Preparation of Dimeric Monopentamethylcyclopentadienyltitanium(III) Dihalides and Related Derivatives

Ministerio de Ciencia, Innovación y Universidades de España, Ministerio de Economía y Competitividad de España, Universidad de Alcal

Aplicación del índice de sustentabilidad WSI en la cuenca Lerma-Chapala

Los indicadores ambientales para medir la sustentabilidad se usan a partir de la década de los años setenta, cuando la defensa del medio ambiente se convirtió en uno de los temas más importantes de las campañas y agendas políticas en varios países. Se hace necesario, por lo tanto, contar con herramientas que permitan cuantificar de forma apropiada este concepto de sustentabilidad asociado con la gestión de recursos hídricos en zonas áridas. Parte de estas herramientas son dichos indicadores, cuyo propósito es representar, de manera cuantitativa, una serie de atributos que caracterizan el sistema analizado y que, contrastados con una escala de referencia, permiten establecer, por un lado, en qué estado se encuentra el sistema respecto a la condición de referencia, y por otro, cómo ha sido su evolución y cuál es su estado potencial futuro. La problemática ambiental que actualmente se presenta en la cuenca Lerma-Chapala es el resultado de la interacción entre los actores políticos, económicos y sociales, y su entorno. Las prácticas agrícolas y pecuarias intensivas ocasionan una gran degradación de los ecosistemas naturales; el uso urbano de la tierra también ejerce un fuerte impacto en el equilibrio ecológico, el cual se ha visto degradado en décadas recientes debido a la acción antropogénica. En este trabajo se lleva a cabo un análisis desde un enfoque sistémico de jerarquización, en el cual se utiliza la metodología llamada Índice de Sustentabilidad de Cuencas (WSI)

Valence and spin situations in isomeric [(bpy)Ru(Q′)2]n (Q′ = 3,5-di-tert- butyl-N-aryl-1,2-benzoquinonemonoimine). An experimental and DFT analysis

The article deals with the ruthenium complexes, [(bpy)Ru(Q′)2] (1–3) incorporating two unsymmetrical redox-noninnocent iminoquinone moieties [bpy = 2,2′-bipyridine; Q′ = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, aryl = C6H5 (Q′1), 1; m-Cl2C6H3 (Q′2), 2; m-(OCH3)2C6H3 (Q′3), 3]. 1 and 3 have been preferentially stabilised in the cc-isomeric form while both the ct- and cc-isomeric forms of 2 are isolated [ct: cis and trans and cc: cis and cis with respect to the mutual orientations of O and N donors of two Q′]. The isomeric identities of 1–3 have been authenticated by their single-crystal X-ray structures. The collective consideration of crystallographic and DFT data along with other analytical events reveals that 1–3 exhibit the valence configuration of [(bpy)RuII(Q′Sq)2]. The magnetization studies reveal a ferromagnetic response at 300 K and virtual diamagnetic behaviour at 2 K. DFT calculations on representative 2a and 2b predict that the excited triplet (S = 1) state is lying close to the singlet (S = 0) ground state with singlet–triplet separation of 0.038 eV and 0.075 eV, respectively. In corroboration with the paramagnetic features the complexes exhibit free radical EPR signals with g [similar]2 and 1HNMR spectra with broad aromatic proton signals associated with the Q′ at 300 K. Experimental results in conjunction with the DFT (for representative 2a and 2b) reveal iminoquinone based preferential electron-transfer processes leaving the ruthenium(II) ion mostly as a redox insensitive entity: [(bpy)RuII(Q′Q)2]2+ (12+–32+) [leftrightharpoons] [(bpy)RuII(Q′Sq)(Q′Q)]+ (1+–3+) [leftrightharpoons] [(bpy)RuII(Q′Sq)2] (1–3) [leftrightharpoons] [(bpy)RuII(Q′Sq)(Q′Cat)]−/[(bpy)RuIII(Q′Cat)2]− (1−–3−). The diamagnetic doubly oxidised state, [(bpy)RuII(Q′Q)2]2+ in 12+–32+ has been authenticated further by the crystal structure determination of the representative [(bpy)RuII(Q′3)2](ClO4)2 [3](ClO4)2 as well as by its sharp 1H NMR spectrum. The key electronic transitions in each redox state of 1n–3n have been assigned by TD–DFT calculations on representative 2a and 2b

Steric, Activation Method and Solvent Effects on the Structure of Paddlewheel Diruthenium Complexes

Conventional heating and solvothermal synthetic methods (with or without microwave activation) have been used to study the reaction of o-, m- and p-methoxybenzoic acid with [Ru2Cl(μ-O2CMe)4]. The tetrasubstituted series [Ru2Cl(µ-O2CC6H4-R)4], with R = o-OMe, m-OMe and p-OMe, has been prepared by the three procedures. Depending on the synthetic method and the experimental conditions, three compounds have been isolated (1a, 1b, 1c) with the o-methoxybenzoate ligand. However, with the m- and p-methoxybenzoate ligands, only the complexes 2 and 3 have been obtained, respectively. Compound 1a, with stoichiometry [Ru2Cl(µ-O2CC6H4-o-OMe)4]n, shows a polymeric structure with the chloride ions bridging the diruthenium units to form linear chains. Compounds 2 and 3, with the same stoichiometry, predictably form zig-zag chains in accordance with their insolubility and their magnetic measurements. Compound 1b, [Ru2Cl(µ-O2CC6H4-o-OMe)4(EtOH)], is a discrete molecular species with a chloride ion and one ethanol molecule occupying the axial positions of the dimetallic unit. Compound 1c is a cation-anion complex, [Ru2(µ-O2CC6H4-o-OMe)4(MeOH)2][Ru2Cl2(µ-O2CC6H4-o-OMe)4]. The cationic complex has two solvent molecules at the axial positions whereas the anionic complex has two chloride ligands at these positions. Complexes have been characterized by elemental analyses, mass spectrometry and IR and UV-vis-NIR spectroscopies. A magnetic study of complexes 1a, 1b, 2 and 3 have also been carried out. The crystal structure of compounds 1b and 1c have been solved by single X-ray crystal methods

Crecimiento de Saccharomyces boulardii con agavinas acetiladas como fuente de carbono

Las agavinas son polímeros de fructosa provenientes del agave. Poseen enlaces β (2-1) y β (2-6), característica que no permite su hidrolisis por enzimas digestivas y las clasifica como oligosacáridos no digeribles. Estas moléculas han tomado relevancia debido a sus diferentes aplicaciones como encapsulantes de componentes bioactivos para liberarlos en sitios específicos y su capacidad prebiótica. Las bacterias del intestino grueso y cepas probióticas como Saccharomyces boulardii pueden fermentar las agavinas, generando cambios positivos en la microbiota. En esta investigación se evaluó la fermentabilidad de agavinas nativas, comerciales y acetiladas por la levadura probiótica S. boulardii, con el fin de compararlos como fuentes de carbono. Como resultado se obtuvo que el desarrollo celular en el medio con agavinas acetiladas fue mayor (9,0x10⁶ UFC/mL) respecto a las comerciales (5,7x10⁶ UFC/mL) y nativas (7,5x10⁵ UFC/mL), sin embargo, su crecimiento no fue mayor al medio con glucosa (3,5x10⁷UFC/mL).Agavins are polymers of fructose from agave that have β (2-1) and β (2-6) bonds, a characteristic that makes them resistant to hydrolysis by digestive enzymes and are classified non-digestible oligosaccharides. Currently, agavins have become relevant due to their different applications as an encapsulant of bioactive compounds to release them at specific sites and for their prebiotic characteristics. Bacteria from the large intestine and probiotic strains such as Saccharomyces boulardii can ferment agavins, generating positive changes in the microbiota. In this research, the fermentability of native, commercial and acetylated agavins by the probiotic yeast S. boulardii was evaluated, in order to compare them as carbon sources. As a result, it was obtained that the cell growth in the medium with acetylated agavins was higher (9,0x10⁶ CFU/mL) compared to commercial ones (5,7x10⁶ CFU/mL) and native agavins (7,5x10⁵ CFU/mL), however, its growth was not greater than the medium with glucosa (3,5x10⁷ CFU/mL)

I.amAble: la ciencia (química) al alcance de toda la sociedad

En este proyecto de innovación, que nace con vocación de continuar en años sucesivos, se persigue mejorar la calidad de la formación de los estudiantes de la Facultad de Ciencias Químicas (F. CC.QQ.) en el ámbito de la docencia teórico-práctica y de la divulgación científica. El trabajo ha consistido en la preparación de unos experimentos prácticos para llevarlos a cabo en centros educativos no universitarios en los que se ha tenido en cuenta la participación conjunta de personas con y sin diversidad funcional, desde una perspectiva inclusiva colaborativa. Estas actividades las han realizado los estudiantes bajo la supervisión de profesores (PDI) y personal de administración y servicios (PAS). Los experimentos se han recogido en fichas didácticas para facilitar su desarrollo y aplicación por parte de otros usuarios. En estas fichas se explica detalladamente cómo realizar las experiencias en formato de taller. Las fichas de los talleres realizados están disponibles en una página web vinculada a la Universidad Complutense bajo el título I.amAble (iamable.ucm.es). Está página ha sido construida por un estudiante de la Facultad de Informática , bajo la supervisión de profesionales, tanto de esa facultad como del Instituto de Tecnología del Conocimiento, y está abierta a contribuciones similares de otras facultades y otras instituciones. La página web está diseñada de manera que resulte lo más intuitiva y accesible posible para todo tipo de público. Entre todos los experimentos se han elegido cuatro para llevarlos a la práctica en centros educativos como actividades inclusivas en las que han participado conjuntamente personas con y sin discapacidad. Con este proyecto se pretende mejorar la calidad docente al ofrecer a los estudiantes la posibilidad de aprender enseñando mediante una actividad semipresencial. El desarrollo por parte de los estudiantes de competencias transversales en educación y en divulgación de la ciencia facilitarán algunas salidas profesionales en el ámbito educativo formal (centros de enseñanza) o informal (museos, animación sociocultural). Otro aspecto importante a resaltar es la potenciación de la colaboración entre todos los miembros de la institución universitaria. Este proyecto pretende contribuir a la mejora de la cultura científica, así como al establecimiento de puentes entre la UCM y la sociedad a la que debe servir. Finalmente, es importante subrayar que incidirá en la inclusión de las personas con discapacidad como parte de la sociedad, a través del acercamiento compartido a la ciencia (Dimensiones de inclusión social y derechos de Schalock; NAVAS MACHO, P. y otros, 2012. Derechos de las personas con discapacidad intelectual: implicaciones de la Convención de Naciones Unidas. Siglo Cero. 43 (243): 7-28.)

Chemical Composition, Starch Digestibility and Antioxidant Capacity of Tortilla Made with a Blend of Quality Protein Maize and Black Bean

Tortilla and beans are the basic components in the diet of people in the urban and rural areas of Mexico. Quality protein maize is suggested for tortilla preparation because it presents an increase in lysine and tryptophan levels. Beans contain important amounts of dietary fiber. The objective of this study was to prepare tortilla with bean and assesses the chemical composition, starch digestibility and antioxidant capacity using a quality protein maize variety. Tortilla with bean had higher protein, ash, dietary fiber and resistant starch content, and lower digestible starch than control tortilla. The hydrolysis rate (60 to 50%) and the predicted glycemic index (88 to 80) of tortilla decreased with the addition of bean in the blend. Extractable polyphenols and proanthocyanidins were higher in the tortilla with bean than control tortilla. This pattern produced higher antioxidant capacity of tortilla with bean (17.6 μmol Trolox eq/g) than control tortilla (7.8 μmol Trolox eq/g). The addition of bean to tortilla modified the starch digestibility and antioxidant characteristics of tortilla, obtaining a product with nutraceutical characteristics

Familial hypercholesterolaemia in children and adolescents from 48 countries: a cross-sectional study

Background: Approximately 450 000 children are born with familial hypercholesterolaemia worldwide every year, yet only 2·1% of adults with familial hypercholesterolaemia were diagnosed before age 18 years via current diagnostic approaches, which are derived from observations in adults. We aimed to characterise children and adolescents with heterozygous familial hypercholesterolaemia (HeFH) and understand current approaches to the identification and management of familial hypercholesterolaemia to inform future public health strategies. Methods: For this cross-sectional study, we assessed children and adolescents younger than 18 years with a clinical or genetic diagnosis of HeFH at the time of entry into the Familial Hypercholesterolaemia Studies Collaboration (FHSC) registry between Oct 1, 2015, and Jan 31, 2021. Data in the registry were collected from 55 regional or national registries in 48 countries. Diagnoses relying on self-reported history of familial hypercholesterolaemia and suspected secondary hypercholesterolaemia were excluded from the registry; people with untreated LDL cholesterol (LDL-C) of at least 13·0 mmol/L were excluded from this study. Data were assessed overall and by WHO region, World Bank country income status, age, diagnostic criteria, and index-case status. The main outcome of this study was to assess current identification and management of children and adolescents with familial hypercholesterolaemia. Findings: Of 63 093 individuals in the FHSC registry, 11 848 (18·8%) were children or adolescents younger than 18 years with HeFH and were included in this study; 5756 (50·2%) of 11 476 included individuals were female and 5720 (49·8%) were male. Sex data were missing for 372 (3·1%) of 11 848 individuals. Median age at registry entry was 9·6 years (IQR 5·8-13·2). 10 099 (89·9%) of 11 235 included individuals had a final genetically confirmed diagnosis of familial hypercholesterolaemia and 1136 (10·1%) had a clinical diagnosis. Genetically confirmed diagnosis data or clinical diagnosis data were missing for 613 (5·2%) of 11 848 individuals. Genetic diagnosis was more common in children and adolescents from high-income countries (9427 [92·4%] of 10 202) than in children and adolescents from non-high-income countries (199 [48·0%] of 415). 3414 (31·6%) of 10 804 children or adolescents were index cases. Familial-hypercholesterolaemia-related physical signs, cardiovascular risk factors, and cardiovascular disease were uncommon, but were more common in non-high-income countries. 7557 (72·4%) of 10 428 included children or adolescents were not taking lipid-lowering medication (LLM) and had a median LDL-C of 5·00 mmol/L (IQR 4·05-6·08). Compared with genetic diagnosis, the use of unadapted clinical criteria intended for use in adults and reliant on more extreme phenotypes could result in 50-75% of children and adolescents with familial hypercholesterolaemia not being identified. Interpretation: Clinical characteristics observed in adults with familial hypercholesterolaemia are uncommon in children and adolescents with familial hypercholesterolaemia, hence detection in this age group relies on measurement of LDL-C and genetic confirmation. Where genetic testing is unavailable, increased availability and use of LDL-C measurements in the first few years of life could help reduce the current gap between prevalence and detection, enabling increased use of combination LLM to reach recommended LDL-C targets early in life

Familial hypercholesterolaemia in children and adolescents from 48 countries: a cross-sectional study

Background Approximately 450 000 children are born with familial hypercholesterolaemia worldwide every year, yet only 2·1% of adults with familial hypercholesterolaemia were diagnosed before age 18 years via current diagnostic approaches, which are derived from observations in adults. We aimed to characterise children and adolescents with heterozygous familial hypercholesterolaemia (HeFH) and understand current approaches to the identification and management of familial hypercholesterolaemia to inform future public health strategies. Methods For this cross-sectional study, we assessed children and adolescents younger than 18 years with a clinical or genetic diagnosis of HeFH at the time of entry into the Familial Hypercholesterolaemia Studies Collaboration (FHSC) registry between Oct 1, 2015, and Jan 31, 2021. Data in the registry were collected from 55 regional or national registries in 48 countries. Diagnoses relying on self-reported history of familial hypercholesterolaemia and suspected secondary hypercholesterolaemia were excluded from the registry; people with untreated LDL cholesterol (LDL-C) of at least 13·0 mmol/L were excluded from this study. Data were assessed overall and by WHO region, World Bank country income status, age, diagnostic criteria, and index-case status. The main outcome of this study was to assess current identification and management of children and adolescents with familial hypercholesterolaemia. Findings Of 63 093 individuals in the FHSC registry, 11 848 (18·8%) were children or adolescents younger than 18 years with HeFH and were included in this study; 5756 (50·2%) of 11 476 included individuals were female and 5720 (49·8%) were male. Sex data were missing for 372 (3·1%) of 11 848 individuals. Median age at registry entry was 9·6 years (IQR 5·8–13·2). 10 099 (89·9%) of 11 235 included individuals had a final genetically confirmed diagnosis of familial hypercholesterolaemia and 1136 (10·1%) had a clinical diagnosis. Genetically confirmed diagnosis data or clinical diagnosis data were missing for 613 (5·2%) of 11 848 individuals. Genetic diagnosis was more common in children and adolescents from high-income countries (9427 [92·4%] of 10 202) than in children and adolescents from non-high-income countries (199 [48·0%] of 415). 3414 (31·6%) of 10 804 children or adolescents were index cases. Familial-hypercholesterolaemia-related physical signs, cardiovascular risk factors, and cardiovascular disease were uncommon, but were more common in non-high-income countries. 7557 (72·4%) of 10 428 included children or adolescents were not taking lipid-lowering medication (LLM) and had a median LDL-C of 5·00 mmol/L (IQR 4·05–6·08). Compared with genetic diagnosis, the use of unadapted clinical criteria intended for use in adults and reliant on more extreme phenotypes could result in 50–75% of children and adolescents with familial hypercholesterolaemia not being identified. Interpretation Clinical characteristics observed in adults with familial hypercholesterolaemia are uncommon in children and adolescents with familial hypercholesterolaemia, hence detection in this age group relies on measurement of LDL-C and genetic confirmation. Where genetic testing is unavailable, increased availability and use of LDL-C measurements in the first few years of life could help reduce the current gap between prevalence and detection, enabling increased use of combination LLM to reach recommended LDL-C targets early in life. Funding Pfizer, Amgen, Merck Sharp & Dohme, Sanofi–Aventis, Daiichi Sankyo, and Regeneron