Methylene spacer-regulated structural variation in cobalt(II/III) complexes with bridging acetate and Salen- or Salpn-type Schiff-base ligands

Two linear, trinuclear mixed-valence complexes, [Co-II{(mu-L-1)(mu-OAc)Co-III (OAc)}(2)] (1) and [Co-II(mu-L-2) (mu-OAc)Co-III(OAc)}(2)] (2) and two mononuclear Con' complexes [Co-III{L-3)(OAc)] (3), and [Co-III {L-4}(OAc)] (4) were prepared and the molecular structures of 1, 2 and 4 elucidated on the basis of X-ray crystallography [OAc = Acetate ion, H2L1 = H(2)Salen 1,6-bis(2-hydroxyphenyl)-2,5-diazahexa-1,5-diene, H2L2 H2Me2-Salen = 2,7-bis(2-hydroxyphenyl)-2,6-diazaocta-2,6-diene, H2L3 = H(2)Salpn = 1,7-bis(2-hydroxyphenyl)-2,6-diazahepta1,6-diene, H2L4 = H(2)Me(2)Salpn = 2,8-bis(2-hydroxyphenyl)3,7-diazanona-2,7-dienel. In complexes I and 2, the acetate groups show both monodentate and bridging bidentate coordination modes, whereas chelating bidentate acetate is present in 4. The terminal (CoN2O4)-N-III centres in 1 and 2 exhibit uniform facial arrangements of both non-bridged N2O and bridging O-3 donor sets and the Co-II centre is coordinated to six (four phenoxo and two acetato) oxygen atoms of the bridging ligands. The effective magnetic moment at room temperature corresponds to the presence of high-spin Coll in both 1 and 2. The complexes 1 and 2 are thus Co-III(S = 0)Co-II(S = 3/2)-Co-II(S = 0) trimers. Complexes 3 and 4 are monomeric and diamagnetic containing low-spin Co-III(S = 0) with chelating tetradentate Schiff base and bidentate acetate. Calculations based on DFT rationalise the formation of trinuclear or monomiclear complexes. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Variation in pituitary expression of mRNAs encoding the putative inhibin co-receptor (betaglycan) and type-I and type-II activin receptors during the chicken ovulatory cycle

Secretion of LH and FSH from the anterior pituitary is regulated primarily by hypothalamic GnRH and ovarian steroid hormones. More recent evidence indicates regulatory roles for certain members of the transforming growth factor beta (TGF beta) superfamily including inhibin and activin. The aim of this study was to identify expression of mRNAs encoding key receptors and ligands of the inhibin/activin system in the hen pituitary gland and to monitor their expression throughout the 24-25-h ovulatory cycle. Hens maintained on long days (16 h light/8 h dark) were killed 20, 12, 6 and 2 h before predicted ovulation of a midsequence egg (n = 8 per group). Anterior pituitary glands were removed, RNA extracted and cDNA synthesized. Plasma concentrations of LH, FSH, progesterone and inhibin A were measured. Real-time quantitative PCR was used to quantify pituitary expression of mRNAs encoding betaglycan, activin receptor (ActR) subtypes (type I, IIA), GnRH receptor (GnP,H-R), LH beta subunit, FSH beta subunit and GAPDH. Levels of mRNA for inhibin/activin beta A and beta B subunits, inhibin alpha subunit, follistatin and ActRIIB mRNA in pituitary were undetectable by quantitative PCR (< 2 amol/reaction). Significant changes in expression (P < 0.05) of ActRIIA and betaglycan mRNA were found, both peaking 6 h before ovulation just prior to the preovulatory LH surge and reaching a nadir 2 h before ovulation, just after the LH surge. There were no significant changes in expression of ActRI mRNA throughout the cycle although values were correlated with mRNA levels for both ActRIIA (r=0.77; P < 0.001) and betaglycan (r=0.45; P < 0.01). Expression of GnRH-R mRNA was lowest 20 h before ovulation and highest (P < 0.05) 6 h before ovulation; values were weakly correlated with betaglycan (r=0.33; P=0.06) and ActRIIA (r=0.34; P=0.06) mRNA levels. Expression of mRNAs encoding LH beta and FSH beta subunit were both lowest (P < 0.05) after the LH surge, 2 h before ovulation. These results are consistent with an endocrine, but not a local intrapituitary, role of inhibin-related proteins in modulating gonadotroph function during the ovulatory cycle of the hen, potentially through interaction with betaglycan and ActRIIA. In contrast to mammals, intrapituitary expression of inhibin/activin subunits and follistatin appears to be extremely low or absent in the domestic fowl.

Genetic predisposition to type 2 diabetes is associated with impaired insulin secretion but does not modify insulin resistance or secretion in response to an intervention to lower dietary saturated fat

Genome-wide association studies have identified SNPs reproducibly associated with type 2 diabetes (T2D). We examined the effect of genetic predisposition to T2D on insulin sensitivity and secretion using detailed phenotyping in overweight individuals with no diagnosis of T2D. Furthermore, we investigated whether this genetic predisposition modifies the responses in beta-cell function and insulin sensitivity to a 24-week dietary intervention. We genotyped 25 T2D-associated SNPs in 377 white participants from the RISCK study. Participants underwent an IVGTT prior to and following a dietary intervention that aimed to lower saturated fat intake by replacement with monounsaturated fat or carbohydrate. We composed a genetic predisposition score (T2D-GPS) by summing the T2D risk-increasing alleles of the 25 SNPs and tested for association with insulin secretion and sensitivity at baseline, and with the change in response to the dietary intervention. At baseline, a higher T2D-GPS was associated with lower acute insulin secretion (AIRg 4% lower/risk allele, P = 0.006) and lower insulin secretion for a given level of insulin sensitivity, assessed by the disposition index (DI 5% lower/risk allele, P = 0.002), but not with insulin sensitivity (Si). T2D-GPS did not modify changes in insulin secretion, insulin sensitivity or the disposition index in response to the dietary interventions to lower saturated fat. Participants genetically predisposed to T2D have an impaired ability to compensate for peripheral insulin resistance with insulin secretion at baseline, but this does not modify the response to a reduction in dietary saturated fat through iso-energetic replacement with carbohydrate or monounsaturated fat.

Functional model for catecholase-like activity: A mechanistic approach with manganese(III) complexes of salen type Schiff base ligands

Three new Mn(III) complexes [MnL1(OOCH)(OH2)] (1), [MnL2(OH2)(2)][Mn2L22(NO2)(3)] (2) and [Mn2L21(NO2)(2)] (3) (where H2L1 = H(2)Me(2)Salen = 2,7-bis(2-hydroxyphenyl)-2,6-diazaocta-2,6-diene and H2L2 = H(2)Salpn = 1,7-bis(2-hydroxyphenyl)-2,6-diazahepta-1,6-diene) have been synthesized. X-ray crystal structure analysis reveals that 1 is a mononuclear species whereas 2 contains a mononuclear cationic and a dinuclear nitrite bridged (mu-1 kappa O:2 kappa O') anionic unit. Complex 3 is a phenoxido bridged dimer containing terminally coordinated nitrite. Complexes 1-3 show excellent catecholase-like activity with 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. Kinetic measurements suggest that the rate of catechol oxidation follows saturation kinetics with respect to the substrate and first order kinetics with respect to the catalyst. Formation of bis(mu-oxo)dimanganese(III,III) as an intermediate during the course of reaction is identified from ESI-MS spectra. The characteristic six line EPR spectra of complex 2 in the presence of 3,5-DTBC supports the formation of manganese(II)-semiquinonate as an intermediate species during the catalytic oxidation of 3,5-DTBC.

A ‘Boscastle-type’ quasi-stationary convective system over the UK Southwest Peninsula

An investigation is presented of a quasi-stationary convective system (QSCS) which occurred over the UK Southwest Peninsula on 21 July 2010. This system was remarkably similar in its location and structure to one which caused devastating flash flooding in the coastal village of Boscastle, Cornwall on 16 August 2004. However, in the 2010 case rainfall accumulations were around four times smaller and no flooding was recorded. The more extreme nature of the Boscastle case is shown to be related to three factors: (1) higher rain rates, associated with a warmer and moister tropospheric column and deeper convective clouds; (2) a more stationary system, due to slower evolution of the large-scale flow; and (3) distribution of the heaviest precipitation over fewer river catchments. Overall, however, the synoptic setting of the two events was broadly similar, suggesting that such conditions favour the development of QSCSs over the Southwest Peninsula. A numerical simulation of the July 2010 event was performed using a 1.5-km grid length configuration of the Met Office Unified Model. This reveals that convection was repeatedly initiated through lifting of low-level air parcels along a quasi-stationary coastal convergence line. Sensitivity tests are used to show that this convergence line was a sea breeze front which temporarily stalled along the coastline due to the retarding influence of an offshore-directed background wind component. Several deficiencies are noted in the 1.5-km model’s representation of the storm system, including delayed convective initiation; however, significant improvements are observed when the grid length is reduced to 500 m. These result in part from an improved representation of the convergence line, which enhances the associated low-level ascent allowing air parcels to more readily reach their level of free convection. The implications of this finding for forecasting convective precipitation are discussed.

TOWARD UNDERSTANDING THE B[e] PHENOMENON. III. PROPERTIES OF THE OPTICAL COUNTERPART OF IRAS 00470+6429

FS CMa type stars are a group of Galactic objects with the B[e] phenomenon. They exhibit strong emission-line spectra and infrared excesses, which are most likely due to recently formed circumstellar dust. The group content and identification criteria were described in the first two papers of the series. In this paper we report our spectroscopic and photometric observations of the optical counterpart of IRAS 00470+6429 obtained in 2003-2008. The optical spectrum is dominated by emission lines, most of which have P Cyg type profiles. We detected significant brightness variations, which may include a regular component, and variable spectral line profiles in both shape and position. The presence of a weak Li I 6708 angstrom line in the spectrum suggests that the object is most likely a binary system with a B2-B3 spectral-type primary companion of a luminosity log L/L(circle dot) = 3.9 +/- 0.3 and a late-type secondary companion. We estimate a distance toward the object to be 2.0 +/- 0.3 kpc from the Sun.

A thermoelastic system of memory type in noncylindrical domains

In this paper, we consider a hyperbolic thermoelastic system of memory type in domains with moving boundary. The problem models vibrations of an elastic bar under thermal effects according to the heat conduction law of Gurtin and Pipkin. Global existence is proved by using the penalty method of Lions. (c) 2007 Elsevier Inc. All rights reserved.

A new tick Kunitz type inhibitor, Amblyomin-X, induces tumor cell death by modulating genes related to the cell cycle and targeting the ubiquitin-proteasome system

The aim of this study was to evaluate the anti-tumor activity of Amblyomin-X, a serine protease Kunitz-type inhibitor. Amblyomin-X induced tumor mass regression and decreased number of metastatic events in a B16F10 murine melanoma model. Alterations on expression of several genes related to cell cycle were observed when two tumor cell lines were treated with Amblyomin-X. PSMB2, which encodes a proteasome subunit, was differentially expressed, in agreement to inhibition of proteasomal activity in both cell lines. In conclusion, our results indicate that Amblyomin-X selectively acts on tumor cells by inducing apoptotic cell death, possibly by targeting the ubiquitin-proteasome system. (C) 2010 Elsevier Ltd. All rights reserved.

Voltammetric determination of L-dopa using an electrode modified with trinuclear ruthenium ammine complex (Ru-red) supported on Y-type zeolite

The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson's disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH3)(5)Ru-III-O-Ru-IV(NH3)(4)-O-Ru-III(NH3)(5)](6+) (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2 x 10(-4) and 1.0 x 10(-2) Mol l(-1) (r = 0.9988) with a detection limit of 8.5 x 10(-5) mol l(-1). The variation coefficient for a 1.0 x 10(-3) mol l(-1) L-dopa (n = 10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa. (C) 2004 Elsevier B.V. All rights reserved.

Exploring S-type orbits in the Pluto-Charon binary system

This work generates, through a sample of numerical simulations of the restricted three-body problem, diagrams of semimajor axis and eccentricity which defines stable and unstable zones for particles in S-type orbits around Pluto and Charon. Since we consider initial conditions with 0 <= e <= 0.99, we found several new stable regions. We also identified the nature of each one of these newly found stable regions. They are all associated to families of periodic orbits derived from the planar circular restricted three-body problem. We have shown that a possible eccentricity of the Pluto-Charon system slightly reduces, but does not destroy, any of the stable regions.

Insulin secretion, insulin sensitivity, and hepatic insulin extraction in first-degree relatives of type 2 diabetic patients

To identify early metabolic abnormalities in type 2 diabetes mellitus, we measured insulin secretion, sensitivity to insulin, and hepatic insulin extraction in 48 healthy normal glucose-tolerant Brazilians, first-degree relatives of type 2 diabetic patients (FH+). Each individual was matched for sex, age, weight, and body fat distribution with a person without history of type 2 diabetes (FH-). Both groups were submitted to a hyperglycemic clamp procedure (180 mg/dl). Insulin release was evaluated in its two phases. The first was calculated as the sum of plasma insulin at 2.5, 5.0, 7.5, and 10.0 min after the beginning of glucose infusion, and the second as the mean plasma insulin level in the third hour of the clamp procedure. Insulin sensitivity index (ISI) was the mean glucose infusion rate in the third hour of the clamp experiment divided by the mean plasma insulin concentration during the same period of time. Hepatic insulin extraction was determined under fasting conditions and in the third hour of the clamp procedure as the ratio between C-peptide and plasma insulin levels. FH+ individuals did not differ from FH- individuals in terms of the following parameters [median (range)]: a) first-phase insulin secretion, 174 (116-221) vs 207 (108-277) µU/ml, b) second-phase insulin secretion, 64 (41-86) vs 53 (37-83) µU/ml, and c) ISI, 14.8 (9.0-20.8) vs 16.8 (9.0-27.0) mg kg-1 min-1/µU ml-1. Hepatic insulin extraction in FH+ subjects was similar to that of FH- ones at basal conditions (median, 0.27 vs 0.27 ng/µU) and during glucose infusion (0.15 vs 0.15 ng/µU). Normal glucose-tolerant Brazilian FH+ individuals well-matched with FH- ones did not show defects of insulin secretion, insulin sensitivity, or hepatic insulin extraction as tested by hyperglycemic clamp procedures.

Central nitrergic system regulation of neuroendocrine secretion, fluid intake and blood pressure induced by angiotensin-II

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

Regulation of angiotensin type 2 receptor in bovine granulosa cells

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of adhesive system type and tooth region on the bond strength to dentin

Purpose: This study evaluated the bond strength of two etch-and-rinse adhesive systems (two- and three-step) and a self-etching system to Coronal and root canal dentin.Materials and Methods: The root canals of 30 human incisors and canines were instrumented and prepared with burs. The posts used for luting were duplicated with dual resin cement (Duo-link) inside Aestheti Plus #2 molds. Thus, three groups were formed (n = 10) according to the adhesive system employed: All-Bond 2 (TE3) + resin cement post (rcp) + Duo-link (DI); One-Step Plus (TE2) + rcp + DI; Tyrian/One-Step Plus (SE) + rcp + DI. Afterwards, 8 transverse sections (1.5 mm) were cut from 4 mm above the CEJ up to 4 mm short of the root canal apex, comprising coronal and root canal dentin. The sections were submitted to push-out testing in a universal testing machine EMIC (1 mm/min). Bond strength data were analyzed with two-way repeated measures ANOVA and Tukey's test (p < 0.05).Results: The relationship between the adhesives was not the same in the different regions (p < 0.05). Comparison of the means achieved with the adhesives in each region (Tukey; p < 0.05) revealed that TE3 (mean standard deviation: 5.22 +/- 1.70) was higher than TE2 (2.60 +/- 1.74) and SE (1.68 +/- 1.85).Conclusion: Under the experimental conditions, better bonding to dentin was achieved using the three-step etch-and-rinse system, especially in the coronal region. Therefore, the traditional etch-and-rinse three-step adhesive system seems to be the best choice for teeth needing adhesive endodontic restorations.

Behavioral and biological correlates of medicine use in type 2 diabetic patients attended by Brazilian public healthcare system

A relação entre atividade física e consumo de medicamentos não é clara. Assim, o objetivo do estudo foi investigar a relação entre nível de atividade física e uso de medicamentosem diabéticos tipo 2 atendidos pelo Sistema Único de Saúde. A amostra foi composta por 121 diabéticos do tipo 2 de ambos os sexos atendidos pelos sistema público de saúde. Gordura corporal (antropometria e bioimpedância elétrica), atividade física (Questionário de Baecke) e uso de medicamentos (15 dias prévios a avaliação) foram avaliados. Houve relação entre uso de medicamentos e sexo (r = 0.18; p = 0.045), índice de massa corporal (r = 0.22; p = 0.012), circunferência de cintura (r = 0.19; p = 0.029), percentual de gordura (r = 0.21; p = 0.016), idade (r = 0.23; p = 0.009) e atividade física (r = -0.22; p = 0.012). A regressão linear incluiu no modelo apenas idade (β = 0.718; p = 0.057), IMC BMI (β = 0.057; p = 0.022) e atividade física (β = -0.176; p = 0.044) no modelo multivariado. Conclui-se que a prática de atividade física diminui uso de medicamentos independente da idade e obesidade.