Project description:Polyurethane (PU) is one of the most versatile polymers available and can be found in an infinite number of formats ranging from rigid or flexible foams to elastomers. Currently, most Rigid PU Foam (RPUF) waste is landfilled, even though a small amount is mechanically recycled, in which the material is conditioned in size to a very fine powder, which is introduced as a filler. In this work, chemical recycling of two types of rigid PU foams is studied, the major difference being the aliphatic or aromatic nature of the isocyanate used in the synthesis. A solvolysis process is developed, a chemical depolymerization that breaks the chains by means of a chemical agent, a solvent, in the presence of a catalyst and under controlled process conditions. The glycolysis products are purified by vacuum distillation, centrifugation, and acid water treatment, depending on the most suitable process for each waste type. Optimal process conditions are established to obtain high-purity green polyols by performing a set of catalytic glycolysis reactions at laboratory scale with the previously conditioned RPUF waste samples. The physicochemical properties of the polyols, such as hydroxyl value, acid value, average molecular weight (Mn), and viscosity, are analyzed. The chemical structure and thermal stability of the polyols are studied by means of FTIR and TGA, respectively. Partial substitution of the commercial polyol (up to 15 wt.%) by the recycled polyols for RPUF synthesis is studied and characterized.
Project description:To identify transcriptional adaptations associated with increased alkane production in Nostoc punctiforme, we performed comparative transcriptomic analysis of an alkane overproduction strain. RNA-seq data identified a large number of highly up-regulated genes in the overproduction strain potentially involved in rRNA processing, mycosporine-glycine production, and synthesis of non-ribosomal peptides including nostopeptolide A. Other up-regulated genes encoding helical carotenoid proteins, stress-induced proteins, and those for microviridin synthesis were also up-regulated. The presence of several up-regulated genes or operons on multi-copy plasmids resulted in reduced alkane production, indicating possible targets for mutagenesis that might limit lipid droplet and alkane production.
Project description:Lignocellulosic materials are promising alternatives to non-renewable fossil sources when producing aromatic compounds. Lignins from Populus salicaceae. Pinus radiata and Pinus pinaster from industrial wastes and biorefinery effluents were isolated and characterized. Lignin was depolymerized using homogenous (NaOH) and heterogeneous (Ni-, Cu- or Ni-Cu-hydrotalcites) base catalysis and catalytic hydrogenolysis using Ru/C. When homogeneous base catalyzed depolymerization (BCD) and Ru/C hydrogenolysis were combined on poplar lignin, the aromatics amount was ca. 11 wt.%. Monomer distributions changed depending on the feedstock and the reaction conditions. Aqueous NaOH produced cleavage of the alkyl side chain that was preserved when using modified hydrotalcite catalysts or Ru/C-catalyzed hydrogenolysis in ethanol. Depolymerization using hydrotalcite catalysts in ethanol produced monomers bearing carbonyl groups on the alkyl side chain. The analysis of the reaction mixtures was done by size exclusion chromatography (SEC) and diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR). 31P NMR and heteronuclear single quantum coherence spectroscopy (HSQC) were also used in this study. The content in poly-(hydroxy)-aromatic ethers in the reaction mixtures decreased upon thermal treatments in ethanol. It was concluded that thermo-solvolysis is key in lignin depolymerization, and that the synergistic effect of Ni and Cu provided monomers with oxidized alkyl side chains.
Project description:The Jeotgalicoccus sp. peroxygenase cytochrome P450 OleTJE (CYP152L1) is a hydrogen peroxide-driven oxidase that catalyzes oxidative decarboxylation of fatty acids, producing terminal alkenes with applications as fine chemicals and biofuels. Understanding mechanisms that favor decarboxylation over fatty acid hydroxylation in OleTJE could enable protein engineering to improve catalysis or to introduce decarboxylation activity into P450s with different substrate preferences. In this manuscript, we have focused on OleTJE active site residues Phe79, His85, and Arg245 to interrogate their roles in substrate binding and catalytic activity. His85 is a potential proton donor to reactive iron-oxo species during substrate decarboxylation. The H85Q mutant substitutes a glutamine found in several peroxygenases that favor fatty acid hydroxylation. H85Q OleTJE still favors alkene production, suggesting alternative protonation mechanisms. However, the mutant undergoes only minor substrate binding-induced heme iron spin state shift toward high spin by comparison with WT OleTJE, indicating the key role of His85 in this process. Phe79 interacts with His85, and Phe79 mutants showed diminished affinity for shorter chain (C10-C16) fatty acids and weak substrate-induced high spin conversion. F79A OleTJE is least affected in substrate oxidation, whereas the F79W/Y mutants exhibit lower stability and cysteine thiolate protonation on reduction. Finally, Arg245 is crucial for binding the substrate carboxylate, and R245E/L mutations severely compromise activity and heme content, although alkene products are formed from some substrates, including stearic acid (C18:0). The results identify crucial roles for the active site amino acid trio in determining OleTJE catalytic efficiency in alkene production and in regulating protein stability, heme iron coordination, and spin state.
Project description:Injection molding is a polymer processing technology used for manufacturing parts with elastic hinges. Elastic hinges are widely used in FMCG (Fast Moving Consumer Goods) packaging (e.g., bottle closures of shampoos, sauces) and in the electrical engineering industry. Elastic hinge is a thin film that connect two regions of the injection molded part, where significant shear rates are present, which can lead to the degradation of polymers and the decrease in mechanical properties. Selective induction heating is the method that improves the flow of the polymer melt through thin regions by the local increase in mold temperature. In this study, selective induction heating was used to improve mechanical properties of elastic hinges by the reduction of material degradation due to high shear rates. To verify the change of shear rates, selective induction heating simulation and injection molding simulations were performed. The linear relation between mold temperature and maximum shear rate in the cross-section was identified and the mechanical tests showed significant differences in hinge stiffness, tensile strength and elongation at break.
Project description:The first catalytic strategy to harness imidate radicals has been developed. This approach enables alkene difunctionalization of allyl alcohols by photocatalytic reduction of their oxime imidates. The ensuing imidate radicals undergo consecutive intra- and intermolecular reactions to afford (i) hydroamination, (ii) aminoalkylation, or (iii) aminoarylation, via three distinct radical mechanisms. The broad scope and utility of this catalytic method for imidate radical reactivity is presented, along with comparisons to other N-centered radicals and complementary, closed-shell imidate pathways.
Project description:In this study, the waste V2O5-WO3/TiO2 denitrification catalysts from the coal-fired power plant were washed with water or nitric acid, followed by impregnating different contents of V2O5. The effects of the HNO3 concentration and the additional amount of vanadium on the low-temperature selective catalytic reduction denitrification activity were investigated under the condition of high concentration of SO2 and H2O. The catalysts were characterized by inductively coupled plasma optical emission spectrometry, X-ray powder diffraction , N2 adsorption/desorption, H2-temperature-programmed reduction, NH3-temperature-programmed desorption , Fourier transform infrared spectroscopy , and Raman spectroscopy. The evaluation results revealed that optimum activity was achieved by using 0.8 mol/L HNO3 solution and loading 1.60 wt % V2O5 to make the total V2O5 reach 2.3 wt %. The characterization results showed that nitric washing can remove most of the ammonium salts deposited on the surface of the waste catalyst and produce crystalline WO3, which can effectively inhibit the agglomeration of vanadium species in the process of impregnation. Furthermore, it can also increase the amount of oligomeric VO x , which can improve the denitration activity.
Project description:The dimeric ?-diketiminato magnesium hydride, [(BDI)MgH]2, reacts at 80 °C with the terminal alkenes, 1-hexene, 1-octene, 3-phenyl-1-propene and 3,3-dimethyl-butene to provide the respective n-hexyl, n-octyl, 3-phenylpropyl and 3,3-dimethyl-butyl magnesium organometallics. The facility for and the regiodiscrimination of these reactions are profoundly affected by the steric demands of the alkene reagent. Reactions with the phenyl-substituted alkenes, styrene and 1,1-diphenylethene, require a more elevated temperature of 100 °C with styrene providing a mixture of the 2-phenylethyl and 1-phenylethyl products over 7 days. Although the reaction with 1,1-diphenylethene yields the magnesium 1,1-diphenylethyl derivative as the sole reaction product, only 64% conversion was achieved over a 21 day timeframe. Reactions with the ?,?-dienes, 1,5-hexadiene and 1,7-octadiene, provided divergent results. The initial 5-alkenyl magnesium reaction product of the shorter chain diene undergoes 5-exo-trig cyclisation via intramolecular carbomagnesiation to provide a cyclopentylmethyl derivative, which was shown by X-ray diffraction analysis to exist as a three-coordinate monomer. In contrast, 1,7-octadiene provided a mixture of two compounds, a magnesium oct-7-en-1-yl derivative and a dimagnesium-octane-1,4-diide, as a result of single or two-fold activation of the terminal C[double bond, length as m-dash]C double bonds. The magnesium hydride was unreactive towards internal alkenes apart from the strained bicycle, norbornene, allowing the characterisation of the resultant three-coordinate magnesium norbornyl derivative by X-ray diffraction analysis. Computational analysis of the reaction between [(BDI)MgH]2 and 1-hexene using density functional theory (DFT) indicated that the initial Mg-H/C[double bond, length as m-dash]C insertion process is rate determining and takes place at the intact magnesium hydride dimer. This exothermic reaction (?H = -14.1 kcal mol-1) traverses a barrier of 18.9 kcal mol-1 and results in the rupture of the dinuclear structure into magnesium alkyl and hydride species. Although the latter three-coordinate hydride derivative may be prone to redimerisation, it can also provide a further pathway to magnesium alkyl species through its direct reaction with a further equivalent of 1-hexene, which occurs via a lower barrier of 15.1 kcal mol-1. This Mg-H/C[double bond, length as m-dash]C insertion reactivity provides the basis for the catalytic hydrosilylation of terminal alkenes with PhSiH3, which proceeds with a preference for the formation of the anti-Markovnikov organosilane product. Further DFT calculations reveal that the catalytic reaction is predicated on a sequence of Mg-H/C[double bond, length as m-dash]C insertion and classical Si-H/Mg-C ?-bond metathesis reactions, the latter of which, with a barrier height of 24.9 kcal mol-1, is found to be rate determining.
Project description:Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis?aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence.
Project description:The ultra-stable Y (H-USY) zeolite is used as catalyst for the conversion of plastic feedstocks into high added value products through catalytic cracking technologies. However, the energy requirements associated with these processes are still high. On the other hand, induction heating by magnetic nanoparticles has been exploited for different applications such as cancer treatment by magnetic hyperthermia, improving of water electrolysis and many other heterogeneous catalytic processes. In this work, the heating efficiency of γ-Fe2O3 nanoparticle impregnated zeolites is investigated in order to determine the potential application of this system in catalytic reactions promoted by acid catalyst centers under inductive heating. The γ-Fe2O3 nanoparticle impregnated zeolite has been investigated by X-ray diffraction, electron microscopy, ammonia temperature program desorption (NH3-TPD), H2 absorption, thermogravimetry and dc and ac-magnetometry. It is observed that the diffusion of the magnetic nanoparticles in the pores of the zeolite is possible due to a combined micro and mesoporous structure and, even when fixed in a solid matrix, they are capable of releasing heat as efficiently as in a colloidal suspension. This opens up the possibility of exploring the application at higher temperatures.