Free radical chemistry of disinfection byproducts. 2. Rate constants and degradation mechanisms of trichloronitromethane (chloropicrin)

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, *OH, and hydrated electron, e(aq)-, reactions were (4.97 +/- 0.28) x 10(7) M(-1) s(-1) and (2.13 +/- 0.03) x 10(10) M(-1) s(-1), respectively. It appears that the *OH adds to the nitro-group, while the e(aq)- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance of the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.     

A combined approach for characterisation of fresh and brined vine leaves by X-ray powder diffraction,NMR spectroscopy and direct infusion high resolution mass spectrometry

X-ray powder diffraction was combined, for the first time, with Nuclear Magnetic Resonance spectroscopy and direct infusion mass spectrometry to characterise fresh and brined grape leaves. Covariance analysis of data generated by the three techniques was performed with the aim to correlate information deriving from the solid part with those obtained for soluble metabolites. The results obtained indicate that crystalline components can be correlated to the metabolites contained in the grape leaves, paving the way to the use of X-ray diffraction analysis for food fingerprinting purposes. Moreover it was ascertained that, differently from most of the metabolites present in the fresh vine leaves, linolenic acid (an omega-3-fatty acid) and quercetin-3-O-glucuronide (a polyphenol metabolite) do not undergo sensible degradation during the brining process, which is used as preservative method for the grape leaves.     

Optical and electrical characterization of carbon nanoparticles produced in laminar premixed flames

Optical and electrical properties of carbonaceous particles produced in laboratory scale, premixed ethylene/air flames are obtained. Light absorption and Raman spectroscopy show that the change in particle nanostructure follows a graphitization trajectory as the flame richness increases. The optical band gap decreases and the size of the aromatic network in the particle increases, while the interlayer spacing between parallel layers decreases. The electrical conductivity of the materials increases by increasing flame richness in agreement to the graphitization trajectory. A non-ohmic behavior has been found and explained in terms of electron tunneling in a percolative network. Our results show that the electrical properties of flame formed carbon nanoparticles are strongly dependent on their nanostructure, and hence they have to be used carefully for the determination of particle concentration with conductometric sensors. Moreover, the dependence of the electrical properties of combustion formed particles might be useful for the development of cheap sensors for the selective detection of different classes of combustion aerosols.     

Analysis of the energy efficiency of solar aided biomass gasification for pure hydrogen production

This paper presents a simulative analysis of the energy efficiency of solar aided biomass gasification for pure hydrogen production. Solar heat has been considered as available at 250 °C in three gasification processes: i) gasification reactor followed by two water gas shift reactors and a pressure swing adsorber; ii) gasification reactor followed by an integrated membrane water gas shift reactor; iii) supercritical gasification reactor followed by two flash separators and a pressure swing adsorber.     

Novel quasi-autothermal hydrogen production process in a fixed-bed using a chemical looping approach: A numerical study

This paper presents a novel quasi-autothermal hydrogen production process. The proposed layout couples a Chemical Looping Combustion (CLC) section and a Steam Methane Reforming (SMR) one. In CLC section, four packed-beds are operated using Ni as oxygen carrier and CH₄ as fuel to continuously produce a hot gaseous mixture of H₂O and CO₂. In SMR section, two fixed-beds filled with Ni-based catalyst convert CH₄ and H₂O into a H₂-rich syngas. Four heat exchangers were employed to recover residual heat content of all the exhaust gas currents. By means of a previously developed 1D numerical model, a dynamic simulation study was carried out to evaluate feasibility of the proposed system in terms of methane conversion (100% circa), hydrogen yield (about 0.65 mol_H2/mol_CH4) and selectivity (about 70%), and syngas ratio (about 2.3 mol_H2/mol_CO). Energetic and environmental analyses of the system performed with respect to conventional steam methane reforming, highlights an energy saving of about 98% and avoided CO₂ emission of about 99%.     

Marie Ménard apples with high polyphenol content and a low‐fat diet reduce 1,2‐dimethylhydrazine‐induced colon carcinogenesis in rats: Effects on inflammation and apoptosis

Inflammation may increase cancer risk, therefore, we studied whether polyphenol‐rich Marie Ménard (MM) apples with reported anti‐inflammatory activity prevent 1,2‐dimethylhydrazine (DMH)‐induced colon carcinogenesis in rats and, likewise whether high‐fat (HF) diet promoting carcinogenesis, may affect inflammation. DMH‐induced rats were fed for 15 weeks with: an HF diet (23% corn oil w/w); an HF diet containing 7.6% w/w lyophilized MM (apple diet (AD)); a low‐fat (LF) diet and an HF diet containing piroxicam (PXC) (0.01% w/w) as control. Mucin depleted foci (MDF), precancerous lesions in the colon, were dramatically reduced in the AD, LF, and PXC groups compared with the HF. Peritoneal macrophage activation, an index of systemic inflammation, was significantly decreased in the AD, LF, and PXC groups. TNF‐α, iNOS, IL‐1β, IL‐6 m‐RNA expression in the colon, as well as CD68 cells and plasmatic PGE2 were lower in the AD, but not in the LF group. Apoptosis in the MDF of both the AD and LF‐fed rats was significantly higher than in HF rats. In conclusion, AD has a strong chemopreventive effect, reducing inflammation, and increasing apoptosis, while the chemopreventive effect of the LF diet seems mediated mainly by increased apoptosis in MDF.     

Design of high fastness acid dyes for silk: a chemometric approach

A chemometric strategy tor the design of acid dyes for silk is reported. A small set of representative dyes was selected by the technique of fractional factorial design, using the principal properties of the substituents as design variables. The selected dyes were synthesised and fastness properties on silk were measured. Wash fastness and light fastness values were related to the chemical structure by the partial least squares (PLS) method. The models were used to predict the fastness of new dyes of the same class and to optimise the structure.     

Thermal Explosion of Powder Mixtures: Numerical Approach

A numerical approach to investigate the heating and the ignition of powder mixtures by radiant energy is presented. The ignition study is based on the possibility of separating the initiation transient from the propagation process, by operating in thermal explosion mode.     

Composites Between Alumina and an Ester‐Ether‐Ester Bioresorbable Copolymer

Composites between alumina and the bioresorbable poly(ε‐caprolactone)‐block‐poly(oxyethylene)‐block‐poly(ε‐caprolactone) copolymer were obtained by reacting ε‐caprolactone with preformed poly(ethylene glycol), in the presence of ceramic alumina powder, at 185°C under vacuum. The mechanical properties, tested by compression and flexural strengths and Young's modulus, show that the copolymer interacts poorly with the alumina grains. Both scanning electron and atomic force microscopy show a scarce wettability between alumina and copolymer, as well as the aggregation of alumina micro‐particles into clusters of big size. Both mechanical and morphological tests seem to indicate a stronger interaction between the alumina micro‐particles than between the alumina surface and the reaction mixture during the polymerization, as well as a “compacting effect” by alumina on the forming copolymer. The FT‐IR spectra of the composites show both copolymer and alumina absorption bands. The FT‐IR analysis on the fractions of an extraction with CHCl₃ indicates the presence of traces of poly(ε‐caprolactone), stably linked to alumina. The polymerization of ε‐caprolactone with alumina alone in the same conditions gives poly(ε‐caprolactone), mainly free and in minor part linked to the alumina surface. Two polymerization mechanisms, simultaneously occurring, are proposed. The most relevant result of this work is the lack of chemical inertness of alumina towards ε‐caprolactone, which leads to reconsider also the use of alumina as a biochemically inert material.