Heart Failure and PAHs,OHPAHs, and Trace Elements Levels in Human Serum: Results from a Preliminary Pilot Study in Greek Population and the Possible Impact of Air Pollution

Cardiovascular diseases (CVDs) have been associated with environmental pollutants. The scope of this study is to assess any potential relation of polycyclic aromatic hydrocarbons (PAHs), their hydroxylated derivatives, and trace elements with heart failure via their direct determination in human serum of Greek citizens residing in different areas. Therefore, we analyzed 131 samples including cases (heart failure patients) and controls (healthy donors), and the respective demographic data were collected. Significantly higher concentrations (p < 0.05) were observed in cases’ serum regarding most of the examined PAHs and their derivatives with phenanthrene, fluorene, and fluoranthene being the most abundant (median of >50 μg L⁻¹). Among the examined trace elements, As, Cd, Cu, Hg, Ni, and Pb were measured at statistically higher concentrations (p < 0.05) in cases’ samples, with only Cr being significantly higher in controls. The potential impact of environmental factors such as smoking and area of residence has been evaluated. Specific PAHs and trace elements could be possibly related with heart failure development. Atmospheric degradation and smoking habit appeared to have a significant impact on the analytes’ serum concentrations. PCA–logistic regression analysis could possibly reveal common mechanisms among the analytes enhancing the hypothesis that they may pose a significant risk for CVD development.     

Polarizable coarse‐grained models for molecular dynamics simulation of liquid cyclohexane

Force field parameters for polarizable coarse‐grained (CG) supra‐atomic models of liquid cyclohexane are proposed. Two different bead sizes were investigated, one representing two fine‐grained (FG) CH₂r united atoms of the cyclohexane ring, and one representing three FG CH₂r united atoms. Electronic polarizability is represented by a massless charge‐on‐spring particle connected to each CG bead. The model parameters were calibrated against the experimental density and heat of vaporization of liquid cyclohexane, and the free energy of cyclohexane hydration. Both models show good agreement with thermodynamic properties of cyclohexane, yet overestimate the self‐diffusion. The dielectric properties of the polarizable models agree very well with experiment. © 2015 Wiley Periodicals, Inc.     

Ion tree‐based structure elucidation of acetophenone dimers (AtA) from Acronychia pedunculata and their identification in extracts by liquid chromatography electrospray ionization LTQ‐Orbitrap mass spectrometry

Acronychia‐type acetophenones (AtA) is a chemical group of compounds of important structural and biological interest, abundant in Acronychia species. However, there are no data available for their characterization using mass spectrometry. In the current work, AtA have been investigated by multistage high resolution mass spectrometry and both electrospray ionization and atmospheric pressure chemical ionization, in positive and negative mode, were utilized for their structure elucidation and identification. The analysis of AtA using a linear ion trap‐Orbitrap analyzer enabled the structural determination of key fragment ions and cleavages, which can be used for the structural characterization thereof. A systematic nomenclature based on protonated and deprotonated fragment ions under collision‐induced dissociation conditions and decision trees for the structural determination of AtA are proposed. Furthermore, taking advantage of the characteristic fragmentation patterns, a selective Ultra High Performance Liquid Chromatography Electrospray Ionization multistage Mass Spectrometry (UHPLC‐ESI(‐)‐MSⁿ) method was developed and successfully applied for the dereplication of known AtA and the identification of potentially new ones in Acronychia extracts. Despite the structure similarity and the presence of isomers, accurate characterization of known and unknown AtA derivatives was possible. Copyright © 2015 John Wiley & Sons, Ltd.     

Nanoporous gold thin films synthesised via de-alloying of Au-based nanoglass for highly active SERS substrates

Nanoporous gold thin films have been fabricated through chemical de-alloying of Au-based nanoglass with a nanocolumnar structure, with composition Au₄₀Cu₂₈Ag₇Pd₅Si₂₀ (at.%), that had previously been deposited by magnetron sputtering. By varying the de-alloying conditions, gold ligaments ranging from 20 to 100?nm were obtained. The microstructure and chemical composition of the as-prepared films were characterised by various techniques. Surface-enhanced Raman scattering (SERS) of thin films was investigated using rhodamine 6G. The results indicate that the main microstructural features with interconnected ligaments and defects of nanoporous gold result in significant SERS enhancement.     

One‐pot Synthesis of Fused Dipyranocoumarins from Dihydroxycoumarins and Propargyl Chlorides under Microwave Irradiation

Dipetalolactone and 4‐methyldipetalolactone are prepared in excellent yield by a one‐pot tandem propargylation/Claisen rearrangement/cyclization reaction of the corresponding 5,7‐dihydroxycoumarins with 3‐chloro‐3‐methylbut‐1‐yne in the presence of Cs₂CO₃ under microwave irradiation. The analogous reactions of propargyl chloride with esculetins or 5,7‐dihydroxycoumarins led to dipropargyloxy derivatives. The later by treatment with gold nanoparticles supported on TiO₂ or BF₃.Et₂O in N,N‐dimethylformamide (DMF) under microwave irradiation resulted in very good to excellent yield to the corresponding fused dipyranocoumarins. The reactions of esculetins with 3‐chloro‐3‐methylbut‐1‐yne gave mainly exomethylene fused dioxino[g]coumarins.     

Singlet Oxygen‐Induced Furan Oxidation for Site‐Specific and Chemoselective Peptide Ligation

A novel chemoselective ligation methodology has been developed for the facile construction of peptide‐based fluorescent probes. Furan‐containing peptides were activated by singlet oxygen and covalently engaged by nitrogen nucleophiles to yield stable conjugates. Singlet oxygen was compatible with sensitive amino acid residues within the peptides and a range of fluorophores, bearing different functionalities, were successfully incorporated, illustrating the broad scope of the developed strategy.