111-57-9Relevant articles and documents
Pharmaceuticals and Surfactants from Alga-Derived Feedstock: Amidation of Fatty Acids and Their Derivatives with Amino Alcohols
Tkacheva, Anastasia,Dosmagambetova, Inkar,Chapellier, Yann,M?ki-Arvela, P?ivi,Hachemi, Imane,Savela, Risto,Leino, Reko,Viegas, Carolina,Kumar, Narendra,Er?nen, Kari,Hemming, Jarl,Smeds, Annika,Murzin, Dmitry Yu.
, p. 2670 - 2680 (2015)
Amidation of renewable feedstocks, such as fatty acids, esters, and Chlorella alga based biodiesel, was demonstrated with zeolites and mesoporous materials as catalysts and ethanolamine, alaninol, and leucinol. The last two can be derived from amino acids present in alga. The main products were fatty alkanol amides and the corresponding ester amines, as confirmed by NMR and IR spectroscopy. Thermal amidation of technical-grade oleic acid and stearic acid at 180°C with ethanolamine were non-negligible; both gave 61% conversion. In the amidation of stearic acid with ethanolamine, the conversion over H-Beta-150 was 80% after 3 h, whereas only 63% conversion was achieved for oleic acid; this shows that a microporous catalyst is not suitable for this acid and exhibits a wrinkled conformation. The highest selectivity to stearoyl ethanolamide of 92% was achieved with mildly acidic H-MCM-41 at 70% conversion in 3 h at 180°C. Highly acidic catalysts favored the formation of the ester amine, whereas the amide was obtained with a catalyst that exhibited an optimum acidity. The conversion levels achieved with different fatty acids in the range C12-C18 were similar; this shows that the fatty acid length does not affect the amidation rate. The amidation of methyl palmitate and biodiesel gave low conversions over an acidic catalyst, which suggested that the reaction mechanism in the amidation of esters was different. Pores versus acidity: The structures and properties of zeolites and mesoporous materials are investigated as catalysts for the amidation of renewable feedstocks, such as fatty acids, esters, and Chlorella alga based biodiesel, with ethanolamine, alaninol, and leucinol as nitrogen sources.
Optimized synthesis and characterization of N-acylethanolamines and O-acylethanolamines, important family of lipid-signalling molecules
Ottria, Roberta,Casati, Silvana,Ciuffreda, Pierangela
, p. 705 - 711 (2012)
The endocannabinoid anandamide (N-arachidonoylethanolamine, AEA), a physiologically occurring bioactive compound on CB1 and CB2 receptors, has multiple physiological functions. Since the discovery of AEA additional non-cannabinoid endogenous compounds such as N-palmitoylethanolamine (PEA), and N-oleoylethanolamine (OEA) have been identified from mammalian tissues. Virodhamine (O-arachidonoylethanolamine, VA) is the only identified new member of the endocannabinoid family that is characterised by an ester linkage between acylic acid and ethanolamine instead of the amide linkage found in AEA and others non-cannabinoid N-acylethanolamines. It has been reported, as a cautionary note for lipid analyses, that VA can be produced nonenzymatically from AEA (and vice versa) as consequence of O,N-acyl migrations. O,N-acyl migrations are well documented in synthetic organic chemistry literature, but are not well described or recognized with regard to methods in lipid isolation or lipid enzyme studies. We here report an economical and effective protocol for large scale synthesis and characterization of some N- and O-acylethanolamines that could be useful as reference standards in order to investigate their possible formation in biological membranes, with potentially interesting biological properties.
Polymorphism of N-stearoylethanolamine: Differential scanning calorimetric, vibrational spectroscopic (FTIR), and crystallographic studies
Wouters,Vandevoorde,Culot,Docquir,Lambert
, p. 13 - 21 (2002)
Based on a series of physicochemical properties (differential scanning calorimetry, powder X-ray crystallographic studies and Fourier-transform infra red spectroscopic analysis) determined for N-stearoylethanolamine (NSEA) (C18:0) at different temperatures, evidence has been given that this compound can exist in (at least) three polymorphic forms. Powder X-ray crystallography clearly demonstrates the presence of three distinct molecular packings at distinct temperatures while spectral changes in the vibrational spectra reveal that the geometry of the CH2-CO functional group of the molecule is affected during the polymorphic transitions. Rationalization of the thermal physicochemical behavior of NSEA in terms of molecular packing is also proposed. It supposes rearrangement of the hydrocarbon chains upon heating of the molecule.
Solvent-free “green” amidation of stearic acid for synthesis of biologically active alkylamides over iron supported heterogeneous catalysts
M?ki-Arvela, P?ivi,Zhu, Jeanne,Kumar, Narendra,Er?nen, Kari,Aho, Atte,Linden, Johan,Salonen, Jarno,Peurla, Markus,Mazur, Anton,Matveev, Vladimir,Murzin, Dmitry Yu.
, p. 350 - 358 (2017)
Stearoyl ethanolamine was synthesized by amidation of stearic acid with ethanolamine in solventless conditions. Iron containing heterogeneous catalysts supported on SiO2, Al2O3, Beta (BEA), ZSM-12 (MTW) and Ferrierite (FER) were used in this work. Sn-modified Ferrierite and H-Ferrierite were also studied for comparison. Fe-modified catalysts synthesized using solid state ion-exchange and evaporation impregnation methods, were thoroughly characterized with X-ray powder diffraction, scanning electron microscope, FTIR with pyridine, nitrogen adsorption, energy dispersive X-ray microanalysis and M?ssbauer spectroscopy. The highest conversion was obtained with Fe-H-FER-20 at 140?°C in 1?h giving 61% conversion and 98% selectivity towards the desired amide. The catalytic performance in terms of turnover frequency per mole of iron was achieved with the catalyst exhibiting the largest amount of Fe3+ species, optimum acidity and a relatively low Br?nsted to Lewis acid site ratio.
Structure and reactivity in langmuir films of amphiphilic alkyl and thio-alkyl esters of ?±-amino acids at the air/water interface
Eliash, Ran,Weissbuch, Isabelle,Weygand, Markus J.,Kjaer, Kristian,Leiserowitz, Leslie,Lahav, Meir
, p. 7228 - 7240 (2004)
The structure and reactivity of alkyl esters of several ?±-amino acids self-assembled at the air/water interface have been investigated as part of our studies on mechanisms that are possibly relevant for the generation of homochiral prebiotic peptides. Grazing incidence X-ray diffraction (GIXD) studies of monolayers of racemic and enantiopure alkyl esters and thio-esters of alanine on the water surface demonstrated that these racemates self-assemble in the form of mixed solid solutions, because of disorder of the headgroups of the two enantiomers (enantiomeric disorder) within the two-dimensional (2D) crystallites. Matrix-assisted laser-desorption ionization time-of-flight Mass Spectrum (MALDI-TOF MS) analysis of the products collected from the air/water interface indicated the formation of low-molecular-weight oligopeptides (primarily dimers) and, in the case of some of the thioesters, small quantities of trimers and tetramers. Mass spectrometric studies on the diastereoisomeric distribution of the oligopeptides, starting from deuterium enantio-labeled monomers, demonstrated binomial statistics, such as that in reactions occurring in an isotropic environment. The alkyl esters of phenylalanine and tyrosine did not form 2D crystallites at the air/water interface, and, upon polycondensation, they yielded only dipeptides. The enantiomeric disorder within the 2D crystallites of the monomers of the alkyl esters and thioesters of racemic serine was absent. Polycondensation of these esters, however, yielded only dipeptides and tripeptides and they were not investigated further. In contrast to previous reports, the present studies demonstrate that this reaction does not proceed beyond the dipeptide stage and, therefore, cannot be regarded as a plausible system for the generation of prebiotic peptides.
Design and synthesis of silicon-containing fatty acid amide derivatives as novel peroxisome proliferator-activated receptor (PPAR) agonists
Kajita, Daisuke,Nakamura, Masaharu,Matsumoto, Yotaro,Ishikawa, Minoru,Hashimoto, Yuichi,Fujii, Shinya
, p. 3350 - 3354 (2015)
Abstract We recently reported that diphenylsilane structure can function as a cis-stilbene mimetic. Here, we investigate whether silyl functionality can also serve as a mimetic of aliphatic cis-olefin. We designed and synthesized various silyl derivatives of oleoylethanolamide (OEA: 8), an endogenous cis-olefin-containing PPARα agonist, and evaluated their PPARα/δ/γ agonistic activity. We found that diethylsilyl derivative 20 exhibited PPARα/δ agonistic activity, and we also obtained a PPARδ-selective agonist, 32. Our results suggest that incorporation of silyl functionality is a useful option for structural development of biologically active compounds.
Alkyl sulfonyl derivatized PAMAM-G2 dendrimers as nonviral gene delivery vectors with improved transfection efficiencies
Morales-Sanfrutos, Julia,Megia-Fernandez, Alicia,Hernandez-Mateo, Fernando,Giron-Gonzalez, Ma Dolores,Salto-Gonzalez, Rafael,Santoyo-Gonzalez, Francisco
, p. 851 - 864 (2011)
Amphiphilic dendrimer-based gene delivery vectors bearing peripheral alkyl sulfonyl hydrophobic tails were constructed using low-generation PAMAM-G2 as the core and functionalized by means of the aza-Michael type addition of its primary amino groups to vinylsulfone derivatives as an efficient tool for surface engineering. While the unmodified PAMAM-G2 was unable to efficiently transfect eukaryotic cells, functionalized PAMAM-G2 dendrimers were able to bind DNA at low N/P ratios, protect DNA from digestion with DNase I and showed high transfection efficiencies and low cytotoxicity. Dendrimers with a C18 alkyl chain produced transfection efficiencies up to 3.1 fold higher than LipofectAMINE 2000 in CHO-k1 cells. The dendriplexes based in functionalized PAMAM-G2 also showed the ability to retain their transfection properties in the presence of serum and the ability to transfect different eukaryotic cell lines such as Neuro-2A and RAW 264.7. Taking advantage of the vinylsulfone chemistry, fluorescent PAMAM-G2 derivatives of these vectors were prepared as molecular probes to determine cellular uptake and internalization through a clathrin-independent mechanism.
Synthesis and biological activity of N-acyl O-indolylalkyl ethanolamines
Jiang, Shaoliang,Gao, Jianrong,Han, Liang
, p. 768 - 770 (2011)
The plant-growth regulators, indole-3-carboxylic acids, were introduced into N-acyl ethanolamines, and a series of N-acyl O-indolylalkyl ethanolamines were prepared. Their biological activities to regulate rape hypocotyl elongation, cucumber cotyledon expansion and common wheat coleoptile growth were tested. The results indicate that the title compounds inhibited rape hypocotyl elongation, especially the indole-3-propionic acid derivatives, whose bioactivity was better than that of indole-3-acetic acid.
Different roles for the acyl chain and the amine leaving group in the substrate selectivity of N-Acylethanolamine acid amidase
Ghidini, Andrea,Scalvini, Laura,Palese, Francesca,Lodola, Alessio,Mor, Marco,Piomelli, Daniele
, p. 1411 - 1423 (2021/07/17)
N-acylethanolamine acid amidase (NAAA) is an N-terminal nucleophile (Ntn) hydrolase that catalyses the intracellular deactivation of the endogenous analgesic and anti-inflammatory agent palmitoylethanolamide (PEA). NAAA inhibitors counteract this process and exert marked therapeutic effects in animal models of pain, inflammation and neurodegeneration. While it is known that NAAA preferentially hydrolyses saturated fatty acid ethanolamides (FAEs), a detailed profile of the relationship between catalytic efficiency and fatty acid-chain length is still lacking. In this report, we combined enzymatic and molecular modelling approaches to determine the effects of acyl chain and polar head modifications on substrate recognition and hydrolysis by NAAA. The results show that, in both saturated and monounsaturated FAEs, the catalytic efficiency is strictly dependent upon fatty acyl chain length, whereas there is a wider tolerance for modifications of the polar heads. This relationship reflects the relative stability of enzyme-substrate complexes in molecular dynamics simulations.
An Aldehyde Responsive, Cleavable Linker for Glucose Responsive Insulins
Mannerstedt, Karin,Mishra, Narendra Kumar,Engholm, Ebbe,Lundh, Morten,Madsen, Charlotte S.,Pedersen, Philip J.,Le-Huu, Priska,Pedersen, S?ren L.,Buch-M?nson, Nina,Borgstr?m, Bj?rn,Brimert, Thomas,Fink, Lisbeth N.,Fosgerau, Keld,Vrang, Niels,Jensen, Knud J.
supporting information, p. 3166 - 3176 (2021/01/21)
A glucose responsive insulin (GRI) that responds to changes in blood glucose concentrations has remained an elusive goal. Here we describe the development of glucose cleavable linkers based on hydrazone and thiazolidine structures. We developed linkers with low levels of spontaneous hydrolysis but increased level of hydrolysis with rising concentrations of glucose, which demonstrated their glucose responsiveness in vitro. Lipidated hydrazones and thiazolidines were conjugated to the LysB29 side-chain of HI by pH-controlled acylations providing GRIs with glucose responsiveness confirmed in vitro for thiazolidines. Clamp studies showed increased glucose infusion at hyperglycemic conditions for one GRI indicative of a true glucose response. The glucose responsive cleavable linker in these GRIs allow changes in glucose levels to drive the release of active insulin from a circulating depot. We have demonstrated an unprecedented, chemically responsive linker concept for biopharmaceuticals.
