In this study we demonstrate that single-chain magnets (SCMs) can be assembled in gel phase and transferred intact on surface. We take advantage of a family of SCMs based on Tb ions and nitronyl-nitroxides radicals functionalized with short alkyl chains known to form crystalline supramolecular nanotubes interacting with heptane acting as crystallizing solvent. When the radicals are functionalized with long aliphatic chains a robust gel is formed with similar structural and functional properties respect to its crystalline parent. Indeed, a small-angle X-ray scattering (SAXS) study unambiguously demonstrates that the gel is made of supramolecular nanotubes: the high stability of the gel allows the determination from SAXS data of precise nanotube metrics such as diameter, helical pitch and monoclinic cell of the folded 2D crystal lattice along the tube direction. Additionally, static and dynamic magnetic investigations show the persistence of the SCM behavior in the metallogel. Last, on-surface gelation provides thick films as well as sub-monolayer deposits of supramolecular nanotubes on surface as evidenced by atomic force microscopy (AFM) observations. This paves the road toward magnetic materials and devices made of SCMs profiting of their isolation on surface as individual chains.
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http://dx.doi.org/10.1039/d2mh01158a | DOI Listing |
Nanomaterials (Basel)
December 2024
Department of Chemistry, University of Sherbrooke, 2500, Blvd de l'Université, Sherbrooke, QC J1K 2R1, Canada.
This study delves into the distinctive selective property exhibited by a non-conjugated cholesterol-based polymer, poly(CEM--EHA), in sorting semiconducting single-walled carbon nanotubes (s-SWCNTs) within isooctane. Comprised of 11 repeating units of cholesteryloxycarbonyl-2-hydroxy methacrylate (CEM) and 7 repeating units of 2-ethylhexyl acrylate (EHA), this non-conjugated polymer demonstrates robust supramolecular interactions across the sp surface structure of carbon nanotubes and graphene. When coupled with the Double Liquid-Phase Extraction (DLPE) technology, the polymer effectively segregates s-SWCNTs into the isooctane phase (nonpolar) while excluding metallic SWCNTs (m-SWCNTs) in the water phase (polar).
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec H3A 0B8, Canada.
ConspectusStructural DNA nanotechnology offers a unique self-assembly toolbox to construct soft materials of arbitrary complexity, through bottom-up approaches including DNA origami, brick, wireframe, and tile-based assemblies. This toolbox can be expanded by incorporating interactions orthogonal to DNA base-pairing such as metal coordination, small molecule hydrogen bonding, π-stacking, fluorophilic interactions, or the hydrophobic effect. These interactions allow for hierarchical and long-range organization in DNA supramolecular assemblies through a DNA-minimal approach: the use of fewer unique DNA sequences to make complex structures.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai, China.
The shortwave infrared (SWIR) region is an ideal spectral window for next-generation bioimaging to harness improved penetration and reduced phototoxicity. SWIR spectral activity may also be accessed via supramolecular dye aggregation. Unfortunately, development of dye aggregation remains challenging.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Key Laboratory of Bioorganic Phosphorous and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China.
Zigzag aromatic hydrocarbon belts, ultrashort segments of zigzag carbon nanotubes, have been fascinating in the chemistry community for more than a half century because of their aesthetically appealing molecular nanostructures and tantalizing applications. Precise introduction of heteroatoms of distinct electronegativity and electronic configuration can create various heterocyclic aromatic nanobelts with novel physical and chemical properties. Here, we report the synthesis of unprecedented N-doped zigzag-type aromatic belts, belt[]pyrrole[]pyridines ( = 6-8), from multiple intramolecular C-C homocoupling reactions of readily available azacalix[](3,5-dibromopyridine)s.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry, University of Warwick Coventry CV4 7AL UK
Self-assembling cyclic peptide nanotubes are fascinating supramolecular systems with promising potential for various applications, such as drug delivery, transmembrane ionic channels, and artificial light-harvesting systems. In this study, we present novel pH-responsive nanotubes based on asymmetric cyclic peptide-polymer conjugates. The pH response is introduced by a tertiary amine-based polymer, poly(dimethylamino ethyl methacrylate) (pDMAEMA) or poly(diethylamino ethyl methacrylate) (pDEAEMA) which is protonated at low pH.
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