Abstract Helical <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43577_2025_874_Article_IEq1.gif" Format="GIF" Height="17" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">$\upbeta$</EquationSource> <EquationSource Format="MATHML"><math> <mi mathvariant="normal">β</mi> </math></EquationSource> </InlineEquation>-oligoamides serve as versatile molecular building blocks with the unique ability to maintain stable helical fold and be functionalized by sequence modifications without affecting the folding ability. Fibrous head-to-tail self-assembly of these building blocks provides a platform to develop complex nanomaterials. In this study, the metallosupramolecular structure formed by Cu(II) coordination of the Ac-<InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43577_2025_874_Article_IEq1.gif" Format="GIF" Height="17" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">$\upbeta$</EquationSource> <EquationSource Format="MATHML"><math> <mi mathvariant="normal">β</mi> </math></EquationSource> </InlineEquation>3A<InlineEquation ID="IEq3"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43577_2025_874_Article_IEq1.gif" Format="GIF" Height="17" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">$\upbeta$</EquationSource> <EquationSource Format="MATHML"><math> <mi mathvariant="normal">β</mi> </math></EquationSource> </InlineEquation>3V<InlineEquation ID="IEq4"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43577_2025_874_Article_IEq1.gif" Format="GIF" Height="17" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">$\upbeta$</EquationSource> <EquationSource Format="MATHML"><math> <mi mathvariant="normal">β</mi> </math></EquationSource> </InlineEquation>3S-<InlineEquation ID="IEq5"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43577_2025_874_Article_IEq5.gif" Format="GIF" Height="10" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">$\upalpha$</EquationSource> <EquationSource Format="MATHML"><math> <mi mathvariant="normal">α</mi> </math></EquationSource> </InlineEquation>H-<InlineEquation ID="IEq6"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43577_2025_874_Article_IEq1.gif" Format="GIF" Height="17" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">$\upbeta$</EquationSource> <EquationSource Format="MATHML"><math> <mi mathvariant="normal">β</mi> </math></EquationSource> </InlineEquation>3A<InlineEquation ID="IEq7"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43577_2025_874_Article_IEq1.gif" Format="GIF" Height="17" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">$\upbeta$</EquationSource> <EquationSource Format="MATHML"><math> <mi mathvariant="normal">β</mi> </math></EquationSource> </InlineEquation>3V<InlineEquation ID="IEq8"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="43577_2025_874_Article_IEq1.gif" Format="GIF" Height="17" Rendition="HTML" Resolution="72" Type="Linedraw" Width="13" /> </InlineMediaObject> <EquationSource Format="TEX">$\upbeta$</EquationSource> <EquationSource Format="MATHML"><math> <mi mathvariant="normal">β</mi> </math></EquationSource> </InlineEquation>3A (1 H) oligoamide was characterized with spectroscopic, microscopic, and computational methods. Our findings demonstrate that the hybrid sequence leads to a complex helical structure combining a 13-helix on a 14-helix template, stabilized by bifurcated hydrogen bonds. We observe that the 1 H fibers form in solution, and that copper coordination increases the size of the colloidal structures. When deposited, a homogeneous two-dimensional surface coating was produced, and based on our measurements we are able to propose a structure for the supramolecular framework. These results underline the utility of metallosupramolecular frameworks in bottom-up nanofabrication and nanostructured surface coatings. Graphical abstract Impact statement This work describes a unique concept in designing hierarchical nanostructured framework-type materials using self-assembly principles. These materials incorporate a combination of head-to-tail supramolecular self-assembly of small helical beta-oligoamide units into nanorods, such as a molecular LEGO system, that are then cross-linked in a specific and geometrically defined way with metal coordination. The resulting materials have a definite internal structure that was assessed with a combination of computer modeling and experimental methods, including atomic force microscopy (AFM), small angle x-ray scattering (SAXS), x-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy as well as ultrahigh-resolution STM that made it possible to visualize submolecular details. The ability to form a polynuclear metal complex core in nanoscale fiber bundles in a highly regular but noncrystalline structure opens a range of possibilities for using these materials in, for example, smart fabrics, implants, and potentially molecular electronic and electrooptic applications.

Metal cross-linking of helical oligoamide nanorods serves as platform for hierarchical nanofibers

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2025年4月7日

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Norton G. West,
Rebecca Griffin,
Claire Buchanan,
Andrew Molino,
Alex K. Schenk,
Dongchen Qi,
Jisheng Pan,
Ljiljana Puskar,
Christopher J. Garvey,
David J. D. Wilson,
Christopher I. Pakes,
Adam Mechler

摘要

Abstract

Helical $\upbeta$ $β$ -oligoamides serve as versatile molecular building blocks with the unique ability to maintain stable helical fold and be functionalized by sequence modifications without affecting the folding ability. Fibrous head-to-tail self-assembly of these building blocks provides a platform to develop complex nanomaterials. In this study, the metallosupramolecular structure formed by Cu(II) coordination of the Ac- $\upbeta$ $β$ ³A $\upbeta$ $β$ ³V $\upbeta$ $β$ ³S- $\upalpha$ $α$ H- $\upbeta$ $β$ ³A $\upbeta$ $β$ ³V $\upbeta$ $β$ ³A (1 H) oligoamide was characterized with spectroscopic, microscopic, and computational methods. Our findings demonstrate that the hybrid sequence leads to a complex helical structure combining a 13-helix on a 14-helix template, stabilized by bifurcated hydrogen bonds. We observe that the 1 H fibers form in solution, and that copper coordination increases the size of the colloidal structures. When deposited, a homogeneous two-dimensional surface coating was produced, and based on our measurements we are able to propose a structure for the supramolecular framework. These results underline the utility of metallosupramolecular frameworks in bottom-up nanofabrication and nanostructured surface coatings.

Graphical abstract

Impact statement

This work describes a unique concept in designing hierarchical nanostructured framework-type materials using self-assembly principles. These materials incorporate a combination of head-to-tail supramolecular self-assembly of small helical beta-oligoamide units into nanorods, such as a molecular LEGO system, that are then cross-linked in a specific and geometrically defined way with metal coordination. The resulting materials have a definite internal structure that was assessed with a combination of computer modeling and experimental methods, including atomic force microscopy (AFM), small angle x-ray scattering (SAXS), x-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy as well as ultrahigh-resolution STM that made it possible to visualize submolecular details. The ability to form a polynuclear metal complex core in nanoscale fiber bundles in a highly regular but noncrystalline structure opens a range of possibilities for using these materials in, for example, smart fabrics, implants, and potentially molecular electronic and electrooptic applications.