Precursors PtCl{κ3-N,C,N-py-C6HMe2-py} (1), PtCl{κ3-N,C,N-py-O-C6H3-O-py} (2), Pt(OH){κ3-N,C,N-py-C6HMe2-py} (3), and Pt(OH){κ3-N,C,N-py-O-C6H3-O-py} (4) were used to prepare d8-platinum ...bimetallic complexes. Precursors 1 and 2 react with AgBF4 and 7-azaindole (Haz) to give Pt{κ3-N,C,N-py-C6HMe2-py}{κ1-N-Haz}BF4 (5) and Pt{κ3-N,C,N-py-O-C6H3-O-py}{κ1-N-Haz}BF4 (6) and 3 and 4 with indolo2,3-bindole (H2 ii) to generate Pt{κ1-N-Hii}{κ3-N,C,N-py-C6HMe2-py} (7) and Pt{κ1-N-Hii}{κ3-N,C,N-py-O-C6H3-O-py} (8). Subsequent addition of 3 and 4 to 5-7 affords bimetallic derivatives {Ptκ3-N,C,N-(py-C6HMe2-py)}2{μ-N,N-az}BF4 (9), {Ptκ3-N,C,N-(py-O-C6H3-O-py)}2{μ-N,N-az}BF4 (10), and {Ptκ3-N,C,N-(py-C6HMe2-py)}2{μ-N,N-ii} (11). X-ray structures of 9-11 reveal separations between the metals in sequence 9 (3.0515(4) Å) < 10 (3.2689(9) Å) < 11 (3.2949(2) Å). DFT calculations support σ overlap of the dz2 orbitals of platinum atoms, for 9 and 10. Accordingly, their absorption spectra show a MMLCT transition. Complex 9 is a red emitter. The excited state has 3MMLCT characteristics and a Pt–Pt separation of 2.763 Å. Complex 11 is a dual emitter in the red and NIR regions, in solid. Both excited states have a 3LC/LMCT characteristic and platinum–platinum separations of 3.290 and 3.202 Å. Intermediate 5 is a green emitter that achieves quantum yields close to unity, when diluted in PMMA and 1,2-dichloroethane at low concentrations.
Replacement of the chloride ligand of PtCl{κ3-N,C,N-py-C6HR2-py} (R = H (1), Me (2)) and PtCl{κ3-N,C,N-py-O-C6H3-O-py} (3) by hydroxido gives Pt(OH){κ3-N,C,N-py-C6HR2-py} (R = H (4), Me (5)) and ...Pt(OH){κ3-N,C,N-py-O-C6H3-O-py} (6). These compounds promote deprotonation of 3-(2-pyridyl)pyrazole, 3-(2-pyridyl)-5-methylpyrazole, 3-(2-pyridyl)-5-trifluoromethylpyrazole, and 2-(2-pyridyl)-3,5-bis(trifluoromethyl)pyrrole. The coordination of the anions generates square-planar derivatives, which in solution exist as a unique species or equilibria between isomers. Reactions of 4 and 5 with 3-(2-pyridyl)pyrazole and 3-(2-pyridyl)-5-methylpyrazole provide Pt{κ3-N,C,N-py-C6HR2-py}{κ1-N 1-R′pz-py} (R = H; R′ = H (7), Me (8). R = Me; R′ = H (9), Me (10)), displaying κ1-N 1-pyridylpyrazolate coordination. A 5-trifluoromethyl substituent causes N1-to-N2 slide. Thus, 3-(2-pyridyl)-5-trifluoromethylpyrazole affords equilibria between Pt{κ3-N,C,N-py-C6HR2-py}{κ1-N 1-CF3pz-py} (R = H (11a), Me (12a)) and Pt{κ3-N,C,N-py-C6HR2-py}{κ1-N 2-CF3pz-py} (R = H (11b), Me (12b)). 1,3-Bis(2-pyridyloxy)phenyl allows the chelating coordination of the incoming anions. Deprotonations of 3-(2-pyridyl)pyrazole and its substituted 5-methyl counterpart promoted by 6 lead to equilibria between Pt{κ3-N,C,N-pyO-C6H3-Opy}{κ1-N 1-R′pz-py} (R′ = H (13a), Me (14a)) with a κ-N 1-pyridylpyrazolate anion, keeping the pincer coordination of the di(pyridyloxy)aryl ligand, and Pt{κ2-N,C-pyO-C6H3(Opy)}{κ2-N,N-R′pz-py} (R′ = H (13c), Me (14c)) with two chelates. Under the same conditions, 3-(2-pyridyl)-5-trifluoromethylpyrazole generates the three possible isomers: Pt{κ3-N,C,N-pyO-C6H3-Opy}{κ1-N 1-CF3pz-py} (15a), Pt{κ3-N,C,N-pyO-C6H3-Opy}{κ1-N 2-CF3pz-py} (15b), and Pt{κ2-N,C-pyO-C6H3(Opy)}{κ2-N,N-CF3pz-py} (15c). The N1-pyrazolate atom produces a remote stabilizing effect on the chelating form, pyridylpyrazolates being better chelate ligands than pyridylpyrrolates. Accordingly, reactions of 4–6 with 2-(2-pyridyl)-3,5-bis(trifluoromethyl)pyrrole yield Pt{κ3-N,C,N-py-C6HR2-py}{κ1-N 1-(CF3)2C4(py)HN} (R = H (16), Me (17)) or Pt{κ3-N,C,N-pyO-C6H3-Opy}{κ1-N 1-(CF3)2C4(py)HN} (18), displaying κ1-N 1-pyrrolate coordination. Complexes 7–10 are efficient green phosphorescent emitters (488–576 nm). In poly(methyl methacrylate) (PMMA) films and in dichloromethane, they experience self-quenching, due to molecular stacking. Aggregation occurs through aromatic π–π interactions, reinforced by weak platinum–platinum interactions.
Objective: to describe and explore the relationship of loneliness, anxiety and depression with adoption of the caregiver role among individuals caring for people with chronic diseases in Colombia. ...Methods: this was an exploratory and cross-sectional study involving 960 primary caregivers of individuals with chronic diseases. We applied the Caregiver Role Adoption Scale, the University of California at Los Angeles Loneliness Scale, and the Anxiety and Depression Scale. Principal component and multiple correspondence analyses were performed for clustering. Results: among the participating caregivers, 40.8% reported experiencing depression, 59% reported anxiety, 54.6% reported moderate to severe loneliness, and 88.6% reported satisfactory adoption of the caregiver role. Caregivers who presented basic or insufficient role adoption levels tended to have higher scores for anxiety, depression and loneliness. Conclusion: adoption of the caregiver role is a mediator in the anxiety, depression and loneliness levels among caregivers. Strategies aimed at supporting caregivers should include training for the caregiver role to mitigate the negative impacts of anxiety, depression and loneliness.
Objetivo: descrever e explorar a relação entre a solidão, a ansiedade e a depressão com a adoção do papel de cuidador entre os indivíduos que cuidam de pessoas com doenças crônicas na Colômbia. Método: trata-se de um estudo exploratório e transversal que envolveu 960 cuidadores primários de indivíduos com doenças crônicas. Foi aplicada a Escala de Adoção do Papel de Cuidador, a Escala de Solidão da Universidade da Califórnia em Los Angeles e a Escala de Ansiedade e Depressão. Foram realizadas análises de componentes principais e de correspondência múltipla para o agrupamento. Resultados: entre os cuidadores participantes, 40,8% relataram ter depressão, 59% relataram ansiedade, 54,6% relataram solidão moderada a grave e 88,6% relataram uma adoção satisfatória do papel de cuidador. Os cuidadores que apresentaram níveis básicos ou insuficientes de adoção do papel tenderam a ter pontuações mais elevadas de ansiedade, depressão e solidão. Conclusão: a adoção do papel de cuidador é um mediador nos níveis de ansiedade, depressão e solidão entre os cuidadores. As estratégias destinadas a apoiar os cuidadores devem incluir o treinamento para o papel de cuidador, a fim de atenuar os impactos negativos da ansiedade, da depressão e da solidão.
Objetivo: describir y explorar la relación de la soledad, la ansiedad y la depresión con la adopción del rol de cuidador entre personas que se ocupan de cuidar pacientes con enfermedades crónicas en Colombia. Métodos: se trató de un estudio exploratorio y transversal con la participación de 960 cuidadores principales de personas con enfermedades crónicas. Aplicamos la Escala de Adopción del Rol de Cuidador, la Escala de Soledad de la Universidad de California de Los Ángeles y la Escala de Ansiedad y Depresión. Se realizaron análisis de componentes principales y de correspondencia múltiple para el clustering . Resultados: el 40,8% de los cuidadores que participaron en el estudio informó padecer depresión, el 59% informó ansiedad, el 54,6% indicó soledad de moderada a grave y el 88,6% presentó adopción satisfactoria del rol de cuidador. Los cuidadores que presentaron los niveles básico o insuficiente en términos de adopción del rol tendieron a obtener puntuaciones de ansiedad, depresión y soledad más elevadas. Conclusión: adoptar el rol de cuidador es un mediador de los niveles de ansiedad, depresión y soledad entre los cuidadores. Las estrategias dirigidas a apoyar a los cuidadores deberían incluir preparación para dicho rol a fin de mitigar los efectos negativos de la ansiedad, la depresión y la soledad.
Technological development has profoundly marked the evolution of the economy. The constant changes brought about by scientific and technological advances have been decisive in the transition from an ...analogue to a digital world. In this context, the impact of the fourth industrial revolution (or Industry 4.0) manifests itself in many ways. Environmental impact is one of these. The energy sector has been evolving and changing just like the economy and society. Therefore, a study of this sector, and of the other related elements, is of interest to better understand the 4.0 concept. The promotion of sustainability at both the political and social levels has led to changes in different areas, such as the productive vision, the use of green energies, and the implementation of green taxes. Energy as a key factor in Industry 4.0 involves studying it both quantitatively and qualitatively. This is to understand the lights and shadows that the concept currently presents. Therefore, this work aims to bring the reality of the energy sector closer to reality, both in its positive and negative aspects, considering the main factors of incidence, to show the strengths and weaknesses that can be deduced.
This article presents a study of the catalytic performance of Ni, Co, and Ni–Co–Mg–Al mixed oxides obtained from hydrotalcite precursors for the oxidative steam reforming of ethanol (OSRE) when no ...pretreatment (pre-reduction) is accomplished. Two catalysts (a Ni-based monometallic and an equimolar Ni–Co-based catalyst) achieve in situ reduction over shorter time periods compared with the other bimetallic catalysts and also, exhibit the best catalytic activity. On the contrary, the monometallic Co catalyst did not exhibit good catalytic performance, likely because of the existence of resistant spinel phases to soft reduction processes and/or to the re-oxidation of Co. The equimolar presence of Ni and Co generates a synergistic effect evidenced by the increase in the reducibility, basicity, and mobility of electrophilic oxygen species of the solid. The results yield important information for better understanding the catalytic system under study.
•The increase of reducibility, basicity, and oxygen mobility improve H2 production.•H2 production order: OMCo < OM2Ni1Co < OM1Ni2Co < OMNi = OM1Ni1Co for non-reduced solids.•Nickel-rich catalysts can be reduced “in situ” during OSRE, contrary to the OMCo.•Cooperative effect between Ni and Co increases the properties of the OM1Ni1Co.
The study sought to correlate fear, stress, knowledge regarding COVID-19 in Nursing students and recent graduates in Mexico.
Correlational design, sample comprising 912 nursing students and graduates ...during the last 18 months from public and private universities of Mexico. To measure the variables, the study applied the instrument Fear of COVID-19 Scale, knowledge subscale of the scale Knowledge, attitudes, and practices towards COVID-19, and the instrument COVID Stress Scale.
Relationship was found of the age variable with fear, danger of contamination, traumatic stress, knowledge and minor socioeconomic consequences (p<0.05). Likewise, relationship was observed of fear with stress regarding COVID-19, danger of contamination, socioeconomic consequences, xenophobia, traumatic stress, and compulsive checking (p<0.05). Stress and knowledge explain the presence of fear regarding COVID-19 in 50.3%, and fear and knowledge explain stress regarding COVID-19 in 50.4%.
Nursing students and recent graduates have high levels of stress and fear, besides low level of knowledge. The presence of high stress and low knowledge predict fear regarding COVID-19. Interventions are required on knowledge, stress, and fear regarding COVID-19 in the population studied.
Nursing interventions aimed at family caregivers of palliative cancer patients require not only an objective evaluation, but also subjective consideration of their contributions, and a qualitative ...evaluation that provides an in-depth understanding of these interventions.
This study aimed to explore the perceptions that family caregivers of palliative cancer patients had of the nursing intervention, PalliActive Caregivers, in reducing the uncertainty associated with illness and improving the caregiver's quality of life.
A qualitative approach with content analysis was used. Telephone interviews were conducted with 23 caregivers who participated in the intervention.
Five themes emerged from the content analysis: consolidating physical care, adopting a positive attitude, strengthening the support available to the caregiver, strengthening spirituality and strengthening relationships.
The themes showed a positive impact of the intervention on aspects such as the caregiver's ability to cope, spirituality and social support of caregivers. The results also indicated the possibility of conducting this type of study to identify other assessment variables for future interventions.
The functionalization of the internal surface of macroporous carriers with glyoxyl groups has proven to highly stabilize a large variety of enzymes through multipoint covalent immobilization. In this ...work, we have translated the surface chemistry developed for the fabrication of glyoxyl-agarose carriers to macroporous cellulose (CEL). To that aim, CEL-based microbeads were functionalized with glyoxyl groups through a stepwise alkoxylation (or alkylation)/oxidation synthetic scheme. This functionalization sequence was analyzed by solid-state NMR, while the scanning electron miscroscopy of CEL microbeads reveals that the mild oxidation conditions negligibly affect the morphological properties of the material. Through the optimal functionalization protocol using rac-glycidol, we introduce up to 200 μmols of aldehyde groups per gram of wet CEL, a similar density to the one obtained for the benchmarked agarose-glyoxyl carrier. This novel CEL-based carrier succeeds to immobilize and stabilize industrially relevant enzymes such as d-amino acid oxidase from Trigonopsis variabilis and xylanases from Trichoderma reseei. Remarkably, the xylanases immobilized on the optimal CEL-based materials present a half-life time of 51 h at 60 °C and convert up to 90% of the xylan after four operation cycles for the synthesis of xylooligosaccharides.
Measuring the quality of life in family caregivers of people in palliative care is essential to document the impact of care on the caregiver. This study aimed to adapt and validate a Latin ...American‐Spanish version of the QOLLTI‐F scale in family caregivers of palliative care patients. This study was conducted between May and November 2019 in Medellin, Colombia. We develop three phases: translation and semantic adaptation (n = 17), face and content validity (n = 21), construct validity, internal consistency (n = 208) and test–retest reliability (n = 35). Main family caregivers of stage‐IV cancer patients receiving palliative treatment, participated. In the translation and semantic adaptation, some items were adjusted following the caregivers’ recommendations. In face validity, Fleiss’ Kappa was over 0.65 for family caregivers. In content validity, Fleiss’ Kappa ranged from 0.54 to 1 for experts. In construct validity, the original version seven‐factor structure did not show appropriate model fit indices. The data revealed instead a new 3‐factor structure related to (1) impact of care‐giving, (2) social and healthcare interactions and (3) meaning of life. Cronbach's alpha was 0.83 for the overall scale. Test–retest reliability was 0.87 between measurements 1 and 2. This study found that The Latin American‐Spanish version of the QOLLTI‐F scale is an understandable, useful, and relevant tool for family caregivers of people with cancer receiving palliative care. Future research is needed to confirm the factor structure identified in this study.
The synthesis of a series of Pt{κ3-N,C,N′-L}X (X = Cl, RCC) pincer complexes derived from purine and purine nucleosides is reported. In these complexes, the 6-phenylpurine skeleton provides the ...N,C-cyclometalated fragment, whereas an amine, imine, or pyridine substituent of the phenyl ring supplies the additional N′-coordination point to the pincer complex. The purine N,C-fragment has two coordination positions with the metal (N1 and N7), but the formation of the platinum complexes is totally regioselective. Coordination through the N7 position leads to the thermodynamically favored 6.5-Pt{κ3-N7,C,N′-L}X complexes. However, the coordination through the N1 position is preferred by the amino derivatives, leading to the isomeric kinetic 5.5-Pt{κ3-N1,C,N′-L}X complexes. Extension of the reported methodology to complexes having both pincer and acetylide ligands derived from nucleosides allows the preparation of novel heteroleptic bis-nucleoside compounds that could be regarded as organometallic models of Pt-induced interstrand cross-link. Complexes having amine or pyridine arms are green phosphorescence emitters upon photoexcitation at low concentrations in CH2Cl2 solution and in poly(methyl methacrylate) (PMMA) films. They undergo self-quenching at high concentrations due to molecular aggregation. The presence of intermolecular π–π stacking and weak Pt···Pt interactions was also observed in the solid state by X-ray diffraction analysis.
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