Spin anisotropy effects on the dimerization of the magnetostrictive quasi-one-dimensional XY model

The one-dimensional first-neighbour spin - $\text{1}\text{2}$ magnetostrictive XY model (with crystalline degrees of freedom assumed three- dimensional) with $\text{different}$ X and Y spin coupling constants presents a quite rich spin-Peierls dimerization phase diagram. In the (low anisotropy) - (low temperature) region we recover previous results (in particular the possibility for a first-order phase transition in the absence of external magnetic field); in the other three regions of the temperature-anisotropy space interesting branches of the phase diagram (including the tricritical line) are exhibited (for the first time as far as we know).     

An EPR, ESEEM, structural NMR, and DFT study of a synthetic model for the covalently ring-linked tyrosine-histidine structure in the heme-copper oxidases

We report CW-EPR, ESEEM, and structural NMR results, as well as DFT calculations, on model compounds relevant to the unusual cross-linked Tyr-His (YH) moiety at the active site of the heme-copper oxidases. CW-EPR spectra of an (15)N isotopically labeled 4-methyl-2-(4-methyl-imidazole-1-yl)-phenol radical are nearly identical to those of the natural abundance (14)N compound. We obtain good simulations of these EPR spectra without including hyperfine couplings to the nitrogen nuclei. This implies that the electron distribution of the radical is largely localized on the phenol ring with only a small amount of spin delocalized onto the nitrogens of the imidazole. Using three-pulse ESEEM spectroscopy, we have successfully detected the two imidazole ring nitrogens, one near the "exact cancellation" ESEEM condition and the other more weakly coupled. We assign these to the imino and amino nitrogens, respectively, based on DFT calculations performed on this radical species. The experimental results and the supporting density functional calculations clearly show that the imidazole substituent has only a minor effect on the electronic structure of the substituted phenol radical.     

Border between regular and chaotic quantum dynamics

We identify a border between regular and chaotic quantum dynamics. The border is characterized by a power-law decrease in the overlap between a state evolved under chaotic dynamics and the same state evolved under a slightly perturbed dynamics. For example, the overlap decay for the quantum kicked top is well fitted with [1+(q-1)(t/tau)2](1/(1-q)) (with the nonextensive entropic index q and tau depending on perturbation strength) in the region preceding the emergence of quantum interference effects. This region corresponds to the edge of chaos for the classical map from which the quantum chaotic dynamics is derived.     

Statistics of the One-Dimensional Riemann Walk

The Riemann walk is the lattice version of the Lévy flight. For the one-dimensional Riemann walk of Lévy exponent 0<<2 we study the statistics of the support, i.e., set of visited sites, after t steps. We consider a wide class of support related observables M(t), including the number S(t) of visited sites and the number I(t) of sequences of adjacent visited sites. For t we obtain the asymptotic power laws for the averages, variances, and correlations of these observables. Logarithmic correction factors appear for =2/3 and =1. Bulk and surface observables have different power laws for 1<2. Fluctuations are shown to be universal for 2/3 <2. This means that in the limit t the deviations from average M(t)M(t)–M-0304;(t-0304;) are fully described either by a single M independent stochastic process (when 2/3 <1) or by two such processes, one for the bulk and one for the surface observables (when 1<<2).     

A stochastic approach to optimize Maritime pine (Pinus pinaster Ait.) stand management scheduling under fire risk. An application in Portugal

The paper discusses research aiming at the development of a management scheduling model for even-aged stands that may take into consideration fuel treatments to address the risk of wildfires. A Stochastic dynamic programming (SDP) approach is proposed to determine the policy (e.g. the fuel treatment and thinning schedules and the rotation age) that produces the maximum expected discounted net revenue. Fuel treatment activities encompass shrub cleanings. Emphasis was on combining a deterministic stand-level growth and yield model with wildfire occurrence and damage models to design a SDP network. SDP stages are defined by age and state variables include both the stand basal area and the number of years since the last fuel treatment. Fire occurrence and damage scenarios are addressed at each stage. Results from an application to Maritime pine (Pinus pinaster Ait.) stand management scheduling in Leiria National Forest, Portugal, are presented. Results suggest that the modeling strategy may help assess the impact of wildfire risk on the optimal stand management schedule. They confirm that the maximum expected discounted net revenues decreases. Further, albeit some timber may be salvaged after the wildfire, rotation age also decreases when the risk of fire is considered. Finally, they provide interesting insights about the role of thinning and fuel treatment policies in mitigating risk.     

Opening of Epoxide Rings Catalyzed by Niobium Pentachloride

Abstract

The behavior of several epoxides when treated with NbCl₅ was studied. In general, the studied epoxides reacted rapidly with NbCl₅, giving, in most cases, more than one product (chlorohydrins, products containing solvent residues, as well as rearrangement products). A detailed study was performed to verify the effects of the temperature (rt, 0°C, or ?78°C) and of the NbCl₅ molar concentration on the composition of the products, yield, and time required for the reactions.     

Synthesis of Spiro-β-Methylene-γ-Butyrolactones

The Bakkenolide group 1 ³ of sesquiterpenes present two interesting synthetic problems. The cisdimethyl cis-hydrindane portion 2, because of its structural and stereochemical relationship with the eremophilane sesqui terpenes,⁴ has synthetic solutions available.⁵ The spiro-β-methylene-γ-butyrolactone unit 3,⁶ which is presently unique to this class of natural products, has been synthesised by four different routes.^7–10     

Biomimetic synthesis of diversifolin

The conversion of a germacranolide structure (tagitinin C) into a furanoheliangolide one (diversifolin) was achieved by hydride conjugate addition using Stryker’s reagent.     

Physicochemical and Biochemical Profiling of Diphenyl Diselenide

The objective of the present study was to evaluate the physicochemical and biochemical profiling of diphenyl diselenide (PhSe)₂, a selenoorganic compound with biological activity. Experimental protocols were established for chemical stability in isotonic phosphate buffer (PBS) pH 7.4 and in simulated gastric and intestinal fluids, biological stability (bovine serum albumin (BSA) and plasma), solubility in PBS pH 7.4, distribution coefficient (Log D) in octanol/PBS, and determination of free (PhSe)₂ concentrations in BSA and plasma by using liquid chromatography with ultraviolet detection and tandem mass spectrometry. (PhSe)₂ was found to be chemically stable and not susceptible to degradation in plasma. The aqueous solubility was 0.98?±?0.072 μM and the Log D in octanol/PBS system was found to be 3.13. The percentage of unbound fractions of (PhSe)₂ obtained by equilibrium dialysis from BSA and plasma incubated with 100 μM (PhSe)₂ were 0.69?±?0.12 and 0.44?±?0.09 %, respectively. The findings indicated that (PhSe)₂ presents chemical and biological stability. Though, the compound showed low aqueous solubility, high Log D value and high binding to plasmatic protein. These data contribute to the knowledge of the toxicokinetic properties of (PhSe)₂ and further explain its low bioavailability in experimental models.