Optimization of the photocatalytic degradation process of aromatic organic compounds applied to mangrove sediment.

Polycyclic aromatic hydrocarbons (PAHs) are part of a class of organic compounds resistant to natural degradation. In this way, heterogeneous photocatalysis becomes useful to degrade persistent organic pollutants, however it can be influenced by environmental variables (i.e.: organic matter) and experimental factors such as: mass of the photocatalyst and irradiation time. The objective of this research was to use a factorial design 2k as a function of the multiple response (MR) to evaluate simultaneously experimental conditions for the photodegradation of polycyclic aromatic hydrocarbons in contaminated mangrove sediment and its application in oil from Potiguar Basin in Brazil. The sediment samples collected in Belmonte city (Southern Bahia state) were contaminated with 0.25 mg kg-1 of Acenaphthene, Anthracene, Benzo[a]Anthracene, Indene[1,2,3cd]pyrene, Dibenzo[ah]anthracene, Benzo[ghi]pyrene. Factors such as mass of the photocatalyst and irradiation time were evaluated in factorial design 22, with triplicate from the central point, to 1g of the PAH contaminated sediment. After performing the experiments, it was found that the best experimental condition for the degradation of all PAHs indicated by MR was the central point (0.5 g of photocatalyst and 12h of irradiation). For such conditions, the half-life of PAHs varied from 3.51 to 9.37 h and the degradation speed constant between 0.0740 to 0.1973 h-1. The comparison of the optimized methodology between photolysis tests and heterogeneous photocatalysis was performed using the Kruskal-Wallis test, which indicated a difference for the reference solution, where heterogeneous photocatalysis was more efficient in the degradation of PAHs. The optimized methodology was apply in samples contaminated with crude oil from Potiguar Basin, no significant difference was observed in the aromatic fraction, using for the Kruskal-Wallis test. Heterogeneous photocatalysis has shown to be a promising remediation technique to remedy aromatic organic compounds in mangrove sediments.

aPDT using nanoconcentration of 1,9-dimethylmethylene blue associated to red light is efficacious in killing Enterococcus faecalis ATCC 29212 in vitro.

The Enterococcus faecalis is a microorganism that causes multiple forms of resistance to a wide range of drugs used clinically. aPDT is a technique in which a visible light activates photosensitizer (PS), resulting in generation of reactive oxygen species that kill bacteria unselectively via an oxidative burst. aPDT is an alternative to antibiotics with the advantage of not causing resistance. The search for an alternative treatment of infections caused by E. faecalis, without using antibiotics, is off great clinical importance. The aim of present investigation was to assess the efficacy of using 3.32 ηg/mL of 1,9-dimethylmethylene blue (DMMB) as photosensitizer associated with the use of either Laser (λ660 nm) or LED (λ632 ±â€¯2 nm) using different energy densities (6, 12 and 18 J/cm2) to kill E. faecalis in vitro. Under different experimental conditions, 14 study groups, in triplicate, were used to compare the efficacy of the aPDT carried out with either the laser or LED lights using different energy densities associated to DMMB. The most probable number method (MPN) was used for quantitative analysis. Photodynamic antimicrobial effectiveness was directly proportional to the energy density used, reaching at 18 J/cm2, 99.999998% reduction of the counts of E. faecalis using both light sources. The results of this study showed that the use of 3.32 ηg/mL of DMMB associated with the use 18 J/cm2 of LED light (λ632 ±â€¯2 nm) reduced >7-log counts of planktonic culture of E. faecalis.

Validation of LED spectrofluorimeter for determination of both biodiesel and nontransesterified residual cooking oil in diesel samples.

This paper presents the results of the validation of a LED spectrofluorimeter patented for the analysis of biodiesel in diesel and non-transesterified residual cooking oil (RCO) in diesel. Detection limit, quantification limit and sensitivity were determined from the regression lines. The spectrofluorimeter validated in this study was adequate for quantifying the amount of biodiesel in diesel in the range from 2% to 45% (B02-B45) with an R-squared value of 0.9962 and a detection limit of 3%. For the analysis of non-transesterified RCO in diesel, the linear range was from 2% to 20% with an R-squared value of 0.9872 and a detection limit of 2%. The accuracy of the equipment for the analysis of biodiesel in diesel and non-transesterified RCO in diesel was evaluated using Student's t-test for paired data. With 95% confidence level there was no significant difference between the actual values and those determined by the equipment.

Determination of the oxidation stability of biodiesel and oils by spectrofluorimetry and multivariate calibration.

Oxidation stability is an important quality parameter for biodiesel. In general, the methods used to evaluate the oxidation stability of oils and biodiesels are time-consuming. This work reports the use of spectrofluorimetry, a fast analytical technique, associated with multivariate data analysis as a powerful analytical tool to prediction of the oxidation stability. The prediction of the oxidation stability showed a good agreement with the results obtained by the EN14112 reference method Rancimat. The models presented high correlation (0.99276 and 0.97951) between real and predicted values. The R(2) values of 0.98557 and 0.95943 indicated the accuracy of the models to predict the oxidation stability of soy oil and soy biodiesel, respectively. The residual distribution does not follow a trend with respect to the predicted variables indicating the good quality of the fits.

Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl2(κ3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O.

Chemical reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam, fac-[Ru(NO)Cl(2)(κ(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl·H(2)O ((1-carboxypropyl)cyclam = 3-(1,4,8,11-tetraazacyclotetradecan-1-yl)propionic acid)), (I) are described. Chloride ligands do not undergo aquation reactions (at 25 °C, pH 3). The rate of nitric oxide (NO) dissociation (k(obs-NO)) upon reduction of I is 2.8 s(-1) at 25 ± 1 °C (in 0.5 mol L(-1) HCl), which is close to the highest value found for related complexes. The uncoordinated carboxyl of I has a pK(a) of ∼3.3, which is close to that of the carboxyl of the non coordinated (1-carboxypropyl)cyclam (pK(a) = 3.4). Two additional pK(a) values were found for I at ∼8.0 and ∼11.5. Upon electrochemical reduction or under irradiation with light (λ(irr) = 350 or 520 nm; pH 7.4), I releases NO in aqueous solution. The cyclam ring N bound to the carboxypropyl group is not coordinated, resulting in a fac configuration that affects the properties and chemical reactivities of I, especially as NO donor, compared with analogous trans complexes. Among the computational models tested, the B3LYP/ECP28MDF, cc-pVDZ resulted in smaller errors for the geometry of I. The computational data helped clarify the experimental acid-base equilibria and indicated the most favourable site for the second deprotonation, which follows that of the carboxyl group. Furthermore, it showed that by changing the pH it is possible to modulate the electron density of I with deprotonation. The calculated NO bond length and the Ru/NO charge ratio indicated that the predominant canonical structure is [Ru(III)NO], but the Ru-NO bond angles and bond index (b.i.) values were less clear; the angles suggested that [Ru(II)NO(+)] could contribute to the electronic structure of I and b.i. values indicated a contribution from [Ru(IV)NO(-)]. Considering that some experimental data are consistent with a [Ru(II)NO(+)] description, while others are in agreement with [Ru(III)NO], the best description for I would be a linear combination of the three canonical forms, with a higher weight for [Ru(II)NO(+)] and [Ru(III)NO].