Fluorescence quenching of anthropogenic fulvic acids by Cu(II), Fe(III) and UO(2)(2+)

The quenching of the fluorescence of three anthropogenic fulvic acids (FA) provoked by Cu(II) (pH 6.0), Fe(III) (pH 4.0) and UO₂²⁺ (pH 3.5), was analyzed by a non-linear method and by Stern-Volmer plots. The FA samples were extracted from composted sewage sludges (csFA), composted municipal wastes (mwFA) and composted livestock wastes (lsFA). Synchronous-scan fluorescence (SyF) spectra were collected as a function of metal ion concentration. Spectral data were treated by a self-modeling mixture analysis method (SIMPLISMA) to detect the SyF spectral band with the strongest quenching and to calculate the corresponding quenching profile. The analysis of these profiles by a non-linear method allowed the estimation of conditional stability constants (K) and of the percentage of non-complexing fluorophores. The same quantitative information was obtained by the modified Stern-Volmer equation taking into account the existence of fluorophores that do not participate in the complexation. Good agreement was found between the results of the two procedures. The log K calculated by the non-linear method were (standard deviation in parenthesis): csFA, Cu(II), 4.22 (5); Fe(III), 5.0 (1); UO₂²⁺, 5.2 (2); mwFA, Cu(II), 4.21 (3); Fe(III), 5.6 (2); UO₂²⁺, 4.7 (3); lsFA, Cu(II), 4.51 (8); Fe(III), 5.5 (2); UO₂²⁺, 3.6 (2).     

Chemometric interpretation of pesticide occurence in soil samples from an intensive horticulture area in north Portugal

An extensive monitoring programme of pesticides was carried out in soil samples from an intensive horticulture area in north of Portugal, putting into practice the needs for increased control of soil quality as far as organic pollution is concerned. The area under investigation was additionally defined as vulnerable to nitrates due to local soil and aquifer characteristics, which might be extended to pesticides contamination. Five sampling sites were selected and soils analysed at three depths in eight sampling campaigns, for the period of 2 years. A stepwise multivariate statistical approach was selected to uncover most relevant patterns inside a complex environmental data matrix. Cluster analysis was applied both to group pesticides and samples, giving a primary and unsupervised overlook of privileged relationships. Clusters of persistent pesticides and selected herbicides were identified, whereas sample classes were also formed and disposed geographically. Thirty eight percent of analysed soils samples fell into one class characterized by low contamination (class 1 in cluster analysis), which is entirely representative of the sampling site no. 1. Afterwards, linear discriminant analysis was applied to identify those pesticides, which had a higher impact in the definition of classes. Finally, factor analysis using a five component model was implemented in order to bring to light the constitution and data variance explained by each of the five main principal components, as well as, their relation to pest management practices. A factor was identified (PC1 – 22% variance) composed of chlorinated pesticides, which was representative of one of the investigated sites indicating its high contamination status. Qualitative main findings and class average concentration values were obtained through this multivariate statistical approach.     

Chemical synthesis and firefly luciferase produced dehydroluciferyl-coenzyme A

Dehydroluciferyl-coenzyme A (L-CoA) was chemically synthesized and characterized by MS, UV-vis spectrometry and RP-HPLC. The identity of the chemically synthesized compound with the one that was produced by firefly luciferase was confirmed. Moreover, the reversibility of the enzymatic conversion of dehydroluciferin ? dehydroluciferyl-adenylate ? L-CoA was also confirmed. The chemical synthesis of L-CoA, described here, may help the clarification of the activator effect of CoA on luciferase bioluminescent assays, in which the enzyme catalyzed formation of L-CoA and the consequent destruction of L-AMP is one of the possible explanations for that effect.     

Anaerobic reduction of a sulfonated azo dye, Congo Red, by sulfate-reducing bacteria

The capacity for anaerobic decolorization of a sulfonated azo dye, Congo Red, by a strain of a sulfate-reducing bacterium was evaluated. After optimizing the growth rate of the bacteria on a simple carbon source and terminal electron acceptor pair, lactate and sulfate, respectively, the effect of the dye concentration on their growth rate was analyzed. The decolorization rate was affected by the dye concentration in the growth medium. The azo-bond cleavage mechanism of reductive decolorization with the formation of benzidine was consistent with the results, as this metabolite was identified by high-performance liquid chromatography. Several fractions of the culture medium, including lysed cell extracts, were examined for the capacity to reduce the azo dye. This reduction capacity was found in the culture medium in which the cells had previously grown. The results showed that the mechanism of reductive decolorization of this sulfonated azo dye was extracellular and nonenzymatic, consistent with the production of sulfide anion by the microorganisms while growing on lactate and sulfate. The sulfide anions were the cause of the reduction leading to the disappearance of color in the medium. To increase the rate of decolorization, the presence of ferrous ion was also necessary together with the lactate and sulfate substrates.     

Healable dual organic–inorganic crosslinked sol–gel based polymers: Crosslinking density and tetrasulfide content effect

In this article, the first generation of healable sol–gel based polymers is reported. A dual organic–inorganic crosslinked network is developed containing non‐reversible crosslinks and reversible (tetrasulfide) groups. The designed polymer architecture allows thermally induced mesoscale flow leading to damage closure followed by interfacial strength restoration due to reformation of the reversible groups. While the reversible bonds are responsible for the flow and the interface restoration, the irreversible crosslinks control the required mechanical integrity during the healing process. The temperature dependent gap closure kinetics is strongly affected by the crosslinking density and tetrasulfide content. Raman spectroscopy is used to explain the gap closure kinetics in air and dry nitrogen. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1953–1961     

A Carbocationic Triarylmethane-Based Porous Covalent Organic Network

A thermally stable carbocationic covalent organic network (CON), named RIO-70 was prepared from pararosaniline hydrochloride, an inexpensive dye, and triformylphloroglucinol in solvothermal conditions. This nanoporous organic material has shown a specific surface area of 990 m² g⁻¹ and pore size of 10.3 Å. The material has CO₂ uptake of 2.14 mmol g⁻¹ (0.5 bar), 2.7 mmol g⁻¹ (1 bar), and 6.8 mmol g⁻¹ (20 bar), the latter corresponding to 3 CO₂ molecules adsorbed per pore per sheet. It is shown to be a semiconductor, with electrical conductivity (σ) of 3.17×10⁻⁷ S cm⁻¹, which increases to 5.26×10⁻⁴ S cm⁻¹ upon exposure to I₂ vapor. DFT calculations using periodic conditions support the findings.     

UV filter 2‐ethylhexyl 4‐methoxycinnamate: a structure,energetic and UV–vis spectral analysis based on density functional theory

2‐Ethylhexyl 4‐methoxycinnamate (EHMC) is a very commonly used UVB filter that is known to isomerize from the (E) to the (Z) isomer in the presence of light. In this study, we have performed high level quantum chemical calculations using density functional theory (DFT) with the B3LYP density functional and extended basis sets to study the gas‐phase molecular structure of EHMC and its energetic stability. Calculations were also performed for related smaller molecules cinnamic acid and 4‐methoxycinnamic acid. Charge delocalization has been analyzed using natural charges and Wiberg bond indexes within the natural bond orbital analysis and using nucleus independent chemical shifts. Density functional theory calculations reveal that the (E) isomer of EHMC is more stable than the (Z) by about 20 kJ mol^?1 in both the gas and aqueous phases. The enthalpy of formation in the gas phase of (E)‐EHMC was derived from an isodesmic bond separation reaction. Long‐range corrected DFT calculations in implicit water were made in order to understand the excited state properties of the (E) and (Z) isomers of EHMC. Copyright © 2013 John Wiley & Sons, Ltd.     

Temperature dependence of the director reorientation of dye-doped nematic liquid crystals subjected to an optical field and its relation with the non-linear absorption coefficient

The temperature behaviour of the torque amplification factor η in the E48-D4 dye-host/liquid crystal-guest dyed system illuminated by a laser beam has been investigated using a single beam Z-Scan experimental technique. A plot of η versus temperature showed a monotonic aspect, different from other anthraquinone dyed liquid crystals. This behaviour, in our case, is consistent with the monotonic dependence on temperature of the linear α_o and non-linear β optical absorption coefficients. In particular, the non-linear optical absorption coefficient related to the reorienting process is negative and of the order of-0.25 mm W^-1. The temperature dependence of η seems to be directly correlated to β and not to α_o. Since drastic conformational modifications on dye molecules are not expected on passing from the ground to the excited state, the role of the electronic structure seems to be dominant in the reorienting process in dyed nematics.