Evaluation of DFT methods for predicting geometries and NMR spectra of Bi(III) dithiocarbamate complexes with antitumor properties.

CONTEXT: Bismuth complexes with dithiocarbamate ligands have attracted attention because of their biological applications, such as antimicrobial, antileishmanial, and anticancer properties. These complexes have high cytotoxic activity against cancer cells, being more active than the standard drugs cisplatin, doxorubicin, and tamoxifen. In the present study, we investigated the ability of some DFT methods to reproduce the geometries and NMR spectra of the Bi(III) dithiocarbamate complexes, selected based on their proven antitumor activity. Our investigation revealed that the M06-L/def2-TZVP/ECP/CPCM method presented good accuracy in predicting geometries, while the TPSSh/def2-SVP/ECP/CPCM method proved effective in analyzing the 13C NMR spectra of these molecules. In general, all examined methods exhibited comparable performance in predicting 1H NMR signals. METHODS: Calculations were performed with the Gaussian 09 program using the def2-SVP and def2-TZVP basis sets, employing relativistic effective core potential (ECP) for Bi and using the CPCM solvent model. The exchange-correlation functionals BP86, PBE, OLYP, M06-L, B3LYP, B3LYP-D3, M06-2X, TPSSh, CAM-B3LYP, and ωB97XD were used in the study. Geometry optimizations were started from crystallographic structures available at the Cambridge Structural Database. The theoretical results were compared with experimental data using the mean root-mean-square deviation (RMSD), mean absolute deviations (MAD), and linear correlation coefficient (R2).

Examining O[Formula: see text] adsorption on pristine and defective popgraphene sheets: A DFT study.

CONTEXT: Popgraphene (PopG) is a two-dimensional carbon-based material with fused pentagonal and octagonal rings. Like graphene, it exhibits a metallic band gap and exceptional thermal, dynamic, and mechanical stability. Here, we theoretically study the electronic and structural properties of PopG monolayers, including their doped and vacancy-endowed versions, as O[Formula: see text] adsorbers. Our findings show that pristine and vacancy-endowed PopG sheets have a comparable ability to adsorb O[Formula: see text] molecules, with adsorption energies ranging from [Formula: see text]0.57 to [Formula: see text]0.59 eV (physisorption). In these cases, octagonal rings play a dominant role in the adsorption mechanism. Platinum and Silicon doping enhance the O[Formula: see text] adsorption in areas close to the octagonal rings, resulting in adsorption energies ranging from [Formula: see text]1.13 to [Formula: see text]2.56 eV (chemisorption). Furthermore, we computed the recovery time for the adsorbed O[Formula: see text] molecules. The results suggest that PopG/O[Formula: see text] interaction in pristine and vacancy-endowed cases can change the PopG electronic properties before O[Formula: see text] diffusion. METHODS: Density Functional Theory (DFT) simulations, with Van der Waals corrections (DFT-D, within the Grimme scheme), were performed to study the structural and electronic properties of PopG/O[Formula: see text] systems using the DMol3 code within the Biovia Materials Studio software. The exchange and correlation functions are treated within the generalized gradient approximation (GGA) as parameterized by Perdew-Burke-Ernzerhof (PBE) functional. We used the double-zeta plus polarization (DZP) for the basis set in these cases. We also considered the BSSE correction through the counterpoise method and the nuclei-valence electron interactions by including semi-core DFT pseudopotentials.

Pharmacokinetic and toxicological prediction of the chemical constituents of the essential oil of the leaves of Croton heliotropiifolius Kunth.

The development of new drugs through studies of candidate molecules is a complex undertaking; however, computational or in silico approaches aimed at optimizing molecules with greater development potential are being utilized for predictions of pharmacokinetic properties such as absorption, distribution, metabolism and excretion (ADME) as well as toxicological parameters. The objective of this study was to examine in silico and in vivo pharmacokinetic and toxicological properties of the chemical constituents present in the essential oil of Croton heliotropiifolius Kunth leaves. The following Pubchem platform as well as Software SwissADME and PreADMET software were employed for in silico studies while micronucleus (MN) testing for in vivo determination of mutagenicity, using Swiss adult male Mus musculus mice. In silico findings demonstrated that all chemical constituents presented (1) high oral absorption (2) medium cellular permeability and (3) high blood brain permeability. As for toxicity, these chemical constituents exhibited low to medium risk of occurrence of cytotoxicity. Regarding in vivo evaluation, peripheral blood samples obtained from animals tested with the oil showed no significant differences in number of MN compared to negative controls. Data indicate that further investigations are necessary to corroborate the findings of this study. Our data suggest that essential oil extracted from Croton heliotropiifolius Kunth leaves may serve as a candidate for new drug development.

Opinion Dynamics Systems on Barabási-Albert Networks: Biswas-Chatterjee-Sen Model.

A discrete version of opinion dynamics systems, based on the Biswas-Chatterjee-Sen (BChS) model, has been studied on Barabási-Albert networks (BANs). In this model, depending on a pre-defined noise parameter, the mutual affinities can assign either positive or negative values. By employing extensive computer simulations with Monte Carlo algorithms, allied with finite-size scaling hypothesis, second-order phase transitions have been observed. The corresponding critical noise and the usual ratios of the critical exponents have been computed, in the thermodynamic limit, as a function of the average connectivity. The effective dimension of the system, defined through a hyper-scaling relation, is close to one, and it turns out to be connectivity-independent. The results also indicate that the discrete BChS model has a similar behavior on directed Barabási-Albert networks (DBANs), as well as on Erdös-Rènyi random graphs (ERRGs) and directed ERRGs random graphs (DERRGs). However, unlike the model on ERRGs and DERRGs, which has the same critical behavior for the average connectivity going to infinity, the model on BANs is in a different universality class to its DBANs counterpart in the whole range of the studied connectivities.

Tratamento cirúrgico para úlceras pré-tibiais utilizando retalho de músculo sóleo com fluxo invertido / Surgical treatment of pre tibial wound with soleus muscle flap through reverse flow

Os autores apresentam uma revisäo de quatro casos clínicos no período de seis meses. Abordam a utilizaçäo cirúrgica do retalho de fluxo invertido de músculo sóleo na reparaçäo de perdas de substância dos terços medial e inferior da perda. Além disso, mostram resultados estéticos satisfatórios, apesar da gravidade das lesöes tratadas

Tumor gigante epidermo-ateromatoso da regiäo glútea / Giant atheromatous epidermoid cyst of the buttook

Os autores relatam um caso de tumor gigante epidermo-ateromatoso da regiäo glútea esquerda. Discutem o diagnóstico diferencial com o auxílio da ressonância magnética, e o procedimento cirúrgico plástico reparador

Tratamento cirurgico do nervo facial na patologia cirurgica da parotida / Surgical treatment of the facial nerve in diseases of the parotid stand

Os aspectos cirurgicos da preservacao do nervo facial durante o tratamento dos tumores da parotida sao apresentados

Melanoma maligno da vulva. Relato de caso / Vulva's malignant melanoma. Relato de caso

Melanoma maligno e uma doença cutanea rara. Os autores relatam um caso de uma mulher de 58 anos de idade, branca, tratada por ressecçaocirurgica, localizado na regiao vulvar. Os metodos alternativos de imunoterapia sao discutidos