The availability of green and cheap technologies to recover polyhydroxyalkanoates (PHAs) from microbial biomass is crucial for the development of a reliable and sustainable production chain. Here, two novel protocols are proposed to extract PHAs from Cupravidus necator. The first method is based on PHA-extraction with dimethyl carbonate (DMC), a green solvent that is completely biodegradable and less harmful to humans and the environment than most solvents. The procedure can be applied directly to concentrated microbial slurries or to dry biomass, affording very high polymer recovery (>85%) and excellent purity (>95%). No degradation/decomposition of the polymer is observed in both cases. The second protocol uses fatty acid carboxylates as surfactants, which disrupt cell membranes, providing excellent polymer recovery (>99%) and high purity (>90%). Ammonium laurate can be successfully used and easily recycled (98%) by lowering the pH through CO 2 addition. Therefore, both protocols reported here are effective and sustainable: the recovery and purity of the obtained PHAs are very high, the use of toxic chemicals is avoided, and the recycling of various solvents/surfactants used in the processes is optimal.
Extraction of PHB with organic solventsFreeze-dried biomass extraction. C. necator freeze-dried samples (50 mg) were extracted with organic solvents (2 mL) for 1-4 h. The tested solvents and the corresponding temperatures of extraction were: DMC (90°C and 50°C), PC (90°C), DEC (90°C), ethyl acetate (80°C) and CH 2 Cl 2 (50°C). At the end of the extraction, the solutions were centrifuged at 4000 rpm for 1 min and then filtered with polypropylene membrane filters of 0.45 µm porosity. The polymer was recovered by solvent evaporation or by precipitation with EtOH, then dried at 60°C under vacuum overnight.Each extraction was performed in quadruplicate.
HyFlex EDM revealed peculiar structural properties, such as increased phase transformation temperatures and hardness. Present results corroborated previous findings and shed light on the enhanced mechanical behaviour of these instruments.
2-dimensional (2D) nanosheets such as graphene, graphene oxide, boron nitride or transition metal dichalcogenides can be produced on a large scale by exfoliation techniques. The lateral shape of these 2D materials is typically considered random and irregular, and their average size is often estimated using techniques characterized by strong approximations or poor statistical significance. Here we measure in a quantitative, objective way the size and shape of 2D monoatomic nanosheets using a combination of optical, electronic and scanning probe techniques. We measure, one by one, the size and shape of thousands of sheets of graphene oxide as they undergo a standard ultrasonication treatment. Using automatic image processing and statistical modelling we identify two different fragmentation processes in 2D at the nanoscale, related to two populations of nanosheets described by gamma and exponential size distributions respectively. The two populations of sheets coexist during the fragmentation process, each one retaining its average size and shape. Our results explain the size reduction commonly observed in nanosheets upon sonication as an effect of changes in the respective weights of the two populations of nanosheets present in the material.
Cured and uncured scraps from manufacturing of epoxy based carbon fiber reinforced composites were treated with a pyrolytic process to provide, as solid residue, carbon fibers to be re-used in new composites production. The industrial scraps were pyrolyzed at different temperatures in a 70 kg batch pilot plant and the pyrolysis products (gas, oil, and solid) were fully characterized. The solid residue (carbon fibers covered by a carbonaceous layer) was subjected to a further oxidative step at 500 and 600 C for different residence times to provide fibers devoid of any organic residue that did not volatilize during pyrolysis. The effects of both pyrolysis and oxidative process on the recovered fibers were evaluated by scanning electron microscopy and Raman Spectroscopy. The reinforcement behavior of pyrolyzed and pyrolyzed/oxidized chopped fibers, compared to virgin fibers, was tested in the production of new Chopped Carbon Fiber Reinforced Composites. The optimized double pyrolysis/ oxidation process was found to provide fibers whose performance in the composites were comparable to the virgin ones. POLYM. COMPOS., 36:1084-1095, 2015
To investigate interchromophore interactions in azobenzene polymers, we have undertaken a thorough spectroscopic analysis of the azodye [(S)-3-pivaloyloxy-1-(4'-nitro-4-azobenzene)pyrrolidine] by modeling the repeating unit of poly[(S)-3-methacryloyloxy-1-(4'-nitro-4-azobenzene)pyrrolidine) and its dimeric derivative whose synthesis is presented here. The analysis of the electronic and Raman spectra of the azodye in several solvents is based on a previously proposed model for polar chromophores in solution. Electronic and CD spectra of the dimeric unit are collected and analyzed within the framework of a new model. On the basis of the information collected from the spectroscopic analysis of the solvated dye, this model accounts for interchromophore interactions in the dimer. The large CD signal measured for the dimer (amounting to about a third of the signal measured for the polymer) suggests the presence of important chiral interactions in the dimeric unit, and is modeled in terms of a right-handed relative orientation of the two chromophores.
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