Photophysics of polyaniline: Sequence-length distribution dependence of photoluminescence quenching as studied by fluorescence measurements and Monte Carlo simulations

The dependence of the fluorescence quenching of electropolymerized poly(aniline-co-m-chloroaniline) with polymer composition has been investigated. Fluorescence emission in polyaniline is quenched when the polymer is oxidized (brought to emeraldine state); the copolymers exhibit decreasing quenching as chloroaniline contents increases. Quenching shows a strong decrease in the presence of 0.1% m-chloroaniline monomers in the feed. The presence of dichloroaniline units in the copolymer was confirmed by XPS measurements and a terpolymerization reaction scheme was developed, obtaining the kinetic parameters. By Monte Carlo simulation the sequence length distributions for different compositions were obtained and compared; it was found that quenching, for low aniline contents, requires aniline sequences of at least three units. The strong decrease in quenching at low m-chloroaniline contents is attributed to a double effect: breaking of conjugation in the emeraldine form by the presence of the chlorinated unit, and a disruption of the close chain packing in the crystalline domains, preventing state delocalization and thus efficient quenching.     

Assessment of the bioavailability of toxic and non-toxic arsenic species in seafood samples

Bioavailability of total arsenic, toxic (arsenite, As(III); and arsenate, As(V)), and non-toxic (monomethylarsonic acid, MA; dimethylarsonic acid, DMA; arsenobetaine, AB; and arsenocholine, AC) arsenic species has been assessed in different raw seafood samples (white fish, cold water fish and molluscs) by using an in vitro model that combines simulated gastric and intestinal digestion/dialysis methods. Correlations between arsenic species bioavailability and seafood nutrient contents (fat and protein) have also been established. Total arsenic content in seafood samples, and dialyzable and non-dialyzable fractions, were analyzed by inductively coupled plasma – mass spectrometry (ICP–MS) after a microwave-assisted acid digestion treatment. The determination of the different arsenic species concentrations in the samples (after an optimised matrix solid phase dispersion (MSPD) approach) and in the dialyzable fraction was done by high performance liquid chromatography (HPLC) coupled to ICP-MS as a selective detector. Accuracy of the procedure (total arsenic determination) was assessed by analyzing DORM-2 and BCR-627 certified reference materials. The accuracy of the in vitro procedure was established through a mass-balance study. After statistical evaluation (95% confidence interval), good accuracy of the whole in vitro process, for total arsenic and for arsenic speciation, was observed. High dialyzability percentages for total arsenic and for arsenic species were found (i.e. from 84.6 ± 1.7% to 106 ± 2.6%). Bioavailability of arsenic exhibits a negative correlation with the fat content of the seafood. However, no correlation was observed between the bioavailable fraction of total arsenic and arsenic species and the protein content of the seafood studied.     

Remote sensing of wetlands in South America: status and challenges

South America has a large proportion of wetlands compared with other continents. While most of these wetlands were conserved in a relatively good condition until a few decades ago, pressures brought about by land use and climate change have threaten their integrity in recent years. The aim of this article is to provide a bibliometric analysis of the available scientific literature relating to the remote sensing of wetlands in South America. From 1960 to 2015, 153 articles were published in 63 different journals, with the number of articles published per year increasing progressively since 1990. This rise is also paralleled by an increase in the contribution of local authors. The most intensively studied regions are the wetland macrosystems of South American mega-rivers: the Amazon and Paraná Rivers, along with the Pantanal at the headwaters of Paraguay River. Few studies spanned more than two countries. The most frequent objectives were mapping, covering all types of wetlands with optical data, and hydrology, focusing on floodplain wetlands with microwave data as the preferred data source. The last decade substantial growth reflects an increase in technological and scientific capacities. Nevertheless, the state of the art regarding the remote sensing of wetlands in South America remains enigmatic. Fundamental questions and guidelines which may contribute to the understanding of the functioning of these ecosystems are yet to be fully defined and there is considerable dispersion in the use of data and remote-sensing approaches.     

Investigating the chlorination of acidic pharmaceuticals and by-product formation aided by an experimental design methodology

The degradation of seven acidic drugs and two metabolites during chlorination was investigated by liquid chromatography-mass spectrometry (LC-MS). A triple-quadrupole (QqQ) system was used to follow the time course of the pharmaceuticals and by-products, while a quadrupole time-of-flight (Q-TOF) system was also used for the identification of the by-products. Under strong chlorination conditions (10 mg/L Cl₂, 24 h), only four of the target compounds were significantly degraded: salicylic acid, naproxen, diclofenac and indomethacine. The degradation kinetics of these four compounds were investigated at different concentrations of chlorine, bromide and pH by means of a Box-Behnken experimental design. Depending on these factors, measured pseudo-first order half-lives were in the ranges: 23-573 h for salicylic acid, 13-446 min for naproxen, 5-328 min for diclofenac and 0.4-13.4 min for indomethacine. Also, it was observed that chlorine concentration was the overall most significant factor, followed by the bromide concentration (except for indomethacine), resulting in increased degradation kinetics as they are increased. The degradation path of salicylic acid, naproxen and diclofenac consisted of aromatic substitution of one or two hydrogens by chlorine and/or bromide. Moreover, for diclofenac, two other by-products corresponding to a decarboxylation/hydroxylation pathway from the monohalogenated products were also identified. On the other hand, indomethacine degradation did not lead to halogenation products but to oxidation ones. The investigation of these by-products in real samples by LC-MS/MS (QqQ) showed that the halogenated derivates of salicylic acid occurred in all the drinking water and wastewater samples analysed.     

Stability of emulsions formulated with high concentrations of sodium caseinate and trehalose

Stability of emulsions formulated with 10 wt.% oil (concentrated fish oil, CFO, sunflower oil, SFO, or olive oil, OO), sodium caseinate concentrations varying from 0.5 to 5 wt.%, giving oil-to-protein ratios of 20–2, and 0, 20, 30 or 40 wt.% aqueous trehalose solution was studied by Turbiscan. Particle size distribution, microstructure, and small angle X-ray scattering (SAXS) patterns were also obtained. The main mechanism of destabilization in a given formulation strongly depended on oil-to-protein ratio. As evidenced by the BS-profile changes with time, emulsions formulated with 0.5 and 1 wt.% NaCas destabilized mainly by creaming while for the 2 wt.% NaCas concentration, both creaming and flocculation mechanisms, were involved. The main destabilization mechanism for the 3, 4 or 5 wt.% NaCas emulsions was flocculation. Stability of emulsions was also affected by the content of trehalose in the aqueous phase. Trehalose diminished the volume-weighted mean diameter (D_4,3) and greatly improved stability.     

Oil and fungal biomass dispersion in a stirred tank containing a simulated fermentation broth

The production of γ‐decalactone by the filamentous fungus Trichoderma harzianum involves four phases (oil–water–air–mycelium) and its dispersion is crucial during fermentation. Oil and biomass (when present) dispersion, as a function of the volumetric power drawn (P/V), was characterized, in two; three‐ and four‐phase systems agitated with Rushton turbines. Trichoderma harzianum mycelium was used as the solid phase in the four‐phase system. Two stages of the fermentation were simulated: the beginning (15% oil and 1.4 kgm^?3 of mycelium) and the end (2% oil and 10.6 kg m^?3 of mycelium). In the two‐phase system, the use of exhausted broth achieved higher oil dispersions at low P/V values as compared with distilled water. Aeration decreased the oil dispersion for the high‐oil system, but enhanced oil dispersion for the low‐oil system. Compared with the P/V used in the actual fermentation (0.2 kW m^?3), a high segregation of the system was observed for the high‐oil/low‐biomass system, due to the difficulty of mixing the thick oil–air emulsion present at the top of the tank. The system simulating the end of the fermentation reached almost complete homogeneity of oil and biomass, a phenomenon due to the high biomass/oil ratio and the biomass acting as an oil carrier. © 2001 Society of Chemical Industry     

Evaluation and optimization of an on-line admicelle-based extraction-liquid chromatography approach for the analysis of ionic organic compounds

Admicelles-based solid-phase extraction (SPE) was on-line coupled with liquid chromatography/electrospray ionization/ion trap mass spectrometry, and it was proposed for the extraction of ionic organic compounds based on the formation of surfactant-analyte ion pairs. The approach was illustrated by studying the preconcentration of quaternary ammonium herbicides (quats) on sodium dodecyl sulfate (SDS) admicelles produced on alumina. Optimization of the parameters affecting SPE were studied on the basis that admicelles are dynamic entities in equilibrium with the aqueous phase. Some general guidelines could be established for method development from the results obtained. Factors influencing on-line operation were elucidated. On-line regeneration of the sorbent in each run was easily achieved by disruption of SDS admicelles with methanol and posterior coating of the alumina with SDS. The recovery of quats from drinking water samples were found quantitative for paraquat, diquat, and difenzoquat and above to 70% for chlormequat and mepiquat. Concentration factors of about 250, using sample volumes of 50 mL, were achieved. The detection limits ranged from 10 to 30 ng/L. The approach developed permits compliance with the directives of the European Community for drinking waters (100 ng/L) and goes deeply into the basis of solid-phase extractions that use surfactant-coated mineral oxide as sorbents.     

Surfactant to dye binding degree-based methodology for the determination of ionic amphiphilic compounds

A new analytical measurement parameter based on the effect of amphiphilic substances on the degree of binding of a surfactant to dye molecules, which induce the formation of surfactant premicellar aggregates, is presented. The theory for dye-surfactant intermolecular interactions in mixed surfactant systems, which assumes a mononuclear model for the formation of dye-induced premicellar aggregates, has been used to derive an expression that provides linear calibrations for the determination of amphiphilic compounds. The dye-surfactant interactions involved have been investigated, and the variables affecting the measurement analytical parameter have been discussed. The analytical applicability of the surfactant-dye binding degree method is demonstrated by quantifying major anionic surfactants at the nanograms-per-milliliter level and determining the total concentration of these amphiphilic substances in sewage samples (average recoveries ranged from 98 to 102%).