Urea oxidation electrocatalysis on nickel hydroxide: the role of disorder

Journal of Solid State Electrochemistry - The urea oxidation reaction (UOR) is an important challenge in electrocatalysis, in the context of electrolyzers, fuel cells, medical sensing, and...     

Application of nanoscale packed capillary liquid chromatography (75 μm id) and capillary zone electrophoresis/electrospray ionization mass spectrometry to the analysis of macrolide antibiotics

Nanoscale separation techniques, nanoscale packed capillary columns (75 μm id), and capillary zone electrophoresis (CZE), on-line with electrospray mass spectrometry (ESI/MS), were applied to the separation of a series of ten macrolide antibiotics. Both techniques use sub-microliter-per-minute flow rates through the analytical column and therefore require an electrospray probe that incorporates coaxial sheath flow. Positive ion electrospray mass spectra of these compounds yielded mainly protonated molecules. Fragmentation to yield structurally significant fragment ions was achieved by collision-induced dissociation (CID) at increased skimmer voltages. Separations were achieved using both techniques, with CZE/ESI/MS showing improved peak shapes and detection limits combined with faster analysis times. Nanoscale packed capillary columns provided better chromatographic resolution and was less susceptible to peak broadening caused by overloading of the analytes.     

Stochastic Hydrodynamics of Complex Fluids: Discretisation and Entropy Production

Many complex fluids can be described by continuum hydrodynamic field equations, to which noise must be added in order to capture thermal fluctuations. In almost all cases, the resulting coarse-grained stochastic partial differential equations carry a short-scale cutoff, which is also reflected in numerical discretisation schemes. We draw together our recent findings concerning the construction of such schemes and the interpretation of their continuum limits, focusing, for simplicity, on models with a purely diffusive scalar field, such as ‘Model B’ which describes phase separation in binary fluid mixtures. We address the requirement that the steady-state entropy production rate (EPR) must vanish for any stochastic hydrodynamic model in a thermal equilibrium. Only if this is achieved can the given discretisation scheme be relied upon to correctly calculate the nonvanishing EPR for ‘active field theories’ in which new terms are deliberately added to the fluctuating hydrodynamic equations that break detailed balance. To compute the correct probabilities of forward and time-reversed paths (whose ratio determines the EPR), we must make a careful treatment of so-called ‘spurious drift’ and other closely related terms that depend on the discretisation scheme. We show that such subtleties can arise not only in the temporal discretisation (as is well documented for stochastic ODEs with multiplicative noise) but also from spatial discretisation, even when noise is additive, as most active field theories assume. We then review how such noise can become multiplicative via off-diagonal couplings to additional fields that thermodynamically encode the underlying chemical processes responsible for activity. In this case, the spurious drift terms need careful accounting, not just to evaluate correctly the EPR but also to numerically implement the Langevin dynamics itself.     

Study of the lithium thiocyanate quadrupole by ultra-violet absorption spectroscopy

A spectroscopic method for studying quadrupole formation is described, and experimental results are presented for lithium thiocyanate in a tetrahydrofuran/hexane solvent system. From molar absorptivity equations and an equation by Fuoss and Kraus, a direct relationship is derived between the quadrupole formation constant, K_Q, and the dielectric constant of the medium. Experimental results are consistent with the equation and allow an estimate of the distance between lithium and thiocyanate in the ion pair.     

Mass spectrometry in structural and stereochemical problems—CCXXIII:ortho interactions of nitro groups

The mass spectra of C¹³ labeled o- nitrobenzoic acid and o-nitrobenzaldehyde were studied. Earlier proposed fragmentations involving group migration to a charge-carrying vacant ortho position were verified. A completely unexpected interaction in o- nitroanisole was uncovered by O¹⁸labeling.     

Anion recognition by alpha-arylazo-N-confused calix[4]pyrroles

The first example of substitution reaction in the free alpha-position of N-confused calix[4]pyrroles is reported: azo-coupling with various arenediazonium salts. The obtained azocompounds were used for studies of their anion-binding properties by UV-Vis spectroscopy.     

Baryogenesis from the Kobayashi-Maskawa phase

The smallness of quark masses suppresses the CP violation from the Kobayashi-Maskawa phase to a level that is many orders of magnitude below what is required to explain the observed baryon asymmetry. We point out that if, as a result of time variation in the Yukawa couplings, quark masses were large at the time of the electroweak phase transition, then the Kobayashi-Maskawa mechanism could be the source of the asymmetry. The Froggatt-Nielsen mechanism provides a plausible framework where the Yukawa couplings could all be of order 1 at that time, and settle to their present values before nucleo-synthesis. The problems related to a strong first order electroweak phase transition may also be alleviated in this framework. Our scenario reveals a loophole in the commonly held view that the Kobayashi-Maskawa mechanism cannot be the dominant source of CP violation to play a role in baryogenesis.