Structural studies of AgPO3-MoO3 glasses using solid state NMR and vibrational spectroscopies

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

Motivações em competição na variação sociolinguística: o plural dos predicativos na variedade de São José de Rio Preto

O objetivo deste trabalho é o de submeter a um tratamento variacionista, de base quantitativa, dados de marcação variável de plural no SN e no SA em contexto de predicativo, obtidos em córpus coletado na região de São José do Rio Preto. O trabalho procura examinar se a marcação de pluralidade nos predicativos pode ser explicada com base em motivações exclusivamente formais, ou exclusivamente funcionais, ou ainda, com base na interação entre ambas, que consistiriam, assim, em motivações em competição. Os resultados indicam que nem as motivações funcionais, nem as motivações formais regem solitariamente o fenômeno, que aparece fortemente condicionado por uma restrição externa específica, o grau de escolaridade. Por essa razão, a explicação mais plausível para a marcação de pluralidade nos predicativos é a de que há motivações em competição, nos termos de Du Bois (1985), e é a marcação de pluralidade o bem limitado, pelo qual forças múltiplas, as motivações formais ou internas e funcionais ou externas, competem entre si.

Local Er(III) environment in luminescent titanosilicates prepared from microporous precursors

The local environment of Er3+ ions in microporous titanosilicate ETS-10 and in synthetic narsarsukite and glassy materials obtained by calcination of ETS-10 has been investigated by EXAFS, Raman and photoluminescence spectroscopies. Er L-III-edge EXAFS studies of Er3+-doped ETS-10 support the view that the exchanged Er3+ ions reside close to the (negatively charged) TiO6 octahedra. In ETS-10, Er3+ is partially bonded to framework oxygen atoms and hydration water molecules. The Er...Ti distance (3.3 Angstrom) is similar to the Na...Ti distances (3.15-3.20 Angstrom) reported previously for Na-ETS-10. Although the exact location of the ErO6 units within the host structure of Er3+-doped synthetic narsarsukite is still an open question, it is most likely that Er3+ substitutes Ti4+ rather than Na+ ions. EXAFS spectroscopy indicates that no significant clustering of erbium atoms occurs in the titanosilicate samples studied. Evidence for the insertion of Er3+ ions in the framework of narsarsukite has been obtained by Raman spectroscopy. This is indicated by the increasing full-width at half-maximum (FWHM) of the 775 cm(-1) peak and the increasing intensity of the anatase peaks as the erbium content increases. In addition, as the narsarsukite Er3+ content increases a band at ca. 515 cm(-1) firstly broadens and subsequently a new peak appears at ca. 507 cm(-1).Er3+-doped narsarsukite exhibits a characteristic local vibrational frequency, (h) over bar omega ca. 330 cm(-1), with an electron-phonon coupling, g ca. 0.2, which constitutes additional evidence for framework Er3+ insertion. The number of lines in the infrared emission spectrum of synthetic narsarsukite indicates the presence of two optically-active erbium centres with very similar local environments and an average I-4(13/2) lifetime of 7.8 +/- 0.2 ms.

Surgical treatment of erythroleukoplakia in lower lip with carbon dioxide laser radiation

Erythroplakia is considered to represent a premalignant condition and is felt to be at high risk to progress to oral cancer development. When the lesion presents with red and white mucosal alterations concomitantly, the term erythroleukoplakia is used. However, in erythroleukoplakia lesions, the red or erythroplakia areas have been shown to be most likely to demonstrate dysplastic changes compared to the white hyperkeratotic areas. We present a case of patient with erythroleukoplakia involving the lower lip that was treating with carbon dioxide laser radiation (CO2) with 0.8 mm focus, 5 W, power density of 2.5 W/cm(2) in continuous. After the surgery, the vaporized surface was protected with a fibrinolisine + chloramphenicol cream. To date, after 6 months, there has been no clinically evident recurrence on the vermilion area. The functional and esthetic results observed were judged to be excellent.

Structure and ultrastructure of the ventral prostate of isogenic mice (C57B1/6J) submitted to chronic alcohol ingestion

Morphological and functional alterations caused by chronic alcohol ingestion in testes and accessory sex organs have been studied both in man and in laboratory animals. The aim of the present study was to examine the possible occurrence of deleterious effects of chronic alcohol ingestion on the secretory epithelium of the ventral prostate of mice. Twenty-four adult male C57BL/6J mice were divided into three groups. The alcohol-treated group was allowed to drink only 6% (v/v) ethanol, the isocaloric group received a diet of water/sucrose with a calorie content equivalent to a 6% alcohol solution and the control group received water. Both groups were fed ad libitum with solid Purina rat chow. After 120 days, animals from each group were anesthetized with ethyl ether, weighed and processed for light and transmission electron microscopy. The results demonstrated reduction in the glandular epithelium cell height and disorganization of the Golgi complex. Moreover, abundant membrane-bound structures, most likely representing cytoplasmic material, were observed, as well as accumulation of dense bodies. Statistical analysis showed that bodyweight gain was similar for both groups. In conclusion, chronic alcohol ingestion has harmful effects on the secretory epithelium cells of the ventral lobe of the prostate of mice after 120 days of treatment. (C) 2001 Harcourt Publishers Ltd.

Geophagy in the golden-faced saki monkey (Pithecia pithecia chrysocephala) in the Central Amazon

The golden-faced saki monkey Pithecia pithecia chrysocephala (Cebidae, Primates) was observed eating soil from termite nests during a long-term study of a family group in a Central Amazonian forest fragment. In this paper we describe the behaviour involved in the geophagy in these monkeys, and the results of geochemical and physical analyses of the termite nest material, as well as root mat and topsoil samples below the trees, in order to clarify the possible reasons for it. The sakis ate soil from nine arboreal termite nests on 26 soil feeding-bouts (in 853 observation hours); 25 soil feeding-bouts occurred in March 1987 (rainy season), during 19 days or 132 observation hours, and occupied 0.7% of the feeding time. Geophagy frequencies did not differ between sexes (17 feeding-bouts of four females and 8 for two males). Mineral composition was higher in arboreal termitaria than in the topsoil. Kaolinite was the major clay component. Tannin adsorptive capacity, tested through a modified radial diffusion method of Hagerman, was around 10-20%, similar to a control with kaolin (10-20%), but lower than bentonite or celite (30-45%). The observations reported here, although inconclusive as to the function of geophagy in this species, indicate that it is not a mineral supplement during times of scarcity or high consumption of leaves, as has been reported for other primates, nor that it is related to fruit consumption (redressing possible mineral imbalance), as has been suggested for some other frugivorous mammals. Our results do not rule out tannin adsorptive hypothesis for the ingestion of clays, but, being an irregular habit, we argue that it is most likely related to rare and occasional dietary components.

Automated NMR structure determination and disulfide bond identification of the myotoxin crotamine from Crotalus durissus terrificus

Crotamine is one of four major components of the venom of the South American rattlesnake Crotalus durissus terrificus. Similar to its counterparts in the family of the myotoxins, it induces myonecrosis of skeletal muscle cells. This paper describes a new NMR structure determination of crotamine in aqueous solution at pH 5.8 and 20 degrees C, using standard homonuclear (1)H NMR spectroscopy at 900 MHz and the automated structure calculation software ATNOS/CANDID/DYANA. The automatic NOESY spectral analysis included the identification of a most likely combination of the six cysteines into three disulfide bonds, i.e. Cys4-Cys36, Cys11-Cys30 and Cys18-Cys37; thereby a generally applicable new computational protocol is introduced to determine unknown disulfide bond connectivities in globular proteins. A previous NMR structure determination was thus confirmed and the structure refined. Crotamine contains an alpha-helix with residues 1-7 and a two-stranded anti-parallel beta-sheet with residues 9-13 and 34-38 as the only regular secondary structures. These are connected with each other and the remainder of the polypeptide chain by the three disulfide bonds, which also form part of a central hydrophobic core. A single conformation was observed, with Pro13 and Pro21 in the trans and Pro20 in the cis-form. The global fold and the cysteine-pairing pattern of crotamine are similar to the beta-defensin fold, although the two proteins have low sequence homology, and display different biological activities. (c) 2005 Elsevier Ltd. All rights reserved.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO3-x% MoO3 (0 <= x <= 70) glass-forming system by a modified melt method that allowed good optical quality samples to be obtained. The structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), Raman scattering, and solid-state nuclear magnetic resonance (NMR) for P-31, Na-23, and Mo-95 nuclei. Addition of MoO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures up to x = 45, suggesting a significant increase in network connectivity. For this same composition range, vibrational spectra suggest that the Mo6+ ions are bonded to some nonbridging oxygen atoms (Mo-O- or Mo=O bonded species). Mo-O-Mo bond formation occurs only at MoO3 contents exceeding x = 45. P-31 magic-angle spinning (MAS) NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. These sites are denoted as Q(2Mo)((2)), Q(1Mo)((2)), and Q(0Mo)((2)), respectively. For x < 0.45, the populations of these sites can be described along the lines of a binary model, according to which each unit of MoO3 converts two Q(nMo)((2)) sites into two Q((n+1)Mo)((2)) sites (n = 0, 1). This structural model is consistent with the presence of tetrahedral Mo(=O)(2)(O-1/2)(2) environments. Indeed, Mo-95 NMR data suggest that the majority of the molybdenum species are four-coordinated. However, the presence of additional six-coordinate molybdenum in the MAS NMR spectra indicates that the structure of these glasses may be more complicated and may additionally involve sharing of network modifier oxide between the network formers phosphorus and molybdenum. This latter hypothesis is further supported by Na-23{P-31} rotational echo double resonance (REDOR) data, which clearly reveal that the magnetic dipole-dipole interactions between P-31 and Na-23 are increasingly diminished with increasing molybdenum content. The partial transfer of modifier from the phosphate to the molybdate network former implies a partial repolymerization of the phosphate species, resulting in the formation of Q(nMo)((3)) species and accounting for the observed increase in the glass transition temperature with increasing MoO3 content that is observed in the composition range 0 <= x <= 45. Glasses with MoO3 contents beyond x = 45 show decreased thermal and crystallization stability. Their structure is characterized by isolated phosphate species [most likely of the P(OMo)(4) type] and molybdenum oxide clusters with a large extent of Mo-O-Mo connectivity.

Does alveolar soft-part sarcoma exhibit skeletal muscle differentiation? An immunocytochemical and biochemical study of myogenic regulatory protein expression

There has been persistent controversy regarding the nature of cell differentiation in alveolar soft-part sarcoma (ASPS) since its first description in 1952. Some studies suggest that ASPS might represent an unusual variant of skeletal muscle tumor, Given the availability of new monoclonal antibodies to probe for skeletal muscle differentiation and the rapid advance in immunocytochemical techniques for deparaffinized, formalin-fixed tissue sections, we wished to test the proposed hypothesis that ASPS might represent a new type of rhabdomyosarcoma Twelve archival samples of ASPS were retrieved, and we investigated the expression of two myogenic regulatory proteins, MyoD1 and myogenin, as rvell as other muscle-associated proteins, using sensitive immunocytochemical techniques. Despite the presence of desmin immunostaining in six ASPSs, no tumors were positive for either muscle actin or myoglobin Most importantly, no specimen showed nuclear expression of MyoD1 or myogenin, In 11 tumors, however, there was considerable granular immunostaining in the tumor cell cytoplasm with the anti-MyoD1 monoclonal antibody 5.8A, a phenomenon observed in various nonmuscle normal and neoplastic tissues with this antibody, To analyze the exact nature of immunostaining of MyoD1 and desmin in ASPS, biochemical analyses using available fresh frozen tumor tissue were performed, Although a 53-kDa band was noted with antidesmin antibody on Western blot analysis, no specific protein band that corresponds to the 45-kDa MyoD1 was detected with antibody 5.8A. These results confirm the presence of desmin in ASPS but argue against authentic expression of MyoD1, They also suggest that the cytoplasmic immunostaining observed with anti-MyoD1 antibody 5.8A most likely represents a nonspecific cross-reaction with an unknown cytoplasmic antigen, Considering the master role that MyoD1 and myogenin play in skeletal muscle commitment and differentiation and the lack of expression of these two proteins in ASPS as determined immunocytochemically and biochemically, we think that the histogenesis of ASPS remains unknown.

Response to Treatment in a Prospective Cohort of Patients with Large Ulcerated Lesions Suspected to Be Buruli Ulcer (Mycobacterium ulcerans Disease)

Background: The World Health Organization (WHO) advises treatment of Mycobacterium ulcerans disease, also called Buruli ulcer'' (BU), with a combination of the antibiotics rifampicin and streptomycin (R+S), whether followed by surgery or not. In endemic areas, a clinical case definition is recommended. We evaluated the effectiveness of this strategy in a series of patients with large ulcers of >= 10 cm in longest diameter in a rural health zone of the Democratic Republic of Congo (DRC).Methods: A cohort of 92 patients with large ulcerated lesions suspected to be BU was enrolled between October 2006 and September 2007 and treated according to WHO recommendations. The following microbiologic data were obtained: Ziehl-Neelsen (ZN) stained smear, culture and PCR. Histopathology was performed on a sub-sample. Directly observed treatment with R+S was administered daily for 12 weeks and surgery was performed after 4 weeks. Patients were followed up for two years after treatment.Findings: Out of 92 treated patients, 61 tested positive for M. ulcerans by PCR. PCR negative patients had better clinical improvement than PCR positive patients after 4 weeks of antibiotics (54.8% versus 14.8%). For PCR positive patients, the outcome after 4 weeks of antibiotic treatment was related to the ZN positivity at the start. Deterioration of the ulcers was observed in 87.8% (36/41) of the ZN positive and in 12.2% (5/41) of the ZN negative patients. Deterioration due to paradoxical reaction seemed unlikely. After surgery and an additional 8 weeks of antibiotics, 98.4% of PCR positive patients and 83.3% of PCR negative patients were considered cured. The overall recurrence rate was very low (1.1%).Interpretation: Positive predictive value of the WHO clinical case definition was low. Low relapse rate confirms the efficacy of antibiotics. However, the need for and the best time for surgery for large Buruli ulcers requires clarification. We recommend confirmation by ZN stain at the rural health centers, since surgical intervention without delay may be necessary on the ZN positive cases to avoid progression of the disease. PCR negative patients were most likely not BU cases. Correct diagnosis and specific management of these non-BU ulcers cases are urgently needed.

Reduced Insulin Secretion in Protein Malnourished Mice Is Associated with Multiple Changes in the beta-Cell Stimulus-Secretion Coupling

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

Structures of the noncovalent complexes of human and bovine prothrombin fragment 2 with human PPACK-thrombin

Both human and bovine prothrombin fragment 2 (the second kringle) have been cocrystallized separately with human PPACK (D-Phe-Pro-Arg)-thrombin, and the structures of these noncovalent complexes have been determined and refined (R = 0.155 and 0.157, respectively) at 3.3-Å resolution using X-ray crystallographic methods. The kringles interact with thrombin at a site that has previously been proposed to be the heparin binding region. The latter is a highly electropositive surface near the C-terminal helix of thrombin abundant in arginine and lysine residues. These form salt bridges with acidic side chains of kringle 2. Somewhat unexpectedly, the negative groups of the kringle correspond to an enlarged anionic center of the lysine binding site of lysine binding kringles such as plasminogens K1 and K4 and TPA K2. The anionic motif is DGDEE in prothrombin kringle 2. The corresponding cationic center of the lysine binding site region has an unfavorable Arg70Asp substitution, but Lys35 is conserved. However, the folding of fragment 2 is different from that of prothrombin kringle 1 and other kringles: the second outer loop possesses a distorted two-turn helix, and the hairpin β-turn of the second inner loop pivots at Val64 and Asp70 by 60°. Lys35 is located on a turn of the helix, which causes it to project into solvent space in the fragment 2-thrombin complex, thereby devastating any vestige of the cationic center of the lysine binding site. Since fragment 2 has not been reported to bind lysine, it most likely has a different inherent folding conformation for the second outer loop, as has also been observed to be the case with TPA K2 and the urokinase kringle. The movement of the Val64-Asp70 β-turn is most likely a conformational change accompanying complexation, which reveals a new heretofore unsuspected flexibility in kringles. The fragment 2-thrombin complex is only the second cassette module-catalytic domain structure to be determined for a multidomain blood protein and only the third domain-domain interaction to be described among such proteins, the others being factor Xa without a Gla domain and Ca2+ prothrombin fragment 1 with a Gla domain and a kringle. © 1993 American Chemical Society.

ASPECTOS ETIOLOGICOS DA HIPERNASALIDADE CONSEQUENTE A PARALISIA DE PALATO MOLE - RELATO DE 6 CASOS

The authors studied the main aspects of etiology of the palate paralysis in six children suffering from soft palate paralysis. They emphasized the importance of multidisciplinary approach in the management of patients with this disease. In the author's cases the most likely etiologies were: neuropathy post-viral epidemic parotitis, tumors localized in the posterior cerebral fossa and idiopathic. They concluded that it is extremely important in these patients a detailed otorhinolaryngologic, neurologic and fonoaudiologic examinations.

Intercontinental Differences in the Abundance of Solenopsis Fire Ants (Hymenoptera: Formicidae): Escape from Natural Enemies?

The absence of natural enemies often allows exotic pests to reach densities that are much higher than normally occur in their native habitats. When Solenopsis fire ants were introduced into the United States, their numerous natural enemies were left behind in South America. To compare intercontinental fire ant densities, we selected 13 areas in South America and another 12 areas in North America. Sample areas were paired with weather stations and distributed across a broad range of climatic conditions. In each area, we measured fire ant densities at 5 preselected roadside sites that were at least 5 km apart. At each site, we also measured foraging activity, checked for polygyne colonies, and recorded various kinds of environmental data. In most areas, we also measured fire ant densities in lawns and grazing land. Fire ant populations along roadsides in North America were 4-7 times higher than fire ant populations in South America. Similar intercontinental differences were found in lawns and on grazing lands. These intercontinental differences in fire ant abundance were not associated with sampling conditions, seasonal variability, habitat differences, or the frequency of polygyny. Although several correlations were found with long-term weather conditions, careful inspection of the data suggests that these correlations were probably more coincidental than causal. Cultural differences in roadside maintenance may explain some of the intercontinental differences in fire ant abundance, but they did not account for equivalent intercontinental differences in grazing land and mowed lawns. Bait tests showed that competition with other ants was much more important in South America; however, we were not able to determine whether this was a major cause of intercontinental differences or largely a consequence of other factors such as the numerous pathogens and parasites that are found in South America. Because this study was correlational, we were unable to determine the cause(s) of the large intercontinental difference in fire ant abundance that we observed. However, we were able to largely exclude a number of possible explanations for the differences, including sampling, season, polygyny, climate, and aspects of habitat. By a process of elimination, escape from natural enemies remains among the most likely explanations for the unusually high densities of fire ants found in North America.

Determination of the Θ+ parity from γn → K -K+n

It is demonstrated that measurements of photon asymmetry in the γn → K-K+n reaction, can most likely determine the parity of the newly discovered Θ+ pentaquark. We predict that if the parity of Θ+ is positive, the photon asymmetry is significantly positive; if the parity is negative, the photon asymmetry is significantly negative. If the background contribution is large, the photon asymmetry may become very small in magnitude, thereby making it difficult to distinguish between the positive and negative parity results. However, even in this case, a combined analysis of the (K+n) invariant mass distribution and photon asymmetry should allow a determination of the parity of Θ+. © 2004 Published by Elsevier B.V.