Fat utilization in healthy subjects consuming diacylglycerol oil diet: dietary and whole body fat oxidation.

Several studies in animals and humans have reported beneficial effects of diacylglycerol (DAG) on lipid and energy metabolism. We assessed the effect of DAG versus triacylglycerol (TAG) treatment on total energy expenditure (TEE), total fat oxidation (Fox) and respiratory quotient (RQ), and measured the oxidation rate of each oil using a respiratory chamber and the 13C-stable isotope. Eleven healthy subjects participated in a double-blind, randomized crossover study. Subjects consumed an energy maintenance diet consisting of 55% of total calories from carbohydrate, 15% from protein and 30% from fat during both the 3-day pre-chamber and 36-h chamber period. Fifty percent of the fat was test oil, containing either DAG oil or TAG oil. The oxidation rate of ingested test oils was determined by monitoring 13CO2 excretion in the breath from 13C-labeled diolein or 13C-labeled triolein. There were no significant differences in TEE, RQ and total Fox between the DAG and TAG treatment in the overall analysis. In the subgroup analysis, DAG treatment decreased RQ significantly in subjects with a high fat ratio (HFR) compared to TAG treatment. In addition, ingested diolein oxidation in DAG treatment was significantly faster than triolein oxidation in TAG treatment in the HFR group. Enhanced fat utilization with DAG treatment and rapid oxidation of ingested DAG may, at least in part, explain the greater loss of body weight and body fat related to DAG consumption found in the weight-loss studies.

Electron transfer reactions between copper(II) porphyrin complexes and various oxidizing reagents in acetonitrile.

Homogeneous electron transfer reactions of the Cu(II) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) and 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) with various oxidizing reagents were spectrophotometrically investigated in acetonitrile. The reaction products were confirmed to be the pi-cation radicals of the corresponding Cu(II)-porphyrin complexes on the basis of the electronic spectra and the redox potentials of the complexes. The rate of the electron transfer reaction between the Cu(II)-porphyrin complex and solvated Cu(2+) was determined as a function of the water concentration under the pseudo first-order conditions where Cu(2+) is in large excess over the Cu(II)-porphyrin complex. The decrease in the pseudo first-order rate constant with increasing the water concentration was attributed to the stepwise displacement of acetonitrile in [Cu(AN)(6)](2+)(AN = acetonitrile) by water, and it was concluded that only the Cu(2+) species fully solvated by acetonitrile, [Cu(AN)(6)](2+), possesses sufficiently high redox potential for the oxidation of Cu(ii)-OEP and Cu(ii)-TPP. The reactions of the Cu(II)-porphyrin complexes with other oxidizing reagents such as [Ni(tacn)(2)](3+)(tacn = 1,4,7-triazacyclononane) and [Ru(bpy)(3)](3+)(bpy = 2,2'-bipyridine) were too fast to be followed by a conventional stopped-flow technique. Marcus cross relation for the outer-sphere electron transfer reaction was used to estimate the rate constants of the electron self-exchange reaction between Cu(II)-porphyrin and its pi-cation radical: log(k/M(-1) s(-1))= 9.5 +/- 0.5 for TPP and log(k/M(-1) s(-1))= 11.1 +/- 0.5 for OEP at 25.0 degrees C. Such large electron self-exchange rate constants are typical for the porphyrin-centered redox reactions for which very small inner- and outer-sphere reorganization energies are required.