I) Improving low photocurrent of pseudorotaxane based solar cell II) Synthesis and characterization of new Fe(0) cyclopentadienone complexes

Next to conventional solar panels that harvest direct sunlight, p-type dye-sensitized solar cells (DSSCs) have been developed, which are able to harvest diffuse sunlight. Due to unwanted charge recombination events p-type DSSCs exhibit low power conversion efficiencies (PCEs). Previous research has shown that dye-redox mediator (RM) interactions can prevent these recombination events, resulting in higher PCEs. It is unknown how the nature of dye-RM interactions affects the PCEs of pseudorotaxane-based solar cells. In this research this correlation is investigated by comparing one macrocycle, the 3-NDI, in combination with the three dyes that contains a recognition sites. 2D-DOSY-NMR experiments have been conducted to evaluate the diffusion constants (LogD) of the three couple. The research project has been stopped due to the coronavirus pandemic. The continuation of this thesis would have been to synthesize a dye on the basis of the data obtained from the diffusion tests and attempt the construction of a solar cell to then evaluate its effectiveness. During my training period I synthetized new Fe(0) cyclopentadienone compounds bearing a N-Heterocyclic Carbene ligand. The aim of the thesis was to achieve water solubility by modifications of the cyclopentadienone ligand. These new complexes have been modified using a sulfonation reaction, replacing an hydroxyl with a sulfate group, on the alkyl backbone of the cyclopentadienone ligand. All the complexes were characterized with IR, ESI-MS and NMR spectroscopy, and a new Fe(0) cyclopentadienone complex, involved as an intermediate, was obtained as a single crystal and was characterized also with X-Ray spectroscopy.

Aquivion-based spray freeze-dried composite catalysts for the cascade conversion of furfural to γ-valerolactone

Furfural is one of the most promising biomass derived platform molecules. It is to this day produced in volumes above 300 ktons per year from the hydrolysis and dehydration of hemicellulose, one of the main components of lignocellulosic biomass. While the majority of the yearly production is destined to selective reduction to furfuryl alcohol for the production of furan resins, these molecules hold great potential for the production of more valuable chemicals, fuels, fuel additives and solvents. Among these products are alkyl levulinates and γ-valerolactone. To convert furfural to these target products, a cascade process involving Lewis acidity-catalysed reduction steps and Brønsted acidity-catalysed steps. In order to develop catalysts capable of promoting the one-pot domino reaction from furfural to γ-valerolactone, the two kinds of acidity must both be present. To this end, in this work, the spray freeze-drying technique is employed to combine the high activity and strong Brønsted acidity of Aquivion with the structural properties and Lewis acidity of different supporting metal oxide, forming composite catalysts. The flexibility of the spray freeze-drying technique and the modulable composition of the catalysts allowed a thorough study of the complex network of equilibria underlying the cascade reaction, while achieving high selectivities towards the final product.

Niobium-based heterogeneous catalysts synthesised in supercritical carbon dioxide for selective olefin epoxidation

In this work, two different protocols for the synthesis of Nb2O5-SiO2 with a sol-gel route in which supercritical carbon dioxide was used as solvent have been developed. The tailored design of the reactor allowed the reactants to come into contact only when supercritical CO2 is present, and the high-throughput experimentation scCO2 unit allowed the screening of synthetic parameters, that led to a Nb2O5 incorporation into the silica matrix of 2.5 wt%. N2-physisorption revealed high surface areas and the presence of meso- and micropores. XRD allowed to demonstrate the amorphous character of these materials. SEM-EDX proved the excellent dispersion of Nb2O5 into the silica matrix. These materials were tested in the epoxidation of cyclooctene with hydrogen peroxide, which is considered an environmentally friendly oxidant. The catalysts were virtually inactive in an organic, polar, aprotic solvent (1,4-dioxane). However, the most active scCO2 Nb2O5-SiO2 catalyst achieved a cyclooctene conversion of 44% with a selectivity of 88% towards the epoxide when tested in ethanol. Catalytic tests on cyclohexene revealed the presence of the epoxide, which is remarkable, considering that this substrate is easily oxidised to the diol. The behaviour in protic and aprotic solvents is compared to that of TS-1.

Changes In The Bacterial Community Of Soil From A Neutral Mine Drainage Channel.

Mine drainage is an important environmental disturbance that affects the chemical and biological components in natural resources. However, little is known about the effects of neutral mine drainage on the soil bacteria community. Here, a high-throughput 16S rDNA pyrosequencing approach was used to evaluate differences in composition, structure, and diversity of bacteria communities in samples from a neutral drainage channel, and soil next to the channel, at the Sossego copper mine in Brazil. Advanced statistical analyses were used to explore the relationships between the biological and chemical data. The results showed that the neutral mine drainage caused changes in the composition and structure of the microbial community, but not in its diversity. The Deinococcus/Thermus phylum, especially the Meiothermus genus, was in large part responsible for the differences between the communities, and was positively associated with the presence of copper and other heavy metals in the environmental samples. Other important parameters that influenced the bacterial diversity and composition were the elements potassium, sodium, nickel, and zinc, as well as pH. The findings contribute to the understanding of bacterial diversity in soils impacted by neutral mine drainage, and demonstrate that heavy metals play an important role in shaping the microbial population in mine environments.

Iis--integrated Interactome System: A Web-based Platform For The Annotation, Analysis And Visualization Of Protein-metabolite-gene-drug Interactions By Integrating A Variety Of Data Sources And Tools.

High-throughput screening of physical, genetic and chemical-genetic interactions brings important perspectives in the Systems Biology field, as the analysis of these interactions provides new insights into protein/gene function, cellular metabolic variations and the validation of therapeutic targets and drug design. However, such analysis depends on a pipeline connecting different tools that can automatically integrate data from diverse sources and result in a more comprehensive dataset that can be properly interpreted. We describe here the Integrated Interactome System (IIS), an integrative platform with a web-based interface for the annotation, analysis and visualization of the interaction profiles of proteins/genes, metabolites and drugs of interest. IIS works in four connected modules: (i) Submission module, which receives raw data derived from Sanger sequencing (e.g. two-hybrid system); (ii) Search module, which enables the user to search for the processed reads to be assembled into contigs/singlets, or for lists of proteins/genes, metabolites and drugs of interest, and add them to the project; (iii) Annotation module, which assigns annotations from several databases for the contigs/singlets or lists of proteins/genes, generating tables with automatic annotation that can be manually curated; and (iv) Interactome module, which maps the contigs/singlets or the uploaded lists to entries in our integrated database, building networks that gather novel identified interactions, protein and metabolite expression/concentration levels, subcellular localization and computed topological metrics, GO biological processes and KEGG pathways enrichment. This module generates a XGMML file that can be imported into Cytoscape or be visualized directly on the web. We have developed IIS by the integration of diverse databases following the need of appropriate tools for a systematic analysis of physical, genetic and chemical-genetic interactions. IIS was validated with yeast two-hybrid, proteomics and metabolomics datasets, but it is also extendable to other datasets. IIS is freely available online at: http://www.lge.ibi.unicamp.br/lnbio/IIS/.

Avaliação da posição condilar e disfunção temporomandibular em pacientes com má oclusão de Classe II submetidos à protrusão mandibular ortopédica

OBJETIVO: avaliar a participação da protrusão mandibular ortopédica e da posição condilar na prevalência de sinais e sintomas de disfunção temporomandibular (DTM). METODOLOGIA: a amostra foi composta por 60 indivíduos divididos em 3 grupos, sendo o grupo I correspondente a indivíduos não tratados; o grupo II composto por jovens em tratamento com o Bionator; e o grupo III por jovens já tratados com este aparelho. Os indivíduos da amostra responderam a um questionário relativo aos principais sintomas de DTM, permitindo a classificação dos mesmos de acordo com a presença e severidade dessas disfunções. Esses jovens também se submeteram à avaliação da movimentação mandibular, palpação dos músculos mastigatórios e inspeção de ruídos articulares. Radiografias transcranianas padronizadas das ATMs direita e esquerda foram realizadas, para obtenção do grau de concentricidade condilar. RESULTADOS: os testes ANOVA, Kruskal-Wallis e qui-quadrado foram utilizados para análise dos dados. De acordo com os resultados do questionário anamnésico, 66,67% da amostra foram classificados com ausência de DTM; 30% com DTM leve e apenas 3,33% com DTM moderada, sem diferença entre os grupos estudados (p > 0,05). Quanto à concentricidade condilar, o grupo II apresentou os valores de menor concentricidade (côndilos mais anteriorizados), com diferença estatisticamente significante em relação ao grupo I (p < 0,05). Uma associação entre a concentricidade condilar e a prevalência de DTM, no entanto, não foi encontrada. CONCLUSÃO: a protrusão ortopédica, apesar de alterar a posição dos côndilos, não aumentou a prevalência de DTM na população estudada.

Class II malocclusion occlusal severity description

OBJECTIVES: It is well known that the efficacy and the efficiency of a Class II malocclusion treatment are aspects closely related to the severity of the dental anteroposterior discrepancy. Even though, sample selection based on cephalometric variables without considering the severity of the occlusal anteroposterior discrepancy is still common in current papers. In some of them, when occlusal parameters are chosen, the severity is often neglected. The purpose of this study is to verify the importance given to the classification of Class II malocclusion, based on the criteria used for sample selection in a great number of papers published in the orthodontic journal with the highest impact factor. MATERIAL AND METHODS: A search was performed in PubMed database for full-text research papers referencing Class II malocclusion in the history of the American Journal of Orthodontics and Dentofacial Orthopedics (AJO-DO). RESULTS: A total of 359 papers were retrieved, among which only 72 (20.06%) papers described the occlusal severity of the Class II malocclusion sample. In the other 287 (79.94%) papers that did not specify the anteroposterior discrepancy severity, description was considered to be crucial in 159 (55.40%) of them. CONCLUSIONS: Omission in describing the occlusal severity demands a cautious interpretation of 44.29% of the papers retrieved in this study.

Tratamento ortopédico com aparelho de Herbst: ocorrem mudanças verticais no padrão de crescimento facial?

OBJETIVO: o objetivo deste estudo prospectivo de 32 adolescentes com má oclusão de Classe II, divisão 1, associada a retrognatismo mandibular, tratados com aparelho de Herbst, construído sobre bandas e coroas metálicas, foi avaliar cefalometricamente as possíveis mudanças no padrão de crescimento facial. METODOLOGIA: as telerradiografias laterais foram obtidas ao início do tratamento (T1) e imediatamente após 12 meses de tratamento com o referido aparelho ortopédico (T2). Foram utilizados o quociente de Jarabak e o VERT de Ricketts (modificado) para determinação do padrão facial em T1 e T2. RESULTADOS: utilizando o quociente de Jarabak, os resultados evidenciaram que 27 casos (84,4%) apresentaram padrões hipodivergentes em T1 e permaneceram da mesma forma em T2. Cinco casos (15,6%) apresentaram padrão neutro em T1 e não exibiram mudanças em T2. Quando avaliado o VERT de Ricketts (modificado), não ocorreram mudanças no padrão facial em 31 pacientes. Em apenas um caso ocorreu mudança do tipo facial. CONCLUSÃO: baseado nos resultados obtidos, pode-se concluir que, após 12 meses de tratamento com aparelho de Herbst, não ocorreram mudanças verticais no padrão de crescimento facial dos pacientes estudados.

Avaliação cefalométrica das alterações dentoesqueléticas de jovens com má oclusão de Classe II dentária tratados com distalizadores Jones jig

OBJETIVO: esta pesquisa objetivou avaliar cefalometricamente as alterações dentoesqueléticas de jovens com Classe II dentária tratados com o distalizador Jones jig. METODOLOGIA: foram avaliados 30 pacientes, sendo 15 de cada gênero, com média de idades iniciais de 13,63 anos; brasileiros, naturais da cidade de Bauru/SP, caracterizados por má oclusão de Classe II, 1ª e 2ª divisões de Angle sem comprometimento esquelético. Os jovens foram tratados com aparelho Jones jig a fim de distalizar os molares superiores a uma relação molar de "super Classe I"; sendo que esse dispositivo permaneceu, em média, por 0,55 anos. Ao final da sobrecorreção, os molares distalizados receberam um botão de Nance e, como ancoragem extrabucal, o aparelho extrabucal (AEB) com tração média-alta, com o intuito de verticalizar e corrigir a angulação radicular dos molares distalizados. Foram realizadas telerradiografias em normal lateral inicial (T1) e pós-distalização (T2). As medidas cefalométricas foram submetidas ao teste t dependente de Student para avaliar as alterações de T1 para T2. RESULTADOS: com base nos resultados obtidos e a partir da metodologia empregada, observou-se alterações dentárias significativas, como a movimentação distal linear e angular, assim como a intrusão dos segundos e primeiros molares superiores no sentido vertical. Também se confirmou efeitos indesejáveis, como a perda de ancoragem refletida em mesialização, extrusão e angulação mesial dos segundos pré-molares, a protrusão dos incisivos superiores e o aumento do trespasse vertical e horizontal. Pode-se confirmar que certas movimentações dentárias promovem significativas alterações esqueléticas de estruturas localizadas à distância, ou seja, observou-se extrusão significativa dos segundos pré-molares superiores, o que resultou em rotação mandibular, aumento significativo da altura facial anteroinferior e protrusão do lábio inferior. CONCLUSÃO: pode-se concluir que o distalizador Jones jig promove, basicamente, alterações dentárias.

Subcutaneous tissue response of isogenic mice to calcium hydroxide-based pastes with chlorhexidine

This study was evaluated the response of subcutaneous connective tissue of isogenic mice to calcium hydroxide-based pastes with chlorhexidine digluconate (CHX). Seventy isogenic male BALB/c mice aged 6-8 weeks and weighing 15-20 g were randomly assigned to 8 groups. The animals received polyethylene tube implants as follows: Groups I, II, and III (n=10) - Calen® paste mixed with 0.4% CHX (experimental paste; Calen/CHX) for 7, 21, and 63 days, respectively; Groups IV, V, and VI (n=10) - UltraCal™ paste mixed with 2% CHX (experimental paste supplied by Ultradent Products Inc.; Ultracal/CHX) for 7, 21, and 63 days, respectively; and Groups VII and VIII (n=5): empty tube for 7 and 21 days, respectively. At the end of the experimental periods, the implants were removed together with the surrounding tissues (skin and subcutaneous connective tissue). The biopsied tissues were subjected to routine processing for histological analysis. Using a descriptive analysis and a four-point (0-3) scoring system, the following criteria were considered for qualitative and quantitative analysis of the tissue around the implanted materials: collagen fiber formation, tissue thickness and inflammatory infiltrate. A quantitative analysis was performed by measuring the thickness (µm), area (µm²) and perimeter (µm) of the reactionary granulomatous tissue formed at the tube ends. Data were analyzed statistically by the Kruskal-Wallis test and Dunn's post-test (α=0.05). Calen/CHX showed biocompatibility with the subcutaneous and reactionary tissues, with areas of discrete fibrosis and normal conjunctive fibrous tissue, though without statistically significant difference (p>0.05) from the control groups. In Groups I to III, there was a predominance of score 1, while in Groups IV to VI scores 2 and 3 predominated for all analyzed parameters. UltraCal/CHX, on the other hand, induced the formation of an inflammatory infiltrate and abundant exudate, suggesting a persistent residual aggression from the material, even 63 days after implant placement. In conclusion, the Calen paste mixed with 0.4% CHX allowed an adequate tissue response, whereas the UltraCal paste mixed with 2% CHX showed unsatisfactory results.

Oral health in Brazil - Part II: Dental Specialty Centers (CEOs)

The concepts of health promotion, self-care and community participation emerged during the 1970s and, since then, their application has grown rapidly in the developed world, showing evidence of effectiveness. In spite of this, a major part of the population in the developing countries still has no access to specialized dental care such as endodontic treatment, dental care for patients with special needs, minor oral surgery, periodontal treatment and oral diagnosis. This review focuses on a program of the Brazilian Federal Government named CEOs (Dental Specialty Centers), which is an attempt to solve the dental care deficit of a population that is suffering from oral diseases and whose oral health care needs have not been addressed by the regular programs offered by the SUS (Unified National Health System). Literature published from 2000 to the present day, using electronic searches by Medline, Scielo, Google and hand-searching was considered. The descriptors used were Brazil, Oral health, Health policy, Health programs, and Dental Specialty Centers. There are currently 640 CEOs in Brazil, distributed in 545 municipal districts, carrying out dental procedures with major complexity. Based on this data, it was possible to conclude that public actions on oral health must involve both preventive and curative procedures aiming to minimize the oral health distortions still prevailing in developing countries like Brazil.

Clinical and antimicrobial efficacy of NitrAdineTM-based disinfecting cleaning tablets in complete denture wearers

OBJECTIVE: This study evaluated the efficacy of NitrAdineTM-based disinfecting cleaning tablets for complete denture, in terms of denture biofilm removal and antimicrobial action. MATERIAL AND METHODS: Forty complete denture wearers (14 men and 26 women) with a mean age of 62.3±9.0 years were randomly assigned to two groups and were instructed to clean their dentures according to two methods: brushing (control) - 3 times a day with denture brush and tap water following meals; brushing and immersion (Experimental) - brushing the denture 3 times a day with denture brush and tap water following meals and immersion of the denture in NitrAdineTM-based denture tablets (Medical InterporousTM). Each method was used for 21 days. Denture biofilm was disclosed by a 1% neutral red solution and quantified by means of digital photos taken from the internal surface before and after the use of the product. Microbiological assessment was conducted to quantify Candida sp. RESULTS: An independent t-test revealed a significant lower biofilm percentage for the experimental group (4.7, 95% CI 2.4 to 7.9) in comparison with the control group (mean 37.5, 95% CI 28.2 to 48.1) (t38=7.996, p<0.001). A significant reduction of yeast colony forming units could be found after treatment with Medical InterporousTM denture tablets as compared to the control group (Mann-Whitney test, Z=1.90; p<0.05). CONCLUSION: The present findings suggest that NitrAdineTM-based disinfecting cleaning tablets are efficient in removal of denture biofilm. In addition, a clear antimicrobial action was demonstrated. Therefore, they should be recommended as a routine denture maintenance method for the prevention of the development of microbial biofilm induced denture stomatitis.

Effect of eugenol-based endodontic sealer on the adhesion of intraradicular posts cemented after different periods

OBJECTIVE: This study evaluated in vitro the influence of an eugenol-based sealer (EndoFill) on the retention of stainless steel prefabricated posts cemented with zinc phosphate and resin-based (Panavia F) cements after different periods of root canal obturation, using the pull-out test. MATERIAL AND METHODS: Sixty upper canines were decoronated and the roots were embedded in resin blocks. The specimens were distributed into 3 groups, according to the period elapsed between canal obturation and post cementation: Group I - immediately; Group II - 72 h and Group III - 4 months. The groups were subdivided according to the type of cement used for post cementation: A - zinc phosphate and B - Panavia F. Following the experimental periods, specimens were subjected to pullout test in an Instron machine with application of tensile force at a crosshead speed of 0.5 mm/min until post dislodgement. The maximum forces required for post removal were recorded (kN) and means were subjected to statistical analysis by 2-way ANOVA and Tukey-Kramer test (α=0.001) RESULTS: There were statistically significant differences (p<0.01) between the posts cemented with zinc phosphate cement (0.2112 kN) and Panavia F (0.0501 kN). However, no statistically significant differences (p>0.05) were found between the three post cementation periods, regardless of the cement. CONCLUSIONS: It was concluded that the eugenol-based sealer influenced the tensile strength of the posts cemented with the resin cement, but had no influence on the time waited between root canal obturation and post space preparation/post cementation.

Forward Neutral-Pion Transverse Single-Spin Asymmetries in p plus p Collisions at s=200 GeV

We report precision measurements of the Feynman x (x(F)) dependence, and first measurements of the transverse momentum (p(T)) dependence, of transverse single-spin asymmetries for the production of pi(0) mesons from polarized proton collisions at s=200 GeV. The x(F) dependence of the results is in fair agreement with perturbative QCD model calculations that identify orbital motion of quarks and gluons within the proton as the origin of the spin effects. Results for the p(T) dependence at fixed x(F) are not consistent with these same perturbative QCD-based calculations.

Fast ray-tracing algorithm for circumstellar structures (FRACS) II. Disc parameters of the B[e] supergiant CPD-57 degrees 2874 from VLTI/MIDI data

Context. B[e] supergiants are luminous, massive post-main sequence stars exhibiting non-spherical winds, forbidden lines, and hot dust in a disc-like structure. The physical properties of their rich and complex circumstellar environment (CSE) are not well understood, partly because these CSE cannot be easily resolved at the large distances found for B[e] supergiants (typically greater than or similar to 1 kpc). Aims. From mid-IR spectro-interferometric observations obtained with VLTI/MIDI we seek to resolve and study the CSE of the Galactic B[e] supergiant CPD-57 degrees 2874. Methods. For a physical interpretation of the observables (visibilities and spectrum) we use our ray-tracing radiative transfer code (FRACS), which is optimised for thermal spectro-interferometric observations. Results. Thanks to the short computing time required by FRACS (<10 s per monochromatic model), best-fit parameters and uncertainties for several physical quantities of CPD-57 degrees 2874 were obtained, such as inner dust radius, relative flux contribution of the central source and of the dusty CSE, dust temperature profile, and disc inclination. Conclusions. The analysis of VLTI/MIDI data with FRACS allowed one of the first direct determinations of physical parameters of the dusty CSE of a B[e] supergiant based on interferometric data and using a full model-fitting approach. In a larger context, the study of B[e] supergiants is important for a deeper understanding of the complex structure and evolution of hot, massive stars.