Development of Free Radical Products during the Greening Reaction of Caffeic Acid Esters (or Chlorogenic Acid) and a Primary Amino Compound
ESR spectra were measured directly on a marked greening reaction mixture of Et-caffeate and a primary amino compound in alkali solution under aeration. A clear hyperfine structure was commonly detected early in the greening reaction with different amino compounds. Its hyperfine spectrum split into seven peaks was analyzed and found to be due to the oxidized free radical product of the Et-caffeate using an authentic sample system. Another type of hyperfine ESR spectrum was observed later in the reaction, and was altered with different amino compounds. The hyperfine structure for n-butylamine split into 12 lines. The latter type of free radical products were assumed to be a semiquinone type radical compounds of the trihydroxy benzacridine derivative, which was identified as the principal structure of the green and yellow pigments formed by this greening reaction system. A formation mechanism of the green pigment and related products involving these free radical products is proposed.
Structure of Green Pigment Formed by the Reaction of Caffeic Acid Esters (or Chlorogenic acid) with a Primary Amino Compound
A marked greening observed in some foods such as sweet potato, burdock, and others during food processing was shown to be due to green pigment formation by the condensation reaction of two molecules of chlorogenic acid or caffeic acid ester with one molecule of a primary amino compound under aeration in alkaline solution. Reduction of the green pigment by ascorbic acid or NaBH4 gave a yellow product, which readily turn green and then blue in air. The reduced and acetylated product of the green pigment was identified to be a novel trihydroxy benzacridine derivative, and the yellowish ethanol solution of this product immediately turned green upon addition of butyl amine or diluted alkali. Therefore, the green pigment was assumed to be an oxidized quinone type product of trihydroxy benzacridine. This identification of the structure was supported by the correspondence of the measured absorption spectra with those calculated by the molecular orbital method. A possible charge transfer complex between products of different oxidation steps in green solution was proposed.
Influence of pressure and fluidization velocity on the hydrodynamics of a fluidized bed containing horizontal tubes
Abstract An experimental investigation of the influence of horizontal tubes on the bubble behaviour and through-flow velocity of gas inside bubbles was carried out and the influence of pressure and fluidization velocity was studied. The visible bubble flow rate and the gas velocity through the bubbles were measured simultaneously in a pressurized fluidized bed, using capacitance and Pitot-static pressures probes respectively. Silica sand with a mean particle diameter of 0.7 mm was fluidized at pressures between 01. and 1.6 MPa, in a bed of 0.2 × 0.3 m cross-section. Six different horizontal tube configurations were used and comparisons were made with results obtained in the same bed operated without tubes. The results from the bed with tubes show that the influence of pressure and fluidization velocity is basically the same as in the bed without tubes; an increase in pressure and fluidization velocity increases the bubble activity. At low excess gas velocities, the influence of immersed tubes on the bubble behaviour is less pronounced than at high excess gas velocities. Measurements and visual observations show that a small tube pitch gives a more uniform distribution of the visible bubble flow over the bed cross-section. At a combination of high pressure, high excess gas velocity and a large tube pitch, a preferred bubble path was observed in the centre of the bed cross-section. The pressure probe measurements show that the through-flow velocity of gas inside the bubbles is in most cases higher when tubes are present in the bed. The through-flow velocity consistently decreases with increasing pressure in the bed without tubes. The tendency is largely the same at a low excess gas velocity when tubes are present, but at a high excess gas velocity the through-flow velocity first decreases and then increases as the pressure is increased.