Synthesis, characterization and redox behaviour of benzoyldiazenido- and oxorhenium complexes bearing N,N- and S,S-type ligands

The reactions of [ReCl2{eta(2)-N2C(O)Ph}(PPh3)(2)](1) with 2-aminopyrimidine (H(2)Npyrm), 2,2'-bipyridine (bpy) and tetraethylthiuram disulfide (tds), in MeOH upon reflux, lead to the new eta(1)-(benzoyldiazenido)-rhenium(III) complexes [ReCl{eta(1)-N2C(O)Ph}(HNpyrm)(PPh3)(2)](2)and [ReCl2{eta(1)-N2C(O)Ph}(bpy)(PPh3)] (3), and the known oxo(diethyldithiocarbamato)dirhenium(v)complex [Re2O2(mu O){Et2NC(S)S}(4)](4), respectively. The Et2NC(S)S ligands in 4 result from S-S bond rupture of tds molecules. The obtained compounds have been characterized by IR, H-1, P-31{H-1} and C-13{H-1} NMR spectroscopies, FAB(+)-MS, elemental and single-crystal X-ray diffraction (for 2 and 4)analyses. Complex 2 represents the first structurally characterized Re compound derived from 2-aminopyrimidine. Besides, the redox behaviour of 2-4 in CH2Cl2 solution has been studied by cyclic voltammetry, and the Lever electrochemical ligand parameter (E-L)has been estimated, for the first time, for HNpyrm. The electrochemical results are discussed in terms of electronic properties of the Re centres and the ligands.

A soft origin for CKM-type CP violation

We present a two-Higgs-doublet model, with a Z(3) symmetry, in which CP violation originates solely in a soft (dimension-2) coupling in the scalar potential, and reveals itself solely in the CKM (quark mixing) matrix. In particular, in the mass basis the Yukawa interactions of the neutral scalars are all real. The model has only eleven parameters to fit the six quark masses and the four independent CKM-matrix observables. We find regions of parameter space in which the flavour-changing neutral couplings are so suppressed that they allow the scalars to be no heavier than a few hundred GeV. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis of optimization of [11C] Pittsburgh compound B by the captive solvent method

Mestrado em Medicina Nuclear.

Structural characterization and immunogenicity in wild-type and immune tolerant mice of degraded recombinant human interferon Alpha2b

Purpose: This study was conducted to study the influence of protein structure on the immunogenicity in wild-type and immune tolerant mice of well-characterized degradation products of recombinant human interferon alpha2b (rhIFNα2b). Methods: RhIFNα2b was degraded by metal-catalyzed oxidation (M), cross-linking with glutaraldehyde (G), oxidation with hydrogen peroxide (H), and incubation in a boiling water bath (B). The products were characterized with UV absorption, circular dichroism and fluorescence spectroscopy, gel permeation chromatography, reverse-phase high-pressure liquid chromatography, sodium dodecyl sulfate polyacrylamide gel electrophoresis, Western blotting, and mass spectrometry. The immunogenicity of the products was evaluated in wild-type mice and in transgenic mice immune tolerant for hIFNα2. Serum antibodies were detected by enzyme-linked immunosorbent assay or surface plasmon resonance. Results: M-rhIFNα2b contained covalently aggregated rhIFNα2b with three methionines partly oxidized to methionine sulfoxides. G-rhIFNα2b contained covalent aggregates and did not show changes in secondary structure. H-rhIFNα2b was only chemically changed with four partly oxidized methionines. B-rhIFNα2b was largely unfolded and heavily aggregated. Nontreated (N) rhIFNα2b was immunogenic in the wild-type mice but not in the transgenic mice, showing that the latter were immune tolerant for rhIFNα2b. The anti-rhIFNα2b antibody levels in the wild-type mice depended on the degradation product: M-rhIFNα2b > H-rhIFNα2b ∼ N-rhIFNα2b ≫ B-rhIFNα2b; G-rhIFNα2b did not induce anti-rhIFNα2b antibodies. In the transgenic mice, only M-rhIFNα2b could break the immune tolerance. Conclusions: RhIFNα2b immunogenicity is related to its structural integrity. Moreover, the immunogenicity of aggregated rhIFNα2b depends on the structure and orientation of the constituent protein molecules and/or on the aggregate size.

Synthesis and antioxidant activity of new xanthone-type compounds

3rd Portuguese Meeting on Medicinal Chemistry and 1st Portuguese-Spanish-Brazilian Meeting on Medicinal Chemistry, Aveiro, 28-30 Novembro 2012.

Analysis of functionally graded sandwich plate structures with piezoelectric skins, using B-spline finite strip method

Functionally graded materials are composite materials wherein the composition of the constituent phases can vary in a smooth continuous way with a gradation which is function of its spatial coordinates. This characteristic proves to be an important issue as it can minimize abrupt variations of the material properties which are usually responsible for localized high values of stresses, and simultaneously providing an effective thermal barrier in specific applications. In the present work, it is studied the static and free vibration behaviour of functionally graded sandwich plate type structures, using B-spline finite strip element models based on different shear deformation theories. The effective properties of functionally graded materials are estimated according to Mori-Tanaka homogenization scheme. These sandwich structures can also consider the existence of outer skins of piezoelectric materials, thus achieving them adaptive characteristics. The performance of the models, are illustrated through a set of test cases. (C) 2012 Elsevier Ltd. All rights reserved.

Miocene catfishes (Ariidae,Bagridae) from Lisbon: a Nilotic (or Sudanian) type fauna

Miocene catfishes from Lisbon are dealt with. Two distinct sets of pectoral and dorsal pterygiophores are described. That from the Langhian V-b is referred to Arius sp. probably close to A. heudeloti. Another ser from the uppermost Burdigalian V-a may be ascribed to a bagrid, cf. Chrysichthys sp., identified for the first time in this region. The catfish and Lates association is sctrikingly similar to African, nilotic or sudanian ones as far as freshwaters are concerned. In marine, coastal environments, stenotherm warm-water forms (Polynemids, large barracudas and several sharks) indicate, as a model, faunas like chose from Cape Verde to northern Angola. There is some gradation for brackish waters (fig. 1). Catfishes and Lates probably migrated into the Iberian Peninsule in the lower Miocene. They are unknown after Langhian V-b except for a reappearance of Arius in the middle Tortonian VII-b. Decreasing temperatures and aridity account for local extinction at least in freshwaters. Expansion of these fishes have been made easier owing to the displacement of land masses chat narrowed or closed the marine waterway between Europe and Africa. Salinity tolerance is not necessarily the sole explanation for migration. Catfishes plus Lates associations colonized inland waters from both sides of the Paleomediterranean. Local extinction may have weighed more in the development of modern distribution patterns than migration.

Aspectos clínicos e sorológicos de 47 pacientes com paracoccidioidomicose tratados pela anfotericina B

In the present study, clinic and serologic aspects of 47 paracoccidioidomycosis patients were reviewed. The clinic-radiologie-laboratorial data of each patient were obtained from the medical chart before, during and after therapy with Amphotericin B. The age of the patients ranged between 13 to 50 years; the ratio male: female was 10:1. The most frequently associated diseases were alcoholism and tabagism; tuberculosis was present in 14.2% of the cases. Most patients came from Botucatu of adjacent towns (central area of the State of São Paulo). Cough with sputum production, dyspnea and anorexia were the most frequent clinic manifestations. All 47 patients, but 5 presented pulmonary involvement which showed the radiologic pattern of interstitial exudate nodular type and fibrocicatritial lesions in 85.7%. There was associated emphysema in 37.7% of the patients. Blood urea, creatinin and kaliemia increased during therapy with Amphotericin B. Clinic-laboratorial follow-up showed electrocardiographic changes in 13, hypertension in 9 and hyperreactivity in Thorn test in 1 patient. Complement fixation was the best serologic test for monitoring patients with paracoccidioidomycosis. Incomplete dosage of Amphotericin B led to therapeutic ineffectivenes.

A multitask ATPase serving different ABC-type sugar importers in Bacillus subtilis

Journal of Bacteriology (Out 2010) 5312-5318

Miocene c4tfishes (Ariidae, Bagridae) from Lisbon: a Nilotic (or Sudanian) type fauna

Miocene catfishes from Lisbon are dealt with. Two distinct sets of pectoral and dorsal pterygiophores are described. That from the Langhian V-b is referred to Arius sp. probably close to A. Beudeloti. Another set from the uppermost Burdigalian V-a may be ascribed to a bagtid, cf, Chrysichthys sp., identified for the first time in this region. The catfish and Lates association is strikingly similar to African, nilotic or sudanian ones as far as freshwaters are concerned. In marine, coastal environments, stenotherm warm-water forms (Polynemids, large barracudas and several sharks) indicate, as a model, faunas like those from Cape Verde to northern Angola. There is some gradation for brackish waters (fig. 1). Catfishes and Lates probably migrated into the Iberian Peninsule in the lower Miocene. They are unknown after Langhian V-b except for a reappearance of Arius in the middle Tortonian VII-b. Decreasing temperatures and aridity account for local extinction at least in freshwaters. Expansion of these fishes have been made easier owing to the displacement of land masses that narrowed or closed the marine waterway between Europe and Africa. Salinity tolerance is not necessarily the sole explanation for migration. Catfishes plus Lates associations colonized inland waters from both sides of the Paleomediterranean. Local extinction may have weighed more in the development of modern distribution patterns than migration.

Herpes simplex virus type 2 infection in pregnancy: asymptomatic viral excretion at delivery and seroepidemiologic survey of two socioeconomically distinct populations in São Paulo, Brazil

The objective of the present study was to estimate the prevalence of herpes simplex virus type 2 (HSV 2) antibodies in child bearing women of 2 Brazilian populations with different socioeconomic status and to determine the risk of neonatal HSV exposure by means of maternal cultures at the onset of labor. The study was conducted at 2 hospitals: A, serving very low income patients and B, serving middle socioeconomic class. 173 participants from group A and 127 from B answered a questionnaire which showed that the patients had similar ages (27.7 and 26.8 years, respectively) but differed with regard to socioeconomic status, age at first intercourse (18.6 vs 20.6 years), number of sex partners (1.5 vs 1.2) and previous sexually transmitted diseases (15% vs. 1.5%). History of genital herpes was given by 11% of group A participants and by a similar number, 7%, of patients from group B. In addition, 200 serum samples from population A and 455 from B were tested by ELISA for and HSV antibodies and 92% and 86%, respectively, were found to be positive. Sixty seropositive samples from group A and 90 from B were further analyzed by Western blot, which showed the presence of type 2 specific antibodies in 46% and 36%, respectively, suggesting an overall HSV 2 prevalence of 42% in group A and 31% in B. Cervical specimens were obtained for culture from 299 asymptomatic patients of population A and 313 of B. HSV was isolated from one specimen in each group, indicating a 0.3% incidence of asymptomatic viral excretion in both populations. In conclusion, the prevalence of type 2 antibodies in childbearing women was very high, but it did not differ with the socioeconomic status. The risk of HSV perinatal transmission was also similar in the 2 study populations and it was comparable with the data from developed countries. Our findings do not indicate the need of special screening programs for asymptomatic HSV excretion in Brazilian pregnant women.

Progression of Salmonella Enteritidis phage type 4 strains in São Paulo State, Brazil

A total of 574 S. Enteritidis strains (383 from human sources and 191 from non-human sources) isolated between 1975-95, in São Paulo State, Brazil, were phagetyped. Among the strains isolated during the period of 1975-92, 80.9% of them belonged to phage type 8 (PT-8), but in 1993 strains of PT-4 accounted for 65.2% of all the S. Enteritidis isolates. In the following years, PT-4 strains accounted for 99.7% and 98.4% of phagetyped S. Enteritidis strains. The results obtained suggested that the current epidemic of S. Enteritidis in São Paulo State is clearly associated with the progression of PT-4 strains.

Serotype, mating type and ploidy of Cryptococcus neoformans strains isolated from patients in Brazil

Serotype, mating type and ploidy of 84 strains of Cryptococcus neoformans isolated from 61 AIDS and 23 non-AIDS patients admitted in a tertiary teaching hospital in São Paulo, Brazil were examined. Among 61 strains isolated from AIDS patients, 60 strains were var. grubii (serotype A). Only one strain was var. gattii (serotype B). No var. neoformans (serotype D) was found. Among 23 strains isolated from non-AIDS patients, 15 were var. grubii (serotype A) and the remaining 8 were var. gattii, all of which were serotype B. Seventy-three of the 75 serotype A strains were the heterothallic alpha type (MATalpha) and the remaining 2 were untypable (asexual). Most of the MATalpha strains (69/73) were haploid and the remaining 4 strains were diploid. Similarly, both of the 2 asexual strains among the 75 serotype A strains were haploid. There were no alpha-mating type (MATalpha) strains among the 84 isolates. All of the 8 var. gattii strains were serotype B and haploid. Among a total of 84 strains tested, neither serotype AD nor serotype D were found. Neither triploid nor tetraploid were found. These results suggest that the serological, sexual and ploidy characteristics in C. neoformans strains isolated from AIDS patients in São Paulo were rather simple, whereas strains isolated from non-AIDS patients presented serotype A and B with predominance of serotype A.

Molecular typing of dengue virus type 2 in Brazil

Strain typing is a critical tool for molecular epidemiological analysis and can provide important information about the spread of dengue viruses. Here, we performed a molecular characterization of DEN-2 viruses isolated in Brazil during 1990-2000 from geographically and temporally distinct areas in order to investigate the genetic distribution of this serotype circulating in the country. Restriction site-specific polymerase chain reaction (RSS)-PCR presented the same pattern for all 52 Brazilian samples, showing the circulation of just one DEN-2 variant. Phylogenetic analysis using progressive pairwise alignments from 240-nucleotide sequences of the E/NS1 junction in 15 isolates showed that they belong to genotype III (Jamaica genotype).

Genotyping, serotyping and determination of mating-type of Cryptococcus neoformans clinical isolates from São Paulo State, Brazil

The basidiomycetous yeast Cryptococcus neoformans is an important fungal pathogen mainly in immunocompromised patients. In this study, 47 clinical isolates of C. neoformans from regions of São Paulo State were studied serologically by using the Crypto Check Iatron RM 304-K kit, their genetic diversity was estimated by PCR-fingerprinting with a microsatellite-specific sequence (GACA)4, RAPD with primer 6 (Amersham Pharmacia Biotech), PCR-restriction fragment length polymorphism (RFLP) analysis of the phospholipase B gene (PLB1) digested with AvaI and mating type analysis by PCR. All 47 strains isolated from HIV positive patients included in this study were serotype A and MATalpha. The majority of the isolates (45/47) were VNI and only two were VNII by PCR-fingerprinting and PCR-RFLP analysis. High degree of homogeneity was observed when (GACA)4 was used, being highly correlated (> 0.9). In contrast, the RAPD analysis was more heterogeneous with higher number of molecular profiles. By PCR-RFLP, no new molecular type was found, enhancing the suggestion that the differences based on conserved gene as PLB1, can be resultant of ongoing divergent evolution within the C. neoformans complex, into the current eight subtypes. Our results furnish new information on the molecular epidemiology of C. neoformans in the southeast region of Brazil.