Search results for " rate constant"
showing 10 items of 220 documents
Photophysical Properties of Charged Cyclometalated Ir(III) Complexes: A Joint Theoretical and Experimental Study
2011
The photophysical properties of a series of charged biscyclometalated [Ir(ppy)(2)(N boolean AND N)](1+) complexes, where ppyH is 2-phenylpyridine and N boolean AND N is 2,2'-bipyridine (bpy), 6-phenyl-2,2'-bipyridine (pbpy), and 6,6'-dipheny1-2,2'-bipyridine (dpbpy) for complexes 1, 2, and 3, respectively, have been investigated in detail. The photoluminescence performance in solution decreases from 1 to 3 upon attachment of phenyl groups to the ancillary ligand. The absorption spectra recorded over time suggest that complex 3 is less stable compared to complexes 1 and 2 likely due to a nucleophilic-assisted ancillary ligand-exchange reaction. To clarify this behavior, the temperature depen…
Electrochemical reduction and carboxylation of halobenzophenones
2002
Abstract The electrochemical reduction of a series of halogenated benzophenones XC6H4COC6H4Y (1) was studied in aprotic solvents, in the absence and presence of CO2, by cyclic voltammetry (CV) and controlled-potential electrolysis. The mechanism of electroreduction in dimethylformamide (DMF) has been investigated in some detail. Most of the compounds undergo reductive carbonhalogen bond cleavage in the time window of CV. The radical anions derived from difluorobenzophenones (X=Y=4-F; X=2-F, Y=4-F) as well as from the 3-chloro derivative are quite stable with a cleavage rate constant (kc) of the order of 10−2 s−1 or less. With 4-chloro-, 2-chloro-, 4,4′-dichloro- and 2,4′-dichorobenzophen…
EFFICIENT DEGRADATION OF CLOFIBRIC ACID BY HETEROGENEOUS PHOTOCATALYTIC OXIDATION PROCESS
2019
International audience; Emerging pollutants such as pharmaceutical active compounds were detected worldwide in different environmental compartments. Nowadays, multiple studies are focused on the investigation of their environmental fate, as well as to find new, efficient and sustainable removal technologies. Several studies demonstrated that heterogeneous photocatalysis is one of the most promising techniques used for water purification. Thus, the aim of our work was to evaluate the photodegradation efficiency of a refractory emergent compound, named clofibric acid, under UV light in aqueous solution. We report that photodegradation and mineralization efficiency are strongly dependent of th…
Über die Stabilität Von Copolymeren aus 1,3,5-Trioxan mit verschiedenen Lactonen
1976
Der thermische Abbau von Copolymeren aus 1,3,5-Trioxan und den Lactonen β-Propiolacton (3-Propanolid), Pivalolacton (2,2-Dimethyl-3-propanolid) und e-Caprolacton (6-Hexanolid) wurde untersucht. Der langsame und vollstandige Abbau der Copolymeren wird zuruckgefuhrt auf 1 eine statistische acidolytische Kettenspaltung durch Carboxyl-Endgruppen, 2 die Abspaltung von Acrylsaure an den sauren Endgruppen, 3 die statistische Kettenspaltung durch Pyrolyse von Esterbindungen vor allem in Sequenzen aus mehreren β-Propiolactonbausteinen. Die Teilreaktionen (1) und (2) konnen durch Zusatz von Butandiol-Diglycidylather-(1,4-Bis(2,3-epoxypropoxy)butan) oder N-(2-Naphthyl)anilin oder von Epoxiden stark ve…
Sol–gel material as a support of organometallic catalyst for ethylene polymerization
2008
Abstract The sol–gel procedure was applied to obtain powdery materials with different structures and morphology. It was possible to produce almost non-porous silica powder, with an extremely low surface area (ca. 4 m 2 /g) and very high uniformity of spherical particles as well as materials with various uniformity of particles and different porosity, most likely associated with increasing pore volume. Dependent on the properties of the carrier, the resulting supported vanadium catalysts (VOCl 3 /AlEt 2 Cl) showed significant differences concerning activity and stability. It was confirmed that improved hydrophobicity of the carrier’s surface may be useful and improve the activity of the syst…
Determination of Kinetic and Thermochemical Parameters of a Substitution Reaction at a Square-Planar Palladium(II) Complex in Water/AOT/n-Heptane Mic…
1995
Abstract The substitution reaction [Pd(bipy)(en)] 2+ + en → [Pd(en) 2 ] 2+ + bipy (where bipy = 2,2′-bipyridine and en = ethylenediamine) has been studied in water and water/AOT/ n -heptane microemulsions at various values of the molar ratio R ( R = [water]/[AOT]) by flow microcalorimetry. From calorimetric data, molar enthalpies of reaction and rate constants were obtained. These quantities indicate that, by increasing R , the reaction becomes less exothermic and its rate constant decreases, trending to the value observed in water. These features can be reasonably rationalized in terms of the peculiar solvation state of reactants inside the AOT reversed micelles and/or the peculiar physico…
Bidirectional membrane transport: Simulations of transport inhibition in uptake studies explain data obtained with flavonoids
2006
The purpose of the simulations was to obtain an estimate of concentration-dependent uptake curves when two counteracting transporters are present. On the basis of this experimental data obtained with a pair of ovarian carcinoma cell lines, one of which was not expressing the exsorptive transporter P-glycoprotein and one of which was an MDR1-transfected, P-glycoprotein expressing variant, the kinetics of cellular uptake of the radiolabel (3)H-talinolol were calculated and the inhibitory constants at P-gp were determined for different flavonoids. With respect to the inhibition of P-gp function, among others, naringenin and isoquercitrin were identified as inhibitors, yet estimation of the inh…
Disproportionierung und Kombination als Abbruchsmechanismen bei der radikalischen Polymerisation von Styrol, 2. Analyse der temperaturabhängigkeiten
1975
Styrol wurde in Substanz mit 14C-markiertem 2,2′-Azoisobutyronitril im Temperatur-bereich von 30 bis 80°C polymerisiert. Aus der Polymerisationsgeschwindigkeit und der Anzahl der radioaktiven Endgruppen im Polymeren wurden die Effektivitat des Starters f und die Verhaltnisse der Geschwindigkeitskonstanten fur Wachstum, Abbruch und Start k/ka und ka, PR/(kwkst) berechnet. Die Bestimmung der Molekulargewichtsverteilungen mit Hilfe der Gelpermeationschromatographie ermoglichte es, die Ubertragungskonstante CM und das Verhaltnis ka, disp/ka, comb zu berechnen. Die Temperaturabhangigkeiten der Geschwindigkeitskonstanten erwiesen sich als physikalisch sinnvoll. Styrene was bulk polymerised by ini…
Compatibility of surfactants with activated-persulfate for the selective oxidation of PAH in groundwater remediation
2017
Abstract Surfactants foam technology can improve the in situ remediation of hydrophobic organic contaminants by enhancing their solubility and the delivery of remediation chemicals. However, the presence of surfactants may impair the effectiveness of the selective oxidation of those contaminants. To tackle the issue, kinetics and selectivity of phenanthrene (PHE) oxidation in aqueous suspensions and its affecting factors including surfactant concentration (CS) and nature, temperature and persulfate (PS) concentration were studied. Significant differences in selectivity were observed between surfactants, reflecting Coulomb interactions with the anionic oxidizers. Lauryl Betaine (LB) stood ou…
Oxidation of melatonin by oxoferryl hemoglobin: A mechanistic study
2002
Reaction of melatonin with the hypervalent iron centre of oxoferryl hemoglobin, produced in aqueous solution from methemoglobin and H2O2, has been investigated at 37 degrees C and pH 7.4, by absorption spectroscopy. The reaction results in reduction of the oxoferryl moiety with formation of a heme-ferric containing hemoprotein. Stopped-flow spectrophotometric measurements provide evidence that the reduction of oxoferryl-Hb by melatonin is first-order in oxoferryl-Hb and first-order in melatonin. The bimolecular reaction constant at pH 7.4 and 37 degrees C is 112 +/- 1.0 M(-1) s(-1). Two major oxidation products from melatonin have been found by gas chromatography-mass spectroscopy: the cycl…