54549-24-5Relevant articles and documents
Sweet surfactants: Packing parameter-invariant amphiphiles as emulsifiers and capping agents for morphology control of inorganic particles
Voggel, Michael,Meinusch, Rebecca M.,Siewert, Vanessa,Kunkel, Marius,Wittmann, Valentin,Polarz, Sebastian
, p. 7214 - 7227 (2018/09/26)
Surfactants are not only pivotal constituents in any biological organism in the form of phospholipids, they are also essential for numerous applications benefiting from a large, internal surface, such as in detergents, for emulsification purposes, phase transfer catalysis or even nanoparticle stabilization. A particularly interesting, green class of surfactants contains glycoside head groups. Considering the variability of glycosides, a large number of surfactant isomers become accessible. According to established models in surfactant science such as the packing parameter or the hydrophilic lipophilic balance (HLB), they do not differ from each other and should, thus, have similar properties. Here, we present the preparation of a systematic set of glycoside surfactants and in particular isomers. We investigate to which extent they differ in several key features such as critical aggregation concentration, thermodynamic parameters, etc. Analytical methods like isothermal titration calorimetry (ITC), tensiometry, dynamic light scattering (DLS), small angle-X-ray scattering (SAXS), transmission electron microscopy (TEM) and others were applied. It was found that glycosurfactant isomers vary in their emulsification properties by up to two orders of magnitude. Finally, we have investigated the role of the surfactants in a microemulsion-based technique for the generation of zinc oxide (ZnO) nanoparticles. We found that the choice of the carbohydrate head has a marked effect on the shape of the formed inorganic nanocrystals.
Synthesis and Properties of Alkyl β-d-Galactopyranoside
Chen, Guoyong,Li, Zhencao,Chen, Langqiu,Ji, Shanwei,Shen, Wangzhen
, p. 1095 - 1105 (2016/10/18)
A series of alkyl β-d-galactopyranosides were prepared by the trichloroacetimidate method with d-galactose and alcohols with different chain lengths as raw materials. Their solubility, surface tension, emulsification, foaming, wettability, thermotropic liquid crystalline properties, and thermal stability were investigated. Alkyl β-d-galactopyranosides are soluble in water and ethanol, and the solubility decreases with increasing alkyl chain length. Decyl β-d-galactopyranoside was insoluble in water, but soluble in ethanol. Dissolution of alkyl β-d-galactopyranoside in water is an endothermic process with dissolution enthalpies greater than zero. Nonyl β-d-galactopyranoside had an excellent emulsifying?property, better foaming ability and the best foam stability. The CMC values of alkyl β-d-galactopyranosides decrease with increasing of alkyl chain length. Alkyl β-d-galactopyranosides are thermally stable up to 270?°C. Alkyl β-d-galactopyranosides show the distinctive optical texture of a thermotropic liquid crystal smectic A type phase. Decyl β-d-galactopyranoside showed the strongest wettability.
Synthesis of glycotriazololipids and observations on their self-assembly properties
Tyagi, Mohit,Kartha, K.P. Ravindranathan
supporting information, p. 85 - 92 (2015/06/30)
Abstract Various carbohydrate-anchored triazole-linked lipids prepared by solvent-free mechanochemical azide-alkyne click reaction, on analysis by TEM, have been found to spontaneously self-assemble in solvents leading to structures of interesting physicochemical attributes. Interestingly, analogous compounds based on different sugars (e.g., d-glucose, and d-galactose, as also d-lactose) assemble in patterns distinctly different from each other thus reiterating the fact that the structure of the sugar as well as that of the lipid are important factors that determine the size and shape of the supramolecular assembly formed. Besides, the molecular self-assembly was also found to be solvent-as well as temperature-dependent.
Chemoenzymatic synthesis of β-D-glucosides using cellobiose phosphorylase from Clostridium thermocellum
De Winter, Karel,Van Renterghem, Lisa,Wuyts, Kathleen,Pelantová, Helena,K?en, Vladimír,Soetaert, Wim,Desmet, Tom
, p. 1961 - 1969 (2015/06/02)
Abstract Over the past decade, disaccharide phosphorylases have been successfully applied for the synthesis of numerous α-glucosides. In contrast, much less research has been done with respect to the production of β-glucosides. Although cellobiose phosphorylase was already successfully used for the synthesis of various disaccharides and branched trisaccharides, its glycosylation potential towards small organic compounds has not been explored to date. Unfortunately, disaccharide phosphorylases typically have a very low affinity for non-carbohydrate acceptors, which urges the addition of solvents. The ionic liquid AMMOENGTM 101 and ethyl acetate were identified as the most promising solvents, allowing the synthesis of various β-glucosides. Next to hexyl, heptyl, octyl, nonyl, decyl and undecyl β-D-glucopyranosides, also the formation of vanillyl 4-O-β-D-glucopyranoside, 2-phenylethyl β-D-glucopyranoside, β-citronellyl β-D-glucopyranoside and 1-O-β-D-glucopyranosyl hydroquinone was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry. Moreover, the stability of cellobiose phosphorylase could be drastically improved by creating cross-linked enzyme aggregates, while the efficiency of the biocatalyst for the synthesis of octyl β-D-glucopyranoside was doubled by imprinting with octanol. The usefulness of the latter system was illustrated by performing three consecutive batch conversions with octanol imprinted cross-linked enzyme aggregates, yielding roughly 2 g of octyl β-D-glucopyranoside.
Biphasic catalysis with disaccharide phosphorylases: Chemoenzymatic synthesis of α- D -glucosides using sucrose phosphorylase
De Winter, Karel,Desmet, Tom,Devlamynck, Tim,Van Renterghem, Lisa,Verhaeghe, Tom,Pelantova, Helena,Kren, Vladimir,Soetaert, Wim
, p. 781 - 787 (2014/07/08)
Thanks to its broad acceptor specificity, sucrose phosphorylase (SP) has been exploited for the transfer of glucose to a wide variety of acceptor molecules. Unfortunately, the low affinity (Km > 1 M) of SP towards these acceptors typically urges the addition of cosolvents, which often either fail to dissolve sufficient substrate or progressively give rise to enzyme inhibition and denaturation. In this work, a buffer/ethyl acetate ratio of 5:3 was identified to be the optimal solvent system, allowing the use of SP in biphasic systems. Careful optimization of the reaction conditions enabled the synthesis of a range of α-d-glucosides, such as cinnamyl α-d-glucopyranoside, geranyl α-d-glucopyranoside, 2-O-α-d-glucopyranosyl pyrogallol, and series of alkyl gallyl 4-O-α-d-glucopyranosides. The usefulness of biphasic catalysis was further illustrated by comparing the glucosylation of pyrogallol in a cosolvent and biphasic reaction system. The acceptor yield for the former reached only 17.4%, whereas roughly 60% of the initial pyrogallol was converted when using biphasic catalysis.
Preparation of two glycoside hydrolases for use in micro-aqueous media
Lundemo, Pontus,Karlsson, Eva Nordberg,Adlercreutz, Patrick
, p. 1 - 6 (2014/07/22)
Enzymatic synthesis of alkyl glycosides using glycoside hydrolases is well studied, but has yet to reach industrial scale, primarily due to limited yields. Reduced water content should increase yields by limiting the unwanted hydrolytic side reaction. However, previous studies have shown that a reduction in water content surprisingly favors hydrolysis over transglycosylation. In addition, glycoside hydrolases normally require a high degree of hydration to function efficiently. This study compares six enzyme preparation methods to improve resilience and activity of two glycoside hydrolases from Thermotoga neapolitana (TnBgl3B and TnBgl1A) in micro-aqueous hexanol. Indeed, when adsorbed onto Accurel MP-1000 both enzymes increasingly favored transglycosylation over hydrolysis at low hydration, in contrast to freeze-dried or untreated enzyme. Additionally, they displayed 17-70× higher reaction rates compared to freeze-dried enzyme at low water activity, while displaying comparable or lower activity for fully hydrated systems. These results provide valuable information for use of enzymes under micro-aqueous conditions and build toward utilizing the full synthetic potential of glycoside hydrolases.
Ionic liquids as cosolvents for glycosylation by sucrose phosphorylase: Balancing acceptor solubility and enzyme stability
De Winter, Karel,Verlinden, Kristien,Kren, Vladimir,Weignerova, Lenka,Soetaert, Wim,Desmet, Tom
, p. 1949 - 1955 (2013/09/24)
Over the past decade, disaccharide phosphorylases have received increasing attention as promising biocatalysts for glycoside synthesis. Unfortunately, these enzymes typically have a very low affinity for non-carbohydrate acceptors, which urges the addition of cosolvents to increase the dissolved concentration of these acceptors. However, commonly applied solvents such as methanol and dimethyl sulfoxide (DMSO) are not compatible with many intended applications of carbohydrate-derived products. In this work, the solubility of a wide range of relevant acceptors was assessed in the presence of ionic liquids (ILs) as alternative and 'green' solvents. The IL AMMOENG 101 was found to be the most effective cosolvent for compounds as diverse as medium- and long-chain alcohols, flavonoids, alkaloids, phenolics and terpenes. Moreover, this IL was shown to be less deleterious to the stability and activity of sucrose phosphorylase than the commonly used dimethyl sulfoxide. To demonstrate the usefulness of this solvent system, a process for the resveratrol glycosylation was established in a buffer containing 20% AMMOENG 101, 1 M sucrose and saturated amounts of the acceptor. A single regioisomer 3-O-α-d-glucopyranosyl-(E)-resveratrol was obtained as proven by NMR spectroscopy.
Significantly improved equilibrium yield of long-chain alkyl glucosides via reverse hydrolysis in a water-poor system using cross-linked almond meal as a cheap and robust biocatalyst
Wang, Qinqqin,Yu, Huilei,Zhao, Na,Li, Chunxiu,Shang, Yazhuo,Liu, Honglai,Xu, Jianhe
, p. 275 - 280 (2012/06/29)
An array of ten β-D-glucopyranosides with varied alkyl chain lengths were enzymatically synthesized. It was found that for longer alkyl chains a lower initial rate and final yield of glucoside was obtained except for methyl glucoside because of the severe toxicity of methanol to the enzyme. From a thermodynamics point of view, the equilibrium constant and Gibbs free energy variation of the glucoside syntheses were systematically investigated. To improve the final yields of the glucosides containing long alkyl chains the equilibrium of the enzymatic glucoside synthesis was altered. The equilibrium yield of decyl β-D-glucoside increased from 1.9 to 6.1 when the water content was reduced from 10 to 5 (v/v) using tert-butanol as a cosolvent and 0.10 mol/L of glucose as a substrate. As for the other longer alkyl chain glucosides, heptyl β-D-glucoside was found to have significant surface activity as well.
Significantly Improved Equilibrium Yield of Long-Chain Alkyl Glucosides via Reverse Hydrolysis in a Water-Poor System Using Cross-Linked Almond Meal as a Cheap and Robust Biocatalyst
Wang, Qinqqin,Yu, Huilei,Zhao, Na,Li, Chunxiu,Shang, Yazhuo,Liu, Honglai,Xu, Jianhe
, p. 275 - 280 (2016/04/10)
An array of ten β-D-glucopyranosides with varied alkyl chain lengths were enzymatically synthesized. It was found that for longer alkyl chains a lower initial rate and final yield of glucoside was obtained except for methyl glucoside because of the severe toxicity of methanol to the enzyme. From a thermodynamics point of view, the equilibrium constant and Gibbs free energy variation of the glucoside syntheses were systematically investigated. To improve the final yields of the glucosides containing long alkyl chains the equilibrium of the enzymatic glucoside synthesis was altered. The equilibrium yield of decyl β-D-glucoside increased from 1.9% to 6.1% when the water content was reduced from 10% to 5% (v/v) using tert-butanol as a cosolvent and 0.10 mol/L of glucose as a substrate. As for the other longer alkyl chain glucosides, heptyl β-D-glucoside was found to have significant surface activity as well.
Transformation of cellulose into biodegradable alkyl glycosides by following two different chemical routes
Villandier, Nicolas,Corma, Avelino
experimental part, p. 508 - 513 (2012/03/08)
The transformation of cellulose into long-chain alkyl glycoside surfactants has been carried out following two different routes: (1) Direct transformation of cellulose to butyl-, hexyl-, octyl-, decyl- and dodecyl-α,β- glycosides in an ionic liquid media and Amberlyst-15Dry as catalysts, with mass yield of up to 82%; and (2) two steps reaction with transformation of cellulose into methyl glucosides, with a procedure described by Zhang et al., followed by transacetalation with 1-octanol and 1-decanol in the presence of Amberlyst-15Dry. A kinetic study for the direct transformation of cellulose using 1-octanol has shown that depolymerisation of cellulose continues during the Fischer glycosidation. Increasing the chain length of the alcohol decreases the global reaction rate owing to an increase in the lipophilicity of the alcohol that decreases its contact with the carbohydrates. Finally, several acid catalysts were tested and the best results were obtained with Amberlyst-15Dry.
