Thermal investigation and infrared evolved gas analysis of solid trivalent lanthanide and yttrium alpha-hydroxyisobutyrates in N-2 and CO2 atmospheres

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

Values of 13,14-Dihydro-15-Keto-PGF(2 alpha), Progesterone and Oestradiol After Injection of Prostaglandin at Different Periods of Buffalo Puerperium

Knowledge of the effectiveness of prostaglandins in uterine involution process led to the development of protocols with its analogues in postpartum period. However, this hormone mechanism of action is not yet fully elucidated. Thus, the objective of this study was to verify if chloprostenol administration, at early or intermediary puerperium, can induce changes on progesterone, PGFM and oestradiol plasma concentrations. 30 Murrah postpartum buffaloes were randomly divided into three groups: CONT (saline, n = 10); CLO2 (chloprostenol at days 2 and 5 postpartum, n = 10) and; CLO15 (chloprostenol at days 15 and 20 postpartum, n = 10). Blood samples were collected from jugular vein to measure progesterone, PGFM and oestradiol plasma concentrations at days 2, 7, 14, 21 and 28 postpartum. CLO2 group presented lower progesterone and PGFM plasma concentrations in relation to CONT and CLO15 groups (0.23 +/- 0.00 and 0.32 +/- 0.11, 0.19 +/- 0.00 and 0.23 +/- 0.11, 0.23 +/- 0.00 and 0.30 +/- 0.19, for groups CONT, CLO2 and CLO15, respectively; P < 0.05). There was no significant difference in oestradiol plasma concentration between experimental groups (P > 0.05). Prostaglandin synthetic analogue administration induced hormonal changes in postpartum buffaloes, which can partially explain its positive effect under reproductive function of this specie.

Temporal analysis of prostaglandin F2 alpha receptor, caspase 3, and cyclooxygenase 2 messenger RNA expression and prostaglandin F2 alpha receptor and cyclooxygenase 2 protein expression in endometrial tissue from multiparous Nelore (Bos taurus indicus) cows treated with cloprostenol sodium during puerperium

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

Effect of adding a gonadotropin-releasing-hormone treatment at the beginning and a second prostaglandin F-2 alpha treatment at the end of an estradiol-based protocol for timed artificial insemination in lactating dairy cows during cool or hot seasons of the year

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

Induction of luteolysis in mares utilizing a micro-dose of prostaglandin F-2 alpha in the sacral lumbar space

An experiment was conducted to examine the luteolytic effectiveness of using low or micro doses of PGF2α when administered at the BAI HUI acupuncture point, which is frequently used to treat ovarian disturbances in veterinary acupuncture. The results indicate that PGF2α given at a very low micro dose of 0.5 mg (one tenth the conventional recommended dose) administered at the BAI HUI acupuncture point located at the sacral lumbar space is equally effective at inducing luteolysis in mid-luteal phase mares as conventional PGF2α i.m. treatment using a tenfold higher dose. Therefore, based on the results of the present study, we suggest that the BAI HUI sacrai lumbar route somehow provides an extremely efficient pathway for the drug to the ovarian level.

Preliminary X-ray crystallographic studies of a Lys49-phospholipase A(2) homologue from Bothrops pirajai venom complexed with p-bromophenacyl bromide and alpha-tocopherol inhibitors

PrTX-I, a non-catalytic and myotoxic Lys49-PLA(2) from Bothrops pirajai venom has been crystallized alone and in complex with bromophenacyl bromide (BPB), alpha-tocopherol and alpha-tocopherol acetate inhibitors. These crystals have shown to diffract X-rays between 2.34 and 1.65 angstrom resolution. All complexes crystals are isomorphous and belong to the space group P2(1) whereas native PrTX-I crystals belong to the P3(1)21.

Highly stabilized alpha-NiCo(OH)(2) nanomaterials for high performance device application

Improving the charge capacity, electrochemical reversibility and stability of anode materials are main challenges for the development of Ni-based rechargeable batteries and devices. The combination of cobalt, as additive, and electrode material nanostructuration revealed a very promising approach for this purpose. The new alpha-NiCo mixed hydroxide based electrodes exhibited high specific charge/discharge capacity (355-714 C g(-1)) and outstanding structural stability, withstanding up to 700 redox cycles without any significant phase transformation, as confirmed by cyclic voltammetry, electrochemical quartz crystal microbalance and X-ray diffractometry. In short, the nanostructured alpha-NiCo mixed hydroxide materials possess superior electrochemical properties and stability, being strong candidates for application in high performance batteries and devices. (C) 2012 Elsevier B.V. All rights reserved.

Creatine-induced glucose uptake in type 2 diabetes: a role for AMPK-alpha?

This study focused on understanding the signaling mechanisms leading to GLUT-4 translocation and increased skeletal-muscle glucose uptake that follow creatine (Cr) supplementation in type 2 diabetes (n = 10). AMPK-alpha protein content presented a tendency to be higher (p = 0.06) after Cr supplementation (5 g/d for 12w). The changes in AMPK-alpha protein content significantly related (p < 0.001) to the changes in GLUT-4 translocation (r = 0.78) and Hb1Ac levels (r = -0.68), suggesting that AMPK signaling may be implicated in the effects of supplementation on glucose uptake in type 2 diabetes.

DSD Due to 5 alpha-Reductase 2 Deficiency - from Diagnosis to Long Term Outcome

Most of the patients with 5 alpha-RD 2 deficiency are reared in the female social sex due to their severely undervirilized external genitalia but similar to 60% who have not been submitted to orchiectomy in childhood undergo male social sex change at puberty. In our cohort of 30 cases from 18 families, all subjects were registered in the female social sex except for two children-one who had an affected uncle and the other who was diagnosed before being registered. The majority of the patients were satisfied with the long-term results of their treatment and surprisingly, penile length was not associated with satisfactory or unsatisfactory sexual activity. Steroid 5 alpha-RD2 deficiency should be included in the differential diagnosis of all newborns with 46,XY DSD with normal testosterone production before gender assignment or any surgical intervention because these patients should be considered males at birth.

Toll-like receptor 2/MyD88 signaling mediates zymosan-induced joint hypernociception in mice: Participation of TNF-alpha, IL-1 beta and CXCL1/KC

Arthritic pain is a serious health problem that affects a large number of patients. Toll-like receptors (TLRs) activation within the joints has been implicated in pathophysiology of arthritis. However, their role in the genesis of arthritic pain needs to be demonstrated. In the present study, it was addressed the participation of TLR2 and TLR4 and their adaptor molecule MyD88 in the genesis of joint hypernociception (a decrease in the nociceptive threshold) during zymosan-induced arthritis. Zymosan injected in the tibio-tarsal joint induced mechanical hypernociception in C57BL/6 wild type mice that was reduced in TLR2 and MyD88 null mice. On the other hand, zymosan-induced hypernociception was similar in C3H/HePas and C3H/Hej mice (TLR4 mutant mice). Zymosan-induced joint hypernociception was also reduced in TNFR1 null mice and in mice treated with IL-1 receptor antagonist or with an antagonist of CXCR1/2. Moreover, the joint production of TNF-alpha, IL-1 beta and CXCL1/KC by zymosan was dependent on TLR2/MyD88 signaling. Investigating the mechanisms by which TNF-alpha, IL-1 beta and CXCL1/KC mediate joint hypernociception, joint administration of these cytokines produced mechanical hypernociception, and they act in an interdependent manner. In last instance, their hypernociceptive effects were dependent on the production of hypernociceptive mediators, prostaglandins and sympathetic amines. These results indicate that in zymosan-induced experimental arthritis, TLR2/MyD88 is involved in the cascade of events of joint hypernociception through a mechanism dependent on cytokines and chemokines production. Thus, TLR2/MyD88 signaling might be a target for the development of novel drugs to control pain in arthritis. (C) 2011 Elsevier B.V. All rights reserved.

Magnetic properties of selected 3d- and 4f-systems on alpha-Al 2 O 3 substrates

In this work the growth and the magnetic properties of the transition metals molybdenum, niobium, and iron and of the highly-magnetostrictive C15 Laves phases of the RFe2 compounds (R: Rare earth metals: here Tb, Dy, and Tb{0.3}Dy{0.7} deposited on alpha-Al2O3 (sapphire) substrates are analyzed. Next to (11-20) (a-plane) oriented sapphire substrates mainly (10-10) (m-plane) oriented substrates were used. These show a pronounced facetting after high temperature annealing in air. Atomic force microscopy (AFM) measurements reveal a dependence of the height, width, and angle of the facets with the annealing temperature. The observed deviations of the facet angles with respect to the theoretical values of the sapphire (10-1-2) and (10-11) surfaces are explained by cross section high resolution transmission electron microscopy (HR-TEM) measurements. These show the plain formation of the (10-11) surface while the second, energy reduced (10-1-2) facet has a curved shape given by atomic steps of (10-1-2) layers and is formed completely solely at the facet ridges and valleys. Thin films of Mo and Nb, respectively, deposited by means of molecular beam epitaxy (MBE) reveal a non-twinned, (211)-oriented epitaxial growth as well on non-faceted as on faceted sapphire m-plane, as was shown by X-Ray and TEM evaluations. In the case of faceted sapphire the two bcc crystals overgrow the facets homogeneously. Here, the bcc (111) surface is nearly parallel to the sapphire (10-11) facet and the Mo/Nb (100) surface is nearly parallel to the sapphire (10-1-2) surface. (211)-oriented Nb templates on sapphire m-plane can be used for the non-twinned, (211)-oriented growth of RFe2 films by means of MBE. Again, the quality of the RFe2 films grown on faceted sapphire is almost equal to films on the non-faceted substrate. For comparison thin RFe2 films of the established (110) and (111) orientation were prepared. Magnetic and magnetoelastic measurements performed in a self designed setup reveal a high quality of the samples. No difference between samples with undulated and flat morphology can be observed. In addition to the preparation of covering, undulating thin films on faceted sapphire m-plane nanoscopic structures of Nb and Fe were prepared by shallow incidence MBE. The formation of the nanostructures can be explained by a shadowing of the atomic beam due to the facets in addition to de-wetting effects of the metals on the heated sapphire surface. Accordingly, the nanostructures form at the facet ridges and overgrow them. The morphology of the structures can be varied by deposition conditions as was shown for Fe. The shape of the structures vary from pearl-necklet strung spherical nanodots with a diameter of a few 10 nm to oval nanodots of a few 100 nm length to continuous nanowires. Magnetization measurements reveal uniaxial magnetic anisotropy with the easy axis of magnetization parallel to the facet ridges. The shape of the hysteresis is depending on the morphology of the structures. The magnetization reversal processes of the spherical and oval nanodots were simulated by micromagnetic modelling and can be explained by the formation of magnetic vortices.

1,2-Additionen deprotonierter Alpha-Aminonitrile: Umgepolte Imine als vielseitige Synthesebausteine

Von aromatischen Aldehyden abgeleitete α-Aminonitrile können ohne die Anwendung von Schutzgruppen in α-Position deprotoniert werden, wenn keine lithiumhaltigen Basen verwendet werden. Ziel der vorliegenden Arbeit war es, die Reaktionen deprotonierter α-Aminonitrile mit Elektrophilen zu untersuchen. Die Addition von α-Aminocarbanionen an Imine führt unter intramolekularer Eliminierung von HCN zu Endiaminen, die sich in einer Eintopfsynthese abhängig von der Aufarbeitung in 1,2-Diamine oder 1,2-Diimine umwandeln lassen. Die nach Oxidation durch Luftsauerstoff erhaltenen Diimine können mit dem Reduktionsmittel BH3·THF diastereoselektiv reduziert werden. Es hat sich hier gezeigt, dass durch Zugabe einer katalytischen Menge an NaBH4 hauptsächlich die syn-Diamine erhalten werden, der Zusatz von Phthalsäure wiederum liefert bevorzugt die anti-Produkte. In beiden Fällen wird das Produkt in quantitativer Ausbeute erhalten. So konnte also eine effektive diastereoselektive Reduktionsmethode entwickelt werden, die eine freie Wahl der syn- oder anti-Konfiguration ermöglicht. Um enantiomerenreine 1,2-Diamine zu erhalten, wurden verschiedene Methoden getestet. Sowohl auxiliargesteuerte Synthesen mit einem N-Glycosyl-Aminonitril oder mit chiralen Sulfinyliminen als auch die Reduktion durch chirale Borverbindungen (CBS-Katalysatoren, Triacyloxyborhydrid oder Diisopinocamphenylboran), Transferhydrierungen mit chiralen Difluortitanocen-, Noyori- oder Organophosphat-Katalysatoren sowie enantioselektive Hydrierungen mit chiralen Übergangsmetall-katalysatoren waren jedoch nicht erfolgreich. Die Umsetzung der 1,2-Diimine mit Chlormethylethern oder -estern liefert die entsprechenden unsymmetrischen Imidazoliumsalze. Diese konnten zu N-heterocyclischen Carbenen deprotoniert und erfolgreich als Liganden in Suzuki- und Heck-Reaktionen eingesetzt werden. Durch die 1,2-Addition α-deprotonierter Streckerprodukte und anschließende Reduktion im Eintopfverfahren konnten 1,2-Aminoalkohole in mäßigen bis guten Ausbeuten dargestellt werden. Die Umsetzung von α-Aminocarbanionen mit N-Acyliminen erlaubt zudem die Synthese tetrasubstituierter Imidazole und trisubstituierter Oxazole in drei beziehungsweise vier Stufen: Die zunächst gebildeten α-Amino-α-acylaminopropionitrile können isoliert und in Gegenwart von Base einer Retro-Strecker-Reaktion unterworfen werden. Abhängig vom Substitutionsmuster schließt sich in manchen Fällen nach der Eliminierung von HCN direkt die Cyclisierung zum Imidazol an. Nicht cyclisierte Intermediate lassen sich durch Dehydratisierung mit PCl5 zu Imidazolen umsetzen, aber auch unter sauren Bedingungen zu α-Acylaminoketonen hydrolysieren, welche wiederum durch Einwirkung von PCl5 in Oxazole überführt werden können. Auf diese Weise wurden Imidazole und Oxazole in moderaten bis hohen Gesamtausbeuten hergestellt.

Protein kinase C alpha-dependent phosphorylation of the mRNA-stabilizing factor HuR: implications for posttranscriptional regulation of cyclooxygenase-2

In this study, we investigated the molecular mechanisms underlying the ATP analogue adenosine-5'-O-(3-thio)triphosphate-induced nucleocytoplasmic shuttling of the mRNA stabilizing factor HuR in human (h) mesangial cells (MC). Using synthetic protein kinase C (PKC) inhibitors and small interfering RNA approaches, we demonstrated that knockdown of PKC alpha efficiently blocked the ATP-dependent nuclear HuR export to the cytoplasm. The functional importance of PKC alpha in HuR shuttling is highlighted by the high cytosolic HuR content detected in hMC stably overexpressing PKC alpha compared with mock-transfected cells. The ATP-induced recruitment of HuR to the cytoplasm is preceded by a direct interaction of PKC alpha with nuclear HuR and accompanied by increased Ser phosphorylation as demonstrated by coimmunoprecipitation experiments. Mapping of putative PKC target sites identified serines 158 and 221 as being indispensable for HuR phosphorylation by PKC alpha. RNA pull-down assay and RNA electrophoretic mobility shift assay demonstrated that the HuR shuttling by ATP is accompanied by an increased HuR binding to cyclooxygenase (COX)-2 mRNA. Physiologically, the ATP-dependent increase in RNA binding is linked with an augmentation in COX-2 mRNA stability and subsequent increase in prostaglandin E(2) synthesis. Regulation of HuR via PKC alpha-dependent phosphorylation emphasizes the importance of posttranslational modification for stimulus-dependent HuR shuttling.