Supramolecular Hydrogels Based on Glycoamphiphiles: Effect of the Disaccharide Polar Head

Abstract

Supramolecular hydrogelators based on amphiphilic glycolipids have been prepared by clicking different sugar polar heads to a hydrophobic linear chain by copper(I)-catalyzed azide−alkyne [3 + 2] cycloaddition. The influence of the sugar polar head on the gelation properties in water has been studied, and the liquid crystalline properties of the amphiphilic materials have also been characterized. Stable hydrogels at room temperature have been obtained and the fibrillar supramolecular structures formed by the self-assembly have been studied by different microscopic techniques on the dried gel (xerogel) and hydrated conditions in order to characterize the micro-and nanostructures. Self-assembly gives rise to supramolecular ribbons with a torsion that is related to a chiral supramolecular arrangement of amphiphiles. The formation of an opposite helical arrangement of the ribbons has been found to depend on the sugar polar head. This fact was confirmed by circular dichroism (CD).

Ionogels of a Sugar Surfactant in Ionic Liquids

“…Multiple, directional hydroxyl groups in the sugar part make it easier for sugar surfactants to form hydrogen‐bonding networks . The advantage of hydrogen‐bond formation is that sugar surfactants can form gels in various solvents, including water, organic solvents, and RTILs …”

“…[37] The advantage of hydrogen-bond formation is that sugar surfactants can form gels in various solvents, including water,organic solvents, and RTILs. [38][39][40] Herein, we prepared ionogelsb yd issolving as ugar surfactant (HLG;F igure S1 in the Supporting Information) in two imidazolium-based ionic liquids (ILs). The structures were mainly characterized by freeze-fracture (FF) TEM and SEM observations, as well as small-angle X-ray scattering (SAXS) measurements.…”

New insights into the transitional behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside using variable temperature FTIR spectroscopy and X-ray diffraction

“…[8][9][10] Their exciting application potential includes their use as hydrogels or electrolytes whose physical properties can be tuned by external stimuli such as UV light or mechanical forces. [11][12][13][14][15] It is clear that the successful design of new liquid crystal carbohydrates now requires an improved understanding of the empirical relationships between molecular structure and aggregation behaviour. With that aim, recently, we studied the transitional behaviour of a series of monosaccharides, the methyl-6-O-(n-acyl)-α-D-glucopyranosides, as a function of the alkyl chain length, n. [16] At sufficiently high values of n, the compounds exhibit thermotropic liquid crystallinity, specifically, a monotropic smectic A phase seen on cooling from the isotropic phase, and which can be supercooled by ca 30ºC prior to crystallising.…”

Advances in the Development of Supramolecular Polymeric Biomaterials

“…Glycosylated surfaces have been developed and used to study multivalent glycol interfaces. 18 Many reports focus on the immobilization of host-guest-responsive systems on gold or glass substrates, [19][20][21][22] as well as the use of supramolecular polysaccharide moieties in hydrogel development has grown interest in recent years, [23][24][25][26][27][28] which is not covered in this account.…”