José Ciríaco Pinheiro

COMPUTATIONAL MODELING OF ANTIMALARIAL 10-SUBSTITUTED DEOXOARTEMISININS

Nineteen 10-substitued deoxoartemisinin derivatives and artemisinin with activity against D-6 strains of malarial falciparum designated as Sierra Leone are studied. We use molecular electrostatic potential maps in an attempt to identify key structural features of the artemisinins that are necessary for their activities and molecular docking to investigate the interaction with the molecular receptor (heme). Chemometric modeling: Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA), K-Nearest Neighbor (KNN), Soft Independent Modeling of Class Analogy (SIMCA) and Stepwise Discriminant Analysis (SDA) are employed to reduce dimensionality and investigate which subset of descriptors are responsible for the classification between more active (MA) and less active (LA) artemisinins. The PCA, HCA, KNN, SIMCA and SDA studies showed that the descriptors LUMO (Lowest Unoccupied Molecular Orbital) energy, DFeO1 (Distance between the O1 atom from ligand and iron atom from heme), X1A (Average Connectivity Index Chi-1) and Mor15u (Molecular Representation of Structure Based on Electron Diffraction) code of signal 15, unweighted, are responsible for separating the artemisinins according to their degree of antimalarial activity. The prediction study was done with a new set of eight artemisinins by using the chemometric methods and five of them were predicted as active against D-6 strains of falciparum malaria. In order to verify if the key structural features that are necessary for their antimalarial activities were investigated for the interaction with the heme, we also carried out calculations of the molecular electrostatic potential (MEP) and molecular docking. MEP maps and molecular docking were analyzed for more active compounds of the prediction set.

Contracted GTF basis sets applied to the theoretical interpretation of the Raman spectrum of hexaaquachromium(III) ion

Abstract Contracted GTF basis sets designed with aid of the Generator Coordinate Hartree–Fock (GCHF) method for H(2S), O2−(1S), and Cr3+(4F) atomic species are applied to perform theoretical interpretation of the Raman spectrum of hexaaquachromium(III) ion. The 16s, 16s10p, and 24s17p13d GTF basis sets were contracted to [4s] for H atom, [6s4p], and [9s6p3d] for O2− and Cr3+, respectively, by Dunnings scheme. For Cr3+, the [9s6p3d] basis set was enriched with f polarization function and used in combination com [4s] and [6s4p] in the study of our interest. The results obtained in this report show that the contracted GTF basis sets used are a useful alternative for the theoretical interpretation of Raman spectrum of hexaaquachromium(III) ion and that GCHF method is an effective alternative to selection of GTF basis sets for theoretical study of vibrational properties of poliatomic species.

Chemometric Study on Molecules with Anticancer Properties

Cancer is a class of diseases characterized by uncontrolled growth of abnormal cells of an organism. All over the world millions of people die every year owing to one of the different types of cancer. Unfortunately cancer chemotherapy finds a serious limitation since treatment with drugs is followed by drug resistance in the tumorous cells and side effects (Efferth, 2005). So researches have been directed to make chemotherapy treatment more efficient.

Quantum chemical modeling of perovskite: An investigation of piezoelectricity in ferrite of yttrium

In a previous article, we used Hartree-Fock (HF) theory to study the piezoelectricity in BaTiO3. In this paper, we applied the Douglas-Kroll-Hess second order scalar relativistic method to investigate the possible piezoelectric properties in the perovskite YFeO3 structure, which has not yet been studied experimentally. The 30s20p13d and 31s21p17d Gaussian basis sets for the Fe (5D) and Y (2D) atoms, respectively, were built with the Generator Coordinate HF method. After contraction to [13s7p5d] and [13s8p7d], in combination with the 20s14p/6s4p basis set for the O (3P) atom from literature, they had their quality evaluated using calculations of the total and the orbital energies for the 2FeO+1 and 1YO+1 fragments. The dipole moment, the total energy, and the total atomic charges in YFeO3 in Cs space group were calculated. The results and the analysis lead us to believe that the perovskite YFeO3 does not present piezoelectric properties.

Quantum Mechanical Approaches for Piezoelectricity Study in Perovskites

In this chapter, we show the procedures we have been used to theoretically investi‐ gate the piezoelectric effects in perovskites. The construction of extended basis sets using the generator coordinate Hartree-Fock (GCHF) method is shown, as well as the strategies used to contract extended basis sets and to evaluate their quality in molecu‐ lar calculations. Besides, we show adequate procedures to choice polarization and diffuse functions to best represent the studied crystal. In addition, we also discuss conditions under which GCHF basis sets and standard basis sets from literature can be used to theoretical investigation of piezoelectricity in perovskites. We finalize the chapter presenting and discussing the results for investigations of piezoelectricity with standard basis sets for barium and lanthanum titanates. To conclude, we present evidences that BaTiO3 and LaTiO3 may have piezoelectric properties caused by electrostatic interactions.

Quantum Mechanical Study of YTiO3 to the Investigation of Piezoelectricity

In previous articles we reported through theoretical studies the piezoelectric effect in BaTiO3, SmTiO3, and YFeO3. In this paper, we used the Douglas-Kroll-Hess (DKH) second-order scalar relativistic method to investigate the piezoelectricity in YTiO3. In the calculations we used the [6s4p] and [10s5p4d] Gaussian basis sets for the O (3P) and Ti (5S) atoms, respectively, from the literature in combination with the (30s21p16d)/[15s9p6d] basis set for the Y (3D) atom, obtained by generator coordinate Hartree-Fock (GCHF) method, and they had their quality evaluated using calculations of total energy and orbital energies (HOMO and HOMO-1) of the 2TiO