Effect of low intensity helium-neon (HeNe) laser irradiation on experimental paracoccidioidomycotic wound healing dynamics

The effect of HeNe laser on the extracellular matrix deposition, chemokine expression and angiogenesis in experimental paracoccidioidomycotic lesions was investigated. At days 7, 8 and 9 postinfection the wound of each animal was treated with a 632.8 nm HeNe laser at a dose of 3 J cm(-2). At day 10 postinfection, the wounds were examined by using histologic and immunohistochemical methods. Results revealed that laser-treated lesions were lesser extensive than untreated ones, and composed mainly by macrophages and lymphocytes. High IL-1beta expression was shown in the untreated group whereas in laser-treated animals the expression was scarce. On the other hand, the expression of CXCL-10 was found to be reduced in untreated animals and quite intensive and well distributed in the laser-treated ones. Also, untreated lesions presented vascular endothelial growth factor (VEGF) in a small area near the center of the lesion and high immunoreactivity for hypoxia-inducible factor-1 (HIF-1), whereas laser-treated lesions expressed VEGF surrounding blood vessels and little immunoreactivity for HIF-1. Laser-treated lesions presented much more reticular fibers and collagen deposition when compared with the untreated lesion. Our results show that laser was efficient in minimizing the local effects observed in paracoccidioidomycosis and can be an efficient tool in the treatment of this infection, accelerating the healing process.     

Refinements of the Weyl Pure Geometrical Thick Branes From Information‐Entropic Measure

This work aims to analyse the so‐called configurational entropy in the Weyl pure geometrical thick brane model. The Weyl structure plays a prominent role in the brane thickness of this model. We find a set of parameters associated to the brane width where the configurational entropy exhibits critical points. The information‐theoretical measure sets bounds into parameter of Weyl pure geometrical brane model. In addition, we also argue that a similar approach can be useful to analyze the corrections to Newtonian and Coulombian potentials in Weyl scenarios.     

Application of copper(i) iodide/diorganoyl dichalcogenides to the synthesis of 4-organochalcogen isoquinolines by regioselective cn and cchalcogen bond formation

A copper-catalyzed cyclization of (ortho-alkynyl)benzaldimines with diorganoyl dichalcogenides allowed the synthesis of 4-organochalcogen isoquinolines, whereas the presence of base in the reaction medium inhibited the product formation producing the undesirable isoquinoline without the organochalcogen atom at the 4-position. The cyclization reaction was carried out by using CuI (20?%) as a catalyst with diorganoyl dichalcogenides (1.5?equiv) in the presence of DMF at 100?°C. Furthermore, the reaction did not require an argon atmosphere and was carried out in an open flask. The cyclization reaction tolerated a variety of functional groups both in ortho-alkynylbenzaldimines and diorganoyl dichalcogenides, such as trifluoromethyl, chloro, fluorine, and methoxyl, to give the six-membered heterocyclic ring exclusively through a 6-endo-dig cyclization process. The organochalcogen group present at the 4-position of the isoquinoline ring was further subjected to a selective chalcogen-lithium exchange reaction followed by the addition of aldehydes to afford the desired secondary alcohols in good yields. The obtained isoquinolines also proved to be suitable substrates for the Suzuki and Sonogashira coupling conditions affording the corresponding products through C?C bond formation.     

Determination of contact angles, silane coverage, and hydrophobicity heterogeneity of methylated quartz surfaces using ToF-SIMS

Methylated quartz surfaces are extensively used in colloid science for wettability studies and the control and impact of hydrophobicity in key physicochemical processes. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to correlate the surface chemistry of trimethylchlorosilane-methylated quartz surfaces with the contact angle. Models have been developed for the calculation of both advancing and receding contact angles based on measurements of the ToF-SIMS signals for SiC(3)H(9)(+) (TMCS) and Si(+) (quartz). These models enable the contact angle across surfaces and, more importantly, that of individual particles to be determined on a micrometer scale. Distributions of contact angles in large ensembles of particles, therefore, can now be determined. In addition, from the ToF-SIMS analysis, the surface coverage of the methylated species can be quantitatively determined, in line with the Cassie equation. Moreover, advancing and receding contact angle maps can be calculated from ToF-SIMS images, and hence the variation in microscopic hydrophobicity (e.g., at the particle level) can be extracted directly from the images.     

Three-dimensional triazenido layers attained through classical and non-classical hydrogen interactions and its coordination to palladium under prolific occurrence of bifurcated hydrogen bonding

The new ligand 1,3-bis(3-methoxy-4-methylbenzoate) triazene (1, bmmbt), and the already known ligand 1,3-bis(4-acetylphenyl)triazene (bapht), yield the two new palladium(II) complexes [(bmmbt)Pd(PPh₃)₂Cl]·DMSO (2) and [(bapht)Pd(PPh₃)₂Cl] (3) (Ph = phenyl; DMSO = dimethylsulfoxide). Compound 1 shows the existence of more than one interaction promoting the coupling between the triazene chains. Other remarkable types of interactions in 1 are bifurcated hydrogen contacts and non-classical CH···π bonding. Complexes 2 and 3 present a planar geometry, supported also through bifurcated intramolecular Cl···H-C interactions, as well as the occurrence of trifurcated Cl···H-C intermolecular interactions.     

Mixed-Ligand Complex Formation Equilibria of Vanadium(III) with 2,2′-Bipyridine and the Amino Acids Glycine, Proline, α-Alanine and β-Alanine Studied in 3.0 mol?dm?3 KCl at 25 °C

We studied speciation of the mixed-ligand complex formation equilibria of vanadium(III) with both 2,2??-bipyridine (Bipy) and the amino acids glycine (HGly), proline (HPro), ??-alanine (H??Ala), and ??-alanine (H??Ala) by means of electromotive forces measurements emf(H) using 3.0?mol?dm^?3 KCl as the ionic medium at 25 °C. The experimental data were analyzed by means of the computational least-squares program LETAGROP, taking into account the hydrolysis of the vanadium(III) cation, the respective stability constants of the binary complexes, and the acid/base reactions of the ligands which were kept fixed during the analysis. In all four amino acid systems studied we observed the complexes [V₂O(Bipy)(B)]³⁺, [V₂O(Bipy)₂(B)₂]²⁺, [V(OH)(Bipy)(B)₂] and [V(OH)₂(Bipy)(B)], where B represents the deprotonated form of the amino acids studied in this work. The respective stability constants were determined and the species distribution diagrams as a function of pH are briefly discussed.     

Fuzzy optimization for distribution of frozen food with imprecise times

Problems concerning the distribution routes for frozen products need to incorporate constraints that avoid breaks in the cold chain. The decision making process under uncertain environments is a common one in real logistics problems. The purpose of this study is to apply a fuzzy approach which will provide an optimal solution to the distribution of frozen food with uncertainty in its time values. A soft computing approach is used where fuzzy constraints are included in the modeling and the solution of the problem.     

Crystal Structure and Hirshfeld Surface Analysis of (E)-1-(4-Bromophenyl)-2-(2,2-Dichloro-1-(4-Fluorophenyl)vinyl)diazene

Crystallography Reports - The CuCl-catalyzed olefination with CCl4 in the presence of tetramethylethylenediamine in DMSO leads to the formation of...     

Revisiting the structure of Heliannuol L: A computational approach

Recently, structural elucidation of natural products has undergone a revolution. The combined use of different modern spectroscopic methods has allowed obtaining a complete structural assignment of natural products using small amounts of sample. However, despite the extraordinary ongoing advances in spectroscopy, the mischaracterization of natural products has been and remains a recurrent problem, especially when the substance presents several stereogenic centers. The misinterpretation of nuclear magnetic resonance (NMR) data has resulted in frequent reports addressing structural reassignment. In this context, a great effort has been devoted to developing quantum chemical calculations that simulate NMR parameters accurately, allowing to achieve a more precise spectral interpretation. In this work, we employed a protocol for theoretical calculations of ¹H NMR chemical shifts and coupling constants using density functional theory (DFT), followed by the application of the DP4+ method to revisit the structure of Heliannuol L, a member of the Heliannuol class, isolated from Helianthus annuus. Our results indicate that the originally proposed structure of Heliannuol L needs a stereochemical reassignment, placing the hydroxyl bonded to C10 in the opposite side of the methyl and hydroxyl groups bonded to C7 and C8, respectively.     

Functional analysis concepts and Fartree-Fock instability conditions

Concepts of functional analysis, namely, regular points, tangent subspaces, constraint surfaces, Lagrangian matrix restricted to the tangent subspace of a constraint surface, are presented in connection with the Hartree-Fock (HF) problem. The energy functional in LCAO approximation is considered to be a polynomial function of several variables subject to subsidiary conditions. General HF equations and instability conditions for the unrestricted Hartree-Fock (UHF) solutions are derived from this standpoint.