Search results for "transesterification"
showing 10 items of 37 documents
PET/PEN Blends of Industrial Interest as Barrier Materials. Part I. Many-Scale Molecular Modeling of PET/PEN Blends
2006
Mesoscale molecular simulations, based on parameters obtained through atomistic molecular dynamics and Monte Carlo calculations, have been used for modeling and predicting the behavior of PET/PEN blends. Different simulations have been performed in order to study and compare pure homopolymer blends with blends characterized by the presence of PET/PEN block copolymers acting as compatibilizer. A many-scale molecular modeling strategy was devised to evaluate PET/PEN blend characteristics, simulate phase segregation in pure PET/PEN blends, and demonstrate the improvement of miscibility due to the presence of the transesterification reaction products. The behavior of distribution densities and …
Undecylenic acid: A tunable bio-based synthon for materials applications
2016
International audience; An undecylenic acid-based monoglyceride prepared from glycidol and undecylenic acid is used as suitable and tunable synthon for polymerization applications. Epoxidation and acrylation reactions lead to photopolymerizable monomers while transesterification with dimethyl carbonate, metathesis and aminolysis reactions provide access to polyhydroxyurethane-based materials. The successive intermediates were synthesized according to a green chemistry approach implicating solvent-less and catalyzed reactions, and were at each step fully characterized by infrared, 1H and 13C{1H} NMR spectroscopy, elemental analysis and mass spectrometry. Analyses of the resulting polymer mat…
A statistical design of experiments for optimizing the MALDI-TOF-MS sample preparation of polymers. An application in the assessment of the thermo-me…
2011
[EN] The sample preparation procedure for MALDI-TOF MS of polymers is addressed in this study by the application of a statistical Design of Experiments (DoE). Industrial poly (ethylene terephthalate) (PET) was chosen as model polymer. Different experimental settings (levels) for matrixes, analyte/matrix proportions and concentrations of cationization agent were considered. The quality parameters used for the analysis were signal-to-noise ratio and resolution. A closer inspection of the statistical results provided the study not only with the best combination of factors for the MALDI sample preparation, but also with a better understanding of the influence of the different factors, individua…
The Catalytic Mechanism of Carboxylesterases: A Computational Study
2014
The catalytic mechanism of carboxylesterases (CEs, EC 3.1.1.1) is explored by computational means. CEs hydrolyze ester, amide, and carbamate bonds found in xenobiotics and endobiotics. They can also perform transesterification, a reaction important, for instance, in cholesterol homeostasis. The catalytic mechanisms with three different substrates (ester, thioester, and amide) have been established at the M06-2X/6-311++G**//B3LYP/6-31G* level of theory. It was found that the reactions proceed through a mechanism involving four steps instead of two as is generally proposed: (i) nucleophilic attack of serine to the substrate, forming the first tetrahedral intermediate, (ii) formation of the ac…
Cutinases: Characteristics and Insights in Industrial Production
2021
Cutinases (EC 3.1.1.74) are serin esterases that belong to the α/β hydrolases superfamily and present in the Ser-His-Asp catalytic triad. They show characteristics between esterases and lipases. These enzymes hydrolyze esters and triacylglycerols and catalyze esterification and transesterification reactions. Cutinases are synthesize by plant pathogenic fungi, but some bacteria and plants have been found to produce cutinases as well. In nature they facilitate a pathogen’s invasion by hydrolyzing the cuticle that protects plants, but can be also used for saprophytic fungi as a way to nourish themselves. Cutinases can hydrolyze a wide range of substrates like esters, polyesters, triacylglycero…
Improving lipase activity in solvent-free media by interfacial activation-based molecular bioimprinting
1997
Abstract Nine lipases of mammalian, fungal and bacterial origin and two different model reactions, direct esterification and transesterification (alcoholysis), have been used to probe the potential in solvent-free media of the recently reported strategy of interfacial activation-based molecular (bio)imprinting (IAMI) [Mingarro et al., Proc. Natl. Acad. Sci. USA , 92 (1995) 3308]. The results demonstrate that the imprinting treatment permits nonaqueous rate accelerations which are lipase-dependent and span in some cases up to higher than two orders of magnitude. For several lipases, the method allows conversion yields after short reaction times (in either of the model reactions assayed) whic…
Organo-catalyzed synthesis of aliphatic polycarbonates in solvent-free conditions
2012
A new efficient and expeditious route to the synthesis of aliphatic polycarbonates, in solvent-free conditions and using 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) as a catalyst precursor, is described. The protocol consists of a two-step polymerization process involving the transesterification of dimethyl carbonate (DMC) with linear alkane diols and leading to high molecular weight homopolymers. The reaction went to completion quantitatively with the liberation of methanol as the only by-product. The in situ formation of N-heterocyclic carbene species resulting from BMIM-2-CO2 decarboxylation is suggested to be a key feature of the condensation process. The protocol was then …
Extraction of lipids from wet microalga Auxenochlorella protothecoides using pulsed electric field treatment and ethanol-hexane blends
2017
Abstract Pulsed Electric Field (PEF) treatment was used as pre-treatment on the microalgae strain Auxenochlorella protothecoides (A.p.) prior to organic solvent extraction of lipids. Experiments were performed on fresh biomass from mixotrophic or autotrophic culture which both had an evaluated lipid content of 30–35% of cell dry weight. Lipid yield was determined gravimetrically and compared to the reference lipid content assessed by bead-milling and subsequent Soxhlet extraction. The biomass was concentrated at 10% w/w solids prior to PEF-treatment and further dewatered afterwards to approximately 25% w/w before extraction. PEF-treatment with an energy input of 1.5 MJ per kilogram of dry m…
Biodiesel via in situ wet microalgae biotransformation: Zwitter-type ionic liquid supported extraction and transesterification
2017
The production of biodiesel derived from microalgae is among the most forthcoming technologies that provide an ecologic alternative to fossil fuels. Herein, a method was developed that enables the direct extraction and conversion of algal oil to biodiesel without prior isolation. The reaction occurs in aqueous media catalyzed by immobilized Candida antarctica lipase B (Novozyme 435). Zwitter-type ionic liquids were used as cocatalyst to improve the selectivity and reactivity of the enzyme. In a model reaction with sunflower oil, 64% biodiesel was obtained. Applying this method to a slurry of whole-cell Chlorella zof ingiensis in water resulted in 74.8% of lipid extraction, with 27.7% biotra…
Torque rheometry investigation of model transreactions involving condensation polymers: I. Polyesters
2005
The chemical transformations taking place when poly(ethylene terephthalate) (PET) or poly(ethylene naphthalate) (PEN) are blended in the melt with different low molar mass substances containing hydroxyl, carboxyl, or amine functional groups have been investigated as models of the transreactions, undergone by the polyesters in reactive blending operations. The polyester molecular weight changes caused by the alcoholysis, acidolysis, aminolysis, and esterolysis reactions have been monitored by torque-rheometry, using a Brabender Plasticorder static mixer. The degradation of the polyesters by hydrolysis was also studied, under similar conditions, by the addition of a water-releasing substance …