abstract: Most of the sunlight powering natural photosynthesis is absorbed by antenna arrays that transfer, and regulate the delivery of excitation energy to reaction centers in the chloroplast where photosynthesis takes place. Under intense sunlight the plants and certain organisms cannot fully utilize all of the sunlight received by antennas and excess redox species are formed which could potentially harm them. To prevent this, excess energy is dissipated by antennas before it reaches to the reaction centers to initiate electron transfer needed in the next steps of photosynthesis. This phenomenon is called non-photochemical quenching (NPQ). The mechanism of NPQ is not fully understood, but the process is believed to be initiated by a drop in the pH in thylakoid lumen in cells. This causes changes in otherwise nonresponsive energy acceptors which accept the excess energy, preventing oversensitization of the reaction center. To mimic this phenomenon and get insight into the mechanism of NPQ, a novel pH sensitive dye 3'6'-indolinorhodamine was designed and synthesized which in a neutral solution stays in a closed (colorless) form and does not absorb light while at low pH it opens (colored) and absorbs light. The absorption of the dye overlaps porphyrin emission, thus making energy transfer from the porphyrin to the dye thermodynamically possible. Several self-regulating molecular model systems were designed and synthesized consisting of this dye and zinc porphyrins organized on a hexaphenylbenzene framework to functionally mimic the role of the antenna in NPQ. When a dye-zinc porphyrin dyad is dissolved in an organic solvent, the zinc porphyrin antenna absorbs and emits light by normal photophysical processes. Time resolved fluorescence experiments using the single-photon-timing method with excitation at 425 nm and emission at 600 nm yielded a lifetime of 2.09 ns for the porphyrin first excited singlet state. When acetic acid is added to the solution of the dyad, the pH sensitive dye opens and quenches the zinc porphyrin emission decreasing the lifetime of the porphyrin first excited singlet state to 23 ps, and converting the excitation energy to heat. Under similar experimental conditions in a neutral solution, a model hexad containing the dye and five zinc porphyrins organized on a hexaphenylbenzene core decays exponentially with a time constant of 2.1 ns, which is essentially the same lifetime as observed for related monomeric zinc porphyrins. When a solution of the hexad is acidified, the dye opens and quenches all porphyrin first excited singlet states to <40 ps. This converts the excitation energy to heat and renders the porphyrins kinetically incompetent to readily donate electrons by photoinduced electron transfer, thereby mimicking the role of the antenna in photosynthetic photoprotection. / Dissertation/Thesis / Ph.D. Chemistry 2012

Nonphotochemical quenching is an important protective mechanism of photosynthetic proteins against excessive irradiation. In this work, isolation of native light harvesting antennae from alga Chromera velia was optimized using methods of sucrose density centrifugation, isoelectric focusing, ion exchange chromatography and gel electrophoresis. Moreover, the ability of light harvesting antennae to trigger nonphotochemical quenching was studied in vivo and in vitro.

There are many factors related to oxidative stress, one of which is exposure to ultraviolet (UV) radiation, which generates reactive oxygen species (ROS). Calendula officinalis L. presents phenolic compounds, saponins, carotenoids, triterpene alcohols, steroids, terpenoids and triterpenoids. Thus, this work aims to perform a phytochemical evaluation of hydroethanolic extract of calendula, and determine its antioxidant capacity and photoprotection in vitro and in cosmetic formulations developed with this extract. Hydroethanolic extract was obtained by maceration, concentrated in a rotary evaporator and then lyophilized. Phenolics, total flavonoids and condensed tannins were determined spectrophotometrically and the identification and quantification of polyphenols was determined by high performance liquid chromatography (HPLC ). The antioxidant capacity was determined by the DPPH method and SPF determined spectrophotometrically. The antiradical activity was assessed by the hydroxyl radical and superoxide method. Extract was embedded in gel and cream formulations and evaluated for physical and chemical stability during 90 days, where the parameters were the organoleptic characteristics, viscosity and pH. During this period, it was also evaluated the spreadability according with the area obtained in relation to the weight applied. Antioxidant capacity and in vitro SPF determinations were also performed on formulations by the methods previously mentioned. The results show that the plant had good antioxidant activity , which can be related to the presence of flavonoids (24.67 mg/g) , polyphenols (33.90 mg/g) and condensed tannins (27.30 mg/g) and the amount of rutin (37.25 mg/g) and quercetin (6.09 mg/g) found in this study, but SPF was low in the extract (1.89), and in the formulations (around 1.7). Gel samples showed a higher spreadability than the cream. All samples remained stable during the storage period, thus maintaining its physical and chemical characteristics. / Existem muitos fatores relacionados com o estresse oxidativo, sendo um deles a exposição à radiação ultravioleta (UV), que gera espécies reativas de oxigênio (ERO). A Calendula officinalis L. apresenta compostos fenólicos, saponinas, carotenoides, alcoóis triterpênicos, esteroides, terpenóides e triterpenóides. Desta forma, este trabalho objetiva realizar uma avaliação fitoquímica do extrato hidroetanólico da calendula, e determinar a sua capacidade antioxidante e fotoprotetora in vitro e também em formulações cosméticas desenvolvidas com este extrato. O extrato hidroetanólico foi obtido por maceração, concentrado em evaporador rotatório e posteriormente liofilizado. Os compostos fenólicos, flavonoides totais e taninos condensados foram determinados espectrofotometricamente e a identificação e quantificação de polifenois foi determinada por cromatografia líquida de alta eficiência (CLAE). A capacidade antioxidante foi determinada pelo método do DPPH e o FPS determinado espectrofotometricamente. A atividade antirradicalar foi avaliada pelo método do radical hidroxila e superóxido. Após a avaliação do extrato, o mesmo foi incorporado em formulações de creme e gel e avaliados em relação à estabilidade físico-química, durante 90 dias, onde os parâmetros utilizados foram as características organolépticas, viscosidade e pH. Durante este período foi ainda avaliada a espalhabilidade de acordo com a área obtida em relação ao peso aplicado. Nas formulações também foram realizadas as determinações da capacidade antioxidante e FPS in vitro pelos métodos citados anteriormente. Os resultados obtidos mostram que o extrato e as formulações apresentaram uma boa capacidade antioxidante, o que pode estar relacionado com a presença de flavonoides (24,67 mg/g), polifenois (33,90 mg/g) e taninos condensados (27,30 mg/g), bem como a quantidade de rutina (37,25 mg/g) e quercetina (6,09 mg/g) encontradas neste estudo, porém o FPS foi baixo no extrato (1,89) e nas formulações (em torno de 1,75). As amostras de gel apresentaram uma espalhabilidade superior à do creme. Todas as amostras mantiveram-se estáveis durante o período de armazenamento, conservando desta maneira as suas características físico-químicas.

Background: Recommendations to restrict summer sunlight exposure to prevent skin cancer apparently conflict with requirements to protect bone health through adequate 25-hydroxyvitamin D (25[OH]D) levels, as provided by cutaneous ultraviolet (UV)B exposure. Furthermore, sunlight exposure promotes a feeling of euphoria that is felt to drive further sun-seeking behaviour. Objectives: My principal objective was to examine health risk (DNA damage) and health benefits (25[OH]D gain, and potential cutaneous photoprotection) following low-level summer sunlight exposures in people of light (phototype II) and darker (phototype V) skin. A further objective was to evaluate serum endocannabinoid levels, potential drivers of mood elevation, following these exposures, and to assess for evidence of tanning addiction in a cross-section of psoriasis patients who had received similar low dose UV exposures, as medical phototherapy. Methods: During wintertime, 10 white Caucasians and 6 South Asians aged 18 to 60 years, from Greater Manchester, UK, received a simulated summer's sunlight exposures, specifically 1.3 standard erythemal dose, thrice weekly for 6 weeks, whilst casually dressed. Serum and urine samples and skin colour measurements were taken at baseline, Monday, Wednesday and Friday of week 1 and then weekly, and buttock skin that had received differential UVR exposures was biopsied for immunohistochemical analysis. Phototype II individuals, who are at higher risk of sunburn, were subsequently challenged with 2X minimal erythema dose (MED) UVB on small areas of simulated summer-exposed and photoprotected skin. Separately, a link to an online tanning questionnaire survey was sent to all members of the National Psoriasis Foundation (USA) during my USA field trip. Results: The simulated summer resulted in 50% gain in 25(OH)D for both phototype groups, but significantly more cutaneous DNA damage (cyclobutane pyrimidine dimers, CPD) in phototype II than V (p<0.0001). There was no accumulation of cutaneous CPD after 6 weeks compared with a single UVR exposure in either group, while phototype V individuals had repaired a greater proportion of their CPD 24 hours after final UVR exposure (p<0.0001). Urinary oxidative DNA damage was higher in phototype II throughout the simulated summer (p=0.002) and unaffected by UVR. All individuals had significant skin darkening, and in phototype II, stratum corneum thickness increased significantly (p<0.05). This tanning response provided significant photoprotection against a pro-inflammatory UVB (2X MED) challenge, as shown by reduced erythema and neutrophil influx in skin exposed to the simulated summer than in photoprotected skin (p<0.05 for both). Serum endocannabinoid (2-arachidonoyl glycerol) levels increased significantly during the simulated summer in both phototype groups (p<0.01), peaking at week 2-3. The cross-sectional study of 1,832 psoriasis patients revealed 34% had used sunbeds; 11% of current users fulfilled diagnostic criteria for addictive-like tanning behaviour: female sex, younger age, younger age at psoriasis diagnosis, severe disease and prior phototherapy were significant risk factors for addiction. Discussion: These findings should assist public health guidance on safe sunlight exposure and highlight the need for distinct guidance targeted to different phototype groups. Furthermore, individuals with psoriasis, in particular those who previously received regular UVR exposure, are at high risk of tanning addiction that may be driven by the endocannabinoid system.

abstract: Non-photochemical quenching (NPQ) is a photoprotective regulatory mechanism essential to the robustness of the photosynthetic apparatus of green plants. Energy flow within the low-light adapted reaction centers is dynamically optimized to match the continuously fluctuating light conditions found in nature. Activated by compartmentalized decreases in pH resulting from photosynthetic activity during periods of elevated photon flux, NPQ induces rapid thermal dissipation of excess excitation energy that would otherwise overwhelm the apparatus’s ability to consume it. Consequently, the frequency of charge separation decreases and the formation of potentially deleterious, high-energy intermediates slows, thereby reducing the threat of photodamage by disallowing their accumulation. Herein is described the synthesis and photophysical analysis of a molecular triad that mimics the effects of NPQ on charge separation within the photosynthetic reaction centers. Steady-state absorption and emission, time-resolved fluorescence, and transient absorption spectroscopies were used to demonstrate reversible quenching of the first singlet excited state affecting the quantum yield of charge separation by approximately one order of magnitude. As in the natural system, the populations of unquenched and quenched states and, therefore, the overall yields of charge separation were found to be dependent upon acid concentration. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2015

abstract: The first chapter reviews three decades of artificial photosynthetic research conducted by the A. Moore, T. Moore, and D. Gust research group. Several carotenoid (Car) and tetrapyrrole containing molecules were synthesized and investigated for excitation energy transfer (EET), photoregulation, and photoprotective functions. These artificial photosynthetic compounds mimicked known processes and investigated proposed mechanisms in natural systems. This research leads to a greater understanding of photosynthesis and design concepts for organic based solar energy conversion devices. The second and third chapters analyze the triplet energy transfer in carotenoid containing dyads. Transient absorption, time-resolved FTIR and resonance Raman spectra revealed that in a 4-amide linked carotenophthalocyanine dyads the Car triplet state is shared across the larger conjugated system, which is similar to protein complexes in oxygenic photosynthetic organisms. In a carotenopurpurin dyad (CarPur) a methylene ester covalent bond prevents the purpurin (Pur) from influencing the Car triplet based on the transient absorption, time-resolved FTIR and resonance Raman spectra. Thus CarPur resembles the antenna proteins from anoxygenic photosynthetic bacteria. Additional examples of carotenoporphyrin dyads further demonstrates the need for orbital overlap for ultrafast triplet energy transfer and the formations of possible intramolecular charge transfer state. The fourth chapter studies a 4-amino phenyl carotenophthalocyanine and its model compounds using high temporal resolution transient absorption spectroscopy techniques. EET from the Car second excited (S2) state to the phthalocyanine (Pc) was determined to be 37% and a coupled hot ground state (S*)/Pc excited state spectrum was observed. Excitation of the tetrapyrrole portion of the dyad did not yield any kinetic differences, but there was an S* signal during the excited states of the dyad. This demonstrates the EET and photoregulating properties of this artificial photosynthetic compound are similar to those of natural photosynthesis. The last chapter covers the synthesis of silicon Pc (SiPc) dyes and the methods for attaching them to gold nanoparticles and flat gold surfaces. SiPc attached to patterned gold surfaces had unperturbed fluorescence, however the selectivity for the gold was low, so alternative materials are under investigation to improve the dye's selectivity for the gold surface. / Dissertation/Thesis / Ph.D. Chemistry 2014

As mudanças climáticas globais, sem dúvida, vêm impactanto muitas culturas de plantas agrícolas e pastagens, afetando potencialmente o crescimento e a produtividade das plantas. Os efeitos significativos podem ser causados pelo aumento das concentrações de CO2 e temperatura no quadro da mudança global. As plantas C3 em termos de fotossíntese e produção de biomassa geralmente respondem positivamente em elevado CO2 atmosférico do que as plantas C4. No entanto, os efeitos do elevado CO2 e do aquecimento podem ser mais complexos do que previsto anteriormente, devido às interações desses fatores. O objetivo deste estudo foi avaliar os efeitos do elevado CO2 (600 ppm) e aquecimento (2 °C de aumento sobre a temperatura ambiente) sobre a fisiologia e bioquímica da forrageira tropical C4 Panicum maximum Jacq. cultivada em um Trop-T-Face (Tropical-Temperature free-air controlled enhancement and free-air carbon dioxide enrichment) sem limitação de água e nutrientes. Foi estimado que o elevado CO2 quando combinado com o aquecimento (eC+eT) aumentou a massa seca do colmo (93%), a biomassa seca total (52%), a área foliar específica (AFE) (12%) e reduziu a razão folha/colmo (30%). Aos 30 dias de experimento, os açúcares solúveis totais das folhas aumentaram com o elevado CO2 (eC) e aquecimento (eT) e depois de 80 dias os açúcares redutores e amido reduziram em eC+eT. Em relação aos carboidratos estruturais, o teor de celulose nas folhas não sofreu variação significativa entre os tratamentos, no entanto, o teor de lignina aumentou em 100% sob eC. Além do incremento em biomassa as plantas foram capazes de evitar fotoinibição do aparato fotossintético e peroxidação lipídica. No tratamento eT os níveis de clorofila aumentaram em 12% e os níveis de -tocoferol reduziram em média de 55%. Os níveis de zeaxantina e luteína, o ciclo de xantofila (VAZ) e o estado de-epoxidação (DPS) do ciclo da xantofila foram alterados pelo elevado CO2 e aquecimento somente depois de 60 dias. Conclui-se que o elevado CO2 e o aquecimento apesar de promoverem uma redução no mecanismo de fotoproteção, a eficiência fotoquímica do fotossistema (PSII) não é danificada se as plantas são cultivadas em condições de disponibilidade hídrica e sem limitação nutricional. No entanto, apesar do aumento em biomassa com elevado CO2 combinado com aquecimento, o elevado CO2 parece resultar em diminuição da qualidade da forragem. / Global climate change undoubtedly impact many agricultural plant crops and grasslands, potentially affecting plant growth and yield. Significant effects may be caused by increased temperature and CO2 concentrations in the frame of global change. It is generally thought that C3 plants may respond positively to atmospheric CO2 enrichment than C4 plants in terms of photosynthesis and biomass accumulation. However, the effects of elevated CO2 and warming may be more complex than previously anticipated due to interactions between these factors. The aim of this study was to evaluate the effects of elevated CO2 (600 ppm) and warming (2 °C increase above ambient temperature) over physiology and biochemistry of the tropical C4 forage Panicum maximum Jacq. grown in a Trop-T-FACE (Tropical-Temperature free-air controlled enhancement and free-air carbon dioxide enrichment) facility under well-watered conditions without nutrient limitation. The combination of elevated CO2 and warming (eC+eT) increased stem dry weight (93%), total dry biomass (52%), specific leaf area (SLA) and decreased the ratio leaves/stem (30%). After 30 days of experiment, total soluble sugar of leaves increased under elevated CO2 (eC) and warming (eT) and carbohydrate sugars and starch decreased in elevated CO2 combined with warming, after 80 days. Regarding structural carbohydrates, cellulose content in leaves had no significant variation between treatments, however, lignin content increased 100% under eC. Furthermore, beyond increase in biomass, plants were able to avoid photoinhibition of the photosynthetic apparatus and lipid peroxidation in response to elevated CO2 and warming. In treatment eT chlorophyll levels increased by 12% and -tocopherol levels decreased by 55%. The de-epoxidation state (DPS) of the xanthophyll cycle, an indicator of excess energy dissipation as heat, xanthophyll cycle pool (VAZ) and both zeaxanthin and lutein levels were changed by elevated CO2 and warming only after 60 days. We conclude that the elevated CO2 and warming while promoting a reduction in photoprotection mechanism, the photochemical efficiency of photosystem (PSII) is not damaged if plants are grown under well-watered and adequate nutritional conditions. However, despite growth increase with elevated CO2 combined warming, elevated CO2 appears to result in decreased quality of forage.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-09-19T19:05:00Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese Rebeca Rivas 2016.pdf: 1582628 bytes, checksum: 8d454ed55a6236c15d5debaa8f636e54 (MD5) / Made available in DSpace on 2016-09-19T19:05:00Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese Rebeca Rivas 2016.pdf: 1582628 bytes, checksum: 8d454ed55a6236c15d5debaa8f636e54 (MD5) Previous issue date: 2016-05-23 / CAPES / Calotropis procera (Apocynaceae) é nativa de áreas áridas e semiáridas. Essa espécie sempre verde e de metabolismo fotossintético C3, é um excelente modelo de estudo para a compreensão da tolerância aos fatores abióticos. A seca é o estresse abiótico que mais influencia no crescimento, no desenvolvimento e na produtividade das espécies vegetais. O presente estudo visa avaliar sob aspectos ecofisiológicos, anatômicos e bioquímicos duas populações de C. procera, durante as estações seca e chuvosa de 2012 e 2013, em condições ambientais diferentes: uma no semiárido e outra no litoral; bem como avaliar plantas jovens de C. procera sob déficit hídrico em condições de casa-de-vegetação. Foram avaliadas as trocas gasosas, quantificação de solutos do metabolismo primário, atividade de enzimas do sistema antioxidativo, análise de atributos anatômicos foliar. Calotropis procera mesmo exposta a ambientes contrastantes apresentou alta taxa fotossintética mesmo na estação seca sob déficit de pressão de vapor (DPV) e densidade de fluxo de fótons fotossintéticos (DFFF) elevados. Também foi observado aumento de pigmentos fotossintéticos, acúmulo de açúcares e aumento na atividade de enzimas do ciclo antioxidativo em ambas as localidades no período seco. Contudo, os ajustes anatômicos foram contrastantes, enquanto no semiárido houve aumento na espessura do mesofilo no período seco, no litoral houve aumento na espessura da cutícula e aumento na densidade de tricomas. As plantas jovens de C. procera alcançaram o máximo estresse após 10 dias de suspensão de rega, quando a condutância estomática (gs) chegou a zero. Para minimizar a perda d’água C. procera reduziu a gs, número de folhas, aumentou na espessura da cutícula e na densidade estomática. O aumento da fotorrespiração, da respiração mitocondrial do dia (Rd), do quenching não fotoquímico (NPQ), dos carotenóides, carboidratos solúveis totais (CST), aminoácidos livres totais (ALT), prolina e aumento na atividade da superóxido dismutase (SOD) garantiram a fotoproteção ao aparato fotoquímico. Com base nos resultados obtidos, C. procera apresenta alta performance fotossintética mesmo sob seca. O metabolismo bioquímico primário apresenta ajustes diferentes nas diferentes condições estudadas. Entretanto, C. procera no litoral e em casa de vegetação sob seca apresentaram estratégias semelhantes quanto aos atributos anatômicos. O conjunto de dados nos faz entender como uma espécie C3, sempre verde apresenta um metabolismo fotossintético intenso sob seca, divergindo da maioria das plantas de metabolismo C3. / Calotropis procera (Apocynaceae) is native from arid and semiarid areas. This species evergreen, and C3 photosynthetic metabolism is an excellent study model for the understanding of the tolerance to abiotic factors. Drought is the most abiotic stress harmful the growth, development and productivity of plant species. This study aims to evaluate in ecophysiological, anatomical and biochemical aspects of two populations of C. procera, during the dry and rainy seasons of 2012 and 2013 in different environments: one in semiarid and another on the seacoast; and evaluate young plants of C. procera under drought at greenhouse conditions. We evaluated the gas exchange, solute quantification of the primary metabolism, enzyme activity of the antioxidant system, analysis of leaf anatomical. Calotropis procera even exposed to contrasting environments showed high photosynthetic rate even the dry season under high vapor pressure deficit (VPD) and photosynthetic photon flux density (PPFD). In addiction was observed increase in photosynthetic pigments, accumulation of sugars and increase in antioxidant enzyme activity in both locations during the dry season. However, the anatomical adjustments were contrasting, while in the semiarid region was observed increase in mesophyll thickness in the dry season, on the seacoast was observed increase in cuticle thickness and increase in trichomes density. Young plants of C. procera reached the maximum stress after 10 days withhold water, when stomatal conductance (gs) reached zero. To minimize water loss, C. procera reduced gs, leaf number, increased cuticle thickness and stomata density. The increase in photorespiration, mitochondrial day respiration (Rd) of non-photochemical quenching (NPQ), carotenoids, soluble carbohydrates, free amino acids, proline and increase in superoxide dismutase (SOD) activity garantee the photoprotection to the photochemical apparatus. Based on the results obtained, C. procera present high photosynthetic performance even under drought. The primary biochemical metabolism has different settings under different conditions. However, C. procera on the seacoast and in greenhouse under drought showed similar strategies regarding the anatomical attributes. The data set help us understand how C3 species, evergreen, present an intense photosynthetic metabolism under drought, diverging of the most C3 plants.

Luz e oxigênio induzem reações de degradação (foto-oxidação) que modificam as propriedades físicas e químicas da matéria, efeitos nocivos da radiação ultravioleta (UV) podem causar descoloração de corantes e pigmentos, amarelamento de plásticos, perda de brilho e da propriedade mecânica (cracking) de materiais, queimaduras, câncer de pele, entre outros problemas relacionados à luz UV. A fim de reduzir os efeitos nocivos da radiação UV e alcançar uma adequada conservação das propriedades dos materiais surgem os absorvedores ou filtros UV. Uma vez que materiais nanométricos a base de cério apresentam atividade fotocatalítica menor e elevada absorção na região do UV tornam-se filtros solares com aplicabilidade em diversas áreas quando comparados aos óxidos utilizados atualmente com função de filtros solares (ZnO e TiO2). Fosfatos de cério (III) (CePO4) foram preparados por Pechini (modificado), síntese hidrotermal e microemulsão reversa; as amostras foram submetidas a tratamento térmico em distintas temperaturas com o intuito de averiguar a estrutura do CePO4 e influência desta na capacidade da absorção UV. Sistemas de óxidos metálicos contendo cério também foram estudados, sendo sintetizados por sol-gel não-alcoóxido e aplicados na forma de pó e filme fino sobre substrato de vidro. A preocupação com a morfologia e o tamanho dos materiais motivou a escolha pelas metodologias de síntese empregadas. Neste trabalho foram exploradas e elucidadas as propriedades dos materiais a base de cério em absorver luz UV, devido às transições 4f-5d dos íons Ce3+ e/ou às transições entre banda de condução e banda de valência. As amostras foram analisadas por espectroscopia de absorção no UV-Vis e na região do infravermelho (FTIR), difração de raios X (XRD), difração de elétrons, susceptibilidade magnética (MS), microscopia eletrônica de varredura (SEM), microscopia eletrônica de transmissão (TEM), espectroscopia de reflectância difusa (DRS), atividade fotocatalítica (AF) e ressonância paramagnética de elétrons (EPR). As excelentes propriedades morfológicas, ópticas e fotocatalíticas indicam a possível aplicação dos materiais à base de cério, foco de investigação do presente trabalho, como filtros solares em proteção cosmetológica (cremes, shampoos, sprays etc) ou de materiais (tintas, vernizes, vidros e outros). / Light and oxygen induce degradation reactions (photo-oxidation) that modify the physical and chemical properties of the matter. The damaging UV radiation is responsible for the discoloration of dyes and pigments, weathering, yellowing of plastics, loss of gloss and mechanical properties (cracking), sunburnt skin and other problems associated to UV light. UV absorbers or UV filters have been used in order to reduce these damaging effects and achieve an adequate conservation of the properties of the materials. In front of this problem, cerium based nanomaterials are promising inorganic UV absorbers for the substitution of zinc and titanium oxide, once it presents high UV absorptivity, a lower refraction index than TiO2 and ZnO, and a higher chemical inertia (and thus a lower photocatalytic activity). Nanostructured cerium phosphates (CePO4) were prepared by Pechini, hydrothermal and reverse microemulsion synthesis, and some parameters (calcinations temperature and reactants rate) employed in each synthesis were investigated. Cerium metal oxide systems synthesized by sol-gel (non-alcooxide) and applied as powder and thin films materials were investigated too. The methodology of the synthesis were chosen aiming ideal morphology and particles size. In this work we explored and elucidated the properties of UV absorber cerium based nanomaterials , due to 4f-5d transitions of Ce3+ ions, charge transference of Ce4+ and, a little portion is due to the contribution of valence and conduction band. The samples were characterized by UV-Vis absorption spectroscopy , Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), electron diffraction, magnetic susceptibility (MS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), photocatalytic activity (PA) and electron paramagnetic resonance (EPR). The excellent morphological, optical and photocatalytic properties indicate the possible application of cerium based materials in solar protection for cosmetics (creams, shampoos, sprays etc.) or materials (paints, varnishes, glass and others).

A associação de filtros solares a compostos bioativos tem sido estudada com ênfase na última década. Contudo, a solubilidade limitada dos compostos naturais, tais como a rutina, restringe o desenvolvimento de preparações cosméticas seguras, funcionais e estáveis. A proposta deste estudo envolveu a obtenção de nanoestruturas de gelatina (contendo ou não rutina) para aplicação em protetores solares. Os objetivos específicos foram: (1) preparar partículas de gelatina; (2) realizar a caracterização física, físico-química, morfológica, térmica e funcional (in vitro); (3) avaliar a citotoxicidade e a penetração/permeação curtânea in vitro dos sistemas; (4) desenvolver fotoprotetores bioativos de eficácia estimada in vitro; e (5) determinar a segurança e eficácia clínica fotoprotetora das preparações contendo as estruturas proteicas. As nanopartículas apresentaram-se esféricas e com diâmetro médio e índice de polidispersividade variando entre 318,9 ± 6,9 (B-NC) a 442,8 ± 4,9 nm (R-NC) e 0,06 ± 0,03 (B-NC) a 0,12 ± 0,01 (R-NC), respectivamente. Os valores do potencial zeta apresentaram-se entre -28,5 ± 0,9 mV (B-NC) e -26,6 ± 0,5 mV (R-NC). R-NC apresentou eficiência de associação equivalente a 51,8 ± 1,4%. Os ensaios de segurança das nanopartículas evidenciaram perfil citotóxico adequado para aplicação cosmética, bem como, a ausente tendência de penetração/permeação cutânea. Tendo em vista os resultados obtidos in vitro, as nanopartículas contendo rutina apresentaram capacidade antioxidante 74% superior à rutina em seu estado livre e contribuíram para o aumento de 48% do fator de proteção solar (FPS) quando associada à avobenzona (butyl methoxydibenzoylmethane), ao p-metoxicinamato de octila (ethylhexyl methoxycinnamate) e ao octil dimetil PABA (ethylhexyl dimethyl PABA). A avaliação da eficácia clínica das formulações evidenciou a influência da nanopartícula, sem adição do flavonoide, na proteção da pele contra a formação do eritema UV induzido. Por meio da avaliação dos aspectos funcionais, foi possível constatar, in vitro e in vivo, que a adição das nanopartículas em sistemas fotoprotetores influenciou seu perfil de transmitância da radiação UV, bem como, seus efeitos sobre o eritema UV induzido. Os resultados obtidos apresentaram perspectivas de aplicação prática no desenvolvimento de produtos cosméticos fotoprotetores associados a substâncias bioativas, por meio de plataforma nanotecnológica. / Especially, in the last decade, the association of chemical filters and bioactive compounds has been studied by several authors. However, the limited solubility of natural compounds, such as rutin restricts the development of safe and stable cosmetic preparations. The aim of this work was the development of gelatin nanoparticles (with or without rutin) as an ingredient in sunscreens. The specific goals were: (1) the development of rutin-loaded gelatin nanoparticles; (2) to perform the physical, physical-chemical, morphological, thermal and functional (in vitro) analysis; (3) to assess the cytotoxicity and skin penetration / permeation in vitro of the nanoparticles; (4) to develop bioactive sunscreens and to perform the in vitro photoprotection efficacy assay; and (5) to evaluate the in vivo sun protection factor (SPF) of the formulations. The nanoparticles were spherical with an average size and polydispersive index between 318.9 ± 6.9 nm (B-NC) at 442.8 nm ± 4.9 (R-NC), and 0.06 ± 0, 03 (B-NC) to 0.12 ± 0.01 (R-NC). The zeta potential values were high and negative, ranging from - 28.5 ± 0.9 mV (B-NC) and -26.6 ± 0.5 mV (R-NC). R-NC entrapment efficient was 51.8 ± 1.4%. The nanoparticle safety assessment showed a cytotoxic profile suitable for cosmetic application, as well as the absent trend of penetration/ permeation of the skin. The in vitro results indicated that the rutin-loaded gelatin nanoparticles increased 74% the antioxidant profile in comparison with free rutin and also increased 48% the SPF (in vitro) when combined with butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate and ethylhexyl dimethyl PABA. The assessment of the clinical efficacy assays showed the influence of blank nanoparticle in the protection of the skin against UV-induced erythema response. It was established in vitro and in vivo that the addition of gelatin nanoparticles in sunscreens influenced its UV transmittance profile, as well as its anti-erythema effects on the skin. The results have practical application in the development of sunscreen with bioactive ingredients and at the design of an innovative ingredient with a chemopreventive profile.