A review of the uses of saliva biomarkers, detection methods and requirements for new biomarkers.

Simulations and experiments are reported which investigate the size of a macro disc electrode necessary to quantitatively show the chronoamperometric or voltammetric behaviour predicted by the Cottrell equation or the RandlesSevcik equation on the basis of exclusive one-dimensional diffusional mass transport. For experimental time scales of several seconds, the contribution of radial diffusion is seen to be measurable even for electrodes of millimetres in radius. Recommendations on the size of macro electrodes for quantitative study are given and should exceed 4 mm radius in aqueous solution.

The kinetics and mechanisms of the copper(II)-catalyzed GSH (glutathione) oxidation are examined in the light of its biological importance and in the use of blood and/or saliva samples for GSH monitoring. The rates of the free thiol consumption were measured spectrophotometrically by reaction with DTNB (5,5'-dithiobis-(2-nitrobenzoic acid)), showing that GSH is not auto-oxidized by oxygen in the absence of a catalyst. In the presence of Cu , reactions with two timescales were observed. The first step (short timescale) involves the fast formation of a copper-glutathione complex by the cysteine thiol. The second step (longer timescale) is the overall oxidation of GSH to GSSG (glutathione disulfide) catalyzed by copper(II). When the initial concentrations of GSH are at least threefold in excess of Cu , the rate law is deduced to be -d[thiol]/dt=k[copper-glutathione complex][O ] [H O ] . The 0.5 reaction order with respect to O reveals a pre-equilibrium prior to the rate-determining step of the GSSG formation. In contrast to [Cu ] and [O ], the rate of the reactions decreases with increasing concentrations of GSH. This inverse relationship is proposed to be a result of the competing formation of an inactive form of the copper-glutathione complex (binding to glutamic and/or glycine moieties).

The oxidative dissolution of citrate-capped silver nanoparticles (AgNPs, ∼50 nm diameter) is investigated herein by two electrochemical techniques: nano-impacts and anodic stripping voltammetry. Nano-impacts or single nanoparticle-electrode collisions allow the detection of individual nanoparticles. The technique offers an advantage over surface-immobilized methods such as anodic stripping voltammetry as it eliminates the effects of particle agglomeration/aggregation. The electrochemical studies are performed in different electrolytes (KNO , KCl, KBr and KI) at varied concentrations (≤20 mm). In nano-impact measurements, the AgNP undergoes complete oxidation upon impact at a suitably potentiostated electrode. The frequency of the nanoparticle-electrode collisions observed as current-transient spikes depends on the electrolyte identity, its concentration and the potential applied at the working electrode. The frequencies of the spikes are significantly higher in the presence of halide ions and increase with increasing potentials. From the frequency, the rate of AgNP oxidation as compared with the timescale the AgNP is in electrical contact with the electrode can be inferred, and hence is indicative of the relative kinetics of the oxidation process. Primarily based on these results, we propose the initial formation of the silver (I) nucleus (Ag , AgCl, AgBr or AgI) as the rate-determining process of silver oxidation on the nanoparticle.

Understanding mass transport is prerequisite to all quantitative analysis of electrochemical experiments. While the contribution of diffusion is well understood, the influence of density gradient-driven natural convection on the mass transport in electrochemical systems is not. To date, it has been assumed to be relevant only for high concentrations of redox-active species and at long experimental time scales. If unjustified, this assumption risks misinterpretation of analytical data obtained from scanning electrochemical microscopy (SECM) and generator-collector experiments, as well as analytical sensors utilizing macroelectrodes/microelectrode arrays. It also affects the results expected from electrodeposition. On the basis of numerical simulation, herein it is demonstrated that even at less than 10 mM concentrations and short experimental times of tens of seconds, density gradient-driven natural convection significantly affects mass transport. This is evident from in-depth numerical simulation for the oxidation of hexacyanoferrate (II) at various electrode sizes and electrode orientations. In each case, the induced convection and its influence on the diffusion layer established near the electrode are illustrated by maps of the velocity fields and concentration distributions evolving with time. The effects of natural convection on mass transport and chronoamperometric currents are thus quantified and discussed for the different cases studied.