Synthesis, characterization, X-ray structure and in vitro anti mycobacterial and antitumoral activities of Ru(II) phosphine/diimine complexes containing the "SpymMe(2)" ligand, SpymMe(2)=4,6-dimethyl-2-mercaptopyrimidine

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Synthesis of 4-aminoquinoline analogues and their platinum(II) complexes as new antileishmanial and antitubercular agents

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Consistência interna e reprodutibilidade da versão em português do critério de diagnóstico na pesquisa para desordens temporomandibulares (RDC/TMD - Eixo II)

OBJETIVO: Estudar a confiabilidade, da versão em português, do questionário para o diagnóstico psicológico e psicossocial dos indivíduos com desordens temporomandibulares (RDC/TMD). MÉTODOS: Foram entrevistados 109 indivíduos, de ambos sexos, que demandaram atendimento junto à Clínica de Fisioterapia do Centro Universitário de Araraquara, de janeiro a julho de 2006. Os questionários foram aplicados por um único examinador. Após duas semanas, o mesmo foi reaplicado em 36 indivíduos. Para avaliação da consistência interna do método, utilizou-se o Coeficiente Alfa de Cronbach; para análise da reprodutibilidade intra-examinador, o Coeficiente de Correlação Intraclasse (ro) e a estatística Kappa (kapa), respectivamente às variáveis de natureza quantitativa e qualitativa. RESULTADOS: A consistência interna para as dimensões intensidade da dor crônica e incapacidade; limitação da função mandibular; sintomas físicos não-específicos, incluindo os itens de dor; sintomas físicos não-específicos, excluindo os itens de dor e depressão foi de 0,8479, 0,8971, 0,8673, 0,8080 e 0,9270 respectivamente, atestando ao método excelente validade interna. Obteve-se excelente concordância intra-examinador para as questões referentes ao tempo de presença da dor e sua gradação, e boa para a questão referente à dor presente. Os menores valores de kapa relacionaram-se aos itens de sintomas físicos e depressão. A percepção de estalos ou rangidos pelos indivíduos apresentou concordância regular bem como a questão referente à procura de profissional para tratamento da dor. As demais questões apresentaram reprodutibilidade boa e ótima, sendo que a maioria dessas apresentou nível máximo de concordância. CONCLUSÃO: A versão adaptada para o português mostrou-se confiável para detecção das alterações psicológicas e psicossociais associadas às desordens temporomandibulares.

Theoretical study on the molecular mechanism for the reaction of VO2+ with C2H4

The complex reaction between VO2+ ((1)A(1)/(3)A) and C2H4 (Ag-1(g)/(3)A(1)) to yield VO+ ((1)Delta/(3)Sigma) and CH3CHO ('A'/(3)A) has been studied by means of B3LYP/6-31G* and B3LYP/6-311G(2d,p) calculations. The structures of all reactants, products, intermediates, and transition structures of this reaction have been optimized and characterized at the fundamental singlet and first excited triplet electronic states. Crossing points are localized, and possible spin inversion processes are discussed by means of the intrinsic reaction coordinate approach. Relevant stationary points along the most favorable reaction pathways have been studied at the CCSD/6-311G(2d,p)//B3LYP/6-311G(2d,p) calculation level. The theoretical results allow the development of thermodynamic and kinetic arguments about the reaction pathways of the title process. In the singlet state, the first step is the barrierless obtention of a reactant complex associated with the formation of a V-C bond, while in the triplet state a three-membered ring addition complex with the V bonded to the two C atoms is obtained. Similar behavior is found in the exit channels: the product complexes can be formed from isolated products without barriers. The reactant and product complexes are the most stable stationary points in the singlet and triplet electronic states. From the singlet state reactant complex, two reaction pathways are posssible to reach the triplet state product complex. (i) A mechanism in which a hydrogen transfer process is the first and rate limiting step and the second step is an oxygen transfer between vanadium and carbon atoms with a concomitant change in the spin state. The crossing point between singlet and triplet spin states is not kinetically relevant because it takes place at a later stage occurring in the exit channel. (ii) A mechanism in which the first stage renders a four-membered ring between vanadyl cation and the ethylene fragment and an oxygencarbon bond is formed; on going from this minimum to the second transition structure, associated with a carbon-vanadium bond breaking process, the crossing point between singlet and triplet spin states is reached. The final step is the hydrogen transfer between both carbon atoms to yield the product complex. In this case the spin change opens a lower barrier pathway. The transition structures with larger values of relative energies for both reactive channels of VO2+ ((1)A(1)) + C2H4 (Ag-1) --> VO+ ((3)Sigma) + CH3CHO ((1)A') present similar energies, and the two reaction pathways can be considered as competitive.

4-amine-2-mercaptopyrimidine modified silica gel applied in Cd(II) and Pb(II) extraction from an aqueous medium

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Preconcentration and determination of Cu(II) in a fresh water sample using modified silica gel as a solid-phase extraction adsorbent

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

An Oligosilsesquioxane Cage Functionalized with Molybdenum(II) Organometallic Fragments

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Maxillo-mandibular counter-clockwise rotation and mandibular advancement with TMJ Concepts (R) total joint prostheses Part II - Airway changes and stability

The purpose of this study was to evaluate the anatomical changes and stability of the oropharyngeal airway and head Posture following TMJ reconstruction and mandibular advancement with TMJ Concepts custom-made total joint prostheses and maxillary osteotomies with counter-clockwise rotation of the maxillo-mandibular complex. All patients were operated at Baylor University Medical Center, Dallas TX, USA, by one surgeon (Wolford). The lateral cephalograms of 47 patients were analyzed to determine surgical and post-surgical changes of the oropharyngeal airway, hyoid bone and head posture. Surgery increased the narrowest retroglossal airway space 4.9 mm. Head Posture showed flexure immediately after surgery (-5.6 +/- 6.7 degrees) and extension long-term post surgery (1.8 +/- 6.7 degrees); cervical curvature showed no significant change. Surgery increased the distances between the third cervical vertebrae and the menton 11.7 +/- 9.1 mm and the third cervical vertebrae and hyoid 3.2 +/- 3.9 mm, and remained stable. The distance from the hyoid to the mandibular plane decreased during surgery (-3.8 +/- 5.8 mm) and after surgery (-2.5 +/- 5.2 mm), Maxillo-mandibular advancement with counter-clockwise rotation and TMJ reconstruction with total joint prostheses produced immediate increase in oropharyngeal airway dimension, which was influenced by long-term changes in head posture but remained stable over the follow-up period.

Synthesis and characterization of TiO2 chemically modified by Pd(II) 2-aminothiazole complex for the photocatalytic degradation of phenol

An investigation was made into the photocatalytic activity of in situ synthesized TiO2 chemically modified by Pd(II) 2-aminothiazole complex for phenol degradation at different pH values. At longer reaction times, the bare titania presented far poorer pbotoactivity than the modified catalysts in the entire range of pH studied. The catalyst complexed with Pd(II) was more efficient than the metal-free Pd, irrespective of pH and reaction time, suggesting that metal plays an important role. A cooperative mechanism is proposed, involving the possible photoactivation of both TiO2 and sensitizer. (C) 2007 Elsevier B.V. All rights reserved.

Bronsted Acid Catalyzed Morita-Baylis-Hillman Reaction: A New Mechanistic View for Thioureas Revealed by ESI-MS(/MS) Monitoring and DFT Calculations

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ligninolytic activity from newly isolated basidiomycete strains and effect of these enzymes on the azo dye orange II decolourisation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Theoretical study of omeprazole behavior: Racemization barrier and decomposition reaction

omeprazole is a substituted benzimidazole which suppresses gastric-acid secretion by means of H+, K+-ATPase inhibition. It is an optically active drug with the sulfur of the sulfoxide being the chiral center. This pro-drug can be easily converted into its respective sulfenamide at low pH. In this work, omeprazole has been studied in relation to racemization barrier and decomposition reaction. Quantum chemistry coupled to PCA chemometric method were used to find all minimum energy structures. Conformational analysis and calculation of racemization barriers were carried out by PM3 semiempirical method (Gaussian 98). The average racemization energy barrier for all minimum energy structures (43.56 kcal mol(-1)) can be related to the velocity constant in Eyring's equation. The enormous half-life time at 100 degrees C (9.04 x 10(4) years) indicates that the process cannot be observed in human time scale. on the other hand, the difference of free energy change (Delta(Delta G) = -266.78 kcal mol(-1)) for the decomposition reaction shows that the process is favorable to the sulfenamide formation. The highly negative Delta(Delta G) obtained for the decomposition reaction shows that this process is extremely exothermic. This result explains why omeprazole decomposes and does not racemize. (C) 2008 Wiley Periodicals, Inc.

Dynamics in dumbbell domains II. The limiting problem

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermal Behavior of Sr(II) and Ba(II)-Diclofenac Complexes in Solid State: Study of the Dehydration and Thermal Decomposition

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Thermal Study in Solid State of Zn(II)-Diclofenac Complex: Behavior Kinetic of the Dehydration, Transition Phase and Thermal Decomposition

The dehydration, thermal decomposition and transition phase stage of Zn(II)-diclofenac compound were studied by simultaneous TG-DTA and DSC techniques. The TG and DSC curves of this compound were obtained with the mass of sample of 2 and 5 mg. Additionally, DSC curves were carried out in opened and closed alpha-alumina pans under static and nitrogen atmosphere. The DTA and DSC curves show that this compound possesses exothermic transition phase between 170-180 degrees C, which it is irreversible (monotropic reaction) The kinetics study of this transition phase stage was evaluated by DSC under non-isothermal conditions. The obtained data were evaluated with the isoconversional method, where the values of activation energy (E(a) / kJ mol(-1)) was plotted in function of the conversion degree (alpha). The results show that due to mass sample, different activation energies were obtained From these curves a tendency can be seen where the plots maintain the same profile for closed lids and almost run parallel to each other.