Kinetics and selectivity of permanganate chemiluminescence: a study of hydroxyl and amino disubstituted benzene positional isomers

Examination of the chemiluminescence reactions of dihydroxybenzenes, aminophenols and phenylenediamines with acidic potassium permanganate has provided a new understanding of the relationships between analyte structure, reaction conditions, kinetics of the light-producing pathway and emission intensity, with broad implications for this widely utilised chemiluminescence detection system. Using a permanganate reagent prepared in a polyphosphate solution and adjusted to pH 2.5, large differences in the rate of reaction with different positional isomers were observed, with the meta-substituted forms reacting far slower and therefore exhibiting much lower chemiluminescence intensities in flow analysis systems. The preliminary partial reduction of permanganate to form significant concentrations of Mn(III) increased the rate of reaction with all analytes tested, resulting in comparable or (in the case of aminophenol and phenylenediamine) even greater emission intensities for the meta-isomers, demonstrating the opportunity to tune the selectivity of the reagent towards certain classes of compound or even specific positional isomers of the same compound. Using more acidic permanganate reagents, in which polyphosphates are not required, the discrepancy between the chemiluminescence intensities was still observed, but was less prominent due to the generally faster rates of reaction. The enhancement of these chemiluminescence reactions by on-line addition of formic acid or formaldehyde can in part also be attributed to the generation of significant pools of the key Mn(III) precursor to the emitting species.     

Hecke algebras from groups acting on trees and HNN extensions

We study Hecke algebras of groups acting on trees with respect to geometrically defined subgroups. In particular, we consider Hecke algebras of groups of automorphisms of locally finite trees with respect to vertex and edge stabilizers and the stabilizer of an end relative to a vertex stabilizer, assuming that the actions are sufficiently transitive. We focus on identifying the structure of the resulting Hecke algebras, give explicit multiplication tables of the canonical generators and determine whether the Hecke algebra has a universal $C^1$-completion. The paper unifies algebraic and analytic approaches by focusing on the common geometric thread. The results have implications for the general theory of totally disconnected locally compact groups.     

Structural characterization and magnetoimpedance effect in amorphous and nanocrystalline AlGe-substituted FeSiBNbCu ribbons

Two series of rapidly solidified FINEMET (Fe_73.5Si_13.5B₉Nb₃Cu₁) alloys with and without partial substitution of Al (1.5 at%)/Ge (1 at%) were prepared by melt-spinning technique. The nanocrystallization process was carried out by the heat treatment of the as-spun ribbons at 560 °C for 1 h in a vacuum furnace. X-ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimeter (DSC), Mössbauer spectroscopy, and magnetoimpedance (MI) measurements were conducted on the as-quenched and heat-treated alloys to investigate their structural and magnetic properties. The average crystallite sizes obtained for the heat-treated samples were in the range of 10–12 nm as confirmed by our XRD and TEM data. The ultrasoft magnetic behavior observed for the Al/Ge-substituted nanocrystalline alloys was confirmed both by our magnetic data and magnetoimpedance ratio (MIR%) results. A twofold increase in the magnitude of the MIR% (99%) was observed for the Al/Ge-substituted nanocrystalline alloy against that of the pure FINEMET alloy (∼48%) measured at 5.5 MHz. This is believed to be related to the decrease of the magnetocrystalline anisotropy as well as magnetostriction decline due to the Al substitution for Fe atoms in this nanostructured alloy.     

Improvement of the spin polarization lifetime in the 85Rb vapor cell by octadecyltrichlorosilane coating

Effective surface coatings allow for long spin polarization in alkali metal cells, suppressing the magnetic field gradient effect and providing an improvement in atomic magnetometer sensitivity. In this work, the effect of an octadecyltrichlorosilane (OTS) surface coating on the longitudinal and transverse spin polarization lifetime of an optically pumped ⁸⁵Rb vapor cell has been studied. Our results showed that the spin polarization lifetime significantly increased in the OTS lined cell compared to the unlined cell. The relaxation rate due to alkali metal atoms wall collisions and the magnetic field gradient has been decreased by using an OTS surface coating. A longer spin polarization lifetime in the lined cell causes a narrower magnetic resonance line width and subsequently a more sensitive atomic magnetometer.     

Valonea Tannin: Tyrosinase Inhibition Activity,Structural Elucidation and Insights into the Inhibition Mechanism

Valonea tannin is a natural product readily extracted from acorn shells that has been suggested to have potential skin whitening properties. This study investigated the tyrosinase inhibition activity of extracted valonea tannin and the associated structure–function activity. Nuclear magnetic resonance spectroscopy and molecular weight analysis with gel permeation chromatography revealed that valonea tannin could be characterized as a hydrolysable tannin with galloyl, hexahydroxydiphenoyl and open formed-glucose moieties and an average molecular weight of 3042 ± 15 Da. Tyrosinase inhibition assays demonstrated that valonea tannin was 334 times more effective than gallic acid and 3.4 times more effective than tannic acid, which may relate to the larger molecular size. Kinetic studies of the inhibition reactions indicated that valonea tannin provided tyrosinase inhibition through mixed competitive–uncompetitive way. Stern–Volmer fitted fluorescence quenching analysis, isothermal titration calorimetry analysis and in silico molecule docking showed valonea tannin non-selectively bound to the surface of tyrosinase via hydrogen bonds and hydrophobic interactions. Inductively coupled plasma-optical emission spectroscopy and free radical scavenging assays indicated the valonea tannin had copper ion chelating and antioxidant ability, which may also contribute to inhibition activity. These results demonstrated the structure–function activity of valonea tannin as a highly effective natural tyrosinase inhibitor that may have commercial application in dermatological medicines or cosmetic products.     

Equilibrium states on the Cuntz–Pimsner algebras of self-similar actions

We consider a family of Cuntz–Pimsner algebras associated to self-similar group actions, and their Toeplitz analogues. Both families carry natural dynamics implemented by automorphic actions of the real line, and we investigate the equilibrium states (the KMS states) for these dynamical systems. We find that for all inverse temperatures above a critical value, the KMS states on the Toeplitz algebra are given, in a very concrete way, by traces on the full group algebra of the group. At the critical inverse temperature, the KMS states factor through states of the Cuntz–Pimsner algebra; if the self-similar group is contracting, then the Cuntz–Pimsner algebra has only one KMS state. We apply these results to a number of examples, including the self-similar group actions associated to integer dilation matrices, and the canonical self-similar actions of the basilica group and the Grigorchuk group.