Theoretical investigation of [Ru(bpy)2(HAT)]2+ (HAT = 1,4,5,8,9,12-hexaazatriphenylene; bpy = 2,2'-bipyridine): Photophysics and reactions in excited state.

In this article, Density Functional Theory based calculations, including dispersion corrections, PBE0(D3BJ)/Def2-TZVP(-f), were performed to elucidate the photophysics of the [Ru(bpy)2(HAT)]2+ complex in water. In addition, the thermodynamics of the charge and electron transfer excited state reactions of this complex with oxygen, nitric oxide and Guanosine-5'-monophosphate nucleotide (GMP) were investigated. The first singlet excite state, S1, strongly couples with the second and third triplet excited states (T2 and T3) giving rise to a high intersystem crossing rate of 6.26 × 1011 s-1 which is ∼106 greater than the fluorescence rate decay. The thermodynamics of the excited reactions revealed that all electron transfer reactions investigated are highly favorable, due mainly to the high stability of the triply charged radical cation 2PS•3+ species formed after the electron has been transferred. Excited state electron transfer from the GMP nucleotide to the complex is also highly favorable (ΔGsol = -92.6 kcal/mol), showing that this complex can be involved in the photooxidation of DNA, in line with experimental findings. Therefore, the calculations allow to conclude that the [Ru(bpy)2(HAT)]2+ complex can act in Photodynamic therapy through both mechanisms type I and II, through electron transfer from and to the complex and triplet-triplet energy transfer, generating ROS, RNOS and through DNA photooxidation. In addition, the work also opens a perspective of using this complex for the in-situ generation of the singlet nitroxyl (1NO-) species, which can have important applications for the generation of HNO and may have, therefore, important impact for physiological studies involving HNO.

Historical geographic overlap of human rickettsiosis with animal reservoirs in Juiz de Fora, Minas Gerais, Brazil / Sobreposição geográfica histórica da riquetsiose humana com reservatórios animais em Juiz de Fora, Minas Gerais, Brasil

Background and objectives: we investigated the existence of a historical geographic overlap between the location of spotted fever group rickettsiosis human cases, a disease caused by the gram-negative bacterium Rickettsia sp., and that of mammalian reservoirs, specifically domestic horses and capybaras, in the urban perimeter of the city of Juiz de Fora, Minas Gerais, Brazil. Methods: cases of human rickettsiosis that occurred during a period of 17 years (2003-2020) were geolocated and the distribution of cases in time and geographic space was assessed using 1st and 2nd order geospatial association indicators. We also analyzed the overlap between the locations of human rickettsiosis cases and the area of occurrence of domestic horses and capybaras. Results: men were diagnosed more often than women, but a large proportion of affected women died. The results indicate an aggregation of human rickettsiosis cases in time (cases tend to occur close to each other at each epidemic event) and in geographic space (cases are concentrated in a specific geographic region of the urban perimeter). Human cases seem to be more associated with city regions with: i) higher local frequency of domestic horses and not capybaras; ii) lower rates of family development. Conclusion: it is suggested that, in the local epidemiological scenario, domestic horses appear to be the main sources of the rickettsia infecting humans, not capybaras.(AU)

Justificativa e objetivos: foi investigada a existência de uma sobreposição geográfica histórica entre a localização dos casos de riquetsiose humana do grupo da febre maculosa, um grupo de doenças causadas pela bactéria Gram-negativa Rickettsia sp., e dos reservatórios mamíferos, especificamente cavalos domésticos e capivaras, no perímetro urbano do município de Juiz de Fora, Minas Gerais, Brasil. Métodos: foram geolocalizados os casos de riquetsiose humana ocorridos durante um período de 17 anos (2003-2020), sendo avaliada a distribuição dos casos no tempo e espaço geográfico através de indicadores de associação geoespacial de 1a e 2a ordem. Também analisamos a superposição dos locais dos casos de riquetsiose humana com a área de ocorrência de cavalos domésticos e capivaras. Resultados: homens foram diagnosticados mais frequentemente que as mulheres, mas grande proporção das mulheres acometidas faleceu. Os resultados indicam uma agregação dos casos de riquetsiose humana no tempo (os casos tendem a ocorrer próximos entre si a cada evento epidêmico) e no espaço geográfico (os casos se concentram em uma região geográfica específica do perímetro urbano). Os casos humanos aparentam ser mais associados às regiões da cidade com: i) maior frequência local de cavalos domésticos e não das capivaras; ii) menores índices de desenvolvimento familiar. Conclusão: sugere-se que, no cenário epidemiológico local, são os cavalos domésticos que aparentam ser as principais fontes da riquétsia infectando os humanos, não as capivaras.(AU)

Justificación y objetivos: investigamos la existencia de una superposición geográfica histórica entre la localización de casos de rickettsiosis exantemáticas humana, enfermedad causada por la bacteria gramnegativa Rickettsia sp., y la de mamíferos reservorios, específicamente caballos domésticos y capibaras, en el perímetro urbano de la ciudad de Juiz de Fora, Minas Gerais, Brasil. Métodos: se geolocalizaron los casos de rickettsiosis humana ocurridos durante un período de 17 años (2003-2020), y se evaluó la distribución de casos en el tiempo y espacio geográfico utilizando indicadores de asociación geoespacial de 1er y 2do orden. También analizamos la superposición entre las ubicaciones de los casos de rickettsiosis humana y el área de ocurrencia de los caballos domésticos y capibaras. Resultados: los hombres fueron diagnosticados con más frecuencia que las mujeres, pero una gran proporción de mujeres afectadas fallecieron. Los resultados indican una agregación de casos de rickettsiosis humana en el tiempo (los casos tienden a ocurrir cerca uno del otro en cada evento epidémico) y en el espacio geográfico (los casos se concentran en una región geográfica específica del perímetro urbano). Los casos humanos parecen estar más asociados con regiones urbanas con: i) mayor frecuencia local de caballos domésticos y no de capibaras; ii) menores tasas de desarrollo familiar. Conclusión: se sugiere que, en el escenario epidemiológico local, los caballos domésticos parecen ser las principales fuentes de la rickettsia que infecta a los humanos, no los capibaras.(AU)

Evidence of Leishmania (Leishmania) infantum infection in dogs from Juiz de Fora, Minas Gerais State, Brazil, based on immunochromatographic dual-path platform (DPP®) and PCR assays.

In Brazil, domestic dogs are branded as the primary reservoir for zoonotic visceral leishmaniasis, due to the clear positive correlation observed between human and canine infection rates. This study aimed to carry out a serological survey of canine visceral leishmaniasis (CVL) in dogs housed at a public kennel in the municipality of Juiz de Fora, Minas Gerais State, Brazil, using the immunochromatographic TR DPP® CVL rapid test. Additionally, conventional and/or real time PCR assay was used to detect and confirm L. infantum infection in the DPP positive dogs only. Of the 400 dogs studied, most did not present clinical signs for CVL (p < 0.05), and fifteen (3.8%) were seropositive in the DPP test. There was no statistically significant difference between the DPP seropositive dogs and the clinical signs of the disease (p > 0.05). Both conventional and real time PCR tests confirmed L. infantum infection in nine (75.0%) of the twelve DPP seropositive dogs that remained alive during the follow-up period. This study is the first seroepidemiologic survey of CVL held in the city of Juiz de Fora, and the results reinforce the idea that this disease is currently in a process of expansion and urbanization in Brazil. Furthermore, this study highlights the use of the DPP test as an alternative for diagnosing CVL in large and mid-sized cities, due to its ease of implementation.

EVIDENCE OF Leishmania (Leishmania) infantum INFECTION IN DOGS FROM JUIZ DE FORA, MINAS GERAIS STATE, BRAZIL, BASED ON IMMUNOCHROMATOGRAPHIC DUAL-PATH PLATFORM (DPP®) AND PCR ASSAYS / Evidência de infecção por Leishmania (Leishmania) infantum em cães de Juiz de Fora, Minas Gerais, Brasil, detectada pelo teste imunocromatográfico rápido DPP e PCR

In Brazil, domestic dogs are branded as the primary reservoir for zoonotic visceral leishmaniasis, due to the clear positive correlation observed between human and canine infection rates. This study aimed to carry out a serological survey of canine visceral leishmaniasis (CVL) in dogs housed at a public kennel in the municipality of Juiz de Fora, Minas Gerais State, Brazil, using the immunochromatographic TR DPP® CVL rapid test. Additionally, conventional and/or real time PCR assay was used to detect and confirm L. infantum infection in the DPP positive dogs only. Of the 400 dogs studied, most did not present clinical signs for CVL (p < 0.05), and fifteen (3.8%) were seropositive in the DPP test. There was no statistically significant difference between the DPP seropositive dogs and the clinical signs of the disease (p > 0.05). Both conventional and real time PCR tests confirmed L. infantum infection in nine (75.0%) of the twelve DPP seropositive dogs that remained alive during the follow-up period. This study is the first seroepidemiologic survey of CVL held in the city of Juiz de Fora, and the results reinforce the idea that this disease is currently in a process of expansion and urbanization in Brazil. Furthermore, this study highlights the use of the DPP test as an alternative for diagnosing CVL in large and mid-sized cities, due to its ease of implementation.

No Brasil, cães domésticos são considerados como os principais reservatórios da leishmaniose visceral zoonótica, devido à clara correlação positiva existente entre as curvas de infecção humana e canina. Este estudo objetivou a realização de um inquérito sorológico da leishmaniose visceral canina (LVC) em cães abrigados em um canil público de Juiz de Fora, Minas Gerais, Brasil, através do teste rápido imunocromatográfico TR DPP®. Adicionalmente, a PCR convencional e/ou em tempo real foi usada para detectar/confirmar a infecção por L. infantum apenas nos animais DPP positivos. Dos 400 cães estudados, a maioria não apresentou sinais clínicos para a LVC (p < 0,05) e quinze (3,8%) foram sororreativos ao DPP. Não houve diferença estatisticamente significativa entre os cães com DPP positivo e os sinais clínicos para a doença (p > 0,05). PCR convencional e em tempo real confirmaram a infecção por L. infantum em nove (75,0%) dos doze animais DPP positivos que permaneceram vivos durante o estudo. Este é o primeiro estudo soroepidemiológico sobre LVC realizado no município de Juiz de Fora, e os resultados reforçam a idéia de que esta doença está em processo de expansão e urbanização no Brasil. Além disto, este estudo destaca o uso do DPP como uma alternativa para o diagnóstico da LVC em cidades de médio e grande porte, devido à facilidade de execução.