Synthesis, Photochemical, and Redox Properties of Gold(I) and Gold(III) Pincer Complexes Incorporating a 2,2′:6′,2″-Terpyridine Ligand Framework

Reaction of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) with 2,2′:6′,2″-terpyridine (terpy) leads to complex [Au(C6F5)(η1-terpy)] (1). The chemical oxidation of complex (1) with 2 equiv of [N(C6H4Br-4)3](PF6) or using electrosynthetic techniques affords the Au(III) complex [Au(C6F5)(η3-terpy)](PF6)2 (2). The X-ray diffraction study of complex 2 reveals that the terpyridine acts as tridentate chelate ligand, which leads to a slightly distorted square-planar geometry. Complex 1 displays fluorescence in the solid state at 77 K due to a metal (gold) to ligand (terpy) charge transfer transition, whereas complex 2 displays fluorescence in acetonitrile due to excimer or exciplex formation. Time-dependent density functional theory calculations match the experimental absorption spectra of the synthesized complexes. In order to further probe the frontier orbitals of both complexes and study their redox behavior, each compound was separately characterized using cyclic voltammetry. The bulk electrolysis of a solution of complex 1 was analyzed by spectroscopic methods confirming the electrochemical synthesis of complex 2

Hipertext de Psicologia i comunicació publicitària en clau ECTS

El treball, de caire interdepartamental, s'emmarca en la docència de les matèries de Psicologia en els estudis de Publicitat i Relacions Públiques, i en la docència de les matèries de Publicitat en les estudis de Psicologia.L'adaptació de la titulació de Publicitat i Relacions Públiques als ECTS ens serveix de punt de partida per a la creació d'un hipertex. L'estructura de l'hipertext especifica els coneixements que l'estudiant ha d'aprendre i les competències que desenvoluparà. L'apartat de pràctiques permet als estudiants familiaritzar-se i aplicar els continguts apresos a la pràctica professional. Els diferents exercicis d'avaluació proposats i el contingut desenvolupat ajuden a l'estudiant a realitzar un treball d'anàlisi i síntesi de la informació

The analysis of heterotaxy patients reveals new loss-of-function variants of GRK5

G protein-coupled receptor kinase 5 (GRK5) is a regulator of cardiac performance and a potential therapeutic target in heart failure in the adult. Additionally, we have previously classified GRK5 as a determinant of left-right asymmetry and proper heart development using zebrafish. We thus aimed to identify GRK5 variants of functional significance by analysing 187 individuals with laterality defects (heterotaxy) that were associated with a congenital heart defect (CHD). Using Sanger sequencing we identified two moderately frequent variants in GRK5 with minor allele frequencies <10%, and seven very rare polymorphisms with minor allele frequencies <1%, two of which are novel variants. Given their evolutionarily conserved position in zebrafish, in-depth functional characterisation of four variants (p.Q41L, p.G298S, p.R304C and p.T425M) was performed. We tested the effects of these variants on normal subcellular localisation and the ability to desensitise receptor signalling as well as their ability to correct the left-right asymmetry defect upon Grk5l knockdown in zebrafish. While p.Q41L, p.R304C and p.T425M responded normally in the first two aspects, neither p.Q41L nor p.R304C were capable of rescuing the lateralisation phenotype. The fourth variant, p.G298S was identified as a complete loss-of-function variant in all assays and provides insight into the functions of GRK5

Hypothalamic AMPK-ER Stress-JNK1 Axis Mediates the Central Actions of Thyroid Hormones on Energy Balance

Thyroid hormones (THs) act in the brain to modulate energy balance. We show that central triiodothyronine (T3) regulates de novo lipogenesis in liver and lipid oxidation in brown adipose tissue (BAT) through the parasympathetic (PSNS) and sympathetic nervous system (SNS), respectively. Central T3 promotes hepatic lipogenesis with parallel stimulation of the thermogenic program in BAT. The action of T3 depends on AMP-activated protein kinase (AMPK)-induced regulation of two signaling pathways in the ventromedial nucleus of the hypothalamus (VMH): decreased ceramide-induced endoplasmic reticulum(ER) stress, which promotes BAT thermogenesis, and increased c-Jun N-terminal kinase (JNK) activation, which controls hepatic lipid metabolism. Of note, ablation of AMPK alpha 1 in steroidogenic factor 1 (SF1) neurons of the VMH fully recapitulated the effect of central T3, pointing to this population in mediating the effect of central THs on metabolism. Overall, these findings uncover the underlying pathways through which central T3 modulates peripheral metabolism.Peer reviewe

Gender Dimorphism in Skeletal Muscle Leptin Receptors, Serum Leptin and Insulin Sensitivity

To determine if there is a gender dimorphism in the expression of leptin receptors (OB-R170, OB-R128 and OB-R98) and the protein suppressor of cytokine signaling 3 (SOCS3) in human skeletal muscle, the protein expression of OB-R, perilipin A, SOCS3 and alpha-tubulin was assessed by Western blot in muscle biopsies obtained from the m. vastus lateralis in thirty-four men (age = 27.1±6.8 yr) and thirty-three women (age = 26.7±6.7 yr). Basal serum insulin concentration and HOMA were similar in both genders. Serum leptin concentration was 3.4 times higher in women compared to men (P<0.05) and this difference remained significant after accounting for the differences in percentage of body fat or soluble leptin receptor. OB-R protein was 41% (OB-R170, P<0.05) and 163% (OB-R128, P<0.05) greater in women than men. There was no relationship between OB-R expression and the serum concentrations of leptin or 17β-estradiol. In men, muscle OB-R128 protein was inversely related to serum free testosterone. In women, OB-R98 and OB-R128 were inversely related to total serum testosterone concentration, and OB-R128 to serum free testosterone concentration. SOCS3 protein expression was similar in men and women and was not related to OB-R. In women, there was an inverse relationship between the logarithm of free testosterone and SCOS3 protein content in skeletal muscle (r = −0.46, P<0.05). In summary, there is a gender dimorphism in skeletal muscle leptin receptors expression, which can be partly explained by the influence of testosterone. SOCS3 expression in skeletal muscle is not up-regulated in women, despite very high serum leptin concentrations compared to men. The circulating form of the leptin receptor can not be used as a surrogate measure of the amount of leptin receptors expressed in skeletal muscles

The evolution of the ventilatory ratio is a prognostic factor in mechanically ventilated COVID-19 ARDS patients

Background: Mortality due to COVID-19 is high, especially in patients requiring mechanical ventilation. The purpose of the study is to investigate associations between mortality and variables measured during the first three days of mechanical ventilation in patients with COVID-19 intubated at ICU admission. Methods: Multicenter, observational, cohort study includes consecutive patients with COVID-19 admitted to 44 Spanish ICUs between February 25 and July 31, 2020, who required intubation at ICU admission and mechanical ventilation for more than three days. We collected demographic and clinical data prior to admission; information about clinical evolution at days 1 and 3 of mechanical ventilation; and outcomes. Results: Of the 2,095 patients with COVID-19 admitted to the ICU, 1,118 (53.3%) were intubated at day 1 and remained under mechanical ventilation at day three. From days 1 to 3, PaO2/FiO2 increased from 115.6 [80.0-171.2] to 180.0 [135.4-227.9] mmHg and the ventilatory ratio from 1.73 [1.33-2.25] to 1.96 [1.61-2.40]. In-hospital mortality was 38.7%. A higher increase between ICU admission and day 3 in the ventilatory ratio (OR 1.04 [CI 1.01-1.07], p = 0.030) and creatinine levels (OR 1.05 [CI 1.01-1.09], p = 0.005) and a lower increase in platelet counts (OR 0.96 [CI 0.93-1.00], p = 0.037) were independently associated with a higher risk of death. No association between mortality and the PaO2/FiO2 variation was observed (OR 0.99 [CI 0.95 to 1.02], p = 0.47). Conclusions: Higher ventilatory ratio and its increase at day 3 is associated with mortality in patients with COVID-19 receiving mechanical ventilation at ICU admission. No association was found in the PaO2/FiO2 variation

Determination of trans-Resveratrol and Other Polyphenols in Wines by a Continuous Flow Sample Clean-up System followed by Capillary Electrophoresis Separation

A new method coupling flow injection (FI) with capillary electrophoresis (CE) has been developed using diode array detection to measure the concentration of trans-resveratrol in wines, in particular because of the interest in its biological properties and cancer prevention. A FI system furnished with a C-18 minicolumn was used to clean up the wines by solid phase extraction prior to CE. The analytes were eluted from C-18 by using methanol and then driven from the FI system to the autosampler of the CE equipment by a programmable arm. The 3 detection limit ranged from 0.05 mg l-1 (trans-resveratrol) to 0.36 mg l-1 [(-)epicatechin]. The recoveries of added trans-resveratrol and other polyphenols from synthetic wines were between 92% to 110%, (mean of 99%). The method is faster and simpler than those previously reported which used liquid-liquid extraction and liquid chromatography

Study of hydroxycinnamic acids and malvidin 3-monoglucoside derivatives using capillary zone electrophoresis and ultra-performance liquid chromatography

Model solutions (pH = 3.5, 12% ethanol) of malvidin 3-O-glucoside (Mv3glc), the most common free anthocyanin in grapes and red wines from Vitis vinifera, and three free hydroxycinnamic acids present in wines (caffeic, ferulic and p-coumaric acids) were studied. The stability of the precursors and their derivatives was studied during a storage period of six months at 20 °C. Capillary zone electrophoresis with UV–vis detection (CZE/UV–vis) was used to monitor changes in sample composition. Ultra-performance liquid chromatography coupled to mass detection (UPLC/MS) was used to confirm the presence of the compounds formed. Discussion on the migration times of the new pigments as well as on their UV–vis and mass spectra is reported. Six derivatives were detected in model wine solutions containing Mv3glc and caffeic acid. The six derivatives were identified as three condensation products of caffeic acid, 4-vinylcatechol, 4-vinylsyringol and a compound with a molecular ion at m/z 803, whose structure has been tentatively assigned to a caffeic acid linked to Pinotin A. The derivatives 4-vinylphenol and 4-vinylguaiacol pyranoanthocyanins were detected in solutions containing malvidin 3-O-glucoside together with p-coumaric and ferulic acid, respectively. The malvidin 3-O-glucoside derivative, 4-vinylsyringol was also detected in all solutions containing the anthocyanin regardless of the presence of hydroxycinnamic acid.The authors thank the Consejería de Educación, Cultura y Deportes delGobierno de La Rioja for its financial support (ANGI 2004/10). MPSN thanks the INEM for her contract of employment: mujer-primer empleo and the University of La Rioja for her F.P.I. grant, as well as the MEC/FEDER for the AGL2005-02313/ALI project.Peer reviewe

Analysis of the expression of tachykinins and tachykinin receptors in the rat uterus during early pregnancy

data showed that treatment of rats with a tachykinin NK3R antagonist caused a reduction of litter size. In the present study, we analyzed the expression of tachykinins and tachykinin receptors in the rat uterus during early pregnancy. Uterine samples were obtained from early pregnant rats (Days 1-9 of pregnancy) and from nonpregnant rats during the proestrus stage of the ovarian cycle, and real-time quantitative RT-PCR, immunohistochemistry, and Western blot studies were used to investigate the pattern of expression of tachykinins and tachykinin receptors. We found that all tachykinins and tachykinin receptors were locally synthesized in the uterus of early pregnant rats. The expression of substance P, neurokinin B, and the tachykinin receptors NK1R and NK3R mRNAs and proteins underwent major changes during the days around implantation and they were widely distributed in implantation sites, being particularly abundant in decidual cells. These findings support the involvement of the tachykinin system in the series of uterine events that occur around embryo implantation in the rat.Peer reviewe

Migration order of wine anthocyanins in capillary zone electrophoresis

Capillary zone electrophoresis (CZE) is an advantageous alternative to liquid chromatography (LC) in the analysis of wine anthocyanins in terms of separation efficiency, analysis time and reagent consumption. Thirteen wine anthocyanins of a Tannat wine, including acylated and non-acylated anthocyanin monoglucosides, pyranoanthocyanins and flavanol derivates, were separated using a 46 cm × 75 m (i.d.) fused-silica capillary and a 50 mM sodium tetraborate buffer of pH 8.4 with 15% (v/v) methanol as modifier. Some of the pigments were isolated by LC fractionation and concentrated by lyophilisation. The reconstituted fractions were analysed by CZE in order to identify the compounds in the electrophoregram and to determine their migration times. The migration order found for the wine anthocyanins is discussed taking into account the molecular charge and mass, and the possibility of complex formation with tetraborate molecules. © 2004 Elsevier B.V. All rights reserved