Enzymatic and electrochemical oxidation of uric acid: A mechanism for the peroxidase catalyzed oxidation of uric acid

The oxidation of uric acid has been studied by thin-layer spectroelectrochemistry using an optically transparent gold minigrid electrode and enzymatically using peroxidase. Under both enzymatic and electrochemical conditions a u.v.-absorbing intermediate (λ_max=302–304 nm between pH 7–9.3) is observed. This intermediate is proposed to be an imine-alcohol species formed by rapid hydration of the primary reaction product which is a diimine. Under the conditions employed in both the enzymatic electrochemical studies the imine-alcohol intermediate is hydrated in a first order reaction with an observed rate constant of 3.5×10^?3s^?1 between pH 7–9.3. This study establishes the similarity between the electrochemical and enzymatic oxidation of uric acid and indicates that electrochemical investigations of the redox behavior of purines can provide unique insights into their biological redox properties.     

High Performance Liquid Chromatographic Analysis of Pharmaceuticals Using Oil-In-Water Microemulsion Eluent and Monolithic Column

Novel and efficient separations of pharmaceutical substances were achieved using oil-in-water microemulsion eluent and a conventional C18 packing with a flow rate of 1 mL/min⁻¹. Attempts to decrease analysis time was limited due to the high viscosity of the microemulsion which generated relatively high back-pressures. Monolithic columns gave 3-fold lower back-pressures and allowed flow rates of 4 mL/min⁻¹. with the same microemulsion mobile phase which permitted rapid separations to be achieved. Separation of a test-mix of paraben preservatives was achieved in both isocratic and gradient mode in less than 1 min. The monolith-microemulsion combination was applied to rapidly quantitatively analyse two formulated products with excellent linearity, accuracy and repeatability. Quantitative analysis times were under 90 seconds. Successful quantitation of both nicotine lozenges and naprosyn tablets was performed using this approach.     

ANGIOTENSIN ALTERATIONS INDUCED BY ULTRAVIOLET RADIATION*

Abstract. Angiotensin is readily inactivated by ultraviolet light presumably due to the photosensitivity of its tyrosyl and phenylalanyl residues. Alkalinity promotes and acidity delays the biological decomposition. Under conditions of oxygen exclusion (i.e. under N₂ or H₂) the rate of decomposition is further depressed and when irradiation is carried out under hydrogen a biologically active product is formed. This altered angiotensin, judging from its chromatographic migration and dialysis rate, represents a polymerized form of angiotensin. Under identical irradiation conditions, angiotensin was coupled with C¹⁴ labelled pheny-lalanine which indicates that this residue might be the photoreactive species. The production of altered forms of angiotensin by ultraviolet irradiation was discussed with respect to possible utility in anti-metabolite, antigen or tracer work.     

Scattering Behavior of Restructured Aggregates: A Simulation Study

Simulations of diffusion-limited cluster-cluster aggregation (DLCA) with no restructuring, full restructuring, and partial restructuring have been performed. The scattering patterns produced from these aggregates have been simulated using the Rayleigh-Gans-Debye approximation. Pure DLCA aggregates produced a scattering pattern with the slope of the fractal region being about -1.8. In contrast, the slope of the fractal region of the scattering pattern for fully restructured aggregates was about -2.1, indicating an increase in fractal dimension. Partial restructuring at large length scales produced an upward turn in the scattering pattern at low qr(o), while at high qr(o) the fractal section of the pure DLCA aggregate was retained. This last result was expected and is consistent with the results and postulations of several other workers. This simulation shows that the type of scattering pattern often obtained from orthokinetic or sheared aggregation can be produced by restructuring of aggregates at large length scales. Copyright 2001 Academic Press.     

Plutonium process control using an on-line gamma monitor for uranium,plutonium, and Americium

An On-Line Gamma Monitor profiles the concentration of uranium, plutonium, and americium in waste and product streams of the anion exchange process used to purify plutonium at Los Alamos. The Monitor employs passive gamma Spectrometry to measure the 59.5-KeV and 129-KeV gamma rays of²⁴¹Am and²³⁹Pu, respectively. Because the uranium impurity in typical process streams has no gamma ray suitable for passive measurement, a novel radiotracer technique is used. Uranium-237, always present in plutonium processed at Los Alamos as a minor alpha-decay daughter of²⁴¹Pu, has a 6.8-day half-life and 208-KeV gamma energy, which make it an ideal radiotracer for macro amounts of uranium in the process. The On-Line Gamma Monitor is used routinely to provide Los Alamos operators with continuous, real-time process control information.