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

Cajal, the neuronal theory and the idea of brain plasticity

This paper reviews the importance of Cajal’s neuronal theory (the Neuron Doctrine) and the origin and importance of the idea of brain plasticity that emerges from this theory. We first comment on the main Cajal’s discoveries that gave rise and confirmed his Neuron Doctrine: the improvement of staining techniques, his approach to morphological laws, the concepts of dynamic polarisation, neurogenesis and neurotrophic theory, his first discoveries of the nerve cell as an independent cell, his research on degeneration and regeneration and his fight against reticularism. Second, we review Cajal’s ideas on brain plasticity and the years in which they were published, to finally focus on the debate on the origin of the term plasticity and its conceptual meaning, and the originality of Cajal’s proposal compared to those of other authors of the time

Does posterior capsule opacification affect the results of diagnostic technologies to evaluate the retina and the optic disc?

The visual outcome obtained after cataract removal may progressively decline because of posterior capsular opacification (PCO). This condition can be treated by creating an opening in the posterior lens capsule by Nd:YAG laser capsulotomy. PCO optical imperfections cause several light reflection, refraction, and diffraction phenomena, which may interfere with the functional and structural tests performed in different ocular locations for the diagnosis and follow-up of ocular disease, like macular and optic nerve diseases. Some parameters measured by visual field examinations, scanning laser polarimetry, and optical coherence tomography (OCT) have changed after PCO removal. Imaging quality also changes following capsulotomy. Consequently, the results of ancillary tests in pseudophakic eyes for studying ocular diseases like glaucoma or maculopathies should be correlated with other clinical examinations, for example, slit-lamp biomicroscopy or funduscopy. If PCO is clinically significant, a new baseline should be set for future comparisons following capsulotomy when using automated perimetry and scanning laser polarimetry. To perform OCT in the presence of PCO, reliable examinations (considering signal strength) apparently guarantee that measurements are not influenced by PCO

Autonomic management of a building's multi-HVAC system start-up

Most studies about the control, automation, optimization and supervision of building HVAC systems concentrate on the steady-state regime, i.e., when the equipment is already working at its setpoints. The originality of the current work consists of proposing the optimization of building multi-HVAC systems from start-up until they reach the setpoint, making the transition to steady state-based strategies smooth. The proposed approach works on the transient regime of multi-HVAC systems optimizing contradictory objectives, such as the desired comfort and energy costs, based on the "Autonomic Cycle of Data Analysis Tasks" concept. In this case, the autonomic cycle is composed of two data analysis tasks: one for determining if the system is going towards the defined operational setpoint, and if that is not the case, another task for reconfiguring the operational mode of the multi-HVAC system to redirect it. The first task uses machine learning techniques to build detection and prediction models, and the second task defines a reconfiguration model using multiobjective evolutionary algorithms. This proposal is proven in a real case study that characterizes a particular multi-HVAC system and its operational setpoints. The performance obtained from the experiments in diverse situations is impressive since there is a high level of conformity for the multi-HVAC system to reach the setpoint and deliver the operation to the steady-state smoothly, avoiding overshooting and other non-desirable transitional effects.European CommissionJunta de Comunidades de Castilla-La ManchaMinisterio de Ciencia e Innovació

Whole transcription profile of responders to anti-tnf drugs in pediatric inflammatory bowel disease

Background: Up to 30% of patients with pediatric inflammatory bowel disease (IBD) do not respond to anti-Tumor Necrosis Factor (anti-TNF) therapy. The aim of this study was to identify pharmacogenomic markers that predict early response to anti-TNF drugs in pediatric patients with IBD. Methods: An observational, longitudinal, prospective cohort study was conducted. The study population comprised 38 patients with IBD aged 0.6 or <−0.6 and p value < 0.05). After validation, FCGR1A, FCGR1B, and GBP1 were overexpressed in non-responders two weeks after initiation of anti-TNF treatment (Log2FC 1.05, 1.21, and 1.08, respectively, p value < 0.05). Conclusion: Expression of the FCGR1A, FCGR1B, and GBP1 genes is a pharmacogenomic biomarker of early response to anti-TNF agents in pediatric IBDInstituto de Salud Carlos III número de becas PI16 / 00559 y PI19 / 00792Consejería de Educación y Deporte de la Comunidad de Madrid PEJ16 / MED / AI-1260Instituto de Investigaciones Sanitarias Gregorio Marañón PRE2018-2Fondos Europeos de Desarrollo Regional (FEDER) del Comisión Europe

Geochemical influence of soil on leaf and grape (Vitis vinifera L. 'Cencibel') composition in La Mancha region (Spain)

The main purpose of the study was to evaluate major and trace elements contained in topsoil from representative plots of vineyards located in La Mancha, Spain, to obtain an elemental fingerprint of vines. The samples evaluated were obtained from topsoil in six different plots, belonging to the region of La Mancha, characterized by the cultivation of vineyards (near 189.127 ha). Twenty different vines from each plot were chosen to take samples from grapes, petioles and leaves. Analyses were carried out by X-ray Fluorescence applied on soils and dried vegetal matter. Biological Absorption Coefficient (BAC) was calculated to assess the uptake of minerals by vines as a function of their specific content in soil. The BAC in leaves and grapes was very similar for all studied elements. High contents of Ca, Sr, Ni and rare earth elements (La, Ce and Nd) were found along with low contents in Al, Zr, Ba, Cu, Zn and Pb, and normal contents in the rest of the elements. BAC in grapes was lower for the majority of the studied elements but it is interesting to underline the contents of Cs, K, Nb, Ce, Zn and Sr as possible markers of soil fingerprinting in the resulting wines.

Using radio astronomical receivers for molecular spectroscopic characterization in astrochemical laboratory simulations: A proof of concept

We present a proof of concept on the coupling of radio astronomical receivers and spectrometers with chemical reactorsand the performances of the resulting setup for spectroscopy and chemical simulations in laboratory astrophysics. Several experiments including cold plasma generation and UV photochemistry were performed in a 40\,cm long gas cell placed in the beam path of the Aries 40\,m radio telescope receivers operating in the 41-49 GHz frequency range interfaced with fast Fourier transform spectrometers providing 2 GHz bandwidth and 38 kHz resolution. The impedance matching of the cell windows has been studied using different materials. The choice of the material and its thickness was critical to obtain a sensitivity identical to that of standard radio astronomical observations. Spectroscopic signals arising from very low partial pressures of CH3OH, CH3CH2OH, HCOOH, OCS,CS, SO2 (<1E-03 mbar) were detected in a few seconds. Fast data acquisition was achieved allowing for kinetic measurements in fragmentation experiments using electron impact or UV irradiation. Time evolution of chemical reactions involving OCS, O2 and CS2 was also observed demonstrating that reactive species, such as CS, can be maintained with high abundance in the gas phase during these experiments.Comment: Accepted for publication in Astronomy and Astrophysics in September 21, 2017. 16 pages, 18 figure

Association between canine leishmaniosis and Ehrlichia canis co-infection: a prospective case-control study

Abstract Background In the Mediterranean basin, Leishmania infantum is a major cause of disease in dogs, which are frequently co-infected with other vector-borne pathogens (VBP). However, the associations between dogs with clinical leishmaniosis (ClinL) and VBP co-infections have not been studied. We assessed the risk of VBP infections in dogs with ClinL and healthy controls. Methods We conducted a prospective case-control study of dogs with ClinL (positive qPCR and ELISA antibody for L. infantum on peripheral blood) and clinically healthy, ideally breed-, sex- and age-matched, control dogs (negative qPCR and ELISA antibody for L. infantum on peripheral blood) from Paphos, Cyprus. We obtained demographic data and all dogs underwent PCR on EDTA-blood extracted DNA for haemoplasma species, Ehrlichia/Anaplasma spp., Babesia spp., and Hepatozoon spp., with DNA sequencing to identify infecting species. We used logistic regression analysis and structural equation modelling (SEM) to evaluate the risk of VBP infections between ClinL cases and controls. Results From the 50 enrolled dogs with ClinL, DNA was detected in 24 (48%) for Hepatozoon spp., 14 (28%) for Mycoplasma haemocanis, 6 (12%) for Ehrlichia canis and 2 (4%) for Anaplasma platys. In the 92 enrolled control dogs, DNA was detected in 41 (45%) for Hepatozoon spp., 18 (20%) for M. haemocanis, 1 (1%) for E. canis and 3 (3%) for A. platys. No Babesia spp. or “Candidatus Mycoplasma haematoparvum” DNA was detected in any dog. No statistical differences were found between the ClinL and controls regarding age, sex, breed, lifestyle and use of ectoparasitic prevention. A significant association between ClinL and E. canis infection (OR = 12.4, 95% CI: 1.5–106.0, P = 0.022) was found compared to controls by multivariate logistic regression. This association was confirmed using SEM, which further identified that younger dogs were more likely to be infected with each of Hepatozoon spp. and M. haemocanis, and dogs with Hepatozoon spp. were more likely to be co-infected with M. haemocanis. Conclusions Dogs with ClinL are at a higher risk of co-infection with E. canis than clinically healthy dogs. We recommend that dogs diagnosed with ClinL should be tested for E. canis co-infection using PCR

Transcription of toll-like receptors 2, 3, 4 and 9, FoxP3 and Th17 cytokines in a susceptible experimental model of canine Leishmania infantum infection

Canine leishmaniosis (CanL) due to Leishmania infantum is a chronic zoonotic systemic disease resulting from complex interactions between protozoa and the canine immune system. Toll-like receptors (TLRs) are essential components of the innate immune system and facilitate the early detection of many infections. However, the role of TLRs in CanL remains unknown and information describing TLR transcription during infection is extremely scarce. The aim of this research project was to investigate the impact of L. infantum infection on canine TLR transcription using a susceptible model. The objectives of this study were to evaluate transcription of TLRs 2, 3, 4 and 9 by means of quantitative reverse transcription polymerase chain reaction (qRT-PCR) in skin, spleen, lymph node and liver in the presence or absence of experimental L. infantum infection in Beagle dogs. These findings were compared with clinical and serological data, parasite densities in infected tissues and transcription of IL-17, IL-22 and FoxP3 in different tissues in non-infected dogs (n = 10), and at six months (n = 24) and 15 months (n = 7) post infection. Results revealed significant down regulation of transcription with disease progression in lymph node samples for TLR3, TLR4, TLR9, IL-17, IL-22 and FoxP3. In spleen samples, significant down regulation of transcription was seen in TLR4 and IL-22 when both infected groups were compared with controls. In liver samples, down regulation of transcription was evident with disease progression for IL-22. In the skin, upregulation was seen only for TLR9 and FoxP3 in the early stages of infection. Subtle changes or down regulation in TLR transcription, Th17 cytokines and FoxP3 are indicative of the silent establishment of infection that Leishmania is renowned for. These observations provide new insights about TLR transcription, Th17 cytokines and Foxp3 in the liver, spleen, lymph node and skin in CanL and highlight possible markers of disease susceptibility in this model