Deciphering the H-Bonding Preference on Nucleoside Molecular Recognition through Model Copper(II) Compounds

This research was funded by Agencia Estatal de Investigación, Ministerio de Ciencia, Innovación y Universidades (MICIU) from Spain and co-funded with FEDER-EU (Projects No. PGC2018-102047-B-I00 and CTQ2017-85821-R); Junta de Andalucía (FQM-283), and University of Granada (Project ref. PPJIA2019-03).The data presented in this study are available in this article or supplementary material.The contribution of the undergraduate student Elisabet J. Muela Morales as well as the technical and human support provided by SGIker (UPV/EHU) is gratefully acknowledged. A.D.-M. and M.B.-O. acknowledge support from Cost Action CA18202—Network for Equilibria and Chemical Thermodynamics Advanced Research.The synthetic nucleoside acyclovir is considered an outstanding model of the natural nucleoside guanosine. With the purpose of deepening on the influence and nature of non-covalent interactions regarding molecular recognition patterns, three novel Cu(II) complexes, involving acyclovir (acv) and the ligand receptor N-(2-hydroxyethyl)ethylenediamine (hen), have been synthesized and thoroughly characterized. The three novel compounds introduce none, one or two acyclovir molecules, respectively. Molecular recognition has been evaluated using single crystal X-ray diffraction. Furthermore, theoretical calculations and other physical methods such as thermogravimetric analysis, infrared and UV-Vis spectroscopy, electron paramagnetic resonance and magnetic measurements have been used. Theoretical calculations are in line with experimental results, supporting the relevance of the [metal-N7(acv) + H-bond] molecular recognition pattern. It was also shown that (hen)O-H group is used as preferred H-donor when it is found within the basal coordination plane, since the higher polarity of the terminal (hen)O-H versus the N-H group favours its implication. Otherwise, when (hen)O-H occupies the distal coordination site, (hen)N-H groups can take over.Agencia Estatal de Investigacion, Ministerio de Ciencia, Innovacion y Universidades (MICIU) from SpainEuropean Commission PGC2018-102047-B-I00 CTQ2017-85821-RJunta de Andalucia FQM-283University of Granada PPJIA2019-0

Photochemistry of nanoporous carbons: Perspectives in energy conversion and environmental remediation

The interest in the use of nanoporous carbon materials in applications related to energy conversion and storage, either as catalysts or additives, has grown over recent decades in various disciplines. Since the early studies reporting the benefits of the use of nanoporous carbons as inert supports of semiconductors and as electron acceptors that enhance the splitting of the photogenerated excitons, many researchers have investigated the key role of carbon matrices coupled to all types of photoactive materials. More recently, our group has demonstrated the ability of semiconductor-free nanoporous carbons to convert the absorbed photons into chemical reactions (i.e. oxidation of pollutants, water splitting, reduction of surface groups) opening new opportunities beyond conventional applications in light energy conversion. The aim of this paper is to review the recent progress on the application of nanoporous carbons in photochemistry using varied illumination conditions (UV, simulated solar light) and covering their role as additives to semiconductors as well as their use as photocatalysts in various fields, describing the photochemical quantum yield of nanoporous carbons for different reactions, and discussing the mechanisms postulated for the carbon/light interactions in confined pore spaces.This work was partially funded by the Spanish MINECO (CTM2014/56770-R) and the European Council Research through a Consolidator Grant (ERC-CoG-648161-PHOROSOL).Peer reviewe

Characteristics and Behavior of Di erent Catalysts Used for Water Decontamination in Photooxidation and Ozonation Processes

The objective of this study was to summarize the results obtained in a wide research project carried out for more than 15 years on the catalytic activity of di erent catalysts (activated carbon, metal–carbon xerogels/aerogels, iron-doped silica xerogels, ruthenium metal complexes, reduced graphene oxide-metal oxide composites, and zeolites) in the photooxidation (by using UV or solar radiation) and ozonation of water pollutants, including herbicides, naphthalenesulfonic acids, sodium para-chlorobenzoate, nitroimidazoles, tetracyclines, parabens, sulfamethazine, sodium diatrizoate, cytarabine, and surfactants. All catalysts were synthesized and then texturally, chemically, and electronically characterized using numerous experimental techniques, including N2 and CO2 adsorption, mercury porosimetry, thermogravimetric analysis, X-ray di raction, Fourier-transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, di use reflectance UV–vis spectroscopy, photoluminescence analysis, and transmission electron microscopy. The behavior of these materials as photocatalysts and ozonation catalysts was related to their characteristics, and the catalytic mechanisms in these advanced oxidation processes were explored. Investigations were conducted into the e ects on pollutant degradation, total organic carbon reduction, and water toxicity of operational variables and the presence of di erent chemical species in ultrapure, surface, ground, and wastewaters. Finally, a review is provided of the most recent and relevant published studies on photocatalysis and catalyzed ozonation in water treatments using similar catalysts to those examined in our project.Spanish Ministry of Economy, Industry and Competitiveness CTQ2016-80978-C2-1-REuropean Union (EU) CTQ2016-80978-C2-1-RJunta de Andalucía P18-RT-419

Deciphering the H-Bonding Preference on Nucleoside Molecular Recognition through Model Copper(II) Compounds

The synthetic nucleoside acyclovir is considered an outstanding model of the natural nucleoside guanosine. With the purpose of deepening on the influence and nature of non-covalent interactions regarding molecular recognition patterns, three novel Cu(II) complexes, involving acyclovir (acv) and the ligand receptor N-(2-hydroxyethyl)ethylenediamine (hen), have been synthesized and thoroughly characterized. The three novel compounds introduce none, one or two acyclovir molecules, respectively. Molecular recognition has been evaluated using single crystal X-ray diffraction. Furthermore, theoretical calculations and other physical methods such as thermogravimetric analysis, infrared and UV-Vis spectroscopy, electron paramagnetic resonance and magnetic measurements have been used. Theoretical calculations are in line with experimental results, supporting the relevance of the [metal-N7(acv) + H-bond] molecular recognition pattern. It was also shown that (hen)O-H group is used as preferred H-donor when it is found within the basal coordination plane, since the higher polarity of the terminal (hen)O-H versus the N-H group favours its implication. Otherwise, when (hen)O-H occupies the distal coordination site, (hen)N-H groups can take overThis research was funded by Agencia Estatal de Investigación, Ministerio de Ciencia, Innovación y Universidades (MICIU) from Spain and co-funded with FEDER-EU (Projects No. PGC2018-102047-B-I00 and CTQ2017-85821-R); Junta de Andalucía (FQM-283), and University of Granada (Project ref. PPJIA2019-03)S

Participación del carbón activado en procesos de eliminación de fármacos presentes en las aguas

págs.: 273-324Capítulo incluido en el libro: Desarrollo y aplicaciones de materiales avanzados de carbón. Miguel Ángel Álvarez Merino, Francisco Carrasco Marín, Francisco José Maldonado Hódar (Editores). Sevilla: Univeridad Internacional de Andalucía, 2014. ISBN: 978-84-7993-247-3. Enlace: http://hdl.handle.net/10334

Nuevos tratamientos de aguas mediante tecnologías integradas basadas en el uso de procesos avanzados de oxidación/reducción y carbón activado

En este trabajo se estudia la aplicación de nuevas alternativas a los sistemas de oxidación tradicionales para la eliminación de compuestos orgánicos emergentes de las aguas, considerando el medio de contraste diatrizoato sódico como compuesto modelo.Tesis Univ. Granada. Departamento de Química Inorgánic

Surface Modification of a Nanoporous Carbon Photoanode upon Irradiation

The photocorrosion of a nanoporous carbon photoanode, with low surface functionalization and high performance towards the photoelectrochemical oxidation of water using simulated solar light, was investigated. Two different light configurations were used to isolate the effect of the irradiation wavelength (UV and visible light) on the textural and chemical features of the carbon photoanode, and its long-term photocatalytic performance for the oxygen evolution reaction. A complete characterization of the carbon showed that the photocorrosion of carbon anodes of low functionalization follows a different pathway than highly functionalized carbons. The carbon matrix gets slightly oxidized, with the formation of carboxylic and carbonyl-like moieties in the surface of the carbon anode after light exposure. The oxidation of the carbon occurred due to the photogeneration of oxygen reactive species upon the decomposition of water during the irradiation of the photoanodes. Furthermore, the photoinduced surface reactions depend on the nature of the carbon anode and its ability to photogenerate reactive species in solution, rather than on the wavelength of the irradiation source. This surface modification is responsible for the decreased efficiency of the carbon photoanode throughout long illumination periods, due to the effect of the oxidation of the carbon matrix on the charge transfer. In this work, we have corroborated that, in the case of a low functionalization carbon material, the photocorrosion also occurs although it proceeds through a different pathway. The carbon anode gets gradually slightly oxidized due to the photogeneration of O-reactive species, being the incorporation of the O-groups responsible for the decreased performance of the anode upon long-term irradiation due to the effect of the oxidation of the carbon matrix on the electron transferThis work was partially funded by the Spanish MINECO (CTM2014/56770-R) and the European Council Research through a Consolidator Grant (ERC-CoG-648161, PHOROSOL). A.G.B. thanks the Spanish MINECO for their PhD fellowship (BES-2012-0560410).Peer reviewe

Surface Modification of a Nanoporous Carbon Photoanode upon Irradiation

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Photochemistry of nanoporous carbons: Perspectives in energy conversion and environmental remediation

AbstractThe interest in the use of nanoporous carbon materials in applications related to energy conversion and storage, either as catalysts or additives, has grown over recent decades in various disciplines. Since the early studies reporting the benefits of the use of nanoporous carbons as inert supports of semiconductors and as electron acceptors that enhance the splitting of the photogenerated excitons, many researchers have investigated the key role of carbon matrices coupled to all types of photoactive materials. More recently, our group has demonstrated the ability of semiconductor-free nanoporous carbons to convert the absorbed photons into chemical reactions (i.e. oxidation of pollutants, water splitting, reduction of surface groups) opening new opportunities beyond conventional applications in light energy conversion. The aim of this paper is to review the recent progress on the application of nanoporous carbons in photochemistry using varied illumination conditions (UV, simulated solar light) and covering their role as additives to semiconductors as well as their use as photocatalysts in various fields, describing the photochemical quantum yield of nanoporous carbons for different reactions, and discussing the mechanisms postulated for the carbon/light interactions in confined pore spaces