Uric acid electrochemical oxidation

The problem of selectivity is the most serious drawback to in vivo electrochemical analysis. Many compounds of neurochemical interest oxidize at very similar potentials. While this problem can be overcome somewhat by use of differential waveforms (see Sect. 3.2), many important compounds cannot be resolvai voltammetrically. It is generally not possible to distinguish between dopamine and its metabolite 3,4-dihydroxyphenylacetic acid (DOPAC) or l tween 5-hydroxytryptamine (5-HT) and 5-hydroxyindolacetic acid (5-HIAA). Of even more serious concern, ascorbic acid oxidizes at the same potential as dopamine and uric acid oxidizes at the same potential as 5-HT, both of these interferences are present in millimolar concentrations... 

Fichter and Kern O first reported that uric acid could be electrochemically oxidized. The reaction was studied at a lead oxide electrode but without control of the anode potential. Under such uncontrolled conditions these workers found that in lithium carbonate solution at 40-60 °C a yield of approximately 70% of allantoin was obtained. In sulfuric acid solution a 63% yield of urea was obtained. A complete material balance was not obtained nor were any mechanistic details developed. In 1962 Smith and Elving 2) reported that uric acid gave a voltammetric oxidation peak at a wax-impregnated spectroscopic graphite electrode. Subsequently, Struck and Elving 3> examined the products of this oxidation and reported that in 1 M HOAc complete electrochemical oxidation required about 2.2 electrons per molecule of uric acid. The products formed were 0.25 mole C02,0.25 mole of allantoin or an allantoin precursor, 0.75 mole of urea, 0.3 mole of parabanic acid and 0.30 mole of alloxan per mole of uric acid oxidized. On the basis of these products a scheme was developed whereby uric acid (I, Fig. 1) is oxidized in a primary 2e process to a shortlived dicarbonium ion (Ha, lib, Fig. 1) which, being unstable, under-... 

Fig. 1. Proposed mechanism of electrochemical oxidation of uric acid at a wax-impregnated spectroscopic graphite electrode in 1 M HOAc according to Struck and Elving 3)...

Fig. 3. Primary electrochemical mechanism and products formed on oxidation of uric acid at the PGE in 1 M HOAc...

Correlations between Electrochemical and Biological Oxidations of Uric Acid... 

There is no doubt that electrochemically xanthine is initially oxidized to uric acid, which is then further oxidized to a bis-imine that undergoes hydrolysis giving ultimately alloxan, allantoin and urea. There is no single enzyme in man that will bring about such a fragmentation of xanthine. However, there are organisms that possess a combination of enzymes, e.g., xanthine oxidase and certain peroxidases, that under conditions comparable to those employed in the... 

In the case of the methylated xanthines, particularly theophylline, theobromine and caffeine, the preponderance of data on the metabolism of these compounds in man suggests that a methylated uric acid is the principal product. However, the data presented earlier proposes at best a 77 per cent accounting of the methylated xanthine administered. The question can be raised as to whether the final products observed upon electrochemical oxidation of these compounds aids these studies. Very recently studies of metabolism of caffeine have revealed that 3,6,8-trimethylallantoin is a metabolite of caffeine 48>. This methylated allantoin is, of course, a major product observed electrochemically. The mechanism developed for the electrochemical oxidation seems to nicely rationalize the observed products and electrochemical behavior. The mechanism of biological oxidation could well be very similar, although insufficient work has yet been performed to come to any definite conclusions. There is however, one major difference between the electrochemical and biological reactions which is concerned with the fact that in the former situation no demethylation occurs whereas in the latter systems considerable demethylation appears to take place. 

The first CNT-modified electrode was reported by Britto et al. in 1996 to study the oxidation of dopamine [16]. The CNT-composite electrode was constructed with bro-moform as the binder. The cyclic voltammetry showed a high degree of reversibility in the redox reaction of dopamine (see Fig. 15.3). Valentini and Rubianes have reported another type of CNT paste electrode by mixing CNTs with mineral oil. This kind of electrode shows excellent electrocatalytic activity toward many materials such as dopamine, ascorbic acid, uric acid, 3,4-dihydroxyphenylacetic acid [39], hydrogen peroxide, and NADH [7], Wang and Musameh have fabricated the CNT/Teflon composite electrodes with attractive electrochemical performance, based on the dispersion of CNTs within a Teflon binder. It has been demonstrated that the electrocatalytic properties of CNTs are not impaired by their association with the Teflon binder [15]. 

Biosensors fabricated on the Nafion and polyion-modified palladium strips are reported by C.-J. Yuan [193], They found that Nafion membrane is capable of eliminating the electrochemical interferences of oxidative species (ascorbic acid and uric acid) on the enzyme electrode. Furthermore, it can restricting the oxidized anionic interferent to adhere on its surface, thereby the fouling of the electrode was avoided. Notably, the stability of the proposed PVA-SbQ/GOD planar electrode is superior to the most commercially available membrane-covered electrodes which have a use life of about ten days only. Compared to the conventional three-dimensional electrodes the proposed planar electrode exhibits a similar... 

Faced with this conundrum, I am forced to place more reliance upon the microdialysis findings, in view of the possible contamination of the electrochemical DA signal by other chemical species that oxidize at the same voltage as DA (for example, 3,4-dihydroxyphenylacetic acid [DOPAC], ascorbic acid, uric acid) (see Gardner, Chen, and Paredes... 

The electrochemical oxidation of several N-methylated uric acids,405 406 as well as application of thin-layer, spectroelectrochemical, and GLC-MS techniques,407 supported the sequence of the reaction steps shown in Eq, (137). 

Uric acid in blood Direct electrochemical oxidation at bare SPCE swv Scan from —0.2 to + 1.0V 200-1000 pM <300pM Chen et al. [131]... 

The electrochemical behavior of ascorbic acid (1) and uric acid (3) in the presence of micelles and their selective determination were investigated. Aqueous cetylpyridinium bromide (cpb) and sodium dodecylbenzenesulfonate (sdbs) miceUar solutions have been used. The oxidation peak potentials for 1 and 3 are separated by 270 mV in the presence of cpb in aqueous phosphate buffer solution (pH 6.8), thus allowing their selective determination, as well as the selective determination of 3 in the presence of excess of 1. The method is simple, inexpensive and rapid with no need to modify the electrode surface by tedious procedures, and it was applied to 3 determination in samples of human urine and serum. Abnormal levels of uric acid in urine and serum are symptomatic of several diseases (gout, hyperuricaemia and Lesch-Nyhan syndrome) . 

Another application of Zinc oxide nanostructure is immobilization of uricace onto ZnO nanorod and fabrication a sensitive biosensor for uric acid detection [167], The biosensor successfully used for micromolar detection of uric acid in the presence serious interferences, glucose, ascorbic acid, and 1-cysteine. The apparent KM value for the uric acid biosensor is 0.238 mM, showing high affinity of the biosensor. Direct electron transfer of SOD at a physical vapor deposited zinc oxide nanoparticles surface was investigated [168], In comparison to SOD immobilized onto ZnO nanodisks [169], the electron transfer rate constant is small and a quasi- reversible electrochemical behavior observed. A novel... 

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