Multiple unknown degradants generated from the insect repellent DEET by photoinduced processes on TiO2

This paper deals with the photocatalytic transformation of N,N-diethyl-m-toluamide (DEET), one of the most widespread and efficient mosquito repellents, under simulated solar irradiation using titanium dioxide as the photocatalytic source of oxidizing species. The investigation involved monitoring of the DEET decomposition, the identification of intermediate compounds and the assessment of mineralization. High-resolution mass spectrometry was employed to assess the evolution of the photocatalyzed process over time. Fifty-one main species were identified after DEET transformation. Several isomeric species were formed and were characterized by analyzing MS and MS(n) spectra in full, and by comparison with parent molecule fragmentation pathways. In the DEET molecule, the initial transformation involved mono- and polyhydroxylation followed by oxidation of the alcohol groups, cleavage of the alkyl chains or ring opening. All these intermediates are easily degraded and DEET is completely mineralized after 4 h of irradiation. Microtox bioassay (Vibrio fischeri) was employed to evaluate the ecotoxicity of solutions treated by photocatalysis.     

Chemical composition and bioactivity of Citrus medica L. cv. Diamante essential oil obtained by hydrodistillation, cold-pressing and supercritical carbon dioxide extraction

The chemical composition of the essential oil of Citrus medica L. cv. Diamante peel obtained by hydrodistillation, cold-pressing and supercritical carbon dioxide extraction techniques was determined by GC/MS analysis. Forty-six components were fully characterised. Limonene and γ-terpinene were the major components of the oils obtained by hydrodistillation (HD) and cold-pressing (CP), while citropten was the major constituent in the oil obtained by supercritical carbon dioxide extraction (SFE). Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitory activities were evaluated. The essential oil obtained by hydrodistillation exerted the highest inhibitory activity against BChE (IC?? value of 154.6 μg mL?1) and AChE (IC?? value of 171.3 μg mL?1. Interestingly, the oil obtained by cold-pressing exhibited a selective inhibitory activity against AChE. The essential oils have also been evaluated for the inhibition of NO production in LPS induced RAW 264.7 macrophages. The oil obtained by hydrodistillation exerted a significant inhibition of NO production with an IC?? value of 17 μg mL?1 (IC?? of positive control 53 μg mL?1).     

Study of OSEM with different subsets in grating-based X-ray differential phase-contrast imaging

Impressive developments in X-ray imaging are associated with X-ray phase contrast computed tomography based on grating interferometry, a technique that provides increased contrast compared with conventional absorption-based imaging. A new "single-step" method capable of separating phase information from other contributions has been recently proposed. This approach not only simplifies data-acquisition procedures, but, compared with the existing phase step approach, significantly reduces the dose delivered to a sample. However, the image reconstruction procedure is more demanding than for traditional methods and new algorithms have to be developed to take advantage of the "single-step" method. In the work discussed in this paper, a fast iterative image reconstruction method named OSEM (ordered subsets expectation maximization) was applied to experimental data to evaluate its performance and range of applicability. The OSEM algorithm with different subsets was also characterized by comparison of reconstruction image quality and convergence speed. Computer simulations and experimental results confirm the reliability of this new algorithm for phase-contrast computed tomography applications. Compared with the traditional filtered back projection algorithm, in particular in the presence of a noisy acquisition, it furnishes better images at a higher spatial resolution and with lower noise. We emphasize that the method is highly compatible with future X-ray phase contrast imaging clinical applications.     

Interaction of cationic liposomes with cell membrane models

The colloidal dispersion stability of nano-sized graphene sheets in supercritical fluid (SCF) media is very important for developing SCF-based exfoliation and dispersion technologies for stabilization and solubilization of graphenes. We carried out molecular dynamics simulations to elucidate the stability mechanism of graphene in supercritical CO(2) (scCO(2)). The potential of mean force (PMF) between two graphene nanosheets in scCO(2) was simulated, and the effect of scCO(2) density and temperature on the PMF behavior has been investigated. The simulation results demonstrate that there exists a free energy barrier between graphenes in the scCO(2) fluid, possibly obstructing the aggregation of graphenes. The single-layer confined CO(2) molecules between the graphene sheets can induce a dominating repulsion interaction between graphene sheets. At higher scCO(2) fluid density, there are more confined CO(2) molecules within the interplate regions, resulting in a stronger repulsive free energy barrier. The effect of temperature on the PMF is relatively minor. The scCO(2) solvent structure shows layered confined arrangement in the interfacial region near the graphene nanosheets, which is correlated well with the PMF profile curve.     

Effect of the Zn2+ and Hg2+ ions on the structure of liquid water

The effect of ions on the structure of liquid water is still not completely understood, despite extensive experimental and theoretical studies. A combined XANES and molecular dynamics investigation on diluted Zn(2+) and Hg(2+) aqueous solutions reveals that the influence of a single ion on the bonding pattern of water molecules is strongly dependent on the nature of the ion. While the structure of water is not altered by the presence of the Zn(2+) ion, the Hg(2+) cation has a strong impact on the hydrogen-bond network of water that extends beyond the first coordination shell.     

Bergamot (<Emphasis Type="Italic">Citrus bergamia</Emphasis> Risso) fruit extracts and identified components alter expression of interleukin 8 gene in cystic fibrosis bronchial epithelial cell lines

Background  

Cystic fibrosis (CF) airway pathology is a fatal, autosomal, recessive genetic disease characterized by extensive lung inflammation. After induction by TNF-α, elevated concentrations of several pro-inflammatory cytokines (i.e. IL-6, IL-1β) and chemokines (i.e. IL-8) are released from airway epithelial cells. In order to reduce the excessive inflammatory response in the airways of CF patients, new therapies have been developed and in this respect, medicinal plant extracts have been studied. In this article we have investigated the possible use of bergamot extracts (Citrus bergamia Risso) and their identified components to alter the expression of IL-8 associated with the cystic fibrosis airway pathology.     

Quinic acids from Aster caucasicus and from transgenic callus expressing a beta-amyrin synthase

Several different classes of secondary metabolites, including flavonoids, triterpenoid saponins and quinic acid derivatives, are found in Aster spp. (Fam. Asteraceae). Several Aster compounds revealed biological as well as pharmacological activities. In this work, a phytochemical investigation of A. caucasicus evidenced the presence of quinic acid derivatives, as well as the absence of triterpene saponins. To combine in one species the production of different phytochemicals, including triterpenes, an Agrobacterium-mediated transformation of A. caucasicus was set up to introduce A. sedifolius beta-amyrin synthase (AsOXA1)-encoding gene under the control of the constitutive promoter CaMV35S. The quali-quantitative analysis of transgenic calli with ectopic expression of AsOXA1 showed, in one sample, a negligible amount of triterpene saponins combined with higher amount of quinic acid derivatives as compared with the wild type callus.     

Chemical composition and possible in vitro antigermination activity of three Hypericum essential oils

The essential oils of Hypericum perforatum, H. perfoliatum and H. hircinum, growing in Southern Italy, were analyzed by GC and GC/MS. In the three oils, 111 compounds in all were identified: 53 for the oil of H. hircinum (93.7% of the total oil), 55 for H. perforatum (96.5% of the total oil) and 63 for H. perfoliatum (98.7% of the total oil). The major fraction of the essential oils of H. perforatum and H. hircinum was represented by sesquiterpene hydrocarbons, while the monoterpene alpha-pinene, and the phenol thymol were the most abundant compounds in the essential oil of H. perfoliatum. The oils were evaluated for their potential in vitro phytotoxic activity against germination and early radicle elongation of Raphanus sativus and Lepidium sativum. The germination of this latter was significantly inhibited by the essential oil of H. hircinum, at the highest doses tested, whereas radicle elongation of garden cress was significantly inhibited by the essential oils of H. perfoliatum and H. hircinum. The radicle elongation of radish was inhibited by the essential oil of H. hircinum to a major extent and by H. perforatum and perfoliatum in a minor measure.