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The photolysis of thiochrome (THC), an oxidation product of thiamine (vitamin B 1 ) (THE), used for its fluorimetric assay, has been studied in the pH range 7.0-12.0. THC undergoes photooxidation to oxodihydrothiochrome (ODTHC) which is oxidized to a non-fluorescent compound (OP1) on UV irradiation. The kinetics of the consecutive first-order reactions: THC→k 1 ODTHC→k 2 OP1, has been evaluated and the values of first-order rate constants, k 1 (0.58-4.20 × 10 -5 , s -1 ) and k 2 (0.05-2.03 × 10 -5 , s -1 ), at pH 7.0-12.0 have been determined. The rates of degradation of THC and ODTHC are enhanced with pH and the second-order rate constants k 1 ' and k 2 ' for the OH - ion-catalyzed reaction are in the range of 0.002-58.3 M -1  s -1 . The quantum yields of the photolysis of THC and ODTHC in the pH range 7.0-12.0 have been determined. THC, ODTHC and OP1 have been identified by chromatographic, spectrometric and fluorimetric methods. THC and ODTHC have similar fluorescence characteristics and emit at 450 and 445 nm, respectively. THC, ODTHC and OP1 with distinct absorption maxima (370, 344 and 290 nm, respectively) have been determined by a newly developed and validated multicomponent spectrometric method during the photolysis reactions. The on-line formation of THC by the photooxidation of THE may lead to the degradation of THC and give erroneous results in the fluorimetric assay of THE. A scheme for the photolysis reactions of THC in aqueous solution is presented., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The photodegradation of ascorbic acid (AH 2 ) in the presence of nicotinamide (NA) at pH 2.0-12.0 has been studied using a 30 W UV radiation source. The reaction follows first-order kinetics and the values of apparent first-order rate constants (k obs ) at 1 × 10 -3  M NA concentration range from 1.17 (pH 2.0) to 3.61 × 10 -3  min -1 (pH 12.0). The values of these rate constants (k 0 ) in the absence of NA range from 0.50 (pH 2.0) to 1.75 × 10 -3  min -1 (pH 12.0), indicating that the values of k obs for the photodegradation of AH 2 in the presence of NA are about 2 fold compared to those of the AH 2 alone. The second-order rate constants (k ' ) for the photochemical interaction of AH 2 and NA are in the range of 0.67 (pH 2.0) and 1.86 × 10 -3  M -1  min -1 (pH 12.0). The k'-pH profile shows a gradual increase in the rate as a function of pH. This is due to the ionization of AH 2 to give ascorbyl anions (AH - ) which are more susceptible to photodegradation compared to the neutral molecule (AH 2 ). NA appears to undergo photochemical interaction with AH 2 during the reaction by acting as an electron acceptor to enhance its rate of photodegradation. The concentrations of AH 2 and NA in degraded solutions have been determined by a two-component spectrometric method at 243 and 261 nm (pH 2.0) with a precision of ±2%. The method has been validated and the results are comparable to the HPLC method., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The effect of metal ion complexation on the photolysis of riboflavin (RF) using various metal ions (Ag + , Ni 2+ , Co 2+ , Fe 2+ , Ca 2+ , Cd 2+ , Cu 2+ , Mn 2+ , Pb 2+ , Mg 2+ , Zn 2+ , Fe 3+ ) has been studied. Ultraviolet and visible spectral and fluorimetric evidence has been obtained to confirm the formation of metal-RF complexes. The kinetics of photolysis of RF in metal-RF complexes at pH7.0 has been evaluated. The apparent first-order rate constant (k obs ) for the photolysis of RF and the formation of lumichrome (LC) and lumiflavin (LF) (0.001M phosphate buffer) and LC, LF and cyclodehydroriboflavin (CDRF) (0.2-0.4M phosphate buffer) have been determined. The values of k obs indicate that the rate of photolysis of RF is promoted by divalent and trivalent metal ions. The second-order rate constants (k' ) for the interaction of metal ions with RF are in the order: Zn 2+ >Mg 2+ >Pb 2+ >Mn 2+ >Cu 2+ >Cd 2+ >Fe 2+ >Ca 2+ >Fe 3+ >Co 2+ >Ni 2+ >Ag + . In phosphate buffer (0.2-0.4M), an increase in the metal ion concentration leads to a decrease in the formation of LC compared to that of CDRF by different pathways. The photoproducts of RF have been identified and RF and the photoproducts have simultaneously been assayed by a multicomponent spectrometric method. The mode of photolysis of RF in metal-RF complexes has been discussed., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A study of the effect of ionic strength on the photodegradation reactions (photoreduction and photoaddition) of riboflavin (RF) in phosphate buffer (pH7.0) has been carried out using a specific multicomponent spectrometric method. It has been found that the rates of photodegradation reactions of RF are dependent upon the ionic strength of the solutions at different buffer concentrations. The apparent first-order rate constants (kobs) for the photodegradation of riboflavin at ionic strengths of 0.1-0.5 (0.5M phosphate) lie in the range of 7.35-30.32 × 10(-3) min(-1). Under these conditions, the rate constants for the formation of the major products, lumichrome (LC) by photoreduction pathway, and cyclodehydroriboflavin (CDRF) by photoaddition pathway, are in the range of 3.80-16.03 and 1.70-6.07 × 10(-3) min(-1), respectively. A linear relationship has been observed between log kobs and √μ/1+√μ. A similar plot of log k/ko against √μ yields a straight line with a value of ~+1 for ZAZB showing the involvement of a charged species in the rate determining step. NaCl appears to promote the photodegradation reactions of RF probably by an excited state interaction. The implications of ionic strength on RF photodegradation by different pathways and flavin-protein interactions have been discussed., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A study of the formulation of liposomal preparations of riboflavin (RF) with compositional variations in the content of phosphatidylcholine (PC) and their entrapment efficiency (26-42%) have been conducted. Light transmission characteristics of the liposomal preparations have been determined to evaluate their effect on the amount of light passing through the system to initiate a photochemical reaction. Dynamic light scattering (DLS) and atomic force microscopy (AFM) have been used to study the physical characteristics of liposomes. The liposomal preparations of RF have been subjected to photolysis using visible light and the apparent first- order rate constant, kobs, for the degradation of RF have been determined. The values of kobs (1.73-2.29×10(-3)min(-1)) have been found to decrease linearly with an increase in PC concentration in the range of 12.15 to 14.85 mM. Thus, an increase in PC concentration of liposomes leads to an increase in the stability of RF. RF and its main photoproduct, lumichrome (LC), formed in liposomes have been assayed by a two-component spectrometric method at 356 and 445 nm using an irrelevant absorption correction to compensate for the interference of liposomal components. The fluorescence measurements of RF in liposomes indicate excited singlet state quenching and the formation of a charge-transfer complex between RF and PC. It results in electron transfer from PC to RF to cause photoreduction and stabilization of RF., (Copyright © 2015 Elsevier B.V. All rights reserved.)