Functionalization of Reduced Graphite Oxide Sheets with a Zwitterionic Surfactant

Films of a few layers in thickness of reduced graphite oxide (RGO) sheets functionalized by the zwitterionic surfactant N‐dodecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propanesulfonate (DDPS) are obtained by using the Langmuir–Blodgett method. The quality of the RGO sheets is checked by analyzing the degrees of reduction and defect repair by means of X‐ray photoelectron spectroscopy, atomic force microscopy (AFM), field‐emission scanning electron microscopy (SEM), micro‐Raman spectroscopy, and electrical conductivity measurements. A modified Hummers method is used to obtain highly oxidized graphite oxide (GO) together with a centrifugation‐based method to improve the quality of GO. The GO samples are reduced by hydrazine or vitamin C. Functionalization of RGO with the zwitterionic surfactant improves the degrees of reduction and defect repair of the two reducing agents and significantly increases the electrical conductivity of paperlike films compared with those prepared from unfunctionalized RGO.     

Isolation and structure elucidation of ovatoxin-a, the major toxin produced by Ostreopsis ovata

Since 2005, the benthic dinoflagellate Ostreopsis cf. ovata has bloomed across the Mediterranean basin, provoking serious toxic outbreaks. LC/MS studies have identified a number of palytoxin-like compounds, termed ovatoxins, along with trace amounts of putative palytoxin as the causative agents of the O. cf. ovata -related human sufferings. So far, any risk assessment for ovatoxins as well as establishment of their allowance levels in seafood has been prevented by the lack of pure toxins. The present paper reports on the isolation, NMR-based structural determination, and preliminary mouse lethality evaluation of ovatoxin-a, the major toxic compound contained in O. cf. ovata extracts. Availability of pure ovatoxin-a will open the double prospect of fully evaluating its toxicity and preparing reference standards to be employed in LC/MS quantitative analyses. Elucidation of ovatoxin-a's complex structure will ultimately herald the understanding of the molecular bases of ovatoxins bioactivity.     

Shear flow effects on polymer melts crystallization: kinetics features

In this work the kinetics of the isothermal crystallization from the melt of isotactic polyolefins in quiescent conditions as well as after the application of a step-shear flow is investigated by means of rheological measurements. It is shown that the kinetics of the crystallization, as measured by the increase of the storage modulus, is not affected by the strain amplitude and the frequency of the oscillation, once they are properly chosen. A strong enhancement of the crystallization kinetics has been obtained when the step-shear flow was applied at the crystallization temperature T_C=92°C for two different molecular weight poly(1-butene) samples (i-PB400 and i-PB200) and at T_C=137°C for a polypropylene (i-PP). In particular, the overall-crystallization rate constants of the i-PB400 increased with increasing the applied shear rate at a constant total strain of 60. At higher shear flow temperatures slower kinetics occurred in all the cases until the effect of the applied shear flow was lost. Moreover, the effect of the molecular weight on the flow induced crystallization phenomenon is investigated on the two i-PB samples and the results have clearly shown that the higher molecular weight i-PB200 polymer is much more sensitive than the i-PB400 to the flow history.     

Biphasic Synthesis of Hydrogen Peroxide from Carbon Monoxide,Water, and Oxygen Catalyzed by Palladium Complexes with Bidentate Nitrogen Ligands

Effective and stable Pd catalysts for the biphasic synthesis of hydrogen peroxide from carbon monoxide, oxygen, and water [Eq. (a)] can be obtained by the right choice of bidentate nitrogen ligand. The best turnover numbers (578) for this reaction have been achieved with palladium complexes with 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline ligands.     

Nutrient Removal Efficiency and Physiological Responses of Desmodesmus communis at Different HRTs and Nutrient Stress Condition Using Different Sources of Urban Wastewater Effluents

The objective of the present study was to evaluate the nutrient removal efficiency and the physiological responses in terms of growth, biochemical composition and photosynthetic activity of the autochthonous freshwater algal strain Desmodesmus communis. Microalgae were grown in a primary municipal effluent under different hydraulic retention times (HRTs) and in a two-phases process using both primary and secondary wastewater effluents. Semi-continuous cultures were operated for 7 day at 5-, 3- and 1.5-day HRT and the different dilution rate showed a greater influence on the biomass composition and nutrient removal efficiency. Removal of N-NH₃ and P-PO₄ was over 99 % and the highest accumulation of polysaccharides (57.2 wt.%) was obtained at high HRT (5 day); the maximum content of proteins (26.9 wt.%) was achieved at 1.5-day HRT, even if, under this condition, a clear inefficiency in terms of ammonia removal was observed. Moreover the accumulation of N-NH₃ occurring at 1.5-day HRT caused the decrease of the photosynthetic response in terms of efficiency of light capture (α) and relative electron transport rate (rETR), both parameters extracted from the rapid light curves (RLC) measurements. No significant differences were observed for the total fatty acids (TFAs), with a content of 2–3.5 wt.% for each HRT condition. On the other hand, in the two-phases process, when a nutrient deprivation condition was induced by diluting the culture with the secondary wastewater effluent, the algal cells accumulated TFAs, achieving a maximum content of 9.7 wt.% and a great increment in terms of biomass (1.64?±?0.02 g L^?1) due to the ability of this algal strain to accumulate intracellular N. The wide and accurate investigation of the different aspects related to the whole process represents a relevant point of novelty in this research field and suggests the operational conditions for the start-up of an open pond system for wastewater treatment and biomass production for further applications.     

A Highly Luminescent Tetrahydrocurcumin IrIII Complex with Remarkable Photoactivated Anticancer Activity

Curcumin has chemopreventative properties against a variety of tumours, but has poor bioavailability. Here, two new bis-cyclometallated iridium(III) complexes have been prepared, featuring the natural product curcumin (CUR) or its reduced form, tetrahydrocurcumin (THC), as bidentate, anionic O O-binding ligands. The iridium THC complex is highly luminescent in deoxygenated solution and efficiently generates singlet oxygen under aerated conditions, whereas in the CUR analogue, other non-radiative decay pathways are competitive. The complexes are rapidly taken up by a variety of human tumour cell lines from solutions of micromolar concentration. They show negligible cytotoxicity in the absence of irradiation. When briefly irradiated with visible light, Ir-THC becomes highly phototoxic, inducing rapid apoptosis within 2 h. The results show the high potential of such complexes as sensitizers in photodynamic therapy (PDT).     

Messages in molecules: ligand/cation coding and self-recognition in a constitutionally dynamic system of heterometallic double helicates

Double helicates are known to exhibit self-recognition characteristics determined by the coordination geometry of the metal involved as well as by the topicity of the ligands. Combining tridentate (terpyridine, T) or bidentate (bipyridine, B) subunits in a tritopic strand affords a set of ligands able to assemble by pairs to form double helicates, homo- or heterostranded, homo- or heterotopic, depending on the coordination properties of the metals involved. The four ligand strands, BBB, TTT, BBT, and TBT form constitutionally dynamic sets of double helicates with the metal ions Cu(I), Cu(II), and Zn(II); these helicates correspond to the correct coding of the BB, BT, and TT pairs for tetra-, penta-, and hexacoordinate Cu(I), Cu(II), and Zn(II) cations, respectively.