Dataset Information

Glucosomes: Glycosylated Vesicle-in-Vesicle Aggregates in Water from pH-Responsive Microbial Glycolipid.

ABSTRACT: Vesicle-in-vesicle self-assembled containers, or vesosomes, are promising alternatives to liposomes because of their possible hierarchical encapsulation and high stability. We report herein the first example of sugar-based vesicles-in-vesicles, which we baptize glucosomes. These were prepared by using a natural microbial glycolipid (branched C22 sophorolipid) extracted from the culture medium of the yeast Pseudohyphozyma bogoriensis. Glucosomes spontaneously formed in water between pH 6 and pH 4 at room temperature, without the requirement of any additive. By means of pH-resolved in situ small angle X-ray scattering, we provided direct evidence for the vesicle-formation mechanism. Statistical treatment of the vesicle radii distribution measured by cryo-tansmission electron microscopy by using a derived form of the Helfrich bending free-energy expression provided an order of magnitude for the effective bending constant (the sum of the curvature and the saddle-splay moduli) of the lipid membrane to K=(0.4±0.1) k_BT. This value is in agreement with the bending constant measured for hydrocarbon-based vesicles membranes.

SUBMITTER: Baccile N

PROVIDER: S-EPMC5542763 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Glucosomes: Glycosylated Vesicle-in-Vesicle Aggregates in Water from pH-Responsive Microbial Glycolipid.

Baccile Niki N Le Griel Patrick P Prévost Sylvain S Everaert Bernd B Van Bogaert Inge N A INA Roelants Sophie S Soetaert Wim W

ChemistryOpen 20170712 4

Vesicle-in-vesicle self-assembled containers, or vesosomes, are promising alternatives to liposomes because of their possible hierarchical encapsulation and high stability. We report herein the first example of sugar-based vesicles-in-vesicles, which we baptize glucosomes. These were prepared by using a natural microbial glycolipid (branched C22 sophorolipid) extracted from the culture medium of the yeast <i>Pseudohyphozyma bogoriensis</i>. Glucosomes spontaneously formed in water between pH 6 a ...[more]

PMID: 28794948

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Project description:Novel brush coatings were fabricated with glass surface-grafted chains copolymerized using surface-initiated atom transfer radical polymerization (SI-ATRP) from 2-(2-methoxyethoxy)ethyl methacrylate (OEGMA188) and acrylamide (AAm), taken in different proportions. P(OEGMA188-co-AAm) brushes with AAm mole fraction >44% (determined with XPS and TOF-SIMS spectroscopy) and nearly constant with the depth copolymer composition (TOF-SIMS profiling) exhibit unusual temperature-induced transformations: The contact angle of water droplets on P(OEGMA188-co-AAm) coatings increases by ∼45° with temperature, compared to 17-18° for POEGMA188 and PAAm. The thickness of coatings immersed in water and the morphology of coatings imaged in air show a temperature response for POEGMA188 (using reflectance spectroscopy and AFM, respectively), but this response is weak for P(OEGMA188-co-AAm) and absent for PAAm. This suggests mechanisms more complex than a simple transition between hydrated loose coils and hydrophobic collapsed chains. For POEGMA188, the hydrogen bonds between the ether oxygens of poly(ethylene glycol) and water hydrogens are formed below the transition temperature Tc and disrupted above Tc when polymer-polymer interactions are favored. Different hydrogen bond structures of PAAm include free amide groups, cis-trans-multimers, and trans-multimers of amide groups. Here, hydrogen bonds between free amide groups and water dominate at T < Tc but structures favored at T > Tc, such as cis-trans-multimers and trans-multimers of amide groups, can still be hydrated. The enhanced temperature-dependent response of wettability for P(OEGMA188-co-AAm) with a high mole fraction of AAm suggests the formation at Tc of more hydrophobic structures, realized by hydrogen bonding between the ether oxygens of OEGMA188 and the amide fragments of AAm, where water molecules are caged. Furthermore, P(OEGMA188-co-AAm) coatings immersed in pH buffer solutions exhibit a 'schizophrenic' behavior in wettability, with transitions that mimic LCST and UCST for pH = 3, LCST for pH = 5 and 7, and any transition blocked for pH = 9.

Dataset Information

Glucosomes: Glycosylated Vesicle-in-Vesicle Aggregates in Water from pH-Responsive Microbial Glycolipid.

Publications

Glucosomes: Glycosylated Vesicle-in-Vesicle Aggregates in Water from pH-Responsive Microbial Glycolipid.

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