<i>Nature-like</i>synthetic alkyl branched-chain glycolipids: a review on chemical structure and self-assembly properties

Hashim, Roslan; Sugimura, Akihiko; Minamikawa, Hiroyuki; Heidelberg, Thorsten

doi:10.1080/02678292.2011.614017

Cited by 86 publications

(64 citation statements)

References 85 publications

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“…Based on optical polarising microscopy (OPM) and DSC, the stereochemistry of these Guerbet glycolipids was found to affect the phase behaviour in a similar way to that of the monoalkylated glycosides [16]. However, due to the chain branching, the former tend to adopt liquid crystalline phases at room temperature (apart from the lactoside series; the anomalous behaviour of lactosides and galactosides has been discussed elsewhere [34][35][36]). Moreover, it was observed that the shorter Guerbet glycolipids stabilise a fluid lamellar phase, while the longer branched chains promote inverse non-lamellar phases.…”

Section: Introductionmentioning

confidence: 94%

Thermotropic and lyotropic liquid crystalline phases of Guerbet branched-chain -D-glucosides

et al. 2011

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The effect of chain branching on glycolipid thermotropic and lyotropic phases was investigated for a series of synthetic β-D-glucosides derived from Guerbet alcohols, whose total hydrocarbon chain length ranged from C 8 to C 24 . The compounds, which can be viewed as isosteric mimics for glycoglycerolipids, were synthesised in high purity and their liquid crystalline phases were studied using optical polarising microscopy (OPM), and small-angle X-ray diffraction. When dry, the shortest compound (total C 8 ) exhibits a monotropic L α phase while longer ones (C 16 and C 20 ) adopt inverse hexagonal H II phases. The C 24 compound forms an ordered lamellar phase at room temperature, but exhibits a metastable H II phase upon cooling. Curiously the intermediate chain length homologue (C 12 ) adopts an isotropic inverse micellar (L 2 ) phase in the dry state over the range of temperatures studied. Upon hydration, the C 8 compound dissolves, and the C 12 compound forms a fluid lamellar L α phase. The C 16 Guerbet glucoside (i.e. β-Glc-C 10 C 6 ) exhibits an inverse bicontinuous cubic phase of space group Ia3d in excess water, never previously observed in branched-chain lipids, and very seldom observed in excess water. The C 20 compound remains in the H II phase upon hydrating, with the lattice parameter swelling substantially.

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Section: Introductionmentioning

confidence: 94%

Thermotropic and lyotropic liquid crystalline phases of Guerbet branched-chain -D-glucosides

et al. 2011

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“…Numerous saccharide-baseda mphiphiles have been synthesised and extensively studied, both in bulk and in aqueous solution. [3][4][5][6][7] Alkyl glycosides are an appealing subclass because of their straightforward molecular structure. [8] Changes in the relative size of the alkyl-or saccharide part influence the aggregation in line with the theory of Israelachvili, [9] and so does changing the spatial orientation of the saccharide head group by modifying the anomeric centre.…”

Section: Introductionmentioning

confidence: 99%

Monosaccharides as Versatile Units for Water‐Soluble Supramolecular Polymers

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Jansen

Frissen

et al. 2016

Chemistry A European J

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Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers)Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Abstract: We introduce monosaccharides as versatile watersoluble units to compatibilise supramolecular polymers based on the benzene-1,3,5-tricarboxamide (BTA) moiety with water.Alibrary of monosaccharide-based BTAs is evaluated, varying the length of the alkyl chain (hexyl, octyl, decyl and dodecyl) separating the BTAa nd saccharide units, as well as the saccharideu nits (a-glucose, b-glucose, a-mannose and a-galactose). In all cases, the monosaccharides impart excellent waterc ompatibility. The length of the alkyl chain is the determining factort oo btain either long, one-dimensional supramolecular polymers (dodecyls pacer), small aggregates (decyl spacer) or molecularly dissolved (octyl and hexyl) BTAs in water. For the BTAs comprising ad odecyl spacer, our results suggest that ac ooperative self-assembly process is operative and that the introduction of different monosaccharides does not significantly change the selfassemblyb ehaviour. Finally,w ei nvestigate the potential of post-assembly functionalisation of the formed supramolecular polymers by taking advantage of dynamic covalent bond formation between the monosaccharides and benzoxaboroles. We observe that the supramolecular polymers readily react with af luorescent benzoxaborole derivative permitting imaging of these dynamicc omplexes by confocal fluorescencemicroscopy.

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“…4 Glycolipids give liquid crystalline properties due to the affinity of the de-mixing of the hydrophilic and hydrophobic parts of the molecules. 1 Natural glycolipids usually contain double alkyl chains, which give greater flexibility in self-assembly and enable the formation of various lyotropic phases from simple lamellar to other non-lamellar phases (columnar/hexagonal and cubic), 1,5 which offers a major advantage in biological research. 6 In a dry state and driven by temperature (thermotropic), these glycosides can also form self-assembly phases similar to classical lyotropic organizations, but these are referred to using a set of thermotropic nomenclatures such as smectic A (S A ), columnar/hexagonal (Col or H), and cubic phases (Q).…”

Section: Introductionmentioning

confidence: 99%

Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation

Velayutham

Gan

et al. 2014

The Journal of Chemical Physics

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Glycolipid, found commonly in membranes, is also a liquid crystal material which can self-assemble without the presence of a solvent. Here, the dielectric and conductivity properties of three synthetic glycolipid thin films in different thermotropic liquid crystal phases were investigated over a frequency and temperature range of (10(-2)-10(6) Hz) and (303-463 K), respectively. The observed relaxation processes distinguish between the different phases (smectic A, columnar/hexagonal, and bicontinuous cubic Q) and the glycolipid molecular structures. Large dielectric responses were observed in the columnar and bicontinuous cubic phases of the longer branched alkyl chain glycolipids. Glycolipids with the shortest branched alkyl chain experience the most restricted self-assembly dynamic process over the broad temperature range studied compared to the longer ones. A high frequency dielectric absorption (Process I) was observed in all samples. This is related to the dynamics of the hydrogen bond network from the sugar group. An additional low-frequency mechanism (Process II) with a large dielectric strength was observed due to the internal dynamics of the self-assembly organization. Phase sensitive domain heterogeneity in the bicontinuous cubic phase was related to the diffusion of charge carriers. The microscopic features of charge hopping were modelled using the random walk scheme, and two charge carrier hopping lengths were estimated for two glycolipid systems. For Process I, the hopping length is comparable to the hydrogen bond and is related to the dynamics of the hydrogen bond network. Additionally, that for Process II is comparable to the bilayer spacing, hence confirming that this low-frequency mechanism is associated with the internal dynamics within the phase.

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Nature-likesynthetic alkyl branched-chain glycolipids: a review on chemical structure and self-assembly properties

Cited by 86 publications

References 85 publications

Thermotropic and lyotropic liquid crystalline phases of Guerbet branched-chain -D-glucosides

Thermotropic and lyotropic liquid crystalline phases of Guerbet branched-chain -D-glucosides

Monosaccharides as Versatile Units for Water‐Soluble Supramolecular Polymers

Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation

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