Structural modelling of Eu3+-based siloxane-poly( oxyethylene) nanohybrids

The modelling of the local structure of sol-gel derived Eu3+-based organic/inorganic hybrids is reported, based on Small-Angle X-ray Scattering (SAXS), photoluminescence and mid-infrared spectroscopy. The hybrid matrix of these organically modified silicates, classed as di-ureasils and termed U(2000) and U(600), is formed by poly( oxyethylene) (POE) chains of variable length grafted to siloxane domains by means of urea cross-linkages. Europium triflate, Eu(CF3SO3)(3), was incorporated in the two di-ureasil matrices with compositions 400 greater than or equal ton greater than or equal to 10, n is the molar ratio of ether oxygens per Eu3+. The SAXS data for undoped hybrids (n=infinity) show the presence of a well-defined peak attributed to the existence of a liquid-like spatial correlation of siloxane rich domains embedded in the polymer matrix and located at the ends of the organic segments. The obtained siloxane particle gyration radius Rg(1) is around 5 Angstrom (error within 10%), whereas the interparticle distance d is 25 +/-2 Angstrom and 40 +/-2 Angstrom, for U(600) and U(2000), respectively. For the Eu3+-based nanocomposites the formation of a two-level hierarchical local structure is discerned. The primary level is constituted by strongly spatially correlated siloxane particles of gyration radius Rg(1) (4-6 and 3-8 Angstrom, errors within 5%, for U(600())n Eu(CF3SO3)(3), 200 greater than or equal ton greater than or equal to 40, and U(2000)(n)Eu(CF3SO3)(3), 400 greater than or equal ton greater than or equal to 40, respectively) forming large clusters of gyration radius Rg(2) (approximate to 75 +/- 10 Angstrom). The local coordination of Eu3+ in both di-ureasil series is described combining the SAXS, photoluminescence and mid-infrared results. In the di-ureasils containing long polymer chains, U(2000)(n)Eu(CF3SO3)(3), the cations interact exclusively with the carbonyl oxygens atoms of the urea bridges at the siloxane-POE interface. In the hybrids containing shorter chains, U(600)(n)Eu(CF3SO3)(3) with n ranging from 200 to 60, the Eu3+ ions interact solely with the ether-type oxygens of the polymer chains. Nevertheless, in this latter family of hybrids a distinct Eu3+ local site environment involving the urea cross-linkages is detected when the europium content is increased up to n=40.

Structure of magnetic poly(oxyethylene)-siloxane nanohybrids doped with Fe-II and Fe-III

Hybrid organic - inorganic nanocomposites doped with Fe-II and Fe-III ions and exhibiting interesting magnetic properties have been obtained by the sol - gel process. The hybrid matrix of these ormosils ( organically modified silicates), classed as di-ureasils and termed U( 2000), is composed of poly( oxyethylene) chains of variable length grafted to siloxane groups by means of urea crosslinkages. Iron perchlorate and iron nitrate were incorporated in the diureasil matrices, leading to compositions within the range 80 greater than or equal to n greater than or equal to 10, n being the molar ratio of ether-type O atoms per cation. The structure of the doped diureasils was investigated by small-angle X-ray scattering (SAXS). For Fe-II-doped samples, SAXS results suggest the existence of a two-level hierarchical structure. The primary level is composed of spatially correlated siloxane clusters embedded in the polymeric matrix and the secondary, coarser level consists of domains where the siloxane clusters are segregated. The structure of Fe-III-doped hybrids is different, revealing the existence of iron oxide based nanoclusters, identified as ferrihydrite by wide-angle X-ray diffraction, dispersed in the hybrid matrix. The magnetic susceptibility of these materials was determined by zero-field-cooling and field-cooling procedures as functions of both temperature and field. The different magnetic features between Fe-II- and Fe-III-doped samples are consistent with the structural differences revealed by SAXS. While Fe-II-doped composites exhibit a paramagnetic Curie-type behaviour, hybrids containing Fe-III ions show thermal and field irreversibilities.

Structure and luminescence of Eu3+-doped class I siloxane-poly(ethylene glycol) hybrids

Transparent, flexible, and luminescent EU3+-doped siloxane-poly(ethylene glycol) (PEG) nanocomposites have been obtained by the sol-gel process. The inorganic (siloxane) and organic PEG phases are usually linked by weak bonds (hydrogen bonds or van der Waals forces), and small-angle X-ray scattering (SAXS) measurements suggest that the structure of these materials consists of fractal siloxane aggregates embedded in the PEG matrix. For low Eu3+ contents, n = 300 and n = 80, the aggregates are small and isolated and their fractal dimensions are 2.1 and 1.7, respectively. These values are close to those expected for gelation mechanisms consisting of reaction-limited cluster-cluster aggregation (RLCCA) and diffusion-limited cluster-cluster aggregation (DLCCA). For high Eu3+ content, SAYS results are consistent with a two-level structure: a primary level of siloxane aggregates and a second level, much larger, formed by the coalescence of the primary ones. The observed increase in the glass transition temperature for increasing Eu3+ content is consistent with the structural model derived from SAXS measurements. Extended X-ray absorption fine structure (EXAFS) and luminescence spectroscopy measurements indicate that under the experimental conditions utilized here Eu3+ ions do not strongly interact with the polymeric phase.

Causes of resistant hypertension detected by a standardized algorithm

Resistant hypertension (RH) is characterized by blood pressure above 140 × 90 mm Hg, despite the use, in appropriate doses, of three antihypertensive drug classes, including a diuretic, or the need of four classes to control blood pressure. Resistant hypertension patients are under a greater risk of presenting secondary causes of hypertension and may be benefited by therapeutical approach for this diagnosis. However, the RH is currently little studied, and more knowledge of this clinical condition is necessary. In addition, few studies had evaluated this issue in emergent countries. Therefore, we proposed the analysis of specific causes of RH by using a standardized protocol in Brazilian patients diagnosed in a center for the evaluation and treatment of hypertension. The management of these patients was conducted with the application of a preformulated protocol which aimed at the identification of the causes of resistant hypertension in each patient through management standardization. The data obtained suggest that among patients with resistant hypertension there is a higher prevalence of secondary hypertension, than that observed in general hypertensive ones and a higher prevalence of sleep apnea as well. But there are a predominance of obesity, noncompliance with diet, and frequent use of hypertensive drugs. These latter factors are likely approachable at primary level health care, since that detailed anamneses directed to the causes of resistant hypertension are applied. © 2012 Livia Beatriz Santos Limonta et al.

Desenvolvimento neuropsicomotor de crianças de um ano atendidas em unidades de ESF: fatores de risco e proteção

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A política nacional de juventude: assistencialismo ou inovação?

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

CDX2, a highly sensitive and specific marker of adenocarcinomas of intestinal origin - An immunohistochemical survey of 476 primary and metastatic carcinomas

CDX2 is a recently cloned homeobox gene that encodes an intestine-specific transcription factor, expressed in the nuclei of epithelial cells throughout the intestine, from duodenum to rectum. While expression of CDX2 protein in primary and metastatic colorectal carcinomas has been previously documented, neither the sensitivity nor the specificity of CDX2 expression, as determined by immunohistochemistry, for colorectal adenocarcinoma has been determined. We performed an immunohistochemical survey of 476 tumors with a monoclonal antibody, CDX2-88, including 89 tumors from the colon and duodenum and 95 tumors from other gastrointestinal sites, including the esophagus, stomach, pancreatobiliary system, gastrointestinal carcinoids, and liver. CDX2 was expressed uniformly (that is, in 76-100% of tumor cells) in all but one of the evaluated colorectal and duodenal tumors. High-level expression of CDX2 was also found, however, in mucinous ovarian carcinomas and adenocarcinomas primary to the urinary bladder of which 64% and 100% were positive, respectively. Gastric, gastroesophageal, and pancreatic adenocarcinomas and cholangiocarcinomas all showed similar, heterogeneous patterns of CDX2 expression. Most tumors in each group showed CDX2 expression by a minority of cells, whereas a substantial minority of cases in each group was completely negative and a smaller minority was uniformly positive. Gastrointestinal carcinoids gave similarly varied results, but the majority (58%) was negative. Hepatocellular carcinomas showed no expression of CDX2. Only very rare examples of carcinomas of the genitourinary and gynecologic tracts, breast, lung, and head and neck showed significant levels of CDX2 expression. In this study of primary and metastatic epithelial tumors, uniform CDX2 expression is demonstrated to be an exquisitely sensitive and highly, but incompletely, specific marker of intestinal adenocarcinomas. Compared with villin, a previously described marker of GI adenocarcinomas, CDX2 demonstrated superior sensitivity and comparable specificity. CDX2 expression can be seen, however, in selected non-GI adenocarcinomas such as mucinous ovarian carcinomas and adenocarcinomas of the urinary bladder.

Genotoxicity in primary human peripheral lymphocytes after exposure to radiopacifiers in vitro

Taking into consideration that DNA damage plays an important role in carcinogenesis, the purpose of this study was to evaluate whether some radiopacifiers widely used in clinical practice are able to induce genetic damage in primary human cells in vitro. Human peripheral lymphocytes obtained from 10 healthy volunteers were exposed to barium sulphate (BaSO(4)), zirconium oxide (ZnO(2)) and bismuth oxide (Bi(2)O(3)) at final concentrations ranging from 1 to 1000 mu g/mL for 1 h at 37 degrees C. The negative control group was treated with vehicle control (phosphate buffer solution) for 1 h at 37 degrees C and the positive control group was treated with hydrogen peroxide (at 100 mu M) for 5 min on ice. Results were analyzed by the Friedman non-parametric test. The results pointed all compounds tested out did not induce DNA breakage in human peripheral lymphocytes as depicted by the mean tail moment and tail intensity in all concentrations tested. In summary, our results indicate that exposure to these radiopacifiers may not be a factor that increases the level of DNA lesions in human peripheral lymphocytes as detected by single cell gel (comet) assay.

Digital Radiographic Evaluation of the Level of Alveolar Bone Crest in External Hexagon Implants Submitted to 2 Types of Implant Abutments Under Immediate Loading

Purpose: The aim of this study was to evaluate by means of digital radiography the behavior of the alveolar bone crest in external hexagon implants following the use of 2 different types of abutments, one for conventional cemented prosthesis and one for modified cemented prosthesis.Methods: Ten external hexagon implants (platform 4.1) were placed in 5 patients. Initial instrumentation was carried out to obtain primary stability of the temporary prostheses under immediate loading. Each patient received both abutments for conventional and modified cemented prosthesis. Standardized digital periapical radiographies were performed at times T0 (immediately after implant placement) and T1 (4 months after implant placement). A straight line was initially established from the implant platform to the distal and mesial periimplantar marginal bone tissue (immediately in contact with the implant) and measured by digital radiography, using Sidexis version 2.3 (Sirona Dental Systems GmbH, Bensheim, Germany) software. The data were submitted to paired-samples t-test analysis.Results: There was no significant difference between the conventional and modified cemented prosthesis. In both cases, t-test results were within the null hypothesis level.Conclusion: The abutment for the modified cemented prosthesis resulted in no significant radiographic difference of alveolar bone crest height, when compared with the conventional cemented prostheses.

Luxation injuries in primary teeth: a retrospective study in children assisted at an emergency service

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Migraine is the Most Prevalent Primary Headache in Individuals with Temporomandibular Disorders

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

Annual and short-term variability in primary productivity by phytoplankton and correlated abiotic factors in the Jurumirim Reservoir (São Paulo, Brazil)

A variabilidade anual da produção fotossintética (PP) pelo fitoplâncton na zona da barragem da Represa de Jurumirim (São Paulo, Brasil) foi medida após um estudo no período de três anos sucessivos, com o objetivo de identificar padrões recorrentes e suas causas. Medidas da variabilidade da PP em escala diária foram obtidas em dois períodos do ano (estações seca e chuvosa). Nenhum padrão recorrente foi verificado nos dados de PP, visto não haver relação de sua variabilidade com nenhum fator hidrológico (precipitação, nível e vazão de água e washout) nem, aparentemente, com as condições nutritivas da água. A análise de componentes principais revelou que a PP e a taxa de assimilação foram mais elevadas na época do ano em que o conteúdo de PO4(3-) e N-NH4+ foi mais baixo e quando as razões Z EU/Z MIX foram mais elevadas. A produtividade primária/área pode ser estimada pela razão entre a produtividade volumétrica máxima e o coeficiente de extinção vertical da luz. Entretanto, a biomassa integrada na Z EU foi um pobre preditor da produtividade primária/área. Nenhuma correlação foi encontrada entre a temperatura da água com a produtividade primária (por área e volumétrica máxima). em conseqüência, o estudo da PP em três anos sucessivos mostrou que o padrão de variabilidade é tipicamente caótico. em relação às medidas de curta duração, maior PP foi encontrada na estação seca do que na chuvosa. em ambos os períodos, a variabilidade da PP (por área) foi de aproximadamente 35-40%. O padrão foi atribuído não somente à variação na concentração dos nutrientes mas também à magnitude de penetração de luz na água associado ao regime de circulação. Um comentário sobre a relação entre produção primária pelo fitoplâncton com produção pesqueira é também apresentada.

Chromosomal imbalances detected in primary bone tumors by comparative genomic hybridization and interphase fluorescence in situ hybridization

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

Comparative ablation rate from a Er : YAG laser on enamel and dentin of primary and permanent teeth

This study was conducted to analyze the ablation rate and micromorphological aspects of microcavities in enamel and dentin of primary and permanent teeth using a Er:YAG laser system. Micromorphological evaluation has been performed in terms of permanent teeth; however, little information about Er: YAG laser interaction with primary teeth can be found in the literature. Because children have been the most beneficiary patients with laser therapy in our offices, it is extremely necessary to compare the effects of this kind of laser system on the enamel and dentin of permanent and primary teeth. In this study, we used eleven intact primary anterior exfoliated teeth and six extracted permanent molar teeth. We used a commercial laser system: a Er: YAG Twin Light laser system (Fotona Medical Lasers, Slovenia) at 2940 nm, changing average energy levels per pulse ( 100, 200, 300, and 400 mJ) producing 48 microcavities in enamel and dentin of primary and permanent teeth. Primary teeth are more easily ablated than are permanent teeth, when related to enamel or dentin. However, while this laser system is capable of slowly revealing the enamel's microstructure, in dentin only the lowest laser energies permit this kind of observation, more easily decomposing the original tissue aspect, when related to primary or permanent teeth. Statistically, the only different factor at the 5% level was an energy per pulse of 400 mJ, confirming the results found in SEM. Our results showed that dentin in both primary and permanent teeth is less resistant to Er: YAG laser ablation; this fact is easily observed under SEM observation and through the ablation rate evaluation.

Periphyton on natural substratum in jurumirim reservoir (São Paulo, Brazil): Community biomass and primary productivity

Seasonal variation in the biomass and primary productivity of the periphyton on natural substratum (internodes of Echiiwchloa polystaclya HBK Hitch.) was studied during one year (from August 1993 to July 1994) in a lagoon with permanent connection with a river. We also analysed the relationships between the hydrological regime, climatic conditions and physico-chemical variables of water with the biological compounds of the periphyton. Values of dry mass, ash-free dry mass, chlorophyll a and phaeophytin of periphyton ranged from 0.55±0.24 g m-2 to 7.86±4.93 g m-2; 0.28±0.18 g m-2 to 3.72±2.23 g m-2; 0.57±0.09 mg m-2 to 15.57±4.52 mg m-2; 0.03±0.03 mg m-2 to 4.74±3.46 mg m-2, respectively. The primary productivity of periphytic algae measured by C14 method ranged from 6.45±1.29 mg C m-2 h-1 to 52.88± 7.55 mg C m-2 h-1. The biomass showed a peak in October 1993, February and April 1994. Higher value of primary productivity was recorded in December 1993 and January 1994 and was due to the peculiar light and nutrition conditions during this period. We conclude that biomass and productivity of the community are controlled mainly by hydrological regime (fluctuations of water level). © INTERNATIONAL SCIENTIFIC PUBLICATIONS.