Gold compounds engage an important place in the field of medicinal chemistry due to their therapeutic properties. Since the last four decades, Au(I) and Au(III) complexes have attracted the attention of researchers due to their anti-tumor proprieties and the different mechanisms of action they display in comparison to conventional anticancer platinum compounds. Au(I/III) complexes can inhibit the activity of enzymes containing thiols including thioredoxin reductase; nevertheless, the affinity for several therapeutic targets has been confirmed in recent years. The properties conferred by auxiliary ligands such as phosphines (PR3) and N-heterocyclic carbenes (NHCs) to gold complexes have been key to the development of more promising anticancer compounds. In the same way, it has happened with the inclusion of some multidentate ligands in Au(III) complexes, increasing their stability and selectivity for tumor cells. In this review, we discuss the anticancer effects of Au(I) complexes containing PR3 and NHCs ligands as well as Au(III) complexes containing multidentate ligands especially those that have high cytotoxicity and information on the mechanism of action, as well as attempts to target identification and validation.

Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) synthesis was monitored by resonance Raman (RR) and surface-enhanced resonance Raman scattering (SERRS) spectroscopies and both the oxidation of the polymer and the effects of chain length were assessed by vibrational analysis. It was supported by theoretical models of oligomers, with charge ranging from 0 to +6 and size varying from 2 to 16 3,4-ethylenedioxythiophene (EDOT) repeat units, described through density functional theory. The symmetric CαCβ stretching band observed at ca. 1426 cm-1 shifts to higher wavenumbers for reaction times varying from 2 to 9 hours and stabilizes at intermediate wavenumbers for longer times. The former behavior was ascribed to the increase of concentration of oxidized species, which was corroborated by calculated wavenumbers for oligomer models when their charges changed from neutral to +6. The behavior observed for longer reaction times was associated with the growth of chains. It was also observed through SERRS spectroscopy that small chains of the polymer, obtained in the early time of the synthesis, adsorbs on gold nanoparticle surfaces through interactions via oxidized residues. In this way, RR and SERRS spectroscopies were valuable tools to follow the synthetic procedures of PEDOT:PSS, allowing the determination of the structural evolution of the polymer.

New insights into the formation of azlactone heterocycles bearing different substituents are hereby presented. The sum of both kinetic and thermodynamic factors contributes for the formation of 2-alkyl or 2-aryl substituted azlactones, while the cyclization of 2-alcoxy azlactones is less favored. These results are in perfect accordance with experimental observations obtained by infrared (IR) and electrospray ionization mass spectrometry (ESI(+)-MS) of the crude reaction mixture.

Single-walled carbon nanotubes are oxidized in the presence of H2SO4/HNO3 mixtures containing distinct concentrations of the nitronium ion, [NO2+]. The spectroscopic analyses of the final samples suggest a higher structural disorder in the oxidized systems with increasing [NO2+]. This is due to a considerable oxygen amount on the tube surface, reaching up to 30%, depending on the reaction time and [NO2+]. Interestingly, if long reaction time is considered, the oxygen amount on the tube surface is maximum for low [NO2+] and reduces slightly for larger [NO2+]. On the other hand, the oxidation process occurs gradually at 4 h, allowing a fine control of the oxidation process. Therefore, if fine tuning of the oxidation degree is desirable, the reaction must be conducted during short time (4 h) using increasing [NO2+] as those obtained from 2:1, 2.5:1 and 3:1 H2SO4/HNO3 acid mixtures to produce increasing content of functionalization.

S-states at oxygen evolving complex (OEC) are widely studied due to its large importance in photo-oxidation water process. The structural aspects involving S0, S1, S2, S3 and S4 states are still not solved theoretically. Particularly, spin states have been analyzed as an important aspect in S-state models. Seeking to obtain a relevant and simple model to cover high-spin (HS) S0-S4 states we develop a 55-57 atoms model. Through quantum chemical calculations we figured out that our interatomic distance parameters are in agreement with experimental and other theoretical reference values by ca. 10.0 and 3.5%, respectively, being also in good agreement with other theoretical models containing a large number of atoms. Our HS models presented expected oxidation states according to other data on literature for small theoretical models.

In this work, theoretical and experimental infrared spectra of fatty acid methyl esters (FAME) contained in soybean biodiesel were analyzed seeking the assignments of the relevant vibrational modes to characterize crude soybean oil and soybean biodiesel. The results showed the usefulness of infrared spectra for monitoring saturated and unsaturated compounds as well as impurities (mainly glycerol) in raw samples. This is the first step toward proposing an efficient molecular spectroscopy routine to certify biodiesel fuel.

No presente artigo o efeito do pseudopotencial de caroço (ECP) para o átomo de platina no erro de sobreposição de base (BSSE) foi avaliado para as energias de interação entre o complexo cisplatina ([Pt(NH3)2Cl2]) e água. Oito orientações espaciais distintas para os monômeros cisplatina-água foram consideradas na determinação do BSSE utilizando o procedimento padrão "counterpoise". O BSSE foi também avaliado ao longo das curvas de energia potencial, as quais são importantes para a determinação dos parâmetros do potencial de Lennard-Jones. Os cálculos foram feitos em diferentes níveis de teoria, incluindo HF, DFT (funcionais: BLYP, B3LYP, BP86, PBE, PW91) e MP2 com conjunto de funções de base do tipo "split-valence" de Pople e "correlated consistent" de Dunning.

In this article the role played by the effective core potential (Pt atom) on the evaluation of basis set superposition error (BSSE) and interaction energies for the complex between cisplatin ([Pt(NH3)2Cl2]) and water was investigated. Eight distinct spatial monomer orientations in the cisplatin-water complex were considered with the counterpoise procedure being employed to calculate the BSSE. The BSSE effect on potential energy curves, required for the determination of Lennard-Jones parameters, is also discussed. The calculations were performed at the HF, DFT (BLYP, B3LYP, BP86, PBE, PW91 functional) and MP2 level with Pople's split valence and Dunning's correlated consistent basis sets.

Structure and first hyperpolarizability for a series of armchair a(5,5) chemically modified carbon nanotubes (CNT) were calculated at semiempirical and density functional levels of theory. The 4,4´-substituted stilbenes were selected as chromophore with substituents at position 4´ set to X=NO2, H, Cl, OH and NH2. The calculated values for static first hyperpolarizability (β) were almost linearly dependent on the electronic effect of the group X, increasing from NO2 to NH2. At DFT level the effect of inserting the chromophore in the CNT surface was to enhance the β value up to 70% relative to the free 4,4´-substituted stilbene.

The ellipticines constitute a broad class of molecules with antitumor activity. In the present work we analyzed the structure and properties of a series of ellipticine derivatives in the gas phase and in solution using quantum mechanical and Monte Carlo methods. The results showed a good correlation between the solvation energies in water obtained with the continuum model and the Monte Carlo simulation. Molecular descriptors were considered in the development of QSAR models using the DNA association constant (log Kapp) as biological data. The results showed that the DNA binding is dominated by electronic parameters, with small contributions from the molecular volume and area.

In the present work, we analyzed the accuracy of distinct theoretical methods to reproduce the solid state structures of cyclodextrins. The a, b and g-cyclodextrins (CD) were considered and also their hydrates with included water molecules: a-CD.2H2O, b-CD.10H2O and g-CD.12H2O. The geometries were fully optimized using Molecular Mechanics (MM2), semiempirical (AM1 and PM3) and ab initio (HF/3-21G) methods and quantitatively compared with experimental data from X ray diffraction. The results obtained from the classical MM2 method were in best agreement with the experiment. The semiempirical and ab initio structures were also in satisfactory accordance with the experimental data. In general, the PM3 method was found to be more suitable than the AM1 to describe the CD geometries, mainly when the intramolecular hydrogen bonds are considered.

No presente artigo, métodos teóricos foram utilizados na análise da estrutura e propriedades eletrônicas de oligômeros de alquiltiofenos considerando diferentes regiosseletividades. A lacuna de energia entre as bandas de valência e condução foi calculada nos níveis ab initio Hartree-Fock (HF) e teoria do funcional de densidade (DFT) e semi-empírico ZINDO/S-CI. Os resultados mostraram que o isômero Head-Head-Tail-Tail (HH-TT) apresenta menores valores para a lacuna de energia quando oligômeros com mais de três unidades monoméricas são considerados e que a substituição do anel tiofeno por grupos alquila não afeta significativamente a lacuna de energia. Esse resultado é importante no sentido que mostra que polímeros mais processáveis podem ser obtidos através da alquilação sem perda considerável de suas características condutoras.

In the present paper a theoretical analysis of alkylthiophenes with Head-Tail-Head-Tail (HT-HT) and Head-Head-Tail-Tail (HH-TT) regioselectivities up to 6 monomeric units was carried out. Structure and electronic properties for the syn and anti forms were calculated by ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) approaches. The energy gap between the conduction and valence bands was obtained at HF and DFT levels and also calculated with the semiempirical ZINDO/S-CI method. The results showed that the isomer with HH-TT regioselectivity presents lower energy gap for longer oligomers and the substitution of thiophene by alkyl groups does not change significantly the energy gap. This is important in the sense that more processable polymers can be obtained through alkylation without decrease the energy gap that is a molecular properties related to the electronic conductivity. Regarding to the conformational equilibrium, the syn form was found to be stable only for the HT-HT isomer and in this case the energy gap was found to be lower than those calculated for the anti form.

The infrared (IR) spectra of the four distict conformers located on the multidimensional potential energy surface (PES) for the 3-phenyl-1,2,3-oxathiazolidine 2-oxide compound have been calculated using the semiempirical quantum-mechanical method PM3. The band spectra are reported and compared directly with the experimental spectrum. The IR intensities are shown to be much more sensitive to conformational changes than the vibrational frequencies and so, the theoretical analysis of the IR spectrum can be used as a tool for helping in the elucidation of the structure of heterocyclic compounds.