Unexpected nonadditivity of currents encountered in the electrochemistry of mixtures of ferrocene (Fc) and cobaltocenium cation (Cc(+)) as the PF(6)(-) salt has been investigated by direct current (dc) and Fourier-transformed alternating current (ac) cyclic voltammetry in two aprotic (1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate) and three protic (triethylammonium formate, bis(2-hydroxyethyl)ammonium acetate, and triethylammonium acetate) ionic liquids (ILs). The voltammetry of the individual Fc(0/+) and Cc(+/0) couples always exhibits near-Nernstian behavior at glassy carbon and gold electrodes. As expected for an ideal process, the reversible formal potentials and diffusion coefficients at 23 +/- 1 degrees C in each IL determined from measurement on individual Fc and Cc(+) solutions were found to be independent of electrode material, concentration, and technique used for the measurement. However, when Fc and Cc(+) were simultaneously present, the dc and ac peak currents per unit concentration for the Fc(0/+) and Cc(+/0) processes were found to be significantly enhanced in both aprotic and protic ILs. Thus, the apparent diffusion coefficient values calculated for Fc and Cc(+) were respectively found to be about 25 and 35% larger than those determined individually in the aprotic ILs. A similar change in the Fc(0/+) mass transport characteristics was observed upon addition of tetrabutylammonium hexafluorophosphate (Bu(4)NPF(6)), and the double layer capacitance also varied in distinctly different ways when Fc and Cc(+) were present individually or in mixtures. Importantly, the nonadditivity of Faradaic current is not associated with a change in viscosity or from electron exchange as found when some solutes are added to ILs. The observation that the (1)H NMR T(1) relaxation times for the proton resonance in Cc(+) also are modified in mixed systems implies that specific interaction with aggregates of the constituent IL ionic species giving rise to subtle structural changes plays an important role in modifying the mass transport, double layer characteristics, and dynamics when solutes of interest in this study are added to ILs. Analogous voltammetric changes were not observed in studies in organic solvent media containing 0.1 M added supporting electrolyte. Implications of the nonadditivity of Faradaic and capacitance terms in ILs are considered.
We examine the effect of an accretion disc on the orbits of stars in the central star cluster surrounding a central massive black hole by performing a suite of 39 high-accuracy direct N-body simulations using state-of-the art software and accelerator hardware, with particle numbers up to 128k. The primary focus is on the accretion rate of stars by the black hole (equivalent to their tidal disruption rate for black holes in the small to medium mass range) and the eccentricity distribution of these stars. Our simulations vary not only the particle number, but disc model (two models examined), spatial resolution at the centre (characterised by the numerical accretion radius) and softening length. The large parameter range and physically realistic modelling allow us for the first time to confidently extrapolate these results to real galactic centres. While in a real galactic centre both particle number and accretion radius differ by a few orders of magnitude from our models, which are constrained by numerical capability, we find that the stellar accretion rate converges for models with N ≥ 32k. The eccentricity distribution of accreted stars, however, does not converge. We find that there are two competing effects at work when improving the resolution: larger particle number leads to a smaller fraction of stars accreted on nearly-circular orbits, while higher spatial resolution increases this fraction. We scale our simulations to some nearby galaxies and find that the expected boost in stellar accretion (or tidal disruption, which could be observed as X-ray flares) in the presence of a gas disc is about a factor of 10. Even with this boost, the accretion of mass from stars is still a factor of ∼ 100 slower than the accretion of gas from the disc. Thus, it seems accretion of stars is not a major contributor to black hole mass growth.
Advanced data analysis tools such as mathematical optimisation, Bayesian inference and machine learning have the capability to revolutionise the field of quantitative voltammetry.
A detailed analysis of the cooperative two-electron transfer of surface-confined cytochrome c peroxidase (CcP) in contact with pH 6.0 phosphate buffer solution has been undertaken. This investigation is prompted by the prospect of achieving a richer understanding of this biologically important system via the employment of kinetically sensitive, but background devoid, higher harmonic components available in the large-amplitude Fourier transform ac voltammetric method. Data obtained from the conventional dc cyclic voltammetric method are also provided for comparison. Theoretical considerations based on both ac and dc approaches are presented for cases where reversible or quasi-reversible cooperative two-electron transfer involves variation in the separation of their reversible potentials, including potential inversion (as described previously for solution phase studies), and reversibility of the electrode processes. Comparison is also made with respect to the case of a simultaneous two-electron transfer process that is unlikely to occur in the physiological situation. Theoretical analysis confirms that the ac higher harmonic components provide greater sensitivity to the various mechanistic nuances that can arise in two-electron surface-confined processes. Experimentally, the ac perturbation with amplitude and frequency of 200 mV and 3.88 Hz, respectively, was employed to detect the electron transfer when CcP is confined to the surface of a graphite electrode. Simulations based on cooperative two-electron transfer with the employment of reversible potentials of 0.745 ± 0.010 V, heterogeneous electron transfer rate constants of between 3 and 10 s(-1) and charge transfer coefficients of 0.5 for both processes fitted experimental data for the fifth to eighth ac harmonics. Imperfections in theory-experiment comparison are consistent with kinetic and thermodynamic dispersion and other nonidealities not included in the theory used to model the voltammetry of surface-confined CcP.
At present, electrochemical
mechanisms are most commonly identified
subjectively based on the experience of the researcher. This subjectivity
is reflected in bias to particular mechanisms as well as lack of quantifiable
confidence in the chosen mechanism compared to potential alternative
mechanisms. In this paper we demonstrate that a deep neural network
trained to recognize dc cyclic voltammograms for three commonly encountered
mechanisms provides correct classifications within 5 ms without the
problem of subjectivity. To mimic experimental data, the impact of
noise, uncompensated resistance, and dependence on scan rate, factors
that are relevant to practical studies, has also been investigated.
Outcomes with two experimental data sets are also presented.
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