Síntese de compostos organometálicos com potencial aplicação em óptica não linear

Tese de doutoramento em Química (Química Inorgânica), apresentada à Universidade de Lisboa através da Faculdade de Ciências, 2008No presente trabalho é descrita a síntese e caracterização de uma série de novos compostos iónicos do tipo η5-monociclopentadienilo de ruténio(II) e ferro(II), com ligandos coordenados derivados dos compostos 1,2-di-(2-tienil)-eteno, benzo[1,2-b;4,3- b']ditiofeno e tetratia-[7]-heliceno, com vista à obtenção de efeitos significativos de Óptica Não Linear (NLO). Com o mesmo propósito, foram também sintetizados novos compostos de prata com fosfinas coordenadas derivadas do benzo[1,2-b;4,3-b']ditiofeno, e foi tentada a síntese de novos complexos do tipo η5,η1- permetilciclopentadieniloruténio(II). Os compostos foram caracterizados pelos métodos espectroscópicos usuais (IV, UV-vis, RMN 1H, 13C e 31P) e, nalguns casos, por voltametria cíclica, por forma a avaliar a existência de retrodoação π, bandas de transferência de carga metal-ligando ou ligando-metal, e estudar a riqueza electrónica do centro metálico. Alguns compostos foram também caracterizados por difracção de raios- X, por forma a determinar o alinhamento molecular no estado sólido e o grupo espacial. Foi avaliada a resposta óptica não linear de primeira ordem, ao nível molecular, de alguns compostos, tendo-se determinado a primeira hiperpolarizabilidade molecular (ß) usando a técnica de Dispersão de Hyper-Rayleigh (HRS). No Capítulo I é feita uma breve introdução ao fenómeno da NLO, sendo discutidos os efeitos ópticos observados e as suas possíveis aplicações tecnológicas, os requisitos moleculares e macroscópicos necessários à geração desses efeitos e a descrição das principais técnicas usadas na sua determinação. É também apresentada uma breve revisão dos tipos de materiais mais estudados nesta área. Os estudos de HRS dos compostos [M(η5-C5H5)(dppe)(NC(C4H2S)C(H) C(H)(C4H2S)NO2)][PF6] (M = Ru, Fe) confirmaram que o sistema π rígido do 1,2-di-(2- tienil)-eteno permite uma melhor conjugação entre o centro metálico e o grupo aceitador que os sistemas de oligotiofenos, o que resulta numa transferência de carga mais efectiva e em valores de ß, determinados a 1550 nm, mais elevados. Os estudos de HRS dos compostos [Fe(η5-C5H5)(dppe)(NC{bzdt})][PF6] e [Ru(η5-C5H5)(PPh3)2(NC{bzdt})][PF6] não revelaram qualquer quantidade mensurável de radiação de dupla frequência. O valor de ß determinado (1500 nm) para o composto [Fe(η5 C5H5)(dppe)(NC{bzdt}NO2)][PF6] foi de 33 x 10-30 esu, o que mostra que o sistema de anéis orto-fundidos do benzo[1,2-b;4,3-b']ditiofeno é inferior, enquanto cromóforo, aos sistemas π do 1,2-di-(2-tienil)-eteno e de oligo-tiofenos. No Capítulo IV é descrita a síntese e caracterização da família de compostos do tipo η5-monociclopentadienilo de ruténio(II) e ferro(II), com nitrilos coordenados derivados do tetratia-[7]-heliceno. Os dados espectroscópicos, em conjunto com o tamanho do cromóforo, permitem prever valores elevados de ß para estes compostos. A síntese e caracterização dos compostos de prata com fosfinas derivadas do benzo[1,2-b;4,3-b']ditiofeno é descrita no Capítulo V. Os estudos cristalográficos dos compostos [Ag(CF3SO3)(PPh2{bzdt})n] (n = 1, 2, 3) revelaram que estes cristalizam em grupos espaciais centrossimétricos, não tendo sido detectado qualquer fenómeno de empacotamento molecular que faça prever bons resultados de NLO. No Capítulo VI é descrita a tentativa de síntese de novos monociclopentadienilos de ruténio(II), do tipo [Ru(η5,η1-C5Me4C(H)C(H)COO)L2] ou [Ru(η5,η1 C5Me4C(H)C(H)COOMe)(L)Cl], em que o anel Cp e o centro metálico estivessem ligados por uma cadeia π conjugada (η1) para alêm da coordenação normal (η5), a qual não foi conseguida.In this work, new families of ionic compounds of the type η5- monocyclopentadienyl ruthenium(II) and iron(II) were prepared, with coordinated 1,2-di- (2-thienyl)-ethene, benzo[1,2-b;4,3-b']dithiophene and tetrathia-[7]-helicene nitrile derivatives, in view of significant NLO effects. With the same purpose, new silver(I) compounds with coordinatedbenzo[1,2-b;4,3-b']dithiophene phosphine derivatives, were synthesized. The new compounds were characterized by the usual spectroscopic methods (IR, UV-vis, RMN 1H, 13C and 31P) and, in some cases, by cyclic voltammetry, to evaluate the existence of π backdonation, metal-ligand or ligand-metal charge transfer bands, and the study of electronic density at the metal centre. Some compounds were also studied by X-ray diffraction to determine the molecular alignment in the solid state and the spatial group. The second order nonlinear optical response of some compounds was evaluated, at microscopic level, with the determination of the first molecular hyperpolarisability (ß) by Hyper-Rayleigh Scattering (HRS). The first chapter provides a brief introduction to NLO, with the discussion of the observed optical effects and their possible application, the necessary molecular and macroscopic requirements for the observation of these effects and the description of the techniques used to measure NLO properties. A brief review of the NLO materials studied so far is also presented. The second chapter describes the synthesis and characterization of new η5- monocyclopentadienyl ruthenium(II) and iron(II) compounds with coordinated 1,2-di-(2- thienyl)-ethene nitrile derivatives. HRS studies on [M(η5-C5H5)(dppe)(NC(C4H2S)C(H) C(H)(C4H2S)NO2)][PF6] (M = Ru, Fe) confirmed that the rigidity and planarity of 1,2-di- (2-thienyl)-ethene π system allows a superior conjugation between the metal centre and the acceptor group than the oligo-thiophene π system, which results in charge transfer efficiency and good ß values. The third chapter describes the synthesis and characterization of new η5- monocyclopentadienyl ruthenium(II) and iron(II) compounds with coordinated benzo[1,2-b;4,3-b']dithiophene nitrile derivatives. HRS studies on [Fe(η5- C5H5)(dppe)(NC{bzdt})][PF6] and [Ru(η5-C5H5)(PPh3)2(NC{bzdt})][PF6] revealed no x measurable quantity of double frequency radiation. The ß value determined (1500 nm) for compound [Fe(η5 C5H5)(dppe)(NC{bzdt}NO2)][PF6] (33 x 10-30 esu), shows that the orto-fused rings πsystem of benzo[1,2-b;4,3-b']ditiofeno is less effective, as chromophore, than 1,2-di-(2-thienyl)-ethene and oligo-thiophene π systems. The fourth chapter describes the synthesis and characterization of new η5- monocyclopentadienyl ruthenium(II) and iron(II) compounds with coordinated tetrathia- [7]-helicene nitrile derivatives. Spectroscopic data, along with the size of the chromophore allow the prediction of large ß values for these compounds. The synthesis and characterization of silver(I) compounds with coordinated benzo[1,2-b;4,3-b']dithiophene is described in the fifth chapter. Crystallographic studies of [Ag(CF3SO3)(PPh2{bzdt})n] (n = 1, 2, 3) revealed that all crystallize in centrosymmetric spatial groups and no significant packing effects were verified, that could make these compounds interesting for NLO purposes. The attempt to synthesize new monocyclopentadienylruthenium(II) complexes of the type [Ru(η5,η1 C5Me4C(H)C(H)COO)L2] or [Ru(η5,η1-C5Me4C(H)C(H)COOMe) (L)Cl], in witch the Cp ring and the metal centre would be connected by a π conjugated chain (η1) beside the normal η5 coordination, is described in the sixth chapter

Association of knowledge, preventive counseling and personal health behaviors on physical activity and consumption of fruits or vegetables in community health workers

Abstract\ud \ud Background\ud There is evidence that if a health professional is active and has a healthy diet, he/she is more likely to advise patients about the benefits of physical activity and healthy eating The aims of this study were to: (1) describe the personal physical activity, consumption of fruits and vegetables behaviors and nutritional status of community health workers; (2) evaluate the association between knowledge, delivery of preventive counseling and personal behaviors among community health workers.\ud \ud \ud Methods\ud This was a cross-sectional study conducted in a nationally sample of health professionals working in primary health care settings in Brazil in 2011. This survey was part of the second phase of the Guide for Useful Interventions for Activity in Brazil and Latin America project, and data were collected through telephone interviews of 269 community health workers from the Unified Health Care system of Brazil. We applied questionnaires about personal reported behaviors, knowledge and preventive counseling in physical activity and consumption of fruits and vegetables. We calculated the prevalence and associations between the variables with logistic regression.\ud \ud \ud Results\ud The proportion of community health workers that practiced 150 minutes per week of physical activity in leisure time or transportation was high (64.9%). Half of community health workers were overweight and only 26.2% reported consuming five portions/day of fruits or vegetables. Most community health workers reported counseling about physical activity for more than six months (59.7%), and most were not knowledgeable of the fruits and vegetables and physical activity recommendations. Meeting the fruits and vegetables recommendations was associated with correct knowledge (OR = 4.5; CI95% 1.03;19.7), with reporting 150 minutes or more of physical activity per week (OR = 2.0; CI95% 1.03;3.7) and with reporting physical activity in leisure time (OR = 2.0; CI95% 1.05;3.6). Regular physical activity counseling was associated with reporting 10–149 minutes per week (OR = 3.8; CI95% 1.1;13.3) and with more than 150 minutes of physical activity per week (OR = 4.9; CI95% 1.5;16.5).\ud \ud \ud Conclusion\ud Actions to promote physical activity and healthy eating and to improve knowledge among community health workers within the health care system of Brazil could have a potential positive influence on delivery of preventive counseling to patients on this topic

APICULTURA E RESPONSABILIDADE SOCIAL: DESAFIOS DA PRODUÇÃO E DIFICULDADES EM ADOTAR PRÁTICAS SOCIAL E AMBIENTALMENTE RESPONSÁVEIS

RESUMOO artigo objetiva identificar a percepção e as dificuldades que os produtores têm em adotar práticas mais responsáveis social e ambientalmente. Utilizou-se de método qualitativo, com entrevista semiestruturada com cinco das seis pessoas que participam da Associação de Apicultores. Nesse sentido, a pesquisa utilizou a análise categorial temática, com o desmembramento em categorias conforme os temas que emergem do texto identificando o que eles têm em comum, dividida em quatro categorias temáticas: 3.1 - Perfil dos entrevistados; 3.2 - Determinação da criação de abelhas e da produção do mel; 3.3 - Conhecimento da atividade e importância da associação; 3.4 - Comercialização e responsabilidade social e ambiental. A responsabilidade social em relação ao mel foi evidenciada como um diferencial no produto concentrado nas preocupações com o meio ambiente, influenciando as tomadas de decisões dos apicultores em seus negócios, bem como no comprometimento para a melhoria da qualidade de vida e bem-estar social. Os resultados da pesquisa também demonstraram que a apicultura é uma atividade lucrativa. No entanto, se percebeu que, em decorrência dos associados não estarem bem organizados, têm dificuldades em comercializar seus produtos

Status and Trends of Physical Activity Surveillance, Policy, and Research in 164 Countries: Findings From the Global Observatory for Physical Activity—GoPA! 2015 and 2020 Surveys

Background: Physical activity (PA) surveillance, policy, and research efforts need to be periodically appraised to gain insight into national and global capacities for PA promotion. The aim of this paper was to assess the status and trends in PA surveillance, policy, and research in 164 countries. Methods: We used data from the Global Observatory for Physical Activity (GoPA!) 2015 and 2020 surveys. Comprehensive searches were performed for each country to determine the level of development of their PA surveillance, policy, and research, and the findings were verified by the GoPA! Country Contacts. Trends were analyzed based on the data available for both survey years. Results: The global 5-year progress in all 3 indicators was modest, with most countries either improving or staying at the same level. PA surveillance, policy, and research improved or remained at a high level in 48.1%, 40.6%, and 42.1% of the countries, respectively. PA surveillance, policy, and research scores decreased or remained at a low level in 8.3%, 15.8%, and 28.6% of the countries, respectively. The highest capacity for PA promotion was found in Europe, the lowest in Africa and low- and lower-middle-income countries. Although a large percentage of the world’s population benefit from at least some PA policy, surveillance, and research efforts in their countries, 49.6 million people are without PA surveillance, 629.4 million people are without PA policy, and 108.7 million live in countries without any PA research output. A total of 6.3 billion people or 88.2% of the world’s population live in countries where PA promotion capacity should be significantly improved. Conclusion: Despite PA is essential for health, there are large inequalities between countries and world regions in their capacity to promote PA. Coordinated efforts are needed to reduce the inequalities and improve the global capacity for PA promotion

pH-switchability and second-order nonlinear optical properties of monocyclopentadienylruthenium(II)/iron(II) tetrazoles/tetrazolates: synthesis, characterization, and time-dependent density functional theory calculations

Tetrazole/tetrazolate monocydopentadienyliron(II) and ruthenium(II) compounds of general formulas [(eta(5)-C5H5)M(dppe)(N-4(H)CC6H4NO2)][PF6]/[(eta(5)-C5H5)M(dppe)(N4CC6H4NO2] were investigated for their pH-switching second-order nonlinear optical (SONLO) properties. Compounds [(eta(5)-C5H5)M(dppe)(N4CC6H4NO2) (M = Fe, Ru) and compound [(eta(5)-C5H5)Ru(dppe)(N-4(H)CC6H4NO2)][PF6] were fully characterized by (H-1-, C-13-, P-31-) NMR, cyclic voltammetty, and elemental analysis, and compounds [(eta(5)-C5H5)Fe(dppe)(N4CC6H4NO2)] and [(eta(5)-C5H5)Ru(dppe)(N-4(H)CC6H4NO2)][PF6] were further characterized by single-crystal X-ray diffraction; the synthesis of [(eta(5)-C5H5)Fe(dppe)(N-4(H)CC6H4NO2)][PF6] was unsuccessful. Time-dependent density functional theory calculations were performed using PBE0 and CAM-B3LYP functionals to evaluate the first hyperpolarizability (beta(tot)) of the tetrazole/tetrazolate complexes and for a detailed analysis of the experimental data. Both functionals piedict (i) high first hyperpolarizabilities for the tetrazolate complexes [(eta(5)-C5H5)M(dppe)(N4CC6H4NO2)], with beta(tot)[Ru] approximate to 1.2 beta(tot)[Fe], and (ii) a 3-fold reduction in beta(tot)[Ru] protonation, in complex [(eta(5)-C5H5)Ru(dppe)(N-4(H)CC6H4NO2)](+), forecasting [(eta(5)-C5H5)Ru(dppe)(N4CC6H4NO2)]/[(eta(5)-C5H5)Ru(dppe)(N-4(H)CC6H4NO2)](+) complexes as on/off, pH-switchable SONLO forms.info:eu-repo/semantics/publishedVersio

Cyclopentadienyl–Ruthenium(II) and Iron(II) Organometallic Compounds with Carbohydrate Derivative Ligands as Good Colorectal Anticancer Agents

New ruthenium­(II) and iron­(II) organometallic compounds of general formula [(η⁵-C₅H₅)­M­(PP)<b>Lc</b>]­[PF₆], bearing carbohydrate derivative ligands (<b>Lc</b>), were prepared and fully characterized and the crystal structures of five of those compounds were determined by X-ray diffraction studies. Cell viability of colon cancer HCT116 cell line was determined for a total of 23 organometallic compounds and SAR’s data analysis within this library showed an interesting dependency of the cytotoxic activity on the carbohydrate moiety, linker, phosphane coligands, and metal center. More importantly, two compounds, <b>14Ru</b> and <b>18Ru</b>, matched oxaliplatin IC₅₀ (0.45 μM), the standard metallodrug used in CC chemotherapeutics, and our leading compound <b>14Ru</b> was shown to be significantly more cytotoxic than oxaliplatin to HCT116 cells, triggering higher levels of caspase-3 and -7 activity and apoptosis in a dose-dependent manner