Synthesis of Novel Periodic Mesoporous Organosilicas Containing 1,4,5,8-Naphthalenediimides within the Pore Walls and Their Reduction To Generate Wall-Embedded Free Radicals.

Novel periodic mesoporous organosilicas (PMOs) containing 1,4,5,8-Naphthalenediimide (NDI) chromophores as an integral part of the pore walls were synthesized in acidic conditions, in the presence of inorganic tetraethyl orthosilicate, using triblock copolymer surfactant Pluronic P-123 as a template. The NDI precursor, the bridged silsesquioxane N, N'-bis(3-triethoxysilylpropyl)-1,4,5,8-naphthalenediimide, was synthesized by reaction of 1,4,5,8-naphthalenetetracarboxylic dianhydride with excess 3-aminopropyltriethoxysilane. A series of samples containing up to 19% (weight %) of NDI were prepared (the materials were labeled PMONDIs). 13C and 29Si solid-state nuclear magnetic resonance revealed that the NDI moiety was intact in the PMONDIs and efficiently grafted to the silica network. Samples with up to 16% NDI load presented an ordered two-dimensional-hexagonal mesoscopic structure, according to small-angle X-ray scattering, transmission electron microscopy, and nitrogen adsorption isotherms. Fluorescence spectra of the PMONDIs showed excimer formation upon excitation, suggesting high flexibility of the organic moieties. Reduction of PMONDIs with aqueous sodium dithionite led to the formation of wall-embedded NDI anion radicals, as observed by the appearance of new visible/near-infrared absorption bands. The PMONDIs were also shown to be efficient photocatalysts in the degradation of sulfadiazine, an antibiotic selected here as a model pollutant, which is usually present in water bodies and wastewater.

Periodic mesoporous organosilicas containing naphthalenediimides as organic sensitizers for sulfadiazine photodegradation.

In this work, periodic mesoporous organosilicas (PMO) functionalized with the organic sentisizer naphthalenediimide (NDI) were employed as heterogeneous catalysts for the photodegradation of the antibiotic sulfadiazine (SDZ), taken as a model for contaminants of emerging concern (CECs). The catalysts, designated as PMONDI, were prepared by surfactant-directed co-condensation of the precursor N,N'-bis(3-triethoxysilylpropyl)- 1,4,5,8-naphthalenediimide with tetraethoxysilane. The synthesized PMONDI were characterized using transmission electron microscopy, nitrogen adsorption isotherms and small and large angle x-ray scattering. The performance of PMONDI catalysts in the photodegradation of SDZ was compared to that of TiO2 nanoparticles impregnated into SBA-15 mesoporous silica (TiO2/SBA-15), under irradiation with a Hg lamp with a bandpass filter of 320-500 nm. Under optimal conditions, PMONDI degraded 100% of the SDZ in 45 min, while the total degradation of SDZ was achieved only after 150 min with TiO2/SBA-15. PMONDI also performed better than TiO2/SBA-15 in reuse tests. The mechanism of photodegradation with PMONDI involves the formation of excited triplet states of NDI (3NDI*) upon irradiation, which can then react with molecular oxygen to form reactive oxygen species, which degrade SDZ. Analysis of the SDZ degradation products indicated two main pathways: (1) hydroxylation of the aniline ring and (2) SO2 extrusion and rearrangement, followed by oxidation of the aniline ring to nitrobenzene. In conclusion, the great potential of the PMONDI materials as photocatalysts for CECs degradation was demonstrated in this work, encouraging further research on these materials for the degradation of pollutants.

Functionalized mesoporous silicas SBA-15 for heterogeneous photocatalysis towards CECs removal from secondary urban wastewater.

The photocatalytic activity of TiO2 nanoparticles (NPs) supported on mesoporous silica SBA-15 (TiO2/SBA-15) was evaluated for the photodegradation of sulfadiazine (SDZ), as target contaminant of emerging concern (CEC), using either pure water solutions (PW) or a real secondary urban wastewater (UWW) spiked with SDZ. For this purpose, TiO2/SBA-15 samples with 10, 20 and 30% TiO2 (w/w) were prepared by the sol-gel post synthetic method on pre-formed SBA-15, using titanium (IV) isopropoxide as a precursor. The TiO2/SBA-15 materials were characterized by HRTEM, SAXS and XRD, nitrogen adsorption isotherms and UV-vis diffuse reflectance spectroscopy. TiO2 NPs were shown to be attached onto the external surface, decorating the SBA-15 particles. The TiO2/SBA-15 catalysts were active in SDZ photodegradation using the annular FluHelik photoreactor, when irradiated with UVA light. The 30% TiO2/SBA-15 sample presented the best performance in optimization tests performed using PW, and it was further used for the tests with UWW. The photocatalytic activity of 30% TiO2/SBA-15 was higher (56% SDZ degradation) than that of standard TiO2-P25 (32% SDZ degradation) in the removal of SDZ spiked in the UWW ([SDZ] = 2 mg L-1). The photodegradation of SDZ with 30% TiO2/SBA-15 eached 90% for UWW spiked with a lower SDZ concentration ([SDZ] = 40 µg L-1). Aside of SDZ, a suit of 65 other CECs were also identified in the UWW sample using LC-MS spectrometry. A fast-screening test showed the heterogeneous photocatalytic system was able to remove most of the detected CECs from UWW, by either adsorption and/or photocatalysis.

Avaliação das visitas domiciliárias por estudantes e pelas famílias: uma visão de quem as realiza e de quem as recebe / Evaluation of home visits by students and families: a perspective of the visitors and the visited

A Faculdade de Medicina de Marília (Famema) é reconhecida por favorecer o ensino baseado na prática e centrado no estudante. Os estudantes são inseridos em Unidades de Saúde da Família (USF), onde interagem com a comunidade no desenvolvimento de ações - reflexões - ações, por meio da realização de visitas domiciliárias durante os dois primeiros anos dos cursos de Enfermagem e Medicina. Tais visitas são consideradas ferramentas para a compreensão e o cuidado em necessidades de saúde da família. Dessa maneira, elas têm por objetivo englobar os aspectos sociais, psicológicos e econômicos do indivíduo. Objetivo: Esta pesquisa avalia comparativamente a opinião dos estudantes e das famílias que realizaram e receberam visitas domiciliárias. Métodos: Trata-se de um estudo descritivo e quantitativo que informa a opinião das famílias e dos estudantes a respeito das visitas domiciliárias. Conclusões: As famílias e os estudantes consideram importante a valorização e o aprimoramento da prática, visando à construção humanizada do processo saúde-doença, incentivando, desde o princípio, a formação acadêmica e o vínculo integral entre profissional da saúde e paciente.

The Marilia Medical School (Famema) is known for promoting practice-based and student-centred teaching. Students are placed in different Family Health Units (USF), where they can interact with the community in the development of action - reflection - action by performing home visits during the first two years of the Nursing and Medicine courses. Home visits are considered tools for understanding and caring for family health needs and as such embrace the social, psychological and economic aspects of the individual. Objective: This research investigated and compared the opinions of the student visitors and families who received home visits. Methods: This descriptive and quantitative research informs the opinions of the families and students about the visits. Conclusions: The families and students think it is important to continue investing in and improving this practice, aiming toward a humanized construction of the health-disease process and encouraging stronger ties between the health professional and patient since the start of medical academic education.