Structural and vibrational study of 2‐(2′‐ furyl)‐4,5‐1H‐dihydroimidazole

In this study 2‐(2′‐furyl)‐4,5‐1H‐dihydroimidazole (1) was prepared and then characterized by infrared, Raman, and multidimensional nuclear magnetic resonance (NMR) spectroscopies. The crystal and molecular structures of 1 were determined by X‐ray diffraction methods. The density functional theory (DFT) and second‐order Møller–Plesset theory (MP2) with Pople's basis set show that there are two conformers for the title molecule that have been theoretically determined in the gas phase, and that only one of them, conformer I, is present in the solid phase. NMR spectra observed for 1 were successfully compared with the calculated chemical shifts at the B3LYP/6‐311++G** level theorized for this conformer. The harmonic vibrational frequencies for the optimized geometry of the latter conformer were calculated at the B3LYP/6‐311++G** level in the approximation of the isolated molecule. For a complete assignment of the IR and Raman spectra in the solid phase of 1 , DFT calculations were combined with Pulay´s scaled quantum mechanics force field (SQMFF) methodology to fit the theoretical frequency values to the experimental ones. Copyright © 2009 John Wiley & Sons, Ltd.     

An Analytical Method for the Biomonitoring of Mercury in Bees and Beehive Products by Cold Vapor Atomic Fluorescence Spectrometry

Bees and their products are useful bioindicators of anthropogenic activities and could overcome the deficiencies of air quality networks. Among the environmental contaminants, mercury (Hg) is a toxic metal that can accumulate in living organisms. The first aim of this study was to develop a simple analytical method to determine Hg in small mass samples of bees and beehive products by cold vapor atomic fluorescence spectrometry. The proposed method was optimized for about 0.02 g bee, pollen, propolis, and royal jelly, 0.05 g beeswax and honey, or 0.1 g honeydew with 0.5 mL HCl, 0.2 mL HNO₃, and 0.1 mL H₂O₂ in a water bath (95 °C, 30 min); samples were made up to a final volume of 5 mL deionized water. The method limits sample manipulation and the reagent mixture volume used. Detection limits were lower than 3 µg kg⁻¹ for a sample mass of 0.02 g, and recoveries and precision were within 20% of the expected value and less than 10%, respectively, for many matrices. The second aim of the present study was to evaluate the proposed method’s performances on real samples collected in six areas of the Lazio region in Italy.     

Integratomics of Human Dermal Fibroblasts Treated with Low Molecular Weight Hyaluronic Acid

Hyaluronic acid (HA) is a glycosaminoglycan very common in commercial products from pharmaceuticals to cosmetics due to its widespread distribution in humans and its diversified physico-chemical proprieties. Despite its extended use and preliminary evidence showing even also opposite activities to the native form, the precise cellular effects of HA at low-molecular-weight (LWM-HA) are currently unclear. The ‘omics sciences currently in development offer a new and combined perspective on the cellular and organismal environment. This work aims to integrate lipidomics analyses to our previous quantitative proteomics one for a multi-omics vision of intra- and extra-cellular impact of different concentrations (0.125, 0.25, and 0.50%) of LMW-HA (20–50 kDa) on normal human dermal fibroblasts by LC-high resolution mass spectrometry (LC-HRMS). Untargeted lipidomics allowed us to identify 903 unique lipids mostly represented by triacylglycerols, ceramides, and phosphatidylcholines. According to proteomics analyses, LMW-HA 0.50% was the most effective concentration also in the lipidome rearrangement especially stimulating the synthesis of ceramides involved in skin hydration and reparation, cell signaling, and energy balance. Finally, integrative analyses showed 25 nodes covering several intra- and extra-cellular functions. The more complete comprehension of intra- and extra-cellular effects of LMW-HA here pointed out will be useful to further exploit its features and improve current formulations even though further studies on lipids biosynthesis and degradation are necessary.     

The effect of core and lanthanide ion dopants in sodium fluoride-based nanocrystals on phagocytic activity of human blood leukocytes

Sodium fluoride-based β-NaLnF4 nanoparticles (NPs) doped with lanthanide ions are promising materials for application as luminescent markers in bio-imaging. In this work, the effect of NPs doped with yttrium (Y), gadolinium (Gd), europium (Eu), thulium (Tm), ytterbium (Yb) and terbium (Tb) ions on phagocytic activity of monocytes and granulocytes and the respiratory burst was examined. The surface functionalization of <10-nm NPs was performed according to our variation of patent pending ligand exchange method that resulted in meso-2,3-dimercaptosuccinic acid (DMSA) molecules on their surface. Y-core-based NCs were doped with Eu ions, which enabled them to be excited with UV light wavelengths. Cultures of human peripheral blood (n = 8) were in vitro treated with five different concentrations of eight NPs for 24 h. In summary, neither type of nanoparticles is found toxic with respect to conducted test; however, some cause toxic effects (they have statistically significant deviations compared to reference) in some selected doses tested. Both core types of NPs (Y-core and Gd-core) impaired the phagocytic activity of monocytes the strongest, having minimal or none whatsoever influence on granulocytes and respiratory burst of phagocytic cells. The lowest toxicity was observed in Gd-core, Yb, Tm dopants and near-infrared nanoparticles. Clear dose-dependent effect of NPs on phagocytic activity of leukocytes and respiratory burst of cells was observed for limited number of samples.     

Gamma Irradiation Effects on Mechanical and Thermal Properties and Biodegradation of Poly(3-hydroxybutyrate) Based Films

Summary: Their biodegradable properties make polyhydroxyalkanoates (PHAs) ideal candidates for innovative applications. Many studies have been primarily oriented to poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-valerate) (PHBV) and afterwards to blends of PHAs with synthetic biodegradable polymers, such as poly(ε-caprolactone) (PCL). Medical and pharmaceutical devices require sterilization and γ irradiation could provide a proper alternative since it assures storage stability and microbiological safety. This contribution presents the effect of γ irradiation on the mechanical and thermal properties and on the biodegradation of PHB, PHBV and a commercial PHB/PCL blend. Samples, prepared by compression moulding, were irradiated in air at a constant dose rate of 10 kGy/h, from 10 to 179 kGy. Polymer chain scission was assessed by changes in the molecular weight, thermal properties and tensile behaviour. The correlation between absorbed dose and changes in the mechanical properties and biodegradation is discussed in detail. The optimum dose to guarantee microbiological sterilization without damage of the structure or meaningful loss of the mechanical properties is also reported.     

Diffusion-weighted MRI in prostate cancer -- comparison between single-shot fast spin echo and echo planar imaging sequences

Diffusion-weighted (DW) MRI at 1.5 T was carried out in two groups of patients. MRI data were correlated with the biopsy and histopathology (where available). The performance of two sequences -- a single-shot FSE (14 patients) and a single-shot EPI (15 patients) -- was compared. Average ADC values from the normal peripheral zone (PZ), central gland (CG) and the tumour [prostate carcinoma (PCa)] were calculated from b values of 0 and 600. Tukey-Kramer test was used for statistical analysis. EPI produced higher values of ADC (10(-3) mm(2)/s) than FSE sequence: 1.992+/-0.208 vs. 1.573+/-0.270 in PZ (P<.001), 1.518+/-0.126 vs. 1.373+/-0.179 in CG and 1.214+/-0.254 vs. 0.993+/-0.158 in PCa (P<.01). In conclusion, both EPI and FSE sequences showed differences in ADC between normal PZ, CG and PCa; however, EPI produced significantly higher ADC values than FSE.     

Circulating hemocytes from larvae and adults of Carabus (Chaetocarabus) lefebvrei Dejean 1826 (Coleoptera, Carabidae): cell types and their role in phagocytosis after in vivo artificial non-self-challenge

Carabus lefebvrei Dejean 1826 is an helicophagous Italian endemic ground beetle that lives in central and south Apennines mountain forests, from lower altitudes to about 1500 m. In ground beetles, no morphofunctional data about immune system is available, even though they are well known both taxonomically and ecologically and they have been often used as indicators of the habitat quality due to their specificity to certain habitat types. In the current investigation the cellular population in the hemolymph of adult and third instar larvae of C. lefebvrei has been characterized by means of light and electron microscopy analysis and phagocytosis assays were performed in vivo by injection of 0.9 microm carboxylate-modified polystyrene latex beads in order to identify the hemocyte types involved in phagocytosis. Four morphotypes of circulating hemocytes were found both in larvae and in adults: prohemocytes, granulocytes, oenocytoids and plasmatocytes. After in vivo artificial non-self-challenge treatments, C. lefebvrei showed a non-specific immune response involving phagocytosis performed by plasmatocytes, both in adults and in larvae and by oenocitoids in larvae. In untreated animals, the hemocyte type presenting a firm phagocytic activity, the plasmatocytes, presented a percentage significantly higher in larvae than in adults, and after latex beads injections in larvae there was a tendency of significant difference in plasmatocyte percentage compared to controls injected with phosphate saline buffer. We think that these differences could be correlated with the peculiar morphology (less chitinization) and ecology of larval stages that are more sensitive to pathogens than adults.     

The Resting State Makes the Difference: The Influence of the Anchor Group in the ROMP of Norbornene Derivatives

Summary: A model study with four norbornene derivatives with different groups connecting a functional unit to the norbornene reveals that the “anchor groups” influence the polymerisation rate constants of ring opening metathesis (ROM) polymerisations. Consequently, polydispersities and molecular weights are affected. The observed effects are explained by different tendencies of the anchor groups to coordinate to the ruthenium centre during the resting state of the propagation.

A functionalised monomer where F is the functional unit, S is a spacer, A is an anchor group and P is the polymerisable group.     

Hybrid polymer inorganic materials prepared from ternary microemulsions

The microemulsion system containing vinyl acetate (Vac), silane derivatives tetraethoxysilane (TEOS), methacryloxypropyltrimethoxysilane (MPTS), vinyltriethoxysilane (VTES), methyltriethoxysilane (MeTES), octyltriethoxysilane (OTES), nonylphenol etoxylated with 25 mol of ethylene oxyde (NPEO₂₅) and water was studied. It was established that the probability of microemulsion formation increases with surfactant concentration. The microenviroment of the solubilization of the VAc and of silane derivatives in the aggregates of NPEO₂₅ was affected by their polarity. Hybrid materials were obtained by sol-gel reaction of silane derivatives combined with free-radical polymerization of VAc. The change of the glass transition temperature and of thermal stability of the polymer chains in the presence of the inorganic one proved the formation of simultaneous polymer inorganic hybrids.