Bio-inspired synthesis of ZnO polyhedral single crystals under eggshell membrane direction

A simple and versatile technique was developed to prepare hierarchical ZnO single crystals by introducing eggshell membrane (ESM) to a bio-inspired approach. Based on the control of nucleation and gestation, ZnO nanocrystallites could grow at three dimensions into polyhedral single crystals through a surface sol-gel process followed by a calcination treatment. Different from traditional wet chemical techniques, our synthetic process depends more on the restrictive or directing functions of the ESM biomacromolecules. The hierarchical ZnO nanostructures doped with polyhedral single crystallites could be desirable for catalysts, photoelectrochemical devices, especially solar cells.     

Polybrominated diphenyl ethers (PBDEs) in marine sediment of Thermaikos Gulf,Greece

Polybrominated diphenyl ether (PBDE) concentrations were determined in marine sediment samples collected from 7 different locations around Thermaikos Gulf in north Greece. PBDEs were detected in all sampling sites and their average total concentration (ΣPBDEs) ranged from 0.26 to 4.92?ng?g^?1?d.w. Concentrations were an order of magnitude higher in locations outlining the inner part of the Gulf, which were also closer to industrial areas, sewage treatment plant discharges, the city's harbour and landfill area. These findings suggest pollution in the aquatic ecosystem from industrial and urban activities in the area. Congener profiles exhibit predominance of BDE-209, while concentrations of other PBDE congeners were usually lower, when compared to similar studies from other countries globally, indicating that Thermaikos Gulf is among the low-polluted areas. Statistical analysis showed significant differences among the higher polluted sampling stations. Statistically significant differences also existed between sampling stations with high and low PBDE concentrations. Correlations between congeners suggested local contamination sources; however, specific point sources of pollution were not established.     

Iron flux inside the International Space Station is measured to be lower than predicted

Iron abundance in cosmic rays impinging on astronauts in space habitats is of paramount importance when calculating the radiation risk for human space exploration. The concurrent high relative abundance of iron in Galactic Cosmic Rays (GCR) and iron ability to produce damages at cellular and molecular levels, together with recent radiobiology results suggests iron as a major candidate to be studied in order to produce accurate radiation hazard assessments. Iron may be in fact responsible for a large percentage of cancer risk during a long interplanetary voyage, and therefore deserves a specific attention. We built a simple model based on CREME96 for the radiation in the International Space Station (ISS) and tested it against recently performed measurements with the ALTEA and Alteino particle detectors. While we can report a good agreement between 50m and 250 keV/μm (very good for several peaks such as Si, Mg, S) we show an overestimation by this model of iron abundances of about 25–80% when compared to the measurements. New analysis on previously published work, supporting this result, are also reported.Reasons for this overestimation are discussed, they are likely to be related to the not detailed enough transport through the multiplicity of the ISS shielding and to the often used simplification of “aluminum equivalent shielding”. The iron sources in LEO, possibly not yet accurate enough when transported in Low Earth Orbit, can also play a role. New concurrent measurements (inside–outside the ISS) are suggested to help resolving this issue.     

The far infrared spectrum of trans-formic acid: An extension up to 175 cm−1

The far infrared spectrum of HCOOH was recorded at a high resolution (0.0009 cm^?1) and long path length (72 m) at the far-infrared beamline, Canadian Light Source. Spectra were recorded in the region 62–300 cm^?1, showing transitions from the trans-isomer.Ground state rotational transitions with K_a up to 30, were identified up to 175 cm^?1, extending the observation reported in the literature. A total of 3321 transitions were assigned and fitted together with previous (4149) published data. An improved set of rotational parameters was obtained adopting the symmetric top (A) reduction of the rotational Hamiltonian in the I^r representation. The newly measured far infrared transitions allowed the determination of all diagonal and off diagonal 8th order parameters L and of some of the diagonal 10th order parameters P.     

Two negative minima of the first normal stress difference in a cellulose‐based cholesteric liquid crystal: Helix uncoiling

The shear rate dependence of material functions such as shear viscosity (η) and the first normal stress difference (N₁) were given and interpreted earlier by Kiss and Porter. Their widely accepted work revealed the possibility of having a negative minimum of N₁ for polymeric liquid crystals. In this work, we disclose for the first time the evidence of two negative N₁ minima on a sheared cellulosic lyotropic system. The lower shear rate minimum is ascribed to the uncoiling of the cholesteric helix, as theoretically predicted earlier. Our findings contribute also to the understanding of the other minimum already reported in the literature and attributed to the nematic director tumbling mode. Moreover, the elastic change that the LC‐HPC sample undergoes during the helix unwinding of the cholesteric structure is also by means of oscillatory measurements. This study is a contribution for the understanding of the structure‐properties relationship linked with the complex rheological behavior of chiral nematic cellulose‐based systems and may help to improve their further processing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 821–830     

XANES speciation of mercury in three mining districts – Almadén,Asturias (Spain), Idria (Slovenia)

The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found.     

Nanoparticles based on novel amphiphilic polyaspartamide copolymers

In this article, the synthesis of two amphiphilic polyaspartamide copolymers, useful to obtain polymeric nanoparticles without using surfactants or stabilizing agents, is described. These copolymers were obtained starting from α,β-poly-(N-2-hydroxyethyl)-dl-aspartamide (PHEA) by following a novel synthetic strategy. In particular, PHEA and its pegylated derivative (PHEA-PEG₂₀₀₀) were functionalized with poly(lactic acid) (PLA) through 1,1′-carbonyldiimidazole (CDI) activation to obtain PHEA–PLA and PHEA-PEG₂₀₀₀–PLA graft copolymers, respectively. These copolymers were properly purified and characterized by ¹H-NMR, FT-IR, and Size Exclusion Chromatography (SEC) analyses, which confirmed that derivatization reactions occurred. Nanoparticles were obtained from PHEA–PLA and PHEA-PEG₂₀₀₀–PLA graft copolymers by using the high pressure homogenization-solvent evaporation method, avoiding the use of surfactants or stabilizing agents. Polymeric nanoparticles were characterized by dimensional analysis, before and after freeze-drying process, and Scanning Electron Microscopy (SEM). Zeta potential measurements and X-ray Photoelectron Spectroscopy (XPS) analysis demonstrated the presence of PEG and/or PHEA onto the PHEA-PEG₂₀₀₀–PLA and PHEA–PLA nanoparticle surface, respectively.