Braids and their monotone clones

In this paper we investigate properties of the monotone clones of certain ordered sets known asbraids. This class of ordered sets arose naturally in the study of how the clone of monotone functions on an ordered set could satisfy, or fail to satisfy, Mal'cev conditions. One version of the main result can be stated as follows. IfB is a finite braid with reachr(B)>2 (defined in the text), then the only idempotent order-preserving functionsfBⁿB are then projections. It then follows, for example, that no algebra of monotone functions on a finite braidB withr(B)>2 generates a congruence-modular variety.Dedicated to Bjarni Jónsson on the occasion of his 70th birthday.Presented by G. McNulty.This research was supported by ARC grant A68831070 (Davey) and in part by NSF grant 87-03540 (Nation) and 89-04014 (McKenzie).     

Revealing the Magnesium-Storage Mechanism in Mesoporous Bismuth via Spectroscopy and Ab-Initio Simulations

We present mesoporous bismuth nanosheets as a model to study the charge-storage mechanism of Mg/Bi systems in magnesium-ion batteries (MIBs). Using a systematic spectroscopy investigation of combined synchrotron-based operando X-ray diffraction, near-edge X-ray absorption fine structure and Raman, we demonstrate a reversible two-step alloying reaction mechanism Bi↔MgBi↔Mg₃Bi₂. Ab-initio simulation methods disclose the formation of a MgBi intermediate and confirm its high electronic conductivity. This intermediate serves as a buffer for the significant volume expansion (204 %) and acts to regulate Mg storage kinetics. The mesoporous bismuth nanosheets, as an ideal material for the investigation of the Mg charge-storage mechanism, effectively alleviate volume expansion and enable significant electrochemical performance in a lithium-free electrolyte. These findings will benefit mechanistic understandings and advance material designs for MIBs.     

Negative refraction

Light bends the wrong way in materials where both ε and μ are negative as was pointed out in 1968, but the absence of natural materials with this property led to neglect of the subject until 1999 when it was shown how to make artificial materials, metamaterials, with negative μ. The rapid advance of the subject since that date, both in theory and experiment, is reflected in the exponential growth of publications now at the 200 per year level and still growing. This interest is explained by the sudden availability of a qualitatively different class of electromagnetic materials combined with the quite startling properties which these materials appear to have; all of which provokes debate as each new facet of their behaviour is revealed. Experiment has been vital to resolution of controversy and has chiefly been in the microwave region of the spectrum though there is potential in the optical region currently being explored by several groups.     

Effect of slurry mineralogy on slurry ICP-AES

Direct slurry analysis by FI ICP-AES has been tested on seven iron-containing and five zinc-containing minerals. Results indicate that the method can be applied for traces and majors in a range of different materials.     

Concomitant Polymorphs

The simultaneous appearance of polymorphs of a substance has long been recognized but rarely noted or systematically studied. This phenomenon can be useful in the investigation of solid materials and in understanding the relative crystal energetics of polymorphic materials. This review covers the thermodynamic and kinetic factors that govern competitive and concomitant polymorphic crystallization. One of the many examples surveyed is a cyanine/oxonol complex, for which different relative molecular orientations in two of the many reported polymorphs are shown.     

In situ space- and time-resolved sorption kinetics of anionic dyes on individual LDH crystals.

Fluorescence spectroscopy is employed to follow the ion exchange of an emissive dye--a carboxylated perylene imide--on a layered double hydroxide. The exchange of the carboxylate ions starts at the edges of the layered double hydroxide crystals and is followed by diffusion to the basal plane. Such space-resolved observations provide a solid basis for modelling and studying the mechanisms of exchange.     

Evidence for partial quenching of orbital angular momentum upon complex formation in the infrared spectrum of OH-acetylene

The entrance channel leading to the addition reaction between the hydroxyl radical and acetylene has been examined by spectroscopic characterization of the asymmetric CH stretching band of the pi-hydrogen bonded OH-acetylene reactant complex. The infrared action spectrum observed at 3278.6 cm(-1) (origin) consists of seven peaks of various intensities and widths, and is very different from those previously reported for closed-shell HF/HCl-acetylene complexes. The unusual spectrum arises from a partial quenching of the OH orbital angular momentum in the complex, which in turn is caused by a significant splitting of the OH monomer orbital degeneracy into (2)A(') and (2)A(") electronic states. The magnitude of the (2)A(')-(2)A(") splitting as well as the A rotational constant for the OH-acetylene complex are determined from the analysis of this b-type infrared band. The most populated OH product rotational state, j(OH)=9/2, is consistent with intramolecular vibrational energy transfer to the nu2 C triple bonded C stretching mode of the departing acetylene fragment. The lifting of the OH orbital degeneracy and partial quenching of its electronic orbital angular momentum indicate that the electronic changes accompanying the evolution of reactants into products have begun to occur in the reactant complex.     

Micellar structure in gemini nonionic surfactants from small-angle neutron scattering

The size and shape of micelles formed by dimeric polyoxyethylene (nonionic gemini) surfactants having the structure (Cn-2H2n-3CHCH2(OCH2CH2)mOH)2(CH2)6 with alkyl and ethoxy chain lengths ranging from n = 12-20 and m = 5-30 have been determined using small angle neutron scattering (SANS). The surfactants are polydisperse in the hydrophilic groups but otherwise analogous to the widely studied monomeric poly(oxyethylene) alkanols. We find that longer ethoxylated chains are needed to confer solubility on the gemini surfactants and that these chains in the hydrophilic corona around the alkyl core of the micelles are reasonably well described as a homogeneous random coil in a good solvent. Spherical micelles are formed by the surfactants with the longest ethoxylated chains. Shorter chains lead first to rods and ultimately a vesicle dispersion. These solutions exhibit conventional cloud point behavior, and on warming, a sphere to rod transition can be observed. For the n = 20 and m = 15 surfactant, this shape transition is accompanied by a striking increase in viscosity at low concentration and gelation at higher concentrations.     

New atropisomeric biaryl derivatives of 4-aminopyridine—identification of an improved nucleophilic catalyst for asymmetric acylation of sec-alcohols

The synthesis, CSP-HPLC resolution, and absolute configuration assignment of a series of 4-dialkylaminopyridine-based atropisomeric biaryls are described. Screening of these enantiomerically pure catalysts, which differ only in the nature of the 4-dialkylamino substituent, for the kinetic resolution of 1-(1-naphthyl)ethanol reveals the importance of this group on the selectivity of catalysis. The di-n-butylamino derivative displays the most favourable catalytic profile. The utility of this catalyst for the kinetic resolution of a selection of sec-alcohols, including a precursor for the synthesis of the antidepressant fluoxetine hydrochloride (Prozac^®) are reported. The possible role of the dialkylamino group in chirality transfer is discussed.     

Boolean Topological Distributive Lattices and Canonical Extensions

This paper presents a unified account of a number of dual category equivalences of relevance to the theory of canonical extensions of distributive lattices. Each of the categories involved is generated by an object having a two-element underlying set; additional structure may be algebraic (lattice or complete lattice operations) or relational (order) and, in either case, topology may or may not be included. Among the dualities considered is that due to B. Banaschewski between the categories of Boolean topological bounded distributive lattices and the category of ordered sets. By combining these dualities we obtain new insights into canonical extensions of distributive lattices. The second author was supported by Slovak grants VEGA 1/3026/06 and APVV-51-009605.