Suchergebnisse

The synthesis, full characterization, photochemical properties, and cytotoxic activity toward cisplatin-resistant cancer cell lines of new semisquaraine-type Pt(II) complexes are presented. The synthesis of eight semisquaraine-type ligands has been carried out by means of an innovative, straightforward methodology. A thorough structural NMR and X-ray diffraction analysis of the new ligands and complexes has been done. Density functional theory calculations have allowed to assign the trans configuration of the platinum center. Through the structural modification of the ligands, it has been possible to synthesize some complexes, which have turned out to be photoactive at wavelengths that allow their activation in cell cultures and, importantly, two of them show remarkable solubility in biological media. Photodegradation processes have been studied in depth, including the structural identification of photoproducts, thus justifying the changes observed after irradiation. From biological assessment, complexes C7 and C8 have been demonstrated to behave as promising photoactivatable compounds in the assayed cancer cell lines. Upon photoactivation, both complexes are capable of inducing a higher cytotoxic effect on the tested cells compared with nonphotoactivated compounds. Among the observed results, it is remarkable to note that C7 showed a PI > 50 in HeLa cells, and C8 showed a PI > 40 in A2780 cells, being also effective over cisplatin-resistant A2780cis cells (PI = 7 and PI = 4, respectively). The mechanism of action of these complexes has been studied, revealing that these photoactivated platinum complexes would actually present a combined mode of action, a therapeutically potential advantage. ; Instituto de Salud Carlos III ; Spanish Government RTI2018-098027-B-C22 ; European Commission BIO2015-67358-C2-2-P CTQ2016-75363-R ; Spanish Government Instituto de Salud Carlos III Spanish Government ; Generalitat de Catalunya 2017SGR-864

This work was supported by FONDECYT, Project No. 1200748. Y.R.Y. acknowledges funding from Pontificia Universidad Catolica de Chile via a VRI 2015 -2017 fellowship and Ph.D. CONICYT 2018 fellowship No. 21182120. A.M.-S. acknowledges funding from Ph.D. CONICYT fellowship No. 51150322. The authors also gratefully acknowledge financial support from the Ministerio de Ciencia e Innovacion, Spain (grant numbers CTQ2016-77614-P and RED2018-102387-T) and "Plan Propio de I + D + i" of the Universidad Castilla-La Mancha (grant number 2020-GRIN29078). ; A set of trisubstituted guanidine ligands L1H2-L4H2 with general formula (PrHN)(2)CNR (R = Ph (L1H2), R = 2,4,6-Me3C6H2(L2H2), R = p-BrC6H4(L3H2), R = (C5H4)Fe(C5H5), Fc (L4H2)) was employed to synthesize a family of mono- and dinuclear asymmetric methyl aluminum guanidinato compounds ((L2H)AlMe2 (1), (L4H)AlMe2 (2), (L-1)Al2Me4 (3), (L-2)Al2Me4 (4), (L-3)Al2Me4 (5), (L-4)Al2Me4 (6), (L1H)(2)AlMe (7), (L2H)(2)AlMe (8), and (L4H)(2)AlMe (9)) that were characterized by NMR spectroscopy (1-9) and single-crystal X-ray diffraction (4 and 8). These compounds were tested as catalysts for the fixation of carbon dioxide with epoxides to give cyclic carbonates, using tetrabutylammonium iodide (TBAI) as cocatalyst. The reactions were performed under solvent-free conditions at 70 degrees C and 1 bar CO2 pressure. Complexes 1-9 were more active than their respective free guanidines under the same experimental conditions for the synthesis of styrene carbonate (11a). The dinuclear complex 6 was the most efficient and active catalyst for the synthesis of several monosubstituted carbonates (11a-1) with excellent conversions and selectivities. Furthermore, the formation of some disubstituted cyclic carbonates (13a-c) using this dinuclear aluminum catalyst was also studied. ; Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT 1200748 ; Pontificia Universidad Catolica de Chile ; Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) 51150322 21182120 ; Spanish Government CTQ2016-77614-P RED2018-102387-T ; "Plan Propio de I + D + i" of the Universidad Castilla-La Mancha 2020-GRIN29078

The synthesis, characterization and cytotoxic activity against different cancer cell lines of various mesoporous silica-based materials containing folate targeting moieties and a cytotoxic fragment based on a triphenyltin(IV) derivative have been studied. Two different mesoporous nanostructured silica systems have been used: firstly, micronic silica particles of the MSU-2 type and, secondly, mesoporous silica nanoparticles (MSNs) of about 80 nm. Both series of materials have been characterized by different methods, such as powder X-ray diffraction, X-ray fluorescence, absorption spectroscopy and microscopy. In addition, these systems have been tested against four different cancer cell lines, namely, OVCAR-3, DLD-1, A2780 and A431, in order to observe if the size of the silica-based systems and the quantity of incorporated folic acid influence their cytotoxic action. The results show that the materials are more active when the quantity of folic acid is higher, especially in those cells that overexpress folate receptors such as OVCAR-3 and DLD-1. In addition, the study of the potential modulation of the soluble folate receptor alpha (FOLR1) by treatment with the synthesized materials has been carried out using OVCAR-3, DLD-1, A2780 and A431 tumour cell lines. The results show that a relatively high concentration of folic acid functionalization of the nanostructured silica together with the incorporation of the cytotoxic tin fragment leads to an increase in the quantity of the soluble FOLR1 secreted by the tumour cells. In addition, the studies reported here show that this increase of the soluble FOLR1 occurs presumably by cutting the glycosyl-phosphatidylinositol anchor of membrane FR-α and by the release of intracellular FR-α. This study validates the potential use of a combination of mesoporous silica materials co-functionalized with folate targeting molecules and an organotin(IV) drug as a strategy for the therapeutic treatment of several cancer cells overexpressing folate receptors. ; Spanish Government RTI2018-094322-B-I00 CTQ2017-90802-REDT ; Ministry of Research and Innovation, CNCS-UEFISCDI within PNCDI III PN-III-P4-ID-PCCF-2016-0142

This work has been supported by the Regional Government of Madrid (Project ACES2030-CM , S2018/EMT-4319 ), the Spanish Ministry of Science and Innovation , and the Spanish State Research Agency (Project PGC2018-099296-B-I00 ) ; A novel Zn-based-MOF material, called Zn-URJC-8, containing two different organic linkers, 2-aminoterephtallic acid and 4,4-bipyridyl, has been synthetized and used for catalytic purposes for the first time. The structure of Zn-URJC-8 has been determined by single-crystal X-ray diffraction (XRD) showing -NH2 groups inward-facing of narrow pores, providing the material with excellent properties as CO2 adsorbent. The good results obtained by means of carbon dioxide adsorption isotherms have demonstrated the high interaction between CO2 and -NH2 groups with a Qst value of 54 kJ/mol at low coverage. The Zn-URJC-8 material also display promising results as catalyst for CO2 transformation in added value products. Almost complete conversion of epichlorohydrin and CO2 in cycloaddition reaction has been achieved under mild conditions, and the influence of different radical groups coordinated to the epoxides has been evaluated on the reaction yield. The recyclability has been also tested and the structural integrity of the catalyst is maintained after several consecutive reaction cycles. ; Regional Government of Madrid ACES2030-CM, S2018/EMT-4319 ; Ministerio de Ciencia e Innovación ; Agencia Estatal de Investigación PGC2018-099296-B-I00

Red Guipuzcoana de Ciencia, Tecnologia e Innovacion OF218/2018 University of Basque Country GIU 17/13 Basque Government IT1005-16 IT1291-19 IT1310-19 Junta de Andalucia FQM-394 Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) PGC2018-102052-A-C22 PGC2018-102052-B-C21 MAT2016-75883-C2-1-P European Union (EU) ESF ; In this work, three isostructural metal-organic frameworks based on frst row transition metal ions and 2-aminoisonicotinate (2ain) ligands, namely, {[M(μ-2ain)2]·DMF}n [MII=Co (1), Ni (2), Zn (3)], are evaluated for their sensing capacity of various solvents and metal ions by monitoring the modulation of their magnetic and photoluminescence properties. The crystal structure consists of an open diamond-like topological 3D framework that leaves huge voids, which allows crystallizing two-fold interpenetrated architecture that still retains large porosity. Magnetic measurements performed on 1 reveal the occurrence of feld-induced spin-glass behaviour characterized by a frequency-independent relaxation. Solvent-exchange experiments lead successfully to the replacement of lattice molecules by DMSO and MeOH, which, on its part, show dominating SIM behaviour with low blocking temperatures but substantially high energy barriers for the reversal of the magnetization. Photoluminescence studied at variable temperature on compound 3 show its capacity to provide bright blue emission under UV excitation, which proceeds through a ligand-centred charge transfer mechanism as confrmed by timedependent DFT calculations. Turn-of and/or shift of the emission is observed for suspensions of 3 in diferent solvents and aqueous solutions containing metal ions.

We report the formation of five novel multifunctional coordination polymers based on 1H-indazole-4- carboxylic acid (HL). To the best of our knowledge, these complexes are the first examples of coordination compounds constructed with this interesting ligand. These materials were synthesized by solvothermal routes, possess different 2D-structures and show interesting magnetic properties due to the copper compound showing an unusual spin-canted effect while the anisotropic cobalt material behaves as a fieldinduced single molecule magnet. MTT assays performed on human embryonic kidney (HEK293) and mouse skin melanoma (B16-F10) cell lines indicated that the Cd-based compound was the only one exhibiting dose-dependent toxicity on B16-F10 cells, most likely due to the release of toxic Cd(II). Cadmium and zinc polymers exhibit interesting luminescence properties. The fact that zinc polymers did not exhibit inherent toxicity against both cancer and non-cancerous cells make this new family an excellent candidate for further investigation in the field of luminescent materials with biomedical applications. ; Junta de Andalucia FQM-394 FQM-1484 ; Red Guipuzcoana de Ciencia, Tecnologia e Innovacion OF218/2018 ; University of Basque Country GIU 17/13 ; Basque Government IT1005-16 ; Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) PGC2018-102052-A-C22 PGC2018-102052-B-C21 ; Junta de Andalucia FQM-394 FQM-1484 ; European Union (EU) ; ESF ; Government of the Basque Country ; FEDER/MCIU/AEI RYC-2016-21042 JdC-2017

A couple of isostructural coordination polymers with the general formula [Ln4(pymca)4(AcO)8]n have been obtained from reactions between pyrimidine-2-carboxylate (pymca) ligand and rare-earth ions (Ln = Dy (1), Nd (2)). These two-dimensional compounds have been characterized and the crystal structures have been solved by single-crystal X-ray diffraction technique, resulting in layers along the bc plane based on pymca and acetate anions that act as bridging ligands between metal atoms. Given that pymca and acetate anions possess carboxylate and hetero-nitrogen groups, it is possible to build a coordination polymer whose metal centers have a nine coordination. Furthermore, static and dynamic magnetic measurements of compound 1 reveal the lack of single molecule-magnet (SMM) behavior in this system due to the following two effects: (i) the ligand field does not stabilize magnetic ground states well separated from excited states, and (ii) anisotropy axes are not collinear, according to results with Magellan software. On another level, luminescent properties of compounds 1 and 2 are attributed to singlet π-π* transitions centered on pymca ligand as corroborated by time-dependent density functional theory (TD-DFT) calculations. ; Junta de Andalucia FQM-394 ; Red Guipuzcoana de Ciencia, Tecnologia e Innovacion OF218/2018 ; University of Basque Country GIU 17/13 ; Basque Government IT1005-16 ; Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) PGC2018-102052-A-C22 PGC2018-102052-B-C21 PGC2018-102047-B-I00 ; European funding (ERDF) ; European funding (ESF) ; Government of the Basque Country

This research was partially supported by the fellowship H2020-MSCA-IF-2017-794885-SELFSENS and by the Spanish Ministry of Education, Culture and Sport under Grant FPU18/01376 and funded by Spanish ministry of Science and Innovation grant number PGC2018-102052-B-C21. ; In this letter, we present the extension of a previous work on a cost-effective method for fabricating highly sensitive humidity sensors on flexible substrates with a reversible response, allowing precise monitoring of the humidity threshold. In that work we demonstrated the use of three-dimensional metal-organic framework (MOF) film deposition based on the perylene-3,4,9,10-tetracarboxylate linker, potassium as metallic center and the interspacing of silver interdigitated electrodes (IDEs) as humidity sensors. In this work, we study one of the most important issues in efficient and reproducible mass production, which is to optimize the most important processes' parameters in their fabrication, such as controlling the thickness of the sensor's layers. We demonstrate this method not only allows for the creation of humidity sensors, but it also is possible to change the humidity value that changes the actuator state. ; Spanish Ministry of Education, Culture and Sport H2020-MSCA-IF-2017-794885-SELFSENS ; Spanish Government FPU18/01376 ; PGC2018-102052-B-C21

A couple of isostructural coordination polymers with the general formula [Ln (pymca) (AcO) ] have been obtained from reactions between pyrimidine-2-carboxylate (pymca) ligand and rare-earth ions (Ln = Dy (1), Nd (2)). These two-dimensional compounds have been characterized and the crystal structures have been solved by single-crystal X-ray diffraction technique, resulting in layers along the bc plane based on pymca and acetate anions that act as bridging ligands between metal atoms. Given that pymca and acetate anions possess carboxylate and hetero-nitrogen groups, it is possible to build a coordination polymer whose metal centers have a nine coordination. Furthermore, static and dynamic magnetic measurements of compound 1 reveal the lack of single molecule-magnet (SMM) behavior in this system due to the following two effects: (i) the ligand field does not stabilize magnetic ground states well separated from excited states, and (ii) anisotropy axes are not collinear, according to results with Magellan software. On another level, luminescent properties of compounds 1 and 2 are attributed to singlet π-π* transitions centered on pymca ligand as corroborated by time-dependent density functional theory (TD-DFT) calculations. ; Financial support was given by Junta de Andalucía(FQM-394),Red Guipuzcoana de Ciencia, Tecnología e Innovación (OF218/2018), University of the Basque Country (GIU 17/13), Gobierno Vasco/Eusko Jaurlaritza (IT1005-16), and the Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) (PGC2018-102052-A-C22, PGC2018-102052-B-C21, and PGC2018-102047-B-I00). The authors thank for technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). A.Z.-L. is grateful to the Government of the Basque Country for the predoctoral fellowship. The authors thank SGIker of UPV/EHU for technical and human support, and European funding (ERDF and ESF).

Herein, we present, for the first time, a 2D-MOF based on copper and 4-hydroxypyrimidine-5-carbonitrile as the linker. Each MOF layer is perfectly flat and neutral, as is the case for graphene. High pressure X-ray diffraction measurements reveal that this layered structure can be modulated between 3.01 to 2.78 Å interlayer separation, with an evident piezochromism and varying conductive properties. An analysis of the band structure indicates that this material is conductive along different directions depending on the application of pressure or H doping. These results pave the way for the development of novel layered materials with tunable and efficient properties for pressure-based sensors. ; European Union (EU) 604391 ; Swiss National Science Foundation (SNSF) 200020_162861 ; Spanish Government CEX2018-000805-M CTQ2015-69163-CO2R1 PGC2018-102052-B-C21 PGC2018-102052-A-C22 PGC2018102047-B-I00 FIS2016-80434-P PID2019-109539GB-C43 ; Junta de Andalucia FQM-394 ; Comunidad Autonoma de Madrid through the Nanomag COST-CM Program S2018/NMT-4321 ; University of Seville ; National Council for Scientific and Technological Development (CNPq) 405107/2017-0

This work was supported by the Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER,UE) (PGC2018-102052-A-C22, PGC2018-102052-B-C21, PID2020-117344RB-I00 and PID2019-108028GB-C21), Junta de Andalucia (FQM-394, B.FQM.734.UGR20 and P20_00265), Gobierno Vasco/Eusko Jaurlaritza (IT1005-16, IT1291-19), the University of the Basque Country (UPV/EHU) (GIU 17/13). S.R. acknowledges the Juan de la Cierva Fellowship (IJC2019-038894-I). The authors acknowledge the technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). ; Two novel metal-organic frameworks (MOFs), based on dysprosium as the metal and the 5-aminoisophthalic acid (5aip) ligand, have been solvothermally synthesized, with the aim of studying and modulating their luminescence properties according to the variation of solvent in the structure. These materials display intense photo-luminescence properties in the solid state at room temperature. Interestingly, one fascinating sensory capacity of compound 2 regards obtaining a variation of the signal, depending on the solvent to which it is exposed. These results pave the way for a new generation of sensitive chemical sensors. ; Spanish Government PGC2018-102052-A-C22 PGC2018-102052-B-C21 PID2020-117344RB-I00 PID2019-108028GB-C21 ; Junta de Andalucia FQM-394 B.FQM.734.UGR20 P20_00265 ; Basque Government IT1005-16 IT1291-19 ; University of the Basque Country (UPV/EHU) GIU 17/13 ; Juan de la Cierva Fellowship IJC2019-038894-I ; European funding (ERDF) European funding (ESF)

We aimed to study the effect of vanadium(V) exposure on cell viability, nuclear DNA (nDNA) and mitochondrial DNA (mtDNA) and to elucidate if these effects can be reverted by co-exposure to V and manganese (Mn). HepG2 cells were incubated with various concentrations of bis(maltolato)oxovanadium(IV) or MnC12 for 32 h for viability study. The higher concentrations (59 mu M V, 54 nM Mn and 59 mu M V+54 nM Mn) were used to study DNA damage and uptake of V and Mn. Comet assay was used for the study of nDNA damage; mtDNA damage was studied by determining deletions and number of copies of the ND1/ND4 mtDNA region. Cellular content of V and Mn was determined using ICPMS. Cellular exposure to 59 mu M V decreased viability (14%) and damaged nDNA and mtDNA. This effect was partially prevented by the co-exposure to V + Mn. Exposure to V increased the cellular content of V and Mn (812.3% and 153.5%, respectively). Exposure to Mn decreased the content of V and Mn (62% and 56%, respectively). Exposure to V + Mn increased V (261%) and decreased Mn (56%) content. The positive effects on cell viability and DNA damage when incubated with V + Mn could be due to the Mn-mediated inhibition of V uptake. ; Consejeria de Innovacion, Ciencia y Empresa, Andalusian Regional Government P06-CTS-01435

The authors gratefully acknowledge funding support from the Spanish Ministry of Science, Innovation and Universities (PGC2018-102052-B-C21 and PID2020-116460RB-I00) and the Junta de Andaluci ' a (FQM-394 and FQM-134). The authors gratefully acknowledge the funding support of FEDER/Junta de Andaluci ' a Consejeri ' a de Economi ' a y Conocimiento, Grant B-AGR-193-UGR18. O. L. and J. G. F. B. also thank Grant PID2020-116460RB-I00 funded by MCIN/AEI/10.13039/50110 0011033. S. R. acknowledge the Juan de la Cierva Fellowship (IJC2019-038894-I). Mari ' a D. Navarro-Hortal and Jose M. Romero-Ma ' rquez are FPU fellows from the Spanish Ministry of Educacio ' n y Formacio ' n Profesional. ; A new palladium coordination compound based on gliclazide with the chemical formula [Pd(glz)(2)] (where glz = gliclazide) has been synthesized and characterised. The structural characterization reveals that this material consists of mononuclear units formed by a Pd2+ ion coordinated to two molecules of the glz ligand, in which palladium ions exhibit a distorted plane-square coordination sphere. This novel material behaves like a good and selective inhibitor of butyrylcholinesterase, one of the most relevant therapeutic targets against Alzheimer's disease. Analysis of the enzyme kinetics showed a mixed mode of inhibition, the title compound being capable of interacting with both the free enzyme and the enzyme-substrate complex. Finally, the palladium compound shows promising protective activity against A beta-induced toxicity in the Caenorhabditis elegans model, which has never been reported. ; Spanish Government PGC2018-102052-B-C21 PID2020-116460RB-I00 ; Junta de Andalucia FQM-394 FQM-134 ; FEDER/Junta de Andaluci'a Consejeri'a de Economi'a y Conocimiento B-AGR-193-UGR18 ; MCIN/AEI/ PID2020-116460RB-I00 ; Juan de la Cierva Fellowship IJC2019-038894-I

En este trabajo se presentan los resultados de una investigación llevada a cabo en cinco universidades españolas sobre los perfiles docentes que demanda el EEES. Utilizando procedimientos de corte cualitativo se han obtenido en dos momentos consecutivos las percepciones de grupos de profesores sobre las principales competencias docentes necesarias para la armonización de la educación superior en la UE. El análisis de los datos indica, por una parte, la discrepancia entre los tipos de profesores actualmente existentes y los percibidos como necesarios; por otra, ha posibilitado la descripción pormenorizada de los perfiles de competencias docentes que el profesorado percibe como fundamentales para el ejercicio de las nuevas funciones que se le demandan en estos momentos. ; This paper presents the findings of a research study of professors' profiles for the European Higher Education Area (EHEA) conducted in five spanish universities. Through the application of qualitative methods of inquiry, the perceptions of several groups of university professors over the principal teaching qualifications necessary for the coordination of higher education throughout the European Union have been obtained. Data analysis indicates a significant discrepancy between actual Spanish professors and those required by EHEA. It has also made possible the detailed description of teaching competency profiles that professors believe to be fundamental for the new functions demanded of them in the present changing social and educational situation.

En este trabajo se presentan los resultados de una investigación llevada a cabo en cinco universidades españolas sobre los perfiles docentes que demanda el EEES. Utilizando procedimientos de corte cualitativo se han obtenido en dos momentos consecutivos las percepciones de grupos de profesores sobre las principales competencias docentes necesarias para la armonización de la educación superior en la UE. El análisis de los datos indica, por una parte, la discrepancia entre los tipos de profesores actualmente existentes y los percibidos como necesarios; por otra, ha posibilitado la descripción pormenorizada de los perfiles de competencias docentes que el profesorado percibe como fundamentales para el ejercicio de las nuevas funciones que se le demandan en estos momentos. ; This paper presents the findings of a research study of professors' profiles for the European Higher Education Area (EHEA) conducted in five spanish universities. Through the application of qualitative methods of inquiry, the perceptions of several groups of university professors over the principal teaching qualifications necessary for the coordination of higher education throughout the European Union have been obtained. Data analysis indicates a significant discrepancy between actual Spanish professors and those required by EHEA. It has also made possible the detailed description of teaching competency profiles that professors believe to be fundamental for the new functions demanded of them in the present changing social and educational situation.