Classes of Amides that Undergo Selective N-C Amide Bond Activation: The Emergence of Ground-State Destabilization.

Ground-state destabilization of the N-C(O) linkage represents a powerful tool to functionalize the historically inert amide bond. This burgeoning reaction manifold relies on the availability of amide bond precursors that participate in weakening of the nN → π*C=O conjugation through N-C twisting, N pyramidalization, and nN electronic delocalization. Since 2015, acyl N-C amide bond activation through ground-state destabilization of the amide bond has been achieved by transition-metal-catalyzed oxidative addition of the N-C(O) bond, generation of acyl radicals, and transition-metal-free acyl addition. This Perspective summarizes contributions of our laboratory in the development of new ground-state-destabilized amide precursors enabled by twist and electronic activation of the amide bond and synthetic utility of ground-state-destabilized amides in cross-coupling reactions and acyl addition reactions. The use of ground-state-destabilized amides as electrophiles enables a plethora of previously unknown transformations of the amide bond, such as acyl coupling, decarbonylative coupling, radical coupling, and transition-metal-free coupling to forge new C-C, C-N, C-O, C-S, C-P, and C-B bonds. Structural studies of activated amides and catalytic systems developed in the past decade enable the view of the amide bond to change from the "traditionally inert" to "readily modifiable" functional group with a continuum of reactivity dictated by ground-state destabilization.

Predictors of physical activity levels in individuals with Parkinson's disease: a cross-sectional study.

BACKGROUND: To investigate whether modifiable predictors (depressive symptoms, impairment in behavior and mood, balance impairments, and knee extensor muscle strength) are determinants of the physical activity level in Parkinson's disease. MATERIALS AND METHODS: A cross-sectional study with individuals diagnosed with idiopathic Parkinson's disease. Regression analysis of the data was used to investigate whether depressive symptoms, impairments in behavior and mood, balance impairments, or dominant knee extensor muscle strength are predictors of physical activity levels in Parkinson's disease. RESULTS: A total of 50 individuals with mild to moderate Parkinson's disease participated in this study, with a mean age of 67 ± 8 years and 68% male. Balance impairments explained 29% of the variation in the physical activity levels. The explained variance increased to 34% when depressive symptoms were included in the model. CONCLUSION: Among the predictor variables investigated in our study, only balance impairments and depressive symptoms explained the variance in physical activity levels in individuals with Parkinson's disease.

N-Heterocyclic Carbene Complexes of Nickel(II) from Caffeine and Theophylline: Sustainable Alternative to Imidazol-2-ylidenes.

Xanthines, such as caffeine and theophylline, are abundant natural products that are often present in foods. Leveraging renewable and benign resources for ligand design in organometallic chemistry and catalysis is one of the major missions of green and sustainable chemistry. In this Special Issue on Sustainable Organometallic Chemistry, we report the first nickel-N-heterocyclic carbene complexes derived from Xanthines. Well-defined, air- and moisture-stable, half-sandwich, cyclopentadienyl [CpNi(NHC)I] nickel-NHC complexes are prepared from the natural products caffeine and theophylline. The model complex has been characterized by x-ray crystallography. The evaluation of steric, electron-donating and π-accepting properties is presented. High activity in the model Suzuki-Miyaura cross-coupling is demonstrated. The data show that nickel-N-heterocyclic carbenes derived from both Earth abundant 3d transition metal and renewable natural products represent a sustainable alternative to the classical imidazol-2-ylidenes.

Pd-PEPPSI N-Heterocyclic Carbene Complexes from Caffeine: Application in Suzuki, Heck, and Sonogashira Reactions.

The first synthesis of Pd-PEPPSI N-heterocyclic carbene complexes derived from the abundant and renewable natural product caffeine is reported. The catalysts bearing 3-chloro-pyridine, pyridine and N-methylimidazole ancillary ligands were readily prepared from the corresponding N9-Me caffeine imidazolium salt by direct deprotonation and coordination to PdX2 in the presence of N-heterocycles or by ligand displacement of PdX2(Het)2. The model Pd-PEPPSI-caffeine complex has been characterized by x-ray crystallography. The complexes were successfully employed in the Suzuki cross-coupling of aryl bromides, Suzuki cross-coupling of amides, Heck cross-coupling and Sonogashira cross-coupling. Computational studies were employed to determine frontier molecular orbitals and bond order analysis of caffeine derived Pd-PEPPSI complexes. This class of catalysts offers an entry to utilize benign and sustainable biomass-derived Xanthine NHC ligands in the popular Pd-PEPPSI systems in organic synthesis and catalysis.

Telerreabilitação na fisioterapia neurofuncional pediátrica durante a pandemia de COVID-19: percepção dos pais, desafios e contribuições / Telerehabilitation in pediatric neurofunctional physical therapy during the COVID-19 pandemics: parent's perception, challenges and contributions

INTRODUÇÃO: A telerreabilitação é uma modalidade de atendimento realizado à distância que foi considerada um recurso fundamental durante a pandemia da COVID-19. Entretanto, era uma modalidade ainda não vivenciada por muitos profissionais e familiares. OBJETIVO: Descrever a percepção dos pais ou responsáveis por crianças em tratamento fisioterapêutico, sobre os desafios e as contribuições da experiência com a telerreabilitação realizada em serviço ambulatorial durante a pandemia de COVID-19. MATERIAIS E MÉTODOS: Estudo observacional transversal exploratório, realizado com pais ou responsáveis por crianças, com idade entre 0 a 12 anos, com qualquer condição de saúde neurológica ou musculoesquelética em acompanhamento fisioterapêutico por telerreabilitação, no período de junho a agosto de 2021. Um questionário elaborado pelas autoras com perguntas sobre a percepção dos responsáveis, desafios e contribuições da telerreabilitação foi encaminhado para os responsáveis por meio de um link do Google Forms, via e-mail ou aplicativo de mensagem no celular, e foi auto aplicado. Realizaramse análises descritivas dos dados coletados por meio da frequência de respostas dos pais ou responsáveis nas questões específicas. As variáveis numéricas foram apresentadas como média ± desvio-padrão e as variáveis categóricas, como frequências absolutas e relativas. RESULTADOS: Dezoito responsáveis receberam e responderam o questionário completamente. A mãe foi a responsável mais citada, a maioria das crianças recebeu atendimento duas vezes na semana e o diagnóstico mais prevalente foi paralisia cerebral. Setenta e três por cento dos responsáveis avaliaram a telerreabilitação como acima do nível esperado e com contribuição além de suas expectativas. CONCLUSÃO: De acordo com a percepção dos pais, sobre os desafios e as contribuições da experiência com a telerreabilitação realizada em serviço ambulatorial, os benefícios parecem superar os desafios.

INTRODUCTION: Telerehabilitation is a modality of care provided remotely that was considered a fundamental resource during the COVID-19 pandemic. However, it was a modality not yet experienced by many professionals and family members. OBJECTIVE: To describe the perception of parents or guardians of children undergoing physical therapy, about the challenges and contributions of the experience with telerehabilitation performed in an outpatient service during the COVID-19 pandemics. MATERIAL AND METHODS: An exploratory crosssectional observational study carried out with parents or guardians of children, aged between 0 and 12 years old, with any neurological or musculoskeletal health condition in physiotherapeutic treatment by telerehabilitation, from June to August 2021. A questionnaire prepared by the authors with questions about the perception of those responsible, challenges and contributions of telerehabilitation was sent to those responsible through a Google Forms link, by email or mobile messaging app and was self-applied. Descriptive analysis of the data collected was carried out through the frequency of responses from parents or guardians on specific questions. Numerical variables were presented as mean ± standard deviation and categorical variables as absolute and relative frequencies. RESULTS: Eighteen guardians received and answered the questionnaire completely. The mother was the most cited guardian, most children received care twice a week and the most prevalent diagnosis was cerebral palsy. Seventythree percent of those responsible rated telerehabilitation as above the expected level and with a contribution beyond their expectations. According to them, the greatest contribution of telerehabilitation was the satisfactory motor development presented by the children during the period of social isolation. CONCLUSION: According to the parents' perception of the challenges and contributions of the experience with telerehabilitation performed in outpatient service, the benefits seem to outweigh the challenges.

Acessibilidade nas corridas de rua: barreiras percebidas pelas pessoas com deficiência visual / Accessibility in street races: barriers perceived by people with visual impairment / Accesibilidad en las carreras de calle: barreras percibidas por las personas con discapacidad visual

O objetivo deste estudo foi identificar as barreiras percebidas pelas pessoas com deficiência visual para a prática da corrida de rua. Participaram da pesquisa sete indivíduos com deficiência visual residentes de Florianópolis, com idades entre 22 e 54 anos. Foi realizada uma entrevista semiestruturada, objetivando levantar informações sobre as barreiras para a prática esportiva. Por meio dos relatos foram observadas barreiras urbanísticas relacionadas ao terreno e obstáculos e barreiras específicas do esporte por questões de insegurança em virtude da falta de acessibilidade e em relação ao guia e à desigualdade de participação nas competições. Também foram mencionadas barreiras de comunicação e informação, atitudinais, tecnológicas e arquitetônicas. Nota-se que pessoas com deficiência visual enfrentam inúmeras barreiras para a prática da corrida de rua, dificultando sua manutenção. O estudo propõe possibilidades de soluções aos problemas encontrados, diminuindo, significativamente, as principais barreiras e contribuindo para uma prática segura e igualitária

This study aimed at identifying the barriers perceived by people with visual impairment to practice street racing. Participants were seven 22-54-year-old visually impaired residents from Florianópolis. A semi-structured interview was conducted to gather information about the barriers to sports practice. Their accounts pointed to city planning barriers related to the terrain as well as obstacles and barriers specific to sport related to insecurity due to lack of accessibility, guides and unequal participation in competitions. They also mentioned communication and information, attitudinal, technological and architectural barriers. People with visual impairment face numerous barriers to practice street racing, making it difficult to maintain it. The study proposes possible solutions to the problems found, significantly reducing the main barriers and contributing to safe and egalitarian practice

El objetivo de este estudio fue identificar las barreras percibidas por las personas con discapacidad visual para la práctica de carreras de calle. Participaron en la investigación siete individuos con discapacidad visual, residentes de Florianópolis, con edades entre 22 y 54 años. Se realizó una entrevista semiestructurada con el objetivo de obtener informaciones sobre las barreras para la práctica deportiva. A través de los relatos se observaron barreras urbanísticas relacionadas al terreno y obstáculos y barreras específicas del deporte por cuestiones de inseguridad debido a la falta de accesibilidad y en relación al guía y a la desigualdad de participación en las competiciones. También se mencionaron barreras de comunicación e información, actitudinales, tecnológicas y arquitectónicas. Es notorio que personas con deficiencia visual enfrentan innumerables barreras en la práctica de carreras de calle, dificultando mantenerlas. El estudio propone posibilidades de soluciones a los problemas encontrados, disminuyendo, significativamente, las principales barreras y contribuyendo para una práctica segura e igualitaria