The High‐Throughput Synthesis and Phase Characterisation of Amphiphiles: A Sweet Case Study

Feast, George C.; Hutt, Oliver E.; Mulet, Xavier; Conn, Charlotte E.; Drummond, Calum J.; Savage, G. Paul

doi:10.1002/chem.201303514

Cited by 15 publications

(13 citation statements)

References 51 publications

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“…Changes in the relative size of the alkyl‐ or saccharide part influence the aggregation in line with the theory of Israelachvili, and so does changing the spatial orientation of the saccharide head group by modifying the anomeric centre . Introducing different epimers also influences the aggregation behaviour, which is attributed to differences in hydrogen bonding of the alcohol units …”

Section: Introductionsupporting

confidence: 70%

“…Possibly, the small aggregates formed at high temperature act as nucleus for elongation. The minor difference between the temperatures at which the elongation occurs for 1 a and 2 – 4 is surprising because a strong relation between the introduction of different anomers or epimers and the critical micelle concentration (CMC), solubility, and aggregate shape has been observed in alkyl glycosides …”

Section: Resultsmentioning

confidence: 99%

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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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Section: Introductionsupporting

confidence: 70%

Section: Resultsmentioning

confidence: 99%

Monosaccharides as Versatile Units for Water‐Soluble Supramolecular Polymers

Leenders

Jansen

Frissen

et al. 2016

Chemistry A European J

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“…Previous work in this field has been extensively reviewed [44–50]. Azido-sugars are known to react well under CuAAC reaction conditions [51–52] and have recently been used in the synthesis of a glycodendrimer library [53], as well as in our previous work on single-chain sugar amphiphiles [30]. Hence, a diverse sugar screen would provide a wealth of data on the appropriate characteristics for a self-assembled sugar-based amphiphilic drug.…”

Section: Resultsmentioning

confidence: 99%

“…When we combine these results with those from our single-chain amphiphile library (that form normal phases) [30], we are able to achieve lyotropic phases ranging across the structural landscape of normal to inverse micelles. Upon completion of the comprehensive phase behaviour analysis of this second library, using high-throughput small-angle X-ray scattering (SAXS) at the Australian Synchrotron, we predict that amphiphiles will be found of various inverse phases, thus creating a template from which novel amphiphiles can be synthetically designed for a specific end application.…”

Section: Resultsmentioning

confidence: 99%

“…In a follow-up study, this protocol was applied to produce amphiphiles with single-chained saturated, unsaturated, and branched tails with sugar head groups [30]. This library of amphiphiles was analysed by high-throughput synchrotron small-angle X-ray scattering (SSAXS), to determine the liquid-crystalline phases of the individual compounds.…”

Section: Introductionmentioning

confidence: 99%

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The search for new amphiphiles: synthesis of a modular, high-throughput library

Feast¹,

Lepitre²,

Mulet³

et al. 2014

Beilstein J. Org. Chem.

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SummaryAmphiphilic compounds are used in a variety of applications due to their lyotropic liquid-crystalline phase formation, however only a limited number of compounds, in a potentially limitless field, are currently in use. A library of organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide–alkyne cycloaddition (CuAAC) reaction. The tails were synthesised from two core alkyne-tethered intermediates, which were subsequently functionalised with hydrocarbon chains varying in length and degree of unsaturation and branching, while the five sugar head groups were selected with ranging substitution patterns and anomeric linkages. A library of 80 amphiphiles was subsequently produced, using a 24-vial array, with the majority formed in very good to excellent yields. A preliminary assessment of the liquid-crystalline phase behaviour is also presented.

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End‐Group‐Functionalized Poly(α‐olefinates) as Non‐Polar Building Blocks: Self‐Assembly of Sugar–Polyolefin Hybrid Conjugates

2016

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Living coordinative chain-transfer polymerization of a-olefins,f ollowed by chemical functionalization of aZ n(polymeryl) 2 intermediate,p rovides entry to end-group functionalizedp oly(a-olefinates) (x-PAOs) that can serve as an ew class of non-polar building blockw ith tailorable occupied volumes.A pplication of these x-PAOsf or the synthesis and self-assembly of sugar-polyolefin hybrid conjugates demonstrate the ability to manipulate the morphology of the ultra-thin film nanostructure through variation in occupied volume of the x-PAO domain.The self-assembly of amphiphilic materials comprised of chemically linked polar and non-polar segments gives rise to avariety of nanostructures in solution and the solid state that are instrumental for aw ide range of existing and future technological applications.[1] As such, there has long been ac orollary interest in the development of new classes of molecular and macromolecular building blocks for amphiphilic systems that are amenable to programmed structural changes as ameans by which to exert control over the relative magnitudes of entropic and enthalpic contributions to the self-assembly process and thereby over the final nanostructure that is formed.[2] Within these considerations,one of the most important structural parameters to vary is the relative free volume occupied by the polar and non-polar domains of an amphiphile.F or example,i nt he case of surfactants, entropically favorable aggregation of non-polar tails within asolvent that is compatible with polar head groups produces micellar structures that can adopt av ariety of shapes as af unction of the surfactant packing parameter, N s ,w hich is defined by the volume of the non-polar tail, V c ,t he crosssectional area of the polar domain of the assembly, a,and the length of the non-polar chain, L c ,a ccording to N s = V c /aL c . [3] On alonger length scale,the chemical tethering of polar and non-polar macromolecular chains produces amphiphilic block copolymers (BCPs) in which the enthalpic (repulsive) interaction between immiscible block domains can now drive microphase separation within the bulk BCP material to generate periodic arrays with feature sizes on the nanometer length scale.[4] Which specific solid-state microphase-separated morphology is preferred for agiven BCP (for example, body-centered-cubic (BCC) spheres,h exagonally packed cylinders,abicontinuous gyroid phase,o ra lternating lamellae) is then dictated by the magnitude of the Flory-Huggins interaction parameter for the pair of block domains, c,t he relative block domain volume fractions, f,t he overall block copolymer degree of polymerization, N,a nd temperature, T. Finally,g iant surfactants are am ore recent new class of amphiphile that consist of one or more polymer chains that are tethered to af unctionalized nanoparticle or inorganic cluster.[5] Thes elf-assembly and phase behavior of giant surfactants in solution and the solid-state possess characteristic features of both small molecule surfactants and of BCPs, and once a...

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The High‐Throughput Synthesis and Phase Characterisation of Amphiphiles: A Sweet Case Study

Cited by 15 publications

References 51 publications

Monosaccharides as Versatile Units for Water‐Soluble Supramolecular Polymers

Monosaccharides as Versatile Units for Water‐Soluble Supramolecular Polymers

The search for new amphiphiles: synthesis of a modular, high-throughput library

End‐Group‐Functionalized Poly(α‐olefinates) as Non‐Polar Building Blocks: Self‐Assembly of Sugar–Polyolefin Hybrid Conjugates

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