The reduction of oxygen on iron(II) oxide/poly(3,4-ethylenedioxythiophene) composite thin film electrodes

© 2014 Elsevier Ltd. All rights reserved. Conducting polymers (CPs) are currently being investigated for use in many applications owing to their abilities to catalyze a wide range of electrochemical reactions and act as an effective electrode support for various inorganic and organic electrocatalyst materials. Here, we have found that the deposition of poly(3,4-ethylenedioxythiophene) (PEDOT) through the use of an established base-inhibited chemical vapor-phase polymerization (VPP) procedure using an iron(III) tosylate oxidant results in the co-deposition of electrocatalytic iron(II) oxide species within the film. The presence of these species accounts for the 2-electron reduction of hydrogen peroxide that occurs on these electrodes during the series 4-electron oxygen reduction reaction. Furthermore, this realization leads to the possibility of fabricating thin film inorganic/CP composites of various compositions through careful choice of oxidant in a facile, one-step process. A combination of in situ Raman (487.77 nm laser) and in situ UV-Vis spectroscopy was used to probe the oxidation state of PEDOT in the thin film composite electrodes while reducing oxygen in alkaline conditions. These measurements show that the 2-electron electroreduction of hydrogen peroxide (or HO2 -) occurs only on the iron(II) oxide species in a reaction that is facilitated by an effective electron transfer from the delocalized electron orbitals of the PEDOT matrix. This approach could potentially be used in situ to monitor the electrocatalyst/electrode interface quality of conducting polymer-supported electrocatalysts.

Chemiluminescence detection of MDMA in street drug samples using tris (2,2'-bipyridine) ruthenium (III)

Tris(2,2'-bipyridine)ruthenium(II) chemiluminescence was investigated for the detection of 3,4-methylenedioxymethamphetamine (MDMA) and several related compounds in street drug samples. Optimization using flow injection analysis showed that the selectivity of the reagent can be targeted towards the detection of secondary amines by altering the pH of the reaction environment. The greater selectivity of this mode of detection, compared to UV-absorbance, reduces the probability of false positive results from interfering compounds. The detection limit for MDMA under these conditions was 0.48 μM. A HPLC method incorporating post-column tris(2,2'-bipyridine)ruthenium(II) chemiluminescence detection was applied to the determination of MDMA in five street drug samples. The results obtained were in good agreement with quantification performed using traditional UV-absorbance detection, which demonstrates the viability of this method for confirmatory analysis of drug samples. This is the first report of tris(2,2'-bipyridine)ruthenium(II) chemiluminescence for the detection of MDMA and related amphetamine derivatives.

Concepções de licenciandas em pedagogia sobre o ensino de ciências nos ciclos I e II da educação básica

O conteúdo de ciências no Ensino Fundamental dos ciclos I e II é ministrado por um professor polivalente com formação em Pedagogia. Sua formação deve possibilitar uma visão global do fenômeno educativo, o que implica a construção de conhecimentos múltiplos e contextualizados, porém com pouco aprofundamento. Este trabalho objetiva identificar as opiniões e dificuldades de licenciandos de Pedagogia a respeito dos conteúdos de Ciências nos dois primeiros ciclos do Ensino Fundamental, mediado por dois questionamentos: Com relação aos conteúdos de ciências ministrados no I e II ciclos, você os considera fácil ou difícil? Sendo solicitado que justificasse sua resposta; De acordo com seus conhecimentos sobre ciências, cite as principais dificuldades que você teria (tem/teve) em ensinar ciências nos ciclos I e II. Participaram do estudo 29 licenciandas da turma de Ensino das Ciências Naturais II do Curso de Pedagogia da Universidade Federal do Rio Grande do Norte. Com relação ao questionamento referente à consideração dos conteúdos de ciências, 52% das licenciandas consideraram fácil, 31% difícil e 17% não responderam a questão. Foram identificadas três categorias de respostas: processo de elaboração do planejamento (20,5% fácil e 20,5% difícil), nível de conhecimento dos alunos (7% fácil e 0% difícil) e natureza dos conteúdos abordados (14% fácil e 10,5% difícil). Foram classificadas três categorias distintas em relação às dificuldades em ensinar ciências: natureza dos conteúdos abordados (50%), aspectos metodológicos (25%), e conhecimento básico (25%). A análise dos resultados revelou que a principal dificuldade das licenciandas em Pedagogia quanto à aplicabilidade do ensino de ciências nos primeiros ciclos do Ensino Fundamental esta diretamente relacionada à falta de conhecimento básico destes conteúdos, que somente foram estudados por elas no Ensino Básico, indicando a necessidade de incorporação de abordagens de conteúdos de ciências no currículo do curso de Pedagogia.

Identification of Rhizoctonia solani AG 1-IB in lettuce, AG 4 HG-I in tomato and melon, and AG 4 HG-III in broccoli and spinach, in Brazil

Fungi isolated in Brazil, from lettuce, broccoli, spinach, melon and tomato, were identified as Rhizoctonia solani. All lettuce isolates anastomosed with both AG 1-IA and IB subgroups and all isolates from broccoli, spinach, melon and tomato anastomosed with AG 4 subgroup HG-I, as well as with subgroups HG-II and HG-III. DNA sequence analyses of ribosomal internal transcribed spacers showed that isolates from lettuce were AG 1-IB, isolates from tomato and melon were AG 4 HG-I, and isolates from broccoli and spinach were AG 4 HG-III. The tomato isolates caused stem rot symptoms, the spinach, broccoli and melon isolates caused hypocotyl and root rot symptoms on the respective host plants and the lettuce isolates caused bottom rot. This is the first report on the occurrence in Brazil of R. solani AG 4 HG-I in tomato and melon, of AG 4 HG-III in broccoli and spinach and of AG 1-IB in lettuce.

Direct and simultaneous spectrophotometric determination of Ni (II) and Co (II) using diethanoldithiocarbamate as complexing agent

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

Relação da imunoexpressão da bmp-2, bmpr-ia e bmpr-ii com o perfil clínico-patológico em carcinoma epidermóide de lábio inferior

Currently, bone morphogenetic proteins (BMPs) have effective participation in the growth of malignancies. Knowing that there are few studies involving BMPs and oral squamous cell carcinoma, this work constitutes an immunohistochemical study of BMP-2, BMPR IA and BMPR II in squamous cell carcinomas (SCC) of the lower lip relating to the clinical and pathological aspects of this lesion. The sample consisted of 40 cases of SCC of the lower lip, being 20 cases of SCC of the lower lip with regional metastasis and 20 cases without metastasis. We evaluated the intensity of expression (score 1 to mark absent / weak, score 2 for high ) and was found the percentage of labeled cells, where the score was 1 cases with 0 to 50% of positive cells, score 2 with 51 to 75% of positive cells, and score 3 more than 75% of positive cells. The sample comprised 72.5% of men with a mean age of 65.8 years, there was a predominance of stage II and 52.5% of the carcinomas were classified as low grade, being carcinoma with metastasis presenting most cases (70%) as carcinomas of high malignancy grade (p = 0.004). The largest number of cases of SCC of the lower lip that were in stages I / II (61, 9%) were classified as carcinomas of low grade malignancy and carcinomas in stages III / IV were classified as high-grade tumors (p = 0, 024). The BMP-2 showed strong intensity of immunostaining in 82.5%, BMPR-IA showed 55% of cases with an intensity of immunostaining absent / weak and BMPR-II showed 85% of cases with an intensity of immunostaining absent / weak. Only the protein BMPR-IA were significantly associated with all clinic-pathological parameters studied, metastasis (p <0.001), TNM (p <0.001) and histological grade of malignancy with (p = 0.028). The percentage of positive cells, all markers showed the highest number of cases with more than 75% of positive cells (score 3) and only BMPR-II showed statistical difference when related to the presence and absence of metastasis (p = 0.049 ). We conclude that there is disturbance in the BMP signaling pathway in EC-mediated lower lip and that high expression of BMP-2 associated with the expression of BMPR-IA and BMPR-II are associated with metastasis in carcinoma

Consórcio de feijoeiro e milho-verde na entressafra. II- comportamento das cultivares de milho

The green corn demand, production of quality bean grain and better use of land and water resources can be used by small farmers through the intercropping of common bean and green corn in off-season crops. Field experiments were conducted in the Polo Regional Extremo Oeste-APTA, in Andradina -São Paulo State, in 2005 and 2006. The objective was to evaluate the performance of green corn cultivars grown in single crop and intercropped with common bean. The randomized blocks design with 8 treatments constituted by the combination of two corn (CATIVERDE 02 and XB 7012) and three common bean cultivars of different growth habits: IPR Colibri (I), IPR Juriti (II) and IAC Carioca (III), with four repetitions was used. The influence of the intercropping on the performance of corn was not significant. The hybrid XB 7012 was more productive in intercropping and in single crop. The hybrid production more 8000 commercials ears and lengt ears when compared with the variety. The intercropping with the IPR Juriti or IPR Colibri cultivars were the most profitable for the producer.

Absence of TGF-beta RII predicts bone and lung metastasis and is associated with poor prognosis in stage III breast tumors

In the case of operated breast cancer (BC), prognostic markers help to determine if the patient needs additional treatment and predictive markers help the clinician to decide which treatment to use. Thus, a better knowledge of known predictive and prognostic markers and the identification of new markers, may improve the treatment of BC patients. The transforming growth factor-beta type II receptor (TGF-beta RII), a main receptor of transforming growth factor beta pathway, is a potential new prognostic marker. The aims of the present study were to investigate both the predictive and prognostic impact of TGF-beta RII in BC samples. TGF-beta RII protein expression was evaluated using immunohistochemistry on a tissue microarray containing 110 TNM stage III BC samples obtained prior to doxorubicin-based neoadjuvant chemotherapy (NAC). Our results demonstrate that TGF-beta RII did not predict the response to NAC. on the other hand, an association between TGF-beta RII-negative tumor and higher risk of metastasis to lungs and bones was verified. TGF-beta RII negativity was an independent prognostic factor for decreased disease-free and overall survival.

Intrusion of teeth with class III furcation: a clinical, histologic and histometric study in dogs

Aim: To assess orthodontic intrusion effects on periodontal tissues in dogs' pre-molars with class III furcations treated with open flap debridement (OFD) or with guided tissue regeneration (GTR) associated to bone autograft (BA).Material and Methods: Class III furcations were created in the pre-molars of seven mongrel dogs. After 75 days, teeth were randomly treated with OFD or GTR/BA. After 1 month, metallic crowns were assembled on pre-molars and connected apically to mini-implants by nickel-titanium springs. Teeth were randomly assigned to orthodontic intrusion (OFD+I and GTR/BA+I) groups or no movement (OFD and GTR/BA) groups. Dogs were sacrificed after 3 months of movement and 1 month retention.Results: All class III furcations were closed or reduced to class II or I in the intrusion groups, while 50% of the lesions in non-moved teeth remained unchanged. Intruded teeth presented higher probing depth and lower gingival marginal level than non-moved teeth (p < 0.01). Clinical attachment gain was reduced in the intrusion groups by the end of retention (p < 0.05). OFD+I presented smaller soft tissue area and larger bone tissue area than other groups (p < 0.05).Conclusion: Orthodontic intrusion with anchorage via mini-implants improved the healing of class III furcation defects after OFD in dogs. GTR/BA impaired those results.

Bothrops moojeni myotoxin-II, a Lys49-phospholipase A(2) homologue: An example of function versatility of snake venom proteins

MjTX-II, a myotoxic phospholipase A(2) (PLA(2)) homologue from Bothrops moojeni venom, was functionally and structurally characterized. The MjTX-II characterization included: (i) functional characterization (antitumoral, antimicrobial and antiparasitic effects); (ii) effects of structural modifications by 4-bromophenacyl bromide (BPB), cyanogen bromide (CNBr), acetic anhydride and 2-nitrobenzenesulphonyl fluoride (NBSF); (iii) enzymatic characterization: inhibition by low molecular weight heparin and EDTA; and (iv) molecular characterization: cDNA sequence and molecular structure prediction. The results demonstrated that MjTX-II displayed antimicrobial activity by growth inhibition against Escherichia coli and Candida albicans, antitumoral activity against Erlich ascitic tumor (EAT), human breast adenocarcinoma (SK-BR-3) and human T leukemia cells (JURKAT) and antiparasitic effects against Schistosoma mansoni and Leishmania spp., which makes MjTX-II a promising molecular model for future therapeutic applications, as well as other multifunctional homologous Lys49-PLA(2)S or even derived peptides. This work provides useful insights into the structural determinants of the action of Lys49-PLA2 homologues and, together with additional strategies, supports the concept of the presence of others bioactive sites distinct from the catalytic site in snake venom myotoxic PLA(2)s. (c) 2005 Elsevier B.V. All rights reserved.

Molecular characterization and phylogenetic analysis of JussuMP-I: A RGD-P-III class hemorrhagic metalloprotease from Bothrops jararacussu snake venom

Snake venom metalloproteases (SVMPs) embody zinc-dependent multidomain enzymes responsible for a relevant pathophysiology in envenomation. including local and systemic hemorrhage. The molecular features responsible for hemorrhagic potency of SVMPs have been associated with their multidomains structures which can target these proteins them to several receptors of different tissues and cellular types. BjussuMP-I. a SVMP isolated from the Bothrops jararacussu venom, has been characterized as a P-III hemorrhagic metalloprotease. The complete cDNA sequence of BjussuMP-I with 1641bp encodes open reading frames of 547 amino acid residues, which conserve the common domains of P-III high molecular weight hemorrhagic metalloproteases: (i) pre-pro-peptide, (ii) metalloprotease, (iii) disintegrin-like and (iv) rich cysteine domain. BjussuMP-I induced lyses in fibrin clots and inhibited collagen- and ADP-induced platelet aggregation. We are reporting, for the first time, the primary structure of an RGD-P-III class snake venom metalloprotease. A phylogenetic analysis of the BjussuMP-1 metalloprotease/catalytic domain was performed to get new insights into the molecular evolution of the metalloproteases. A theoretical molecular model of this domain was built through folding recognition (threading) techniques and refined by molecular dynamics simulation. Then, the final BjussuMP-I catalytic domain model was compared to other SVMPs and Reprolysin family proteins in order to identify eventual structural differences, which could help to understand the biochemical activities of these enzymes. The presence of large hydrophobic areas and some conserved surface charge-positive residues were identified as important features of the SVMPs and other metalloproteases. (C) 2006 Elsevier B.V. All rights reserved.

Preliminary X-ray crystallographic studies of BthTX-II, a myotoxic Asp49-phospholipase A(2) with low catalytic activity from Bothrops jararacussu venom

For the first time, a complete X-ray diffraction data set has been collected from a myotoxic Asp49-phospholipase A(2) (Asp49-PLA(2)) with low catalytic activity (BthTX-II from Bothrops jararacussu venom) and a molecular-replacement solution has been obtained with a dimer in the asymmetric unit. The quaternary structure of BthTX-II resembles the myotoxin Asp49-PLA(2) PrTX-III (piratoxin III from B. pirajai venom) and all non-catalytic and myotoxic dimeric Lys49-PLA(2)s. In contrast, the oligomeric structure of BthTX-II is different from the highly catalytic and non-myotoxic BthA-I (acidic PLA(2) from B. jararacussu). Thus, comparison between these structures should add insight into the catalytic and myotoxic activities of bothropic PLA(2)s.

Angiotensin II, progesterone, and prostaglandins are sequential steps in the pathway to bovine oocyte nuclear maturation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Early cephalometric characteristics in Class III malocclusion

OBJECTIVE: Early identification of craniofacial morphological characteristics allows orthopedic segmented interventions to attenuate dentoskeletal discrepancies, which may be partially disguised by natural dental compensation. To investigate the morphological characteristics of Brazilian children with Class III malocclusion, in stages I and II of cervical vertebrae maturation and compare them with the characteristics of Class I control patients. METHODS: Pre-orthodontic treatment records of 20 patients with Class III malocclusion and 20 control Class I patients, matched by the same skeletal maturity index and sex, were selected. The craniofacial structures and their relationships were divided into different categories for analysis. Angular and linear measures were adopted from the analyses previously described by Downs, Jarabak, Jacobson and McNamara. The differences found between the groups of Class III patients and Class I control group, both subdivided according to the stage of cervical vertebrae maturation (I or II), were assessed by analysis of variance (ANOVA), complemented by Bonferroni's multiple mean comparisons test. RESULTS: The analysis of variance showed statistically significant differences in the different studied groups, between the mean values found for some angular (SNA, SNB, ANB) and linear variables (Co - Gn, N - Perp Pog, Go - Me, Wits, S - Go, Ar - Go). CONCLUSION: Assessed children displaying Class III malocclusion show normal anterior base of skull and maxilla, and anterior positioning of the mandible partially related to increased posterior facial height with consequent mandibular counterclockwise rotation.

The sensitization of the ligand-field state of the hexaammineruthenium(II) complex ion by organic compounds

The sensitized photolysis of [Ru(NH3)(6)](2+) by the organic dye rhodamine B and biacetyl was studied under conditions in which only the sensitizer absorbs. The reaction products resulting from ammonia aquation and Ru(II) to Ru(III) oxidation are the same for direct and sensitized photolysis. The energy transfer rate constant, calculated from the fluorescence quenching of rhodamine B, is similar to that estimated from the limiting quantum yield of the photosensitized photoaquation of the complex. Both reactions originate from a common reactive low-lying ligand-field (LF) state, which is also responsible for the direct photolysis reactions. This state, which leads directly to photoaquation, seems to have a certain charge transfer to solvent (CTTS) character, which is responsible for the photo-oxidation products. Sensitization is effective with rhodamine B (17 450 cm(-1)) and biacetyl (19 000 cm(-1)), whereas no reaction is observed with neutral red (16 900 cm(-1)). These results show that the excited state responsible for the photochemical reactions lies in the energy range between 16 900 cm(-1) and 17 700 cm(-1) and possesses spin-orbit character.