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

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

Monitoring photolysis and (solar photo)-Fenton of enrofloxacin by a methodology involving EEM-PARAFAC and bioassays: Role of pH and water matrix

[EN] The degradation of enrofloxacin (ENR) by direct photolysis, Fenton and solar photo-Fenton processes has been studied in different water matrices, such as ultra-pure water (MQ), tap water (TW) and highly saline water (SW). Reactions have been conducted at initial pH 2.8 and 5.0. At pH = 2.8, HPLC analyses showed a fast removal of ENR by (solar photo)-Fenton treatments in all studied water matrices, whereas a 40% removal was observed after 120 min of photolysis. However, TOC measurements showed that only solar photo-Fenton was able to produce significant mineralization (80% after 120 min of treatment); differences between ENR removal and mineralization can be attributed to the release of important amounts of reaction by-products. Excitation-emission matrices (EEMs) combined with parallel factor analysis (PARAFAC) were employed to gain further insight into the nature of these by-products and their time-course profile, obtaining a 5-component model. EEM-PARAFAC results indicated that photolysis is not able to produce important changes in the fluoroquinolone structure, in sharp contrast with (solar photo)-Fenton, where decrease of the components associated with fluoroquinolone core was observed. Agar diffusion tests employing E. toll and S. aureus showed that the antibiotic activity decreased in parallel with the destruction of the fluoroquinolone core.This paper is part of a project that has received funding from the European Union's Horizon 2020 - Research and Innovation Framework Programme under the H2020 Marie Sklodowska-Curie Actions grant agreement No 765860. The paper reflects only the authors' view and the Agency is not responsible for any use that may be made of the information it contains.Sciscenko, I.; García-Ballesteros, S.; Sabater Marco, C.; Castillo López, M.; Escudero-Oñate, C.; Oller, I.; Arqués Sanz, A. (2020). Monitoring photolysis and (solar photo)-Fenton of enrofloxacin by a methodology involving EEM-PARAFAC and bioassays: Role of pH and water matrix. Science of The Total Environment. 719:1-9. https://doi.org/10.1016/j.scitotenv.2020.137331S1971

Humic like substances extracted from oil mill wastes in photo-Fenton processes: Characterization, performance and toxicity assesment

[EN] Olive mill waste has been used as sourcing materials for the isolation of humic like substances (OMW-HLS) which have demonstrated its capacity to expand the range of applicability of photo-Fenton process to pH= 5. During the isolation process, membranes of three different pore sizes (300 kDa, 150 kDa and 50 kDa) were employed in order to obtain three batches of OMW-HLS. Four pollutants contained in 2013/39/EC were used as target substances: terbutryn (TBT), diclofenac (DCF), chlorfenvinphos (CVF) and pentachlorophenol (PCP). Results showed that OMW-HLS was able to enhance photo-Fenton at pH = 5, but differences were not significant, either among fractions or with commercial humic substances. Reactions were scaled-up and driven under real sunlight and pollutants removal was faster in the presence of OMW-HLS. Toxicity was monitored according to bioassays based on different organisms or cell lines. Detoxification was observed with and without OMW-HLS, although higher toxicity was detected in the presence of humic acids, most probably due to the surfactant effect, that allows a better contact between pollutant and organism.The authors thank the financial support of the European Union H2020 (2018-2022) (Ref. 776816) Proyect O, and Spanish Ministerio de Ciencia, Innovacion y Universidad (RTI 2018-097997-B-C31) . Paula Garcia Negueroles thanks Spanish Ministerio de Ciencia, Innovacion y Universidades for providing their fellowships BES-2016-0777962.García-Negueroles, P.; García-Ballesteros, S.; Santos-Juanes Jordá, L.; Sabater Marco, C.; Castillo López, M.; López Pérez, MF.; Vicente Candela, R.... (2021). Humic like substances extracted from oil mill wastes in photo-Fenton processes: Characterization, performance and toxicity assesment. Journal of Environmental Chemical Engineering. 9(6):1-8. https://doi.org/10.1016/j.jece.2021.106862189

A new methodology to assess the performance of AOPs in complex samples: Application to the degradation of phenolic compounds by O3 and O3/UV-A Vis

[EN] A methodology combining experimental design methodology, liquid chromatography, excitation emission matrixes (EEM) and bioassays has been applied to study the performance of O3 and O3/UVA-vis in the treatment of a mixture of eight phenolic pollutants. An experimental design methodology based on Doehlert matrixes was employed to determine the effect of pH (between 3 and 12), ozone dosage (02¿1.0¿g/h) and initial concentration of the pollutants (1¿6¿mg/L each). The following conclusions were obtained: a) acidic pH and low O3 dosage resulted in an inefficient process, b) increasing pH and O3 amount produced an enhancement of the reaction, and c) interaction of basic pH and high amounts of ozone decreased the efficiency of the process. The combination of O3/UVA-vis was able to enhance ozonation in those experimental regions were this reagent was less efficient, namely low pH and low ozone dosages. The application of EEM-PARAFAC showed four components, corresponding to the parent pollutants and three different groups of reaction product and its evolution with time. Bioassys indicated important detoxification (from 100% to less than 30% after 1¿min of treatment with initial pollutant concentration of 6¿mg/L, pH¿=¿9 and ozone dosage of 0.8¿g/h) according to the studied methods (D. magna and P. subcapitata). Also estrogenic activity and dioxin-like behavior were significantly decreased.The authors thank the financial support of the European Union(PIRSES-GA-2010-269128, EnvironBOS) and Spanish Ministerio de Educación y Ciencia (CTQ2015-69832-C4-4-R). Sara García-Ballesteros thanks Spanish Ministerio de Economía y Competitividad for providing her fellowship (BES-2013-066201).García-Ballesteros, S.; Mora Carbonell, M.; Vicente Candela, R.; Vercher Pérez, RF.; Sabater Marco, C.; Castillo López, M.; Amat Payá, AM.... (2019). A new methodology to assess the performance of AOPs in complex samples: Application to the degradation of phenolic compounds by O3 and O3/UV-A Vis. Chemosphere. 222:114-123. https://doi.org/10.1016/j.chemosphere.2019.01.015S11412322

Multiagent systems

Our future is that of a mixed society of people and AI artifacts. A multitude of devices in our homes will need not only to make intelligent decisions, but they will also need to coordinate with each other to serve us well. Cars will have to coordinate to allow safe road crossings, avoiding accidents. Also, the industry is already beginning to integrate teams of humans and robots collaborating to solve complex problems...Peer reviewe

COVID-19 vaccine failure

COVID-19 affects the population unequally with a higher impact on aged and immunosuppressed people. Hence, we assessed the effect of SARS-CoV-2 vaccination in immune compromised patients (older adults and oncohematologic patients), compared with healthy counterparts. While the acquired humoral and cellular memory did not predict subsequent infection 18 months after full immunization, spectral and computational cytometry revealed several subsets within the CD8+ T-cells, B-cells, NK cells, monocytes and CD45RA+ CCR7- Tγδ cells differentially expressed in further infected and non-infected individuals not just following immunization, but also prior to that. Of note, up to 7 subsets were found within the CD45RA+ CCR7- Tγδ population with some of them being expanded and other decreased in subsequently infected individuals. Moreover, some of these subsets also predicted COVID-induced hospitalization in oncohematologic patients. Therefore, we hereby have identified several cellular subsets that, even before vaccination, strongly related to COVID-19 vulnerability as opposed to the acquisition of cellular and/or humoral memory following vaccination with SARS-CoV2 mRNA vaccines.This study has been funded through Programa Estratégico Instituto de Biología y Genética Molecular (IBGM Junta de Castilla y León. Ref. CCVC8485), Junta de Castilla y León (Proyectos COVID 07.04.467B04.74011.0) and the European Commission – NextGenerationEU (Regulation EU 2020/2094), through CSIC's Global Health Platform (PTI Salud Global; SGL21-03-026 and SGL2021-03-038)N

CIBERER : Spanish national network for research on rare diseases: A highly productive collaborative initiative

Altres ajuts: Instituto de Salud Carlos III (ISCIII); Ministerio de Ciencia e Innovación.CIBER (Center for Biomedical Network Research; Centro de Investigación Biomédica En Red) is a public national consortium created in 2006 under the umbrella of the Spanish National Institute of Health Carlos III (ISCIII). This innovative research structure comprises 11 different specific areas dedicated to the main public health priorities in the National Health System. CIBERER, the thematic area of CIBER focused on rare diseases (RDs) currently consists of 75 research groups belonging to universities, research centers, and hospitals of the entire country. CIBERER's mission is to be a center prioritizing and favoring collaboration and cooperation between biomedical and clinical research groups, with special emphasis on the aspects of genetic, molecular, biochemical, and cellular research of RDs. This research is the basis for providing new tools for the diagnosis and therapy of low-prevalence diseases, in line with the International Rare Diseases Research Consortium (IRDiRC) objectives, thus favoring translational research between the scientific environment of the laboratory and the clinical setting of health centers. In this article, we intend to review CIBERER's 15-year journey and summarize the main results obtained in terms of internationalization, scientific production, contributions toward the discovery of new therapies and novel genes associated to diseases, cooperation with patients' associations and many other topics related to RD research