[Maternal and child health inequalities among migrants: the case of Haiti and the Dominican RepublicDesigualdades na saúde materno-infantil entre migrantes: o caso do Haiti e da República Dominicana]. / Desigualdades en la salud maternoinfantil de los migrantes: el caso de Haití y la República Dominicana.

OBJECTIVE: To assess coverage and inequalities in maternal and child health interventions among Haitians, Haitian migrants in the Dominican Republic and Dominicans. METHODS: Cross-sectional study using data from nationally representative surveys carried out in Haiti in 2012 and in the Dominican Republic in 2014. Nine indicators were compared: demand for family planning satisfied with modern methods, antenatal care, delivery care (skilled birth attendance), child vaccination (BCG, measles and DPT3), child case management (oral rehydration salts for diarrhea and careseeking for suspected pneumonia), and the composite coverage index. Wealth was measured through an asset-based index, divided into tertiles, and place of residence (urban or rural) was established according to the country definition. RESULTS: Haitians showed the lowest coverage for demand for family planning satisfied with modern methods (44.2%), antenatal care (65.3%), skilled birth attendance (39.5%) and careseeking for suspected pneumonia (37.9%), and the highest for oral rehydration salts for diarrhea (52.9%), whereas Haitian migrants had the lowest coverage in DPT3 (44.1%) and oral rehydration salts for diarrhea (38%) and the highest in careseeking for suspected pneumonia (80.7%). Dominicans presented the highest coverage for most indicators, except oral rehydration salts for diarrhea and careseeking for suspected pneumonia. The composite coverage index was 79.2% for Dominicans, 69.0% for Haitian migrants, and 52.6% for Haitians. Socioeconomic inequalities generally had pro-rich and pro-urban pattern in all analyzed groups. CONCLUSION: Haitian migrants presented higher coverage than Haitians, but lower than Dominicans. Both countries should plan actions and policies to increase coverage and address inequalities of maternal health interventions.

OBJETIVO: Avaliar cobertura e desigualdades nas intervenções em saúde materno-infantil entre os haitianos, migrantes haitianos na República Dominicana e dominicanos. MÉTODOS: Estudo transversal utilizando dados de pesquisas representativas nacionalmente realizadas no Haiti em 2012, e na República Dominicana em 2014. Nove indicadores foram comparados: demanda por planejamento familiar atendida com métodos modernos, atendimento pré-natal, atendimento ao parto (presença de profissional qualificado no parto), vacinação de crianças (BCG, sarampo e DPT3), atendimento de crianças (sais de reidratação oral para diarreia e demanda por assistência por suspeita de pneumonia) e índice composto de cobertura. A riqueza foi medida por meio de índice baseado em recursos, dividido em tercis, e o local de residência (urbano ou rural) foi estabelecido segundo a definição dos países. RESULTADOS: Os haitianos apresentaram a menor cobertura de demanda por planejamento familiar atendida com métodos modernos (44,2%), atendimento pré-natal (65,3%), presença de profissional qualificado no parto (39,5%) e de atendimento por suspeita de pneumonia (37,9%), e a mais alta para sais de reidratação oral na diarreia (52,9%), enquanto os migrantes haitianos tiveram a menor cobertura de DPT3 (44,1%) e sais de reidratação oral para diarreia (38%), e a mais alta na assistência por suspeita de pneumonia (80,7%). Os dominicanos apresentaram a cobertura mais alta para a maioria dos indicadores, exceto para sais de reidratação oral para diarreia e demanda por assistência por suspeita de pneumonia. O índice composto de cobertura foi 79,2% para dominicanos, 69,0% para migrantes haitianos e 52,6% para os haitianos. De forma geral, as desigualdades socioeconômicas apresentaram padrão pró-riqueza e pró-urbano em todos os grupos analisados. CONCLUSÕES: Os migrantes haitianos apresentaram maior cobertura que os haitianos, mas coberturas inferiores aos dominicanos. Ambos os países devem planejar ações e políticas para aumentar a cobertura e abordar as desigualdades nas intervenções em saúde materna.

Desigualdades en la salud maternoinfantil de los migrantes: el caso de Haití y la República Dominicana

[RESUMEN]. Objetivo. Evaluar la cobertura y las desigualdades en las intervenciones de salud maternoinfantil entre haitia-nos, migrantes haitianos en la República Dominicana y dominicanos.Métodos. Estudio transversal con datos de encuestas representativas en el nivel nacional realizadas en Haití en el 2012 y en la República Dominicana en el 2014. Se compararon nueve indicadores: la demanda de pla-nificación familiar satisfecha con métodos modernos, la atención prenatal, la atención del parto (por personal de salud calificado), la vacunación infantil (con vacuna con la tuberculosis, el sarampión y tres dosis de la vacuna triple bacteriana), la gestión de casos de enfermedad en la infancia (administración de sales de rehi-dratación oral para la diarrea y búsqueda de atención sanitaria ante la sospecha de neumonía) e índice de cobertura compuesto. La riqueza se midió mediante un índice basado en los activos, dividido en terciles, y el lugar de residencia (urbano o rural) se determinó según la definición del país.Resultados. La población haitiana mostró la menor cobertura respecto de la demanda de planificación fami-liar satisfecha con métodos modernos (44,2%), atención prenatal (65,3%), asistencia calificada en el parto (39,5%) y búsqueda de atención sanitaria ante la sospecha de neumonía (37,9%), y la mayor cobertura respecto de la administración de sales de rehidratación oral para la diarrea (52,9%); los migrantes haitianos presentaron la menor cobertura en DPT3 (44,1%) y la administración de sales de rehidratación oral para la diarrea (38%) y la mayor cobertura en la búsqueda de atención sanitaria ante la sospecha de neumonía (80,7%). La población dominicana presentó la cobertura más alta en la mayoría de los indicadores, excepto en la administración de sales de rehidratación oral para la diarrea y en la búsqueda de atención sanitaria ante la sospecha de neumonía. El índice de cobertura compuesto fue de 79,2% para los dominicanos, 69,0% para los migrantes haitianos y 52,6% para los haitianos. Las desigualdades socioeconómicas tuvieron, en general, un patrón a favor de los ricos y de las zonas urbanas en todos los grupos analizados.Conclusión. Los migrantes haitianos en la República Dominicana presentaron una mayor cobertura que la población haitiana residente en Haití, pero menor que la población dominicana. Ambos países deberían planificar acciones y políticas para aumentar la cobertura y abordar las desigualdades existentes en las inter-venciones de salud materna.

[ABSTRACT]. Objective. To assess coverage and inequalities in maternal and child health interventions among Haitians, Haitian migrants in the Dominican Republic and Dominicans.Methods. Cross-sectional study using data from nationally representative surveys carried out in Haiti in 2012 and in the Dominican Republic in 2014. Nine indicators were compared: demand for family planning satisfied with modern methods, antenatal care, delivery care (skilled birth attendance), child vaccination (BCG, meas-les and DPT3), child case management (oral rehydration salts for diarrhea and careseeking for suspected pneumonia), and the composite coverage index. Wealth was measured through an asset-based index, divided into tertiles, and place of residence (urban or rural) was established according to the country definition.Results. Haitians showed the lowest coverage for demand for family planning satisfied with modern methods (44.2%), antenatal care (65.3%), skilled birth attendance (39.5%) and careseeking for suspected pneumonia (37.9%), and the highest for oral rehydration salts for diarrhea (52.9%), whereas Haitian migrants had the lowest coverage in DPT3 (44.1%) and oral rehydration salts for diarrhea (38%) and the highest in careseeking for suspected pneumonia (80.7%). Dominicans presented the highest coverage for most indicators, except oral rehydration salts for diarrhea and careseeking for suspected pneumonia. The composite coverage index was 79.2% for Dominicans, 69.0% for Haitian migrants, and 52.6% for Haitians. Socioeconomic inequalities generally had pro-rich and pro-urban pattern in all analyzed groups.Conclusion. Haitian migrants presented higher coverage than Haitians, but lower than Dominicans. Both countries should plan actions and policies to increase coverage and address inequalities of maternal health interventions.

[RESUMO]. Objetivo. Avaliar cobertura e desigualdades nas intervenções em saúde materno-infantil entre os haitianos, migrantes haitianos na República Dominicana e dominicanos. Métodos. Estudo transversal utilizando dados de pesquisas representativas nacionalmente realizadas no Haiti em 2012, e na República Dominicana em 2014. Nove indicadores foram comparados: demanda por planejamento familiar atendida com métodos modernos, atendimento pré-natal, atendimento ao parto (pre-sença de profissional qualificado no parto), vacinação de crianças (BCG, sarampo e DPT3), atendimento de crianças (sais de reidratação oral para diarreia e demanda por assistência por suspeita de pneumonia) e índice composto de cobertura. A riqueza foi medida por meio de índice baseado em recursos, dividido em tercis, e o local de residência (urbano ou rural) foi estabelecido segundo a definição dos países. Resultados. Os haitianos apresentaram a menor cobertura de demanda por planejamento familiar atendida com métodos modernos (44,2%), atendimento pré-natal (65,3%), presença de profissional qualificado no parto (39,5%) e de atendimento por suspeita de pneumonia (37,9%), e a mais alta para sais de reidratação oral na diarreia (52,9%), enquanto os migrantes haitianos tiveram a menor cobertura de DPT3 (44,1%) e sais de reidratação oral para diarreia (38%), e a mais alta na assistência por suspeita de pneumonia (80,7%). Os dominicanos apresentaram a cobertura mais alta para a maioria dos indicadores, exceto para sais de reidratação oral para diarreia e demanda por assistência por suspeita de pneumonia. O índice composto de cobertura foi 79,2% para dominicanos, 69,0% para migrantes haitianos e 52,6% para os haitianos. De forma geral, as desigualdades socioeconômicas apresentaram padrão pró-riqueza e pró-urbano em todos os gru-pos analisados. Conclusões. Os migrantes haitianos apresentaram maior cobertura que os haitianos, mas coberturas inferio-res aos dominicanos. Ambos os países devem planejar ações e políticas para aumentar a cobertura e abordar as desigualdades nas intervenções em saúde materna.

Maternal and child health inequalities among migrants: the case of Haiti and the Dominican Republic.

OBJECTIVE: To assess coverage and inequalities in maternal and child health interventions among Haitians, Haitian migrants in the Dominican Republic and Dominicans. METHODS: Cross-sectional study using data from nationally representative surveys carried out in Haiti in 2012 and in the Dominican Republic in 2014. Nine indicators were compared: demand for family planning satisfied with modern methods, antenatal care, delivery care (skilled birth attendance), child vaccination (BCG, measles and DPT3), child case management (oral rehydration salts for diarrhea and careseeking for suspected pneumonia), and the composite coverage index. Wealth was measured through an asset-based index, divided into tertiles, and place of residence (urban or rural) was established according to the country definition. RESULTS: Haitians showed the lowest coverage for demand for family planning satisfied with modern methods (44.2%), antenatal care (65.3%), skilled birth attendance (39.5%) and careseeking for suspected pneumonia (37.9%), and the highest for oral rehydration salts for diarrhea (52.9%), whereas Haitian migrants had the lowest coverage in DPT3 (44.1%) and oral rehydration salts for diarrhea (38%) and the highest in careseeking for suspected pneumonia (80.7%). Dominicans presented the highest coverage for most indicators, except oral rehydration salts for diarrhea and careseeking for suspected pneumonia. The composite coverage index was 79.2% for Dominicans, 69.0% for Haitian migrants, and 52.6% for Haitians. Socioeconomic inequalities generally had pro-rich and pro-urban pattern in all analyzed groups. CONCLUSION: Haitian migrants presented higher coverage than Haitians, but lower than Dominicans. Both countries should plan actions and policies to increase coverage and address inequalities of maternal health interventions.

OBJETIVO: Evaluar la cobertura y las desigualdades en las intervenciones de salud maternoinfantil entre haitianos, migrantes haitianos en la República Dominicana y dominicanos. MÉTODOS: Estudio transversal con datos de encuestas representativas a nivel nacional realizadas en Haití en 2012 y en la República Dominicana en 2014. Se compararon nueve indicadores: demanda de planificación familiar satisfecha con métodos modernos, atención prenatal, atención del parto (por personal de salud calificado), vacunación infantil (BCG, sarampión y DPT3), gestión de casos de enfermedad en la infancia (administración de sales de rehidratación oral para la diarrea y búsqueda de atención sanitaria ante la sospecha de neumonía), e índice de cobertura compuesto. La riqueza se midió mediante un índice basado en los activos, dividido en terciles, y el lugar de residencia (urbano o rural) se determinó según la definición del país. RESULTADOS: La población haitiana mostró la menor cobertura respecto de la demanda de planificación familiar satisfecha con métodos modernos (44,2%), atención prenatal (65,3%), asistencia calificada en el parto (39,5%) y búsqueda de atención sanitaria ante la sospecha de neumonía (37,9%), y la mayor respecto de la administración de sales de rehidratación oral para la diarrea (52,9%); los migrantes haitianos presentaron la menor cobertura en DPT3 (44,1%) y la administración de sales de rehidratación oral para la diarrea (38%) y la mayor en la búsqueda de atención sanitaria ante la sospecha de neumonía (80,7%). La población dominicana presentó la cobertura más alta en la mayoría de los indicadores, excepto en la administración de sales de rehidratación oral para la diarrea y en la búsqueda de atención sanitaria ante la sospecha de neumonía. El índice de cobertura compuesto fue de 79,2% para los dominicanos, 69,0% para los migrantes haitianos y 52,6% para los haitianos. Las desigualdades socioeconómicas generalmente tenían un patrón prorrico y prourbano en todos los grupos analizados. CONCLUSIÓN: Los migrantes haitianos en la República Dominicana presentaron una mayor cobertura que la población haitiana residente en Haití, pero menor que la población dominicana. Ambos países deberían planificar acciones y políticas para aumentar la cobertura y abordar las desigualdades existentes en las intervenciones de salud materna.

Maternal and child health inequalities among migrants: the case of Haiti and the Dominican Republic

[ABSTRACT]. Objective. To assess coverage and inequalities in maternal and child health interventions among Haitians, Haitian migrants in the Dominican Republic and Dominicans. Methods. Cross-sectional study using data from nationally representative surveys carried out in Haiti in 2012 and in the Dominican Republic in 2014. Nine indicators were compared: demand for family planning satisfied with modern methods, antenatal care, delivery care (skilled birth attendance), child vaccination (BCG, measles and DPT3), child case management (oral rehydration salts for diarrhea and careseeking for suspected pneumonia), and the composite coverage index. Wealth was measured through an asset-based index, divided into tertiles, and place of residence (urban or rural) was established according to the country definition. Results. Haitians showed the lowest coverage for demand for family planning satisfied with modern methods (44.2%), antenatal care (65.3%), skilled birth attendance (39.5%) and careseeking for suspected pneumonia (37.9%), and the highest for oral rehydration salts for diarrhea (52.9%), whereas Haitian migrants had the lowest coverage in DPT3 (44.1%) and oral rehydration salts for diarrhea (38%) and the highest in careseeking for suspected pneumonia (80.7%). Dominicans presented the highest coverage for most indicators, except oral rehydration salts for diarrhea and careseeking for suspected pneumonia. The composite coverage index was 79.2% for Dominicans, 69.0% for Haitian migrants, and 52.6% for Haitians. Socioeconomic inequalities generally had pro-rich and pro-urban pattern in all analyzed groups. Conclusion. Haitian migrants presented higher coverage than Haitians, but lower than Dominicans. Both countries should plan actions and policies to increase coverage and address inequalities of maternal health interventions.

[RESUMEN]. Objetivo. Evaluar la cobertura y las desigualdades en las intervenciones de salud maternoinfantil entre haitianos, migrantes haitianos en la República Dominicana y dominicanos. Métodos. Estudio transversal con datos de encuestas representativas a nivel nacional realizadas en Haití en 2012 y en la República Dominicana en 2014. Se compararon nueve indicadores: demanda de planificación familiar satisfecha con métodos modernos, atención prenatal, atención del parto (por personal de salud calificado), vacunación infantil (BCG, sarampión y DPT3), gestión de casos de enfermedad en la infancia (administración de sales de rehidratación oral para la diarrea y búsqueda de atención sanitaria ante la sospecha de neumonía), e índice de cobertura compuesto. La riqueza se midió mediante un índice basado en los activos, dividido en terciles, y el lugar de residencia (urbano o rural) se determinó según la definición del país. Resultados. La población haitiana mostró la menor cobertura respecto de la demanda de planificación familiar satisfecha con métodos modernos (44,2%), atención prenatal (65,3%), asistencia calificada en el parto (39,5%) y búsqueda de atención sanitaria ante la sospecha de neumonía (37,9%), y la mayor respecto de la administración de sales de rehidratación oral para la diarrea (52,9%); los migrantes haitianos presentaron la menor cobertura en DPT3 (44,1%) y la administración de sales de rehidratación oral para la diarrea (38%) y la mayor en la búsqueda de atención sanitaria ante la sospecha de neumonía (80,7%). La población dominicana presentó la cobertura más alta en la mayoría de los indicadores, excepto en la administración de sales de rehidratación oral para la diarrea y en la búsqueda de atención sanitaria ante la sospecha de neumonía. El índice de cobertura compuesto fue de 79,2% para los dominicanos, 69,0% para los migrantes haitianos y 52,6% para los haitianos. Las desigualdades socioeconómicas generalmente tenían un patrón prorrico y prourbano en todos los grupos analizados. Conclusión. Los migrantes haitianos en la República Dominicana presentaron una mayor cobertura que la población haitiana residente en Haití, pero menor que la población dominicana. Ambos países deberían planificar acciones y políticas para aumentar la cobertura y abordar las desigualdades existentes en las intervenciones de salud materna.

Safety and costs analysis of early hospital discharge after brain tumour surgery: a pilot study.

BACKGROUND: A daily algorithm for hospital discharge (DAHD) is a key point in the concept of Enhanced Recovery After Surgery (ERAS) protocol. We aimed to evaluate the length of stay (LOS), rate of complications, and hospital costs variances after the introduction of the DAHD compared to the traditional postoperative management of brain tumour patients. METHODS: This is a cohort study with partial retrospective data collection. All consecutive patients who underwent brain tumour resection in 2017 were analysed. Demographics and procedure-related variables, as well as clinical outcomes, LOS and healthcare costs within 30 days after surgery were compared in patients before/pre-implementation and after/post-implementation the DAHD, which included: stable neurological examination; oral feeding without aspiration risk; pain control with oral medications; no intravenous medications. The algorithm was applied every morning and discharge was considered from day 1 after surgery if criteria was fulfilled. The primary outcome (LOS after surgery) analysis was adjusted for the preoperative performance status on a multivariable logistic regression model. RESULTS: A total of 61 patients were studied (pre-implementation 32, post-implementation 29). The baseline demographic characteristics were similar between the groups. After the DAHD implementation, LOS decreased significantly (median 5 versus 3 days; p = 0.001) and the proportion of patients who were discharged on day 1 or 2 after surgery increased (44.8% vs 3.1%; p < 0.001). Major and minor complications rates, readmission rate, and unplanned return to hospital in 30-day follow-up were comparable between the groups. There was a significant reduction in the median costs of hospitalization in DAHD group (US$2135 vs US$2765, p = 0.043), mainly due to a reduction in median ward costs (US$922 vs US$1623, p = 0.009). CONCLUSIONS: Early discharge after brain tumour surgery appears to be safe and inexpensive. The LOS and hospitalization costs were reduced without increasing readmission rate or postoperative complications.

Anterior communicating artery duplication associated with a triplication of anterior cerebral artery - A rare anatomical variation.

BACKGROUND: The anterior communicating artery complex may presente several anatomical variations, and many abnormalities have been reported in radiologiacal and cadaveric studies. CASE DESCRIPTION: The authors present a case of a 44-year-old Caucasian female, with a prior history of smoking and arterial systemic hypertension, admitted in the emergency department complaining of a sudden headache, nausea, and vomiting followed by tonic-clonic seizures. Computerized tomography (CT) and angiography (angio- CT) were carried out and showed Fisher Grade IV subarachnoid hemorrhage. Angio-CT revealed an anterior communicating artery (AComA) aneurysm. Minimally invasive craniotomy and microsurgical clipping were performed uneventfully. An unusual anatomical variation of the AComA complex characterized by duplication of the AComA associated with a triplication of anterior cerebral artery (ACA) was observed. The patient was discharged with no neurological deficits. CONCLUISION: This unique anatomical variation of the AComA-ACA complex constitute risck factors for development and rupture of aneurysms.

Relationship between the antiproliferative properties of Cu(II) complexes with the Schiff base derived from pyridine-2-carboxaldehyde and 5,6-diamino-1,3-dimethyluracil and the redox status mediated by antioxidant defense systems on glioma tumoral cells.

A set of new copper(II) complexes containing the Schiff base ligand derived from pyridine-2-carboxaldehyde and 5,6-diamino-1,3-dimethyluracil (6-amino-1,3-dimethyl-5-[(pyridin-2-ylmethylidene)-amino]-pyrimidine-2,4(1H,3H)-dione) with several anions (Cl-, Br-, I-, ClO4-, NO3-) and, two of them with 1,10-phenanthroline, were synthesized and characterized by means of elemental analysis, FT-IR, and single-crystal X-ray diffraction methods. Their ability to act as antitumor agents against C6 glioma cells has been also explored. These complexes contain copper a redox active metal essential for the regulation of cellular pathways that are fundamental for brain function. The antiproliferative activity of the complexes and their effect on cell cycle, apoptosis profile, bioenergetic behavior, intracellular reactive oxygen species (ROS) production, autophagy and enzyme antioxidant defense systems (superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) activities) were analyzed in C6 glioma cells. Although the compounds show limited antiproliferative activity, they are able to modify S-phase of cell cycle and induce G2/M phase arrest. Also, copper(II) complexes promote apoptosis and, in a lesser extent, autophagy, being both processes modulated by ROS generation, due to their property to affect the enzyme antioxidant defense systems, mainly SOD and CAT but not GPx.

Effects on estrogen-dependent and triple negative breast cancer cells growth of Ni(II), Zn(II) and Cd(II) complexes with the Schiff base derived from pyridine-2-carboxaldehyde and 5,6-diamino-1,3-dimethyluracil explored through the renin-angiotensin system (RAS)-regulating aminopeptidases.

A series of Ni(II), Zn(II) and Cd(II) complexes with the Schiff base derived from the condensation 1:1 from pyridine-2-carboxaldehyde and 5,6-diamino-1,3-dimethyluracil (6-amino-1,3-dimethyl-5-[(pyridin-2-ylmethylidene)-amino]pyrimidine-2,4(1H,3H)-dione, DAAUPic) were synthesized and subsequently characterized by means of elemental analysis, FT-IR, NMR and nine of them by X-ray diffraction. Except the [Zn(µ-O,O'-AcO)(N5,N6,N1F-DAAUPicH-1)]2 and [Cd(O,O'-NO3)(µ-O4,(N5,N6,N1F)-DAAUPicH-1)(H2O)]2·2H2O dimers and the [Cd(µ-S,N-SCN)(N5,N6,N1F-DAAUPicH-1)]n chain-like polymer, all of them display monomeric molecular structures. The anticancer activity of compounds was also explored studying their effects on renin-angiotensin system (RAS)-regulating aminopeptidases on estrogen-dependent and triple negative breast cancer cell lines. At the concentrations used, some of the complexes showed different effects on (RAS) peptidases, which support the idea that their effects on cell growth/proliferation could be related to autocrine/paracrine regulatory functions of their corresponding peptide substrates.

La vida normal: living with HIV in Santo Domingo, Dominican Republic.

In this study, we explore how individuals living with HIV in the Dominican Republic strive to live a 'normal' life and the consequences of this pursuit of normalcy. We conducted qualitative in-depth interviews with men (n = 20) and women (n = 20) living with HIV and receiving care at two urban clinics in Santo Domingo. We analysed the data using a combination of narrative analysis and thematic coding. We aimed to identify how fears and/or lived experiences with social rejection and HIV-related stigma and discrimination shaped participants' abilities to maintain social relationships, be economically productive and manage HIV within the context of sexual relationships. Participants used the discourse of una vida normal (a normal life) to frame their response to HIV. This pursuit of normality was driven by the social and economic pressures of living with a chronic condition in a context of HIV-related stigma; trying to keep things 'normal' further added to these pressures. We argue that the normal life discourse fails to recognise the dynamic and complex nature of negotiating this condition and may also create additional burdens for individuals living with HIV that could impact their wellbeing and preventive behaviours.

A combined experimental and DFT investigation on the structure and CO-releasing properties of mono and binuclear fac-ReI(CO)3 complexes with 5-pyridin-2-ylmethylene-amino uracils.

The synthesis, structure and CO-releasing properties of a number of new tricarbonyl rhenium(i) complexes with 5-substituted-6-amino-1,3-dimethyluracils are reported and their structural features discussed on the basis of both spectral and X-ray crystallographic analyses. The 5-substituent library includes -N[double bond, length as m-dash]CH-2py (DAAUPic) and -CH[double bond, length as m-dash]N-N[double bond, length as m-dash]CH-2py (FDUHzPic) as additional metal binding components and chloride, acetonitrile or pyridine acting as ancillary ligands. The compounds have been identified by elemental analysis, NMR, MS and IR spectroscopy. In addition, [ReCl(CO)3(DAAUPic)], [Re(CO)3(FDUHzPic)py]ClO4, [Re(CO)3(FDUHzPic)py]PF6, [Re2Cl2(CO)6(FDUHzPic)] and [Re2Cl(CO)6(FDUHzPicH-1)(H2O)] structures have been solved by X-ray diffraction methods. These studies have clearly shown that the preferred coordination mode to rhenium takes place through the (N1F,N52)-pyridin-2-yl-methyleneamine moiety, the uracil coordinative availability (O4-N51 or N6-N51) being used only to bind the second metal center. The CO-releasing ability of these rhenium compounds has been investigated by the reaction with myoglobin; the corresponding studies have revealed that two of the mononuclear complexes and their related binuclear analogues are able to release CO to a moderate extent. This ability has also been theoretically assessed through a QTAIM analysis. The results, although non-conclusive, may explain somehow possible different preferences in CO releasing power after a comparison between the nature of Re-CO links in mononuclear and binuclear compounds.

Interactions between 2,4-bis-pteridine-1,5-benzodiazepine and group 12 dihalides: synthesis, spectral and XRD structural studies and theoretical calculations.

2,4-Bis(1,3,7-trimethyl-pteridine-2,4(1H,3H)-dione-6-yl)-2,3-dihydro-2-methyl-1H-1,5-benzodiazepine (DLMBZD) has been prepared and its molecular and crystal structures have been determined from spectral and XRD data. The benzodiazepine ligand was reacted with zinc(ii), cadmium(ii) and mercury(ii) chloride, bromide and iodide to give complexes with general formula [M(DLMBZD)X2]. The complexes have been synthesized and characterized by IR, NMR and elemental analysis. The structure of seven complexes has been obtained by single crystal X-ray diffraction. In all the cases, the metal is (2 + 2 + 1)-five-coordinated by two halide ligands, two nitrogen atoms from pyrazine and diazepine rings and a carbonyl oxygen from a pteridine ring. The coordinated-metal environment is a square-based pyramid, with increasing trigonality from Hg(ii) to Zn(ii) complexes. To coordinate the metals, the ligand folds itself, establishing four intramolecular σ-π interactions with the pyrimidine and pyrazine rings. A topological analysis of the electron density using the Quantum Theory of Atoms in Molecules and the complexes stability has been performed.

Silver(I)/6-hydroxyiminolumazine compounds differently modify renin-angiotensin system-regulating aminopeptidases A and N in human neuroblastoma and glioma cells.

We have described that local tissue renin-angiotensin-system (RAS) is involved in tumor growth in a rat model of experimental glioma in vivo, through the modification of their corresponding local proteolytic regulatory enzymes. Thus, we have found a time-dependent significant decrease in aminopeptidase N (APN) and a significant increase in aminopeptidase A (APA) activities concomitantly with tumor growth in tumor tissue whereas no changes were found in circulating aminopeptidase activities; we suggested that angiotensin peptides may play an essential step in both tumor infiltration and associated angiogenesis. Here we analyze in vitro the antiproliferative efficacy, apoptotic properties and effects of three new disilver complexes containing E-6-(hydroxyimino)ethyl-1,3,7-trimethyllumazine (lumazine=pteridine-2,4(1H,3H)-dione) on RAS-regulating APA and APN specific activities in human neuroblastoma and glioma cell lines NB69 and U373-MG. Disilver compounds showed cytotoxicity against both cell lines, although their potency was different for each cell type. Furthermore, NB69 cells need higher concentrations of silver complexes than U373-MG cells to obtain a 50% growth inhibition. All compounds showed apoptotic effects, with U373-MG cells being more susceptible. The three silver complexes tested also show a dose-dependent inhibitory effect on APA activity in NB69 and U373-MG cells, although U373-MG cells are more sensitive. On the contrary, none of them showed effects on APN activity in NB69 neuroblastoma cells whereas the three compounds showed a dose-dependent stimulatory effect on APN activity in U373-MG glioma cells with a similar potency. Disilver complexes show specific antitumor activity against brain tumor cells acting through the paracrine regulating system mediated by local tissue RAS.

Heteropolyhedral silver compounds containing the polydentate ligand N,N,O-E-[6-(hydroxyimino)ethyl]-1,3,7-trimethyllumazine. Preparation, spectral and XRD structural study and AIM calculations.

The oxime derived from 6-acetyl-1,3,7-trimethyllumazine (1) ((E-6-(hydroxyimino)ethyl)-1,3,7-trimethylpteridine-2,4(1H,3H)-dione, DLMAceMox) has been prepared and its molecular and crystal structure determined from spectral and XRD data. The oxime ligand was reacted with silver nitrate, perchlorate, thiocyanate, trifluoromethylsulfonate and tetrafluoroborate to give complexes with formulas [Ag(2)(DLMAceMox)(2)(NO(3))(2)](n) (2), [Ag(2)(DLMAceMox)(2)(ClO(4))(2)](n) (3), [Ag(2)(DLMAceMox)(2)(SCN)(2)] (4), [Ag(2)(DLMAceMox)(2)(CF(3)SO(3))(2)(CH(3)CH(2)OH)]·CH(3)CH(2)OH (5) and [Ag(DLMAceMox)(2)]BF(4) (6). Single-crystal XRD studies show that the asymmetrical residual unit of complexes 2, 3 and 5 contains two quite different but connected silver centers (Ag1-Ag2, 2.9-3.2 Å). In addition to this, the Ag1 ion displays coordination with the N5 and O4 atoms from both lumazine moieties and a ligand (nitrato, perchlorato or ethanol) bridging to another disilver unit. The Ag2 ion is coordinated to the N61 oxime nitrogens, a monodentate and a (O,O)-bridging nitrato/perchlorato or two monodentate O-trifluoromethylsulfonato anions. The coordination polyhedra can be best described as a strongly distorted octahedron (around Ag1) and a square-based pyramid (around Ag2). The Ag-N and Ag-O bond lengths range between 2.22-2.41 and 2.40-2.67 Å, respectively. Although the structure of 4 cannot be resolved by XRD, it is likely to be similar to those described for 2, 3 and 5, containing Ag-Ag units with S-thiocyanato terminal ligands. Finally, the structure of the tetrafluoroborate compound 6 is mononuclear with a strongly distorted tetrahedral AgN(4) core (Ag-N, 2.27-2.43 Å). Always, the different Ag-N distances found clearly point to the more basic character of the oxime N61 nitrogen atom when compared with the pyrazine N5 one. A topological analysis of the electron density within the framework provided by the quantum theory of atoms in molecules (QTAIM) using DFT(M06L) levels of theory has been performed. Every Ag-Ag and Ag-ligand interaction has been characterized in terms of Laplacian of the electron density, [nabla](2)ρ(r), and the total energy density, H(r).

Study of the photoinduced supramolecular chirality in columnar liquid crystals by infrared and VCD spectroscopies.

IR and VCD spectroscopies are employed to clarify the molecular origins of supramolecular chirality in azobenzene-containing columnar liquid crystals. The different columnar mesomorphic assemblies, Colr and Colh, of an achiral and a chiral propeller-like hydrogen-bonded complex, respectively, are used for this study. The mesomorphic behavior of the achiral complex is studied here for the first time, and the structural parameters of its Colr mesophase are determined by X-ray diffraction. Both complexes bear azobenzene units and this makes it possible to implement photoresponsive columnar architectures, the chirality of which can be induced and modulated by irradiation with 488 nm circularly polarized light (CPL). Thin films of the respective rectangular and hexagonal columnar phases of these complexes have been processed in order to study the IR absorption spectra and the vibrational circular dichroism responses upon irradiation with CPL. These studies allow confirming that the outer part of the columns, consisting on azobenzene groups, is mainly involved in the photoinduced supramolecular chirality, rather than the inner part of the columns where a melamine core is located. This supports a structural model based on the helical disposition of the azobenzene groups along the stacked propeller-like complexes.

IR-Raman-VCD study of R-(+)-pulegone: influence of the solvent.

R-(+)-Pulegone is a natural monoterpene obtained from the essential oils of a variety of plants. It is used in flavouring agents, perfumery and aromatherapy. In this work, a study of the molecular structure and the infrared and Raman spectra of this chemical is presented. Theoretical calculations reveal the existence of two conformers depending on the position of the methyl group (axial and equatorial), being the equatorial conformer the most stable. A complete and reliable assignment of the IR and Raman spectra of the title compound is made, and the results are used to carry out a detailed interpretation of the VCD spectrum of this compound in the 4000-900 cm(-1) region. Finally, the influence of the solvent in the VCD bands (intensity and sign) has been tested comparing the neat liquid spectrum with the VCD spectra recorded with four solvents.

Rotational strength sign and normal modes description: A theoretical and experimental comparative study in bicyclic terpenes.

A comparative study of the Vibrational circular dichroism (VCD) patterns in three bicyclic terpenes with related molecular structures, (+)-(R)-α-pinene, (-)-(S)-ß-pinene, and (-)-(S)-verbenone, is carried out. The study is done in the light of normal mode descriptions from a previous vibrational analysis. Although normal modes corresponding to identical molecular moieties shown the same description, rotational strength does not follow the Cahn-Ingold-Prelog descriptor-related sign in some cases, i.e., they do not present opposite signs depending on stereochemical description of the molecule.