Immobilization of Pyrene-Tagged Palladium and Ruthenium Complexes onto Reduced Graphene Oxide: An Efficient and Highly Recyclable Catalyst for Hydrodefluorinatio

The co-immobilization of palladium and ruthenium complexes with pyrene-tagged Nheterocyclic carbene ligands onto reduced grahene oxide allows the formation of a highly efficient catalyst for the hydrodefluorination of a series of fluoroarenes. This procedure constitutes an easy one-pot preparation of materials with homogeneously distributed polymetallic catalysts. The catalytic system can be recycled for up to twelve times without measurable loss of activity. The activity of the catalyst is attributed to the synergistic action of the two metals.Ministerio de Ciencia e Innovación of Spain (CTQ2011- 24055/BQU)

Enhancement of gold catalytic activity and stability by immobilization on the surface of graphene

The catalytic performance of gold complexes is evaluated at the molecular level and when supported onto reduced graphene oxide (rGO). Gold complexes of general formula [(NHC)AuX] catalyse the synthesis of indoles via intramolecular hydroamination reaction of alkynes. The catalytic properties of the molecular gold complexes are highly improved when supported onto graphene. Faster reaction rates and higher catalyst stability are observed for the immobilized gold complexes. The use of graphene as support of molecular complexes has a positive benefit in the catalytic gold properties in terms of activity and stabilityThe authors thank the financial support from MINECO (CTQ2015-69153-C2-2-R), Generalitat Valenciana (AICO/2015/039) and Universitat Jaume I (P1.1B2015-09). D. V-E thanks MINECO for a FPU grant (FPU15/03011

Catalytic applications of magnetic nanoparticles functionalized using iridium N-heterocyclic carbene complexes

synthetic modular methodology allows the preparation of catalytic materials based on magnetic nanoparticles with iridium N-heterocyclic carbene (NHC) complexes. Imidazolium salts containing a ketone/aldehyde as a pendant functional group are the key species prepared. The condensation reaction of the Cp*IrNHC–CHO compound with magnetic nanoparticles containing amine groups on the surface yields the covalent anchoring of the iridium complex to the surface of the magnetite. The catalytic properties have been evaluated in transfer hydrogenation. The iridium complexes and the material are active in the reduction of ketones using isopropanol as the solvent and hydrogen donor. The catalytic results reveal that the catalytic activity of the material and the molecular complex are equivalent. We have not observed any change in activity due to the support. The recyclability properties of the magnetic material have been evaluated. The results show that the catalyst activity is maintained for two runs. This work describes a simple methodology for anchoring molecular complexes on the surface of magnetic nanoparticles.We thank the financial support from the Ministerio de Cienciave Innovación of Spain (CTQ2011-24055/BQU). We thank the ‘Generalitat Valenciana’ for a fellowship (S. Sabater). The authors are grateful to the ‘Serveis Centrals d’Instrumentació Científica (SCIC)’ of the Universitat Jaume I

Identifying masked uncontrolled hypertension in the community pharmacy setting

© 2015 Wolters Kluwer Health, Inc. Masked uncontrolled hypertension (MUCH) is associated with an increased cardiovascular risk. This condition is frequent in the community pharmacy (i.e., CP-MUCH), but there is no evidence on the factors associated with its presence in that setting. The aim of this analysis was to explore these factors. A sample of 98 treated hypertensive patients from the MEPAFAR study, with normal community pharmacy blood pressure (CPBP <135/85 mmHg), were analyzed. Blood pressure (BP) was also measured at home (4 days) and monitored for 24 h. CP-MUCH was identified when either ambulatory (daytime) or home BP averages were equal to or higher than 135/85 mmHg. A multivariate logistic regression analysis was carried out to identify the factors associated with CP-MUCH. The prevalence of CP-MUCH tends to be higher as systolic and diastolic CPBP increase, reaching 47% in patients with both systolicand diastolic CPBP equal to or higher than 123 mmHg and 79 mmHg, respectively.The multivariate regression analysis showed only systolic CPBP as an independent factor of CP-MUCH [≥123 mmHg: odds ratio=16.46 (P=0.012); from 115 to 122.9 mmHg: odds ratio=10.74 (P=0.036); systolic CPBP <115 mmHg as the reference]. Further assessment, using ambulatory and/or home BP monitoring, is recommended in patients with normal CPBP, but systolic CPBP equal to or higher than 115 mmHg. A more feasible approach would be evaluating patients with systolic CPBP equal to or higher than 123 mmHg and diastolic CPBP equal to or higher than 79 mmHg

Revalorization of Broccoli By-Products for Cosmetic Uses Using Supercritical Fluid Extraction

The agri-food industry is currently one of themain engines of economic developmentworldwide. The region ofMurcia is a reference area in Europe for the cultivation of fruits and vegetables and produces the bulk of Spanish exports of broccoli (Brassica oleracea var. italica). The processing of fresh produce generates a huge number of by-products that represent an important economic and environmental problem when discarded. In this work, an advanced extraction technique using environmentally friendly solvents was applied to assess the revalorization of broccoli by-products, by performing a comparative analysis with conventional extraction. To achieve this goal, supercritical fluid extraction based on response surface methodology was performed using CO2 and ethanol as solvents. The results obtained showed that the supercritical fluid extracts were rich in -carotene, phenolic compounds, chlorophylls and phytosterols. Moreover, in bioactivity assays, the supercritical fluid extracts exhibited a high antioxidant activity and a cytoprotective effect in a non-tumorigenic keratinocyte cell line exposed to ultraviolet B light. The results indicate that supercritical fluid extracts from broccoli by-products could potentially serve as an ingredient for cosmetic purposes

In situ decoration of graphene sheets with gold nanoparticles synthetized by pulsed laser ablation in liquids

The demand for nanocomposites of graphene and carbonaceous materials decorated with metallic nanoparticles is increasing on account of their applications in science and technology. Traditionally, the production of graphene-metal assemblies is achieved by the non-environmentally friendly reduction of metallic salts in carbonaceous suspensions. However, precursor residues during nanoparticle growth may reduce their surface activity and promote cross-chemical undesired effects. In this work we present a laser-based alternative to synthesize ligand-free gold nanoparticles that are anchored onto the graphene surface in a single reaction step. Laser radiation is used to generate highly pure nanoparticles from a gold disk surrounded by a graphene oxide suspension. The produced gold nanoparticles are directly immobilized onto the graphene surface. Moreover, the presence of graphene oxide influences the size of the nanoparticles and its interaction with the laser, causes only a slight reduction of the material. This work constitutes a green alternative synthesis of graphene-metal assemblies and a practical methodology that may inspire future developments.The authors thank the financial support from Generalitat Valenciana through the programs PROMETEO-2012-021, AICO/2016/036 and AICO/2015/039, a fellowship (S. Sabater) and a research contract (D. Ventura-Espinosa), the University Jaume I through the projects P1·1B2013-53 and P1.1B2015-09, and the Ministerio de Economía y Competitividad (MINECO) through the projects FIS2013-40666-P and CTQ2015-69153-C2-2-R. The authors are also very grateful to the ‘Serveis Centrals d’Instrumentació Científica (SCIC)’ of the University Jaume I for the use of the femtosecond laser and microscopy facilities. We thank S. Solans for his help with XPS analysis and interpretation. R. Torres-Mendieta gratefully acknowledges the Generalitat Valenciana support for a Santiago Grisolia scholarship GRISOLIA/2013/015

Relationship between Determinants of Health, Equity, and Dimensions of Health Literacy in Patients with Cardiovascular Disease

Background: Health literacy (HL) has been linked to empowerment, use of health services, and equity. Evaluating HL in people with cardiovascular health problems would facilitate the development of suitable health strategies care and reduce inequity. Aim: To investigate the relationship between different dimensions that make up HL and social determinants in patients with cardiovascular disease. Methods: Observational, descriptive, cross-sectional study in patients with cardiovascular disease, aged 50-85 years, accessing primary care services in Valencia (Spain) in 2018-2019. The Health Literacy Questionnaire was used. Results: 252 patients. Age was significantly related with the ability to participate with healthcare providers (p = 0.043), ability to find information (p = 0.022), and understanding information correctly to know what to do (p = 0.046). Level of education was significant for all HL dimensions. Patients without studies scored lower in all dimensions. The low- versus middle-class social relationship showed significant results in all dimensions. Conclusions: In patients with cardiovascular disease, level of education and social class were social determinants associated with HL scores. Whilst interventions at individual level might address some HL deficits, inequities in access to cardiovascular care and health outcomes would remain unjustly balanced unless structural determinants of HL are taken into account

Fitness Trade-Offs Determine the Role of the Molecular Chaperonin GroEL in Buffering Mutations

Molecular chaperones fold many proteins and their mutated versions in a cell and can sometimes buffer the phenotypic effect of mutations that affect protein folding. Unanswered questions about this buffering include the nature of its mechanism, its influence on the genetic variation of a population, the fitness trade-offs constraining this mechanism, and its role in expediting evolution. Answering these questions is fundamental to understand the contribution of buffering to increase genetic variation and ecological diversification. Here, we performed experimental evolution, genome resequencing, and computational analyses to determine the trade-offs and evolutionary trajectories of Escherichia coli expressing high levels of the essential chaperonin GroEL. GroEL is abundantly present in bacteria, particularly in bacteria with large loads of deleterious mutations, suggesting its role in mutational buffering. We show that groEL overexpression is costly to large populations evolving in the laboratory, leading to groE expression decline within 66 generations. In contrast, populations evolving under the strong genetic drift characteristic of endosymbiotic bacteria avoid extinction or can be rescued in the presence of abundant GroEL. Genomes resequenced from cells evolved under strong genetic drift exhibited significantly higher tolerance to deleterious mutations at high GroEL levels than at native levels, revealing that GroEL is buffering mutations in these cells. GroEL buffered mutations in a highly diverse set of proteins that interact with the environment, including substrate and ion membrane transporters, hinting at its role in ecological diversification. Our results reveal the fitness trade-offs of mutational buffering and how genetic variation is maintained in population

Star formation main sequence and Kennicutt-Schmidt law within 12 strong galactic bars observed with IRAM-30m

Comunicación de congreso, póster virtual presentado en el European Astronomical Society Annual Meeting (formerly known as EWASS) 28 June – 2 July 202

Evolutionary dynamics at the tumor edge reveal metabolic imaging biomarkers

Human cancers are biologically and morphologically heterogeneous. A variety of clonal populations emerge within these neoplasms and their interaction leads to complex spatiotemporal dynamics during tumor growth. We studied the reshaping of metabolic activity in human cancers by means of continuous and discrete mathematical models and matched the results to positron emission tomography (PET) imaging data. Our models revealed that the location of increasingly active proliferative cellular spots progressively drifted from the center of the tumor to the periphery, as a result of the competition between gradually more aggressive phenotypes. This computational finding led to the development of a metric, normalized distance from F-18-fluorodeoxyglucose (F-18-FDG) hotspot to centroid (NHOC), based on the separation from the location of the activity (proliferation) hotspot to the tumor centroid. The NHOC metric can be computed for patients using F-18-FDG PET-computed tomography (PET/CT) images where the voxel of maximum uptake (standardized uptake value [SUV]max) is taken as the activity hotspot. Two datasets of F-18-FDG PET/CT images were collected, one from 61 breast cancer patients and another from 161 non-small-cell lung cancer patients. In both cohorts, survival analyses were carried out for the NHOC and for other classical PET/CT-based biomarkers, finding that the former had a high prognostic value, outperforming the latter. In summary, our work offers additional insights into the evolutionary mechanisms behind tumor progression, provides a different PET/CT-based biomarker, and reveals that an activity hotspot closer to the tumor periphery is associated to a worst patient outcome