Search results for "Rate constant"

Energetics and Dynamics of Naphthalene Polyaminic Derivatives. Influence of Structural Design in the Balance Static vs Dynamic Excimer Formation

2003

Two new fluorescent macrocyclic structures bearing two naphthalene (Np) units at both ends of a cyclic polyaminic chain were investigated with potentiometric, fluorescence (steady-state and time-resolved) and laser flash photolysis techniques. The fluorescence emission studies show the presence of an excimer species whose formation depends on the protonation state of the polyamine chains implying the existence of a bending movement (occurring in both the ground and in the first singlet excited state), which allows the two naphthalene units to approach and interact. For comparison purposes, one bis-chromophoric compound containing a rigid chain (piperazine unit) was also investigated. Its em…

Anionische Polymerisation in Schwach Solvatisierenden Lösungsmitteln

2007

The anionic polymerization of styrene initiated by cumylsodium and carried out in cumyl methyl ether has been examined with use of conversion kinetics and molecular weight distribution. The solvent has a weaker solvation power than THF and THP, which have been studied with the same experimental technique. The polymerization rate is first order relative to monomer and the rate constant has a value of ca. 1 mole−1 1. sec.−1 at − 20.5°C. The constant is only slightly dependent on the initiator concentration, but the molecular weight distribution is broader than a Poisson function. Added electrolyte has little effect on the propagation constant but it greatly alters the molecular weight distrib…

Untersuchungen zum oxidativen abbau nativer cellulose, 4. Stöchiometrische verhältnisse zwischen der anzahl der entstehenden spaltstellen, dem sauers…

1978

An investigation of the kinetics of cellulose degradation confirms the scheme proposed by G. V. Schulz and Mertes with the following modifications: the fast pre-stage of the degradation is missing, because there are no faster cleaving bonds in the native cellulose; the first step of the degradation (pre-oxidation) in agreement with the above mentioned authors consists in the uptake of an oxygen atom: in the second step, the scisson proper, the scheme of Staudinger and Roos is replaced by the newer and better founded scheme of Haskins and Hogsed, assuming an alkoxy-elimination; the third step (post-oxidation) finally consists in a limited number of substeps leading to a splitting off of abou…

Rate constants for ion-pair dissociation and association in the anionic two-state polymerization of styrene in THF

1965

Harnessing Fluorescence versus Phosphorescence Branching Ratio in (Phenyl)n-Bridged (n = 0–5) Bimetallic Au(I) Complexes

2013

We have designed and synthesized a series of Au(I) complexes bearing either an alkynyl–(phenylene)n–diphosphine (A-0–A-3) or a (phenylene)n–diphosphine (B-1–B-5) bridge, among which the effective distance between Au(I) and the center of the emitting ππ* chromophore can be fine-tuned via the insertion of various numbers of phenylene spacers. We then demonstrated for the first time in a systematic manner the decrease of rate constant for S1 → T1 intersystem crossing (ISC) kisc as the increase of the effective distance. The results also unambiguously showed that the phosphorescence could be harvested via higher S0 → Sn (n > 1) electronic excitation, followed by fast Sn → Tm ISC and then the po…

Calcium efflux from human erythrocyte ghosts

1970

The passive Ca efflux from human red cell ghosts was studied in media of differing ion compositions and compared to the ATP-dependent Ca efflux. Cells were loaded with(45)Ca during reversible hemolysis, and the loss of radioactivity into the non-radioactive incubation medium was measured, usually for 3 hr at 37°C. Analysis of the efflux curves revealed that(45)Ca efflux followed the kinetics of a simple two-compartment system. In the concentration range between 0 and 1MM Ca in the external solution ([Ca(++)] o ), the rate constant of passive Ca efflux (k min(-1), fraction of(45)Ca lost per minute into the medium) increased from 0.00732 to 0.0150 min(-1). There was no further increase at hig…

Electrocatalytic rate constants from DFT simulations and theoretical models: Learning from each other

2022

Electrochemical interfaces present an extraordinarily complex reaction environment and several, often counter-acting, interactions contribute to rate constants of electrocatalytic reactions. We compile a short review on how electrode potential, solvent, electrolyte, and pH effects on electrocatalytic rates can be understood and modelled using computational and theoretical methods. We address the connections between computational models based on DFT and (semi)analytical model Hamiltonians to extract physical or chemical insights, identify some omissions in present DFT simulation approaches and analytic models, and discuss what and how simulations and models could learn from each other. peerR…

A synergic nanoantioxidant based on covalently modified halloysite–trolox nanotubes with intra-lumen loaded quercetin

2016

We describe the preparation and properties of the first example of a synergic nanoantioxidant, obtained by different functionalizations of the external surface and the inner lumen of halloysite nanotubes (HNTs). Trolox, a mimic of natural α-tocopherol, was selectively grafted on the HNT external surface; while quercetin, a natural polyphenolic antioxidant, was loaded into the inner lumen to afford a bi-functional nanoantioxidant, HNT–Trolox/Que, which was investigated for its reactivity with transient peroxyl radicals and a persistent 1,1-diphenyl-2-picrylhydrazyl (DPPH˙) radical in comparison with the corresponding mono-functional analogues HNT–Trolox and HNT/Que. Both HNT–Trolox and HNT/Q…

Photocatalytic degradation of nitrophenols in aqueous titanium dioxide dispersion

1991

Abstract The results are reported of an investigation into the photodegradation of nitrophenol isomers carried out in aqueous titania (anatase) dispersions under various experimental conditions. We investigated the influence of various parameters on the photodegradation rate, such as the concentrations of the catalyst, dissolved oxygen and organic compound, and the presence of various anions in the dispersion. A plausible explanation is proposed for the influence of these parameters, both mechanistic and kinetic factors being accounted for. Gas chromatography and mass spectrometry were used as analytical methods in order to determine intermediate products. Spectroscopic methods (UV-vis and …

Heterogeneous fenton oxidation using magnesium ferrite nanoparticles for ibuprofen removal from wastewater: optimization and kinetics studies

2020

In this study, the catalytic properties of Fenton-like catalyst based on magnesium ferrite nanoparticles for IBP degradation were examined. Structural and morphological studies showed the low crystallinity and mesoporous structure for the catalyst obtained via a glycine-nitrate method. The influences of catalyst dosage, oxidant concentration, and solution pH on the pollutant degradation were investigated. The pseudo-first-order model describes kinetic data, and under optimal condition (catalyst dose of 0.5 g L-1, H2O2 concentration of 20.0 mM, and pH of 8.0), apparent rate constant reached 0.091 min-1. It was shown that Fenton reaction was mainly induced by iron atoms on the catalyst surfac…