Phenanthroimidazoles as fluorimetric and colourimetric chemosensors in aqueous solution

2,4,5-Triaryl-imidazoles are versatile compounds with application in medicine, due to their biological activity, and materials sciences, for their interesting optical properties. These properties can be tuned by careful selection of substituents at positions 2, 4 and 5: replacement of the aryl group by an heterocyclic group results in larger π-conjugated systems with improved optical properties for application in nonlinear optics, OLEDs, DNA intercalators, and chemosensors. Moreover, it is expected that introducing more conjugation and rigidity into the resulting system will further improve its properties. The development of chromo/fluorescent probes that are capable of detecting ions with high sensitivity and selectivity in aqueous media is currently a topic of strong interest and the design of heteroditopic receptors that contain two or more different binding sites for the simultaneous complexation of cationic and anionic guests is a emerging field of supramolecular chemistry. In this communication, we report the synthesis of new phenanthroimidazoles substituted at position 2 with arylthienyl or arylfuryl moieties possessing substituents of different electronic character, in order to tune the chromo/fluoro response in the presence of relevant anions and metal cations. Their photophysical properties and chemosensory ability were studied in acetonitrile and mixtures of acetonitrile and water, and selective detection of cyanide was achieved in aqueous mixtures for some of the derivatives.

Phenanthroimidazole derivatives as fluorimetric chemosensors in aqueous medium

In recent years the research of sensors with good sensitivity and good selectivity in aqueous medium has been of great interest. Chemosensors soluble in aqueous media are very interesting, because of the importance in revealing a number of biological processes, disease states and environmental pollutions. 2,4,5-Triaryl-imidazoles are versatile compounds with application in medicine, due to their biological activity, and materials sciences, for their interesting optical properties. These properties can be tuned by careful selection of substituents at positions 2, 4 and 5: replacement of the aryl group by a heterocyclic group results in larger π-conjugated systems with improved optical properties for application in nonlinear optics, OLEDs, DNA intercalators, and chemosensors. In this communication, we report the synthesis of new phenanthroimidazoles, substituted at position 2 with (hetero)aryl groups of different electronic character, in order to evaluate their photophysical properties and chemosensory ability. The new derivatives were characterized by the usual techniques and a detailed photophysical study was undertaken. The evaluation of the compounds as fluorimetric chemosensors was carried out by performing titrations in acetonitrile and acetonitrile/water in the presence of relevant organic and inorganic anions, and of alkaline, alkaline-earth and transition metal cations.

Polyethylene glycol 8000+ citrate salts aqueous two-phase systems: Relative hydrophobicity of the equilibrium phases

The Gibbs free energy of transfer of a methylene group, G*(CH2), is reported as a measure of the relative hydrophobicity of the equilibrium phases. Furthermore, G*(CH2) is a characteristic parameter of each tie-line, and for that reason can be used for comparing different tie-lines of a given aqueous two-phase system (ATPS) or even to establish comparisons among different ATPSs. In this work, the partition coefficients of a series of four dinitrophenylated-amino acids were experimentally determined, at 23 °C, in five different tie-lines of PEG8000(sodium or potassium) citrate ATPSs. G*(CH2) values were calculated from the partition coefficients and used to evaluate the relative hydrophobicity of the equilibrium phases. PEG8000potassium citrate ATPSs presented larger relative hydrophobicity than PEG8000sodium citrate ATPSs. Furthermore, the results obtained indicated that the PEG-rich phase (top phase) has higher affinity to participate in hydrophobic hydration interactions than the salt-rich phase (bottom phase).

Alcohol sponsored events: the impact on attitudes and intentions, and the mitigating impact of persuasion knowledge

Doctor of Philosophy in Marketing and Strategy

In vitro mechanical fatigue behavior of poly-ε-caprolactone macroporous scaffolds for cartilage tissue engineering: Influence of pore filling by a poly(vinyl alcohol) gel

Polymeric scaffolds used in regenerative therapies are implanted in the damaged tissue and subjected to repeated loading cycles. In the case of articular cartilage engineering, an implanted scaffold is typically subjected to long term dynamic compression. The evolution of the mechanical properties of the scaffold during bioresorption has been deeply studied in the past, but the possibility of failure due to mechanical fatigue has not been properly addressed. Nevertheless, the macroporous scaffold is susceptible to failure after repeated loading-unloading cycles. In this work fatigue studies of polycaprolactone scaffolds were carried by subjecting the scaffold to repeated compression cycles in conditions simulating the scaffold implanted in the articular cartilage. The behaviour of the polycaprolactone sponge with the pores filled with a poly(vinyl alcohol) gel simulating the new formed tissue within the pores was compared with that of the material immersed in water. Results were analyzed with Morrow’s criteria for failure and accurate fittings are obtained just up to 200 loading cycles. It is also shown that the presence of poly(vinyl alcohol) increases the elastic modulus of the scaffolds, the effect being more pronounced with increasing the number of freeze/thawing cycles.

Effect of NaCl additive on solute-solvent interactions in aqueous polyethylene glycol-sodium sulfate two-phase systems

Abstract Partition behavior of eight small organic compounds and six proteins was examined in poly(ethylene glycol)-8000-sodium sulfate aqueous two-phase systems containing 0.215 M NaCl and 0.5 M osmolyte (sorbitol, sucrose, TMAO) and poly(ethylene glycol)-10000-sodium sulfate-0.215 M NaCl system, all in 0.01 M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. The partition coefficients of all compounds examined (including proteins) were described in terms of solute-solvent interactions. The results obtained in the study show that solute-solvent interactions of nonionic organic compounds and proteins in polyethylene glycol-sodium sulfate aqueous two-phase system change in the presence of NaCl additive.

Investigation on the homogeneity and stability of aqueous nano cellulose suspensions prepared using pluronic F-127

This paper presents the results of experimental investigation on the aqueous dispersion behaviour of micro crystalline cellulose (MCC) prepared using Pluronic F-127. For this purpose, different concentrations (0.5-3.0 wt.%) of MCC were dispersed in water with the help of ultrasonication technique using various concentrations of Pluronic F-127. The homogeneity of the suspensions and agglomerations were characterized by optical and transmission electron microscopy and the concentration of well dispersed MCC was measured using UV-Vis spectroscopy. Also, the suspensions were subjected to high speed ultracentrifugation at 3000 rpm and observed visually for sedimentation and subsequently, concentration was calculated using UV-Vis, in order to assess the long term stability of the suspensions. Based on these experiments, optimum concentration of Pluronic to disperse different MCC concentrations has been suggested.

Erratum: Alcohol-aminosilicate hybrid coatings for corrosion protection of galvanized steel in mortar

Artigo completo publicado na revista "Journal of The Electrochemical Society" 161:6 (2014) C349-C362 e disponível no RepositóriUM em: http://hdl.handle.net/1822/33784

Erratum: Erratum: Alcohol-aminosilicate hybrid coatings for corrosion protection of galvanized steel in mortar

Artigo completo publicado na revista "Journal of The Electrochemical Society" 161:6 (2014) C349-C362 e disponível no RepositóriUM em: http://hdl.handle.net/1822/33784. Errata disponível no RepositóriUM em: http://hdl.handle.net/1822/40064. (Publisher’s note: An erratum that addressed the errors in Figure 9 was originally published on Dec. 10, 2014, however the graphs in that erratum were not correct.)

Desenvolvimento de microcápsulas ativadas por radiação solar para aplicação em painéis cerâmicos exteriores

Dissertação de mestrado integrado em Engenharia de Materiais

Alcohol-dependent patients receiving specialised outpatient care: an overview of gender issues

OBJECTIVE: The objective of the present study, with focus on gender, was aimed at evaluating alcohol-dependent individual in terms of socio-demographic variables related to alcohol consumption and therapeutic interventions. METHODS: This is a retrospective cross-sectional study of 1,051 patients (833 men and 218 women), with diagnosis of alcohol dependence syndrome, according to ICD-10 criteria, who had sought treatment for the first time at a specialised health centre between 2000 and 2006. RESULTS: The results showed that women, compared to men, are more likely to be unemployed and without partner, in addition to having higher educational level, latter age of alcohol initiation, needing less outpatient alcohol detoxification program, consuming more fermented beverage, presenting less psychiatric comorbidities, and using less coadjutant medications during treatment. CONCLUSION: We can state that some peculiarities exist permeating both gender and alcohol consumption. A further focus on the characteristics of each population is needed to facilitate the adequate use of therapeutic interventions according to gender specificities.

Association study of the Ile349val polymorphism of the gene ADH1C and alcohol dependence

OBJECTIVE: The aim of this study was to investigate the polymorphism Ile349Val of the enzyme alcohol dehydrogenase ADH1C gene among individuals with alcohol dependence syndrome (ADS) attending Alcoholics Anonymous (AA) meetings. METHODS: A total of 120 subjects residing in Rio de Janeiro city participated in this study. Subjects were divided into two groups: a group consisting of 54 individuals from the ADS group and 66 individuals that declared not having any alcohol dependence (control group). DNA was extracted from mouth epithelial cells by phenol-chloroform method and further submitted to amplification by polymerase chain reaction (PCR). RESULTS: Our results did not show differences between the genotypes of control individuals and ADS subjects. Nevertheless, we found increased rates of alcoholism in families of ADS subjects as compared to controls. CONCLUSIONS: Our results did not show any genotype difference on the ADH1C gene when control and AA genotypes are compared.

Alcohol Use Disorder Identification Test (AUDIT): explorando seus parâmetros psicométricos

OBJETIVO: O presente estudo teve como objetivo conhecer evidências de validade e precisão do Alcohol Use Disorder Identification Test (AUDIT). MÉTODOS: Contou-se com uma amostra de conveniência (não probabilística) de 547 estudantes universitários de Fortaleza (CE), com idade média de 21,6 anos (dp = 4,86; amplitude de 18 a 53), a maioria do sexo masculino (51,5%), solteira (91,4%) e católica (62,5%). Os participantes responderam ao AUDIT e a perguntas demográficas. Procurando conhecer a estrutura fatorial, além de estatísticas descritivas, realizou-se uma Análise de Componentes Principais. Adicionalmente, a fim de avaliar a precisão do instrumento, efetuaram-se cálculos de alfa de Cronbach (consistência interna), correlações de r de Pearson e coeficiente de correlação intraclasse - ICC (precisão teste-reteste). RESULTADOS: De acordo com a análise de componentes principais com rotação oblimin, a estrutura bifatorial do AUDIT mostrou-se coerente, com todos os itens apresentando saturações satisfatórias, superior a |0,40|, tendo o Fator 1 explicado 47,5% da variância total com alfa de 0,84 e o Fator 2 explicado 11,6% da variância total com alfa de 0,69. Os resultados do teste-reteste indicaram correlação forte entre os dados obtidos na primeira (t1) e segunda (t2) aplicação (r tt = 0,94, p < 0,01), sem diferença significativa de médias nos dois tempos (m t1 = 0,37, dp = 0,49; m t2 = 0,34, dp2= 0,47; p > 0,05), com ICC satisfatório (0,96). CONCLUSÕES: Os achados apoiaram a adequação psicométrica do AUDIT, com as análises fatoriais exploratórias apontando como mais satisfatória a estrutura com dois fatores, bem como atestaram sua boa estabilidade temporal.

Dynamic wet etching of silicon through isopropanol alcohol evaporation

In this paper, Isopropanol (IPA) availability during the anisotropic etching of silicon in Potassium Hydroxide (KOH) solutions was investigated. Squares of 8 to 40 m were patterned to (100) oriented silicon wafers through DWL (Direct Writing Laser) photolithography. The wet etching process was performed inside an open HDPE (High Density Polyethylene) flask with ultrasonic agitation. IPA volume and evaporation was studied in a dynamic etching process, and subsequent influence on the silicon etching was inspected. For the tested conditions, evaporation rates for water vapor and IPA were determined as approximately 0.0417 mL/min and 0.175 mL/min, respectively. Results demonstrate that IPA availability, and not concentration, plays an important role in the definition of the final structure. Transversal SEM (Scanning Electron Microscopy) analysis demonstrates a correlation between microloading effects (as a consequence of structure spacing) and the angle formed towards the (100) plane.

A possible contribution to improving the therapeutic potentials of Babor's Typology of Alcohol Dependent Patients

ABSTRACT Objective The objective of this study was to replicate Babor's Typology and to explore clinical features related to personality traits that may underlie this classification, in order to improve its therapeutic possibilities. Methods Observational prospective study on a group of 273 male alcoholics. After a replication of Babor's variables, Cluster Analysis, Chi-Square – applied on clinical variables related to a Lappda Tipology – and Kappa tests were performed. Results The study identified two distinct clusters that held similar features to those described for the Type A/Type B classification. Besides presenting a lower socio-economic situation, Cluster 2 patients were associated with higher vulnerability and severe clinical features and also differed from Cluster 1 in their response to treatment. These replicated clusters retained connections and also differences in relation to the variables derived from the Lappda Typology. Conclusion Considering that each of the two replicated clusters seem to be associated to different personality traits – according to their correlations to the affective, cognitive and behavioral dimensions brought forward by the Lappda Typology – it is acceptable that this study may contribute to the development of more comprehensive and effective therapeutic strategies specifically tailored to target more specific personality traits of these subgroups of alcoholic patients.