Synthesis, structure, and photophysical properties of platinum(II) (N, C, N) pincer complexes derived from purine nucleobases

The synthesis of a series of Pt{κ3-N,C,N′-[L]}X (X = Cl, RC≡C) pincer complexes derived from purine and purine nucleosides is reported. In these complexes, the 6-phenylpurine skeleton provides the N,C-cyclometalated fragment, whereas an amine, imine, or pyridine substituent of the phenyl ring supplies the additional N′-coordination point to the pincer complex. The purine N,C-fragment has two coordination positions with the metal (N1 and N7), but the formation of the platinum complexes is totally regioselective. Coordination through the N7 position leads to the thermodynamically favored [6.5]-Pt{κ3-N7,C,N′-[L]}X complexes. However, the coordination through the N1 position is preferred by the amino derivatives, leading to the isomeric kinetic [5.5]-Pt{κ3-N1,C,N′-[L]}X complexes. Extension of the reported methodology to complexes having both pincer and acetylide ligands derived from nucleosides allows the preparation of novel heteroleptic bis-nucleoside compounds that could be regarded as organometallic models of Pt-induced interstrand cross-link. Complexes having amine or pyridine arms are green phosphorescence emitters upon photoexcitation at low concentrations in CH2Cl2 solution and in poly(methyl methacrylate) (PMMA) films. They undergo self-quenching at high concentrations due to molecular aggregation. The presence of intermolecular π–π stacking and weak Pt···Pt interactions was also observed in the solid state by X-ray diffraction analysis

Vacuum Energy and Renormalization on the Edge

The vacuum dependence on boundary conditions in quantum field theories is analysed from a very general viewpoint. From this perspective the renormalization prescriptions not only imply the renormalization of the couplings of the theory in the bulk but also the appearance of a flow in the space of boundary conditions. For regular boundaries this flow has a large variety of fixed points and no cyclic orbit. The family of fixed points includes Neumann and Dirichlet boundary conditions. In one-dimensional field theories pseudoperiodic and quasiperiodic boundary conditions are also RG fixed points. Under these conditions massless bosonic free field theories are conformally invariant. Among all fixed points only Neumann boundary conditions are infrared stable fixed points. All other conformal invariant boundary conditions become unstable under some relevant perturbations. In finite volumes we analyse the dependence of the vacuum energy along the trajectories of the renormalization group flow providing an interesting framework for dark energy evolution. On the contrary, the renormalization group flow on the boundary does not affect the leading behaviour of the entanglement entropy of the vacuum in one-dimensional conformally invariant bosonic theories.Comment: 10 pages, 1 eps figur

Evaluation of contingency plans in the care of patients in intensive care units in the COVID-19 pandemic

La expansión de las áreas de cuidados de intensivos ha sido una de las medidas más significativas en esa obligada adaptación a la evolución de las distintas fases de la pandemia por la COVID-19. El objetivo es evaluar el despliegue de los planes de contingencia en la atención a pacientes ingresados en Unidades de Cuidados Intensivos (UCI) durante el periodo del 19 de marzo al 20 de abril de 2020, en un hospital público, referencia para 300.000 habitantes, perteneciente al Servicio Galego de Saúde.Axencia Galega de Innovación (GAIN, Xunta de Galicia), cofinanciado con fondos FEDER (Unión Europea, «Una manera de hacer Europa» | Ref. IN845D-2020/0

Liver injury in non-alcoholic fatty liver disease is associated with urea cycle enzyme dysregulation

The main aim was to evaluate changes in urea cycle enzymes in NAFLD patients and in two preclinical animal models mimicking this entity. Seventeen liver specimens from NAFLD patients were included for immunohistochemistry and gene expression analyses. Three-hundred-and-eighty-two biopsy-proven NAFLD patients were genotyped for rs1047891, a functional variant located in carbamoyl phosphate synthetase-1 (CPS1) gene. Two preclinical models were employed to analyse CPS1 by immunohistochemistry, a choline deficient high-fat diet model (CDA-HFD) and a high fat diet LDLr knockout model (LDLr −/−). A significant downregulation in mRNA was observed in CPS1 and ornithine transcarbamylase (OTC1) in simple steatosis and NASH-fibrosis patients versus controls. Further, age, obesity (BMI > 30 kg/m2), diabetes mellitus and ALT werefound to be risk factors whereas A-allele from CPS1 was a protective factor from liver fibrosis. CPS1 hepatic expression was diminished in parallel with the increase of fibrosis, and its levels reverted up to normality after changing diet in CDA-HFD mice. In conclusion, liver fibrosis and steatosis were associated with a reduction in both gene and protein expression patterns of mitochondrial urea cycle enzymes. A-allele from a variant on CPS1 may protect from fibrosis development. CPS1 expression is restored in a preclinical model when the main trigger of the liver damage disappears

The Rise and Fall of "Respectable" Spanish Liberalism, 1808-1923: An Explanatory Framework

The article focuses on the reasons behind both the consolidation of what I have termed “respectable” liberalism between the 1830s and the 1840s and its subsequent decline and fall between 1900 and 1923. In understanding both processes I study the links established between “respectable” liberals and propertied elites, the monarchy, and the Church. In the first phase these links served to consolidate the liberal polity. However, they also meant that many tenets of liberal ideology were compromised. Free elections were undermined by the operation of caciquismo, monarchs established a powerful position, and despite the Church hierarchy working with liberalism, the doctrine espoused by much of the Church was still shaped by the Counter-Reformation. Hence, “respectable” liberalism failed to achieve a popular social base. And the liberal order was increasingly denigrated as part of the corrupt “oligarchy” that ruled Spain. Worse still, between 1916 and 1923 the Church, monarch, and the propertied elite increasingly abandoned the liberal Monarchist Restoration. Hence when General Primo de Rivera launched his coup the rug was pulled from under the liberals’ feet and there was no one to cushion the fall