications (Cambridge, England)》2002,(15):1636-1637
Polycationic dendrimer 1 forms a well-defined, stoichiometric assembly with eight anionic metal complexes; this assembly is successfully applied as a Lewis acidic catalyst which performs comparably to the unsupported metal complex. 相似文献
106.
Hauke Harms Julien Rime Olivier Leupin Stephan J. Hug Jan Roelof van der Meer 《Mikrochimica acta》2005,151(3-4):217-222
A luminescent bacterial biosensor was used to quantify bioavailable arsenic in artificial groundwater. Its light production
above the background emission was proportional to the arsenite concentration in the toxicologically relevant range of 0 to
0.5 μM. Effects of the inorganic solutes phosphate, Fe(II) and silicate on the biosensor signal were studied. Phosphate at
a concentration of 0.25 g L−1 phosphate slightly stimulated the light emission, but much less than toxicologically relevant concentrations of the much
stronger inducer arsenite. No effect of phosphate was oberved in the presence of arsenite. Freshly prepared sodium silicate
solution at a concentration of 10 mg L−1 Si reduced the arsenite-induced light production by roughly 37%, which can be explained by transient polymerization leading
to sequestration of some arsenic. After three days of incubation, silicate did not have this effect anymore, probably because
depolymerization occurred. In the presence of 0.4 mg L−1 Fe(II), the arsenite-induced light emission was reduced by up to 90%, probably due to iron oxidation followed by arsenite
adsorption on the less soluble Fe(III) possibly along with some oxidation to the stronger adsorbing As(V). Addition of 100 μM
EDTA was capable of releasing all arsenic from the precipitate and to transform it into the biologically measurable, dissolved
state. The biosensor also proved valuable for monitoring the effectiveness of an arsenic removal procedure based on water
filtration through a mixture of sand and iron granules. 相似文献
107.
The rate of nucleation of calcium hydroxide in carefully purified supersaturated solution was observed to be about 10(3) particles, cm(-3). sec(-1), in solutions with activity products a(ca)a(OH)(2) around 4 x 10(-5). These data correspond to a homogeneous nucleus containing about 55Ca(OH)(2) units, and a nucleus-solution interfacial tension of 65 erg cm (2). 相似文献
108.
Summary A polystyrene sample obtained by free radical polymerization has been fractionated by preparative scale GPC and the structure and morphology of the fractions have been studied by13C-NMR spectroscopy, DSC and X-ray measurements. No changes in morphology in the course of fractionation have been obeyed. A distribution of syndiotacticity within the molecular weight distribution does not exist.
List of abbrevations and symbols AIBN a, a-Azo-bis-(iso-butyronitrile) - D Dispersity, M w /M n - DSC Differential scanning calorimetry - EF Efficiency of fractionation - GPC Gel permeation chromatography - m mass of the fraction - M mass of the fractionated polymer sample - MWD Molecular weight distribution - P r content of racemic dyads - PS Polystyrene - THF Tetrahydrofuran - U D-1 - U ss U of the starting sample - U f U of the fraction Auszug aus der Dissertation von U.-D. Standt: Zur Morphologie von Polystyrol, TU Braunschweig 1981. 相似文献
Zusammenfassung Eine Polystyrolprobe, die durch radikalische Polymerisation hergestellt wurde, wurde mit Hilfe der präparativen Gelpermeationschromatographie fraktioniert; die Struktur und Morphologie der Fraktionen wurde mit13C-NMR-Spektroskopie, DSC und Röntgenbeugung untersucht. Im Verlauf der Fraktionierung traten keine Änderungen der Morphologie der Fraktionen auf. Innerhalb der Molekulargewichtsverteilung existiert keine Verteilung der Syndiotaktizität.
List of abbrevations and symbols AIBN a, a-Azo-bis-(iso-butyronitrile) - D Dispersity, M w /M n - DSC Differential scanning calorimetry - EF Efficiency of fractionation - GPC Gel permeation chromatography - m mass of the fraction - M mass of the fractionated polymer sample - MWD Molecular weight distribution - P r content of racemic dyads - PS Polystyrene - THF Tetrahydrofuran - U D-1 - U ss U of the starting sample - U f U of the fraction Auszug aus der Dissertation von U.-D. Standt: Zur Morphologie von Polystyrol, TU Braunschweig 1981. 相似文献
109.
T.
ivkovi M. Randi D. J. Klein H.-Y. Zhu N. Trinajsti 《Journal of computational chemistry》1995,16(4):517-526
We consider rigorous evaluation of conjugated-circuit resonance energies for families of structurally related benzenoid hydrocarbons of increasing size. Local and global aromatic properties of such molecules are investigated with particular interest in modeling high polymers. Using the algebra of large numbers, exact formulas for contributions from individual benzene rings of polymers with up to 25,000 repeating units (close to half a million carbon atoms) were derived. All arithmetic procedures were carried out in terms of whole numbers retaining all digits, of which there were sometimes more than 105. © 1995 by John Wiley & Sons, Inc. 相似文献
110.
Abstract— The influence of excitation wavelength, pH, oxygen and solvents, upon fluorescence quantum yields, were measured for insole Indole in neutral aqueous solution exhibits the same wavelength dependence as tryptophan, which indicates that COO- absorption is not responsible for the effect. Parameters such as pH and oxygen influence only the absolute fluorescence quantum yields but not their relative variation with wavelength, indicating competition with fluorescence emission for S1 deactivation. without any influence upon deactivation of higher excited states. In contrast, solvents exhibit a specific influence upon the wavelength dependence; for indole, the decrease of fluorescence yield excited around 215 nm, compared with the yield in the first absorption band is about 40% in water, 10% in acetonitrile, 70% in n-hexane and cyclohexane, whereas no appreciable decrease occurs in methanol, ethanol or n-butanol. These observations, together with the Stokes shifts of the emission spectra, may be well correlated with Kosower's Z-values, expressing microscopic solvent-solute interactions. 相似文献