PEROXIDASE INDUCED CHEMILUMINESCENCE IN THE OXIDATION OF PYROGALLOL AND PURPUROGALLIN. INFLUENCE OF AZIDE

Abstract— The chemiluminescence (CL) emitted during the peroxidase catalyzed oxidation of purpurogallin and pyrogallol depends on one and two molecules of enzyme, respectively. Using microperoxidase, CL with purpurogallin also depends on two molecules of enzyme (above 0.3 μ M enzyme). Sodium azide inhibits the CL emitted by all reactions depending on two molecules of enzyme but enhances the CL of reactions depending on one molecule of peroxidase (purpurogallin + 0.75 n M horseradish peroxidase). The formation of functional enzyme dimols during the oxidative process is discussed.     

RADICAL GENERATION DURING THE ILLUMINATION OF AQUEOUS SUSPENSIONS OF TUNGSTEN OXIDE IN THE PRESENCE OF METHANOL, SODIUM FORMATE and SODIUM BICARBONATE. DETECTION BY SPIN TRAPPING

Abstract— Free radical intermediates appearing during illumination of aqueous suspensions of tungsten oxide were detected by electron spin resonance using the technique of spin trapping. Solutions irradiated contained methanol, formaldehyde, sodium formate and sodium hydrogen carbonate. Signals assigned to the spin adducts of the •H, •OH, •CO₂^- and •CH₂OH radicals were found.     

SOLVOLYSIS OF CHLORODIALKYLAND DIARYLPHOSPHINES,DIALKYL PHOSPHOROCHLORIDITES AND DIALKYL PHOSPHINYL CHLORIDES

Abstract

The kinetics of solvolysis of chlorodiethylphosphine, chloro(di-n-propyl)phosphine and chlorodiphenylphosphine was studied by conductometry in pure ethanol and in various mixed solvents, and was compared with that of dialkyl phosphorochloridites and of dialkyl and diaryl phosphinyl chlorides. The rate of ethanolysis of chloro(di-n-propyl)phosphine was found to be larger at higher initial concentrations. Addition of sulfuric or perchloric acid enhanced the rate of solvolysis, while sodium perchlorate and lithium chloride had no influence. In ethanof containing water, the rate of solvolysis of chloro(di-n-propylphosphine is approximately proportional to the concentration of water. In formic acid, the solvolysis of chloro(di-n-propyl)phosphine is slower than in ethanol. Addition of acetone to ethanol increases the rate of solvolysis of chloro(di-n-propyl)phosphine—possibly due to a condensation reaction producing a 1-chloroalkyl dialkylphosphine oxide. The rate of ethanolysis of chloro(di-n-propyl)phosphine is considerably enhanced in the presence of isobutylamine, di-n-butylamine and triethylamine. The solvolysis of di-t-butylphosphinyl chloride in absolute ethanol is very much slower than that of dimethyl and diethyl phosphinyl chloride.     

PEROXIDASE MEDIATED CHEMILUMINESCENCE WITH PHENOL DERIVATIVES. PHYSICO-CHEMICAL PARAMETERS AND USES IN BIOLOGICAL ASSAYS

Abstract— The influence of pH and concentration of reagents on the chemiluminescence emitted during peroxidase mediated oxidation of phenol derivatives was studied. Maximal light emission was determined under conditions where chemiluminescence due to auto-oxidation was negligible. With phloroglucinol and purpurogallin as substrates, a direct proportionality was obtained between the concentration of peroxidase and the maximal light emission. p-Phenylenediamine enhances 8-fold the light emitted with purpurogallin. With resorcinol as substrate the relation between concentration of enzyme and maximal light emission gives an S-shaped curve. With pyrogallol the light emitted is proportional to the square of the concentration of peroxidase.