induced scission measurements, imaging with AFM and TEM, and analysis of data. A.J.L. performed FRET measurements and analysis of the data. X.Z., T.C.-T., and Y.C. performed solution X-ray scattering, and analysis of the data. A.J.L. and Y.C. conceptualized nanoribbon thread processing and Y.C. and M.G. prepared nanoribbon threads. M.G. performed tensile testing of nanoribbon threads and analysis of the data. T.C.-T. and Y.C. performed X-ray scattering of solid-state nanoribbon threads and analysis of the data. J.
Traditionally, gels have been defined by their covalently cross-linked polymer networks. Supramolecular gels challenge this framework by relying on non-covalent interactions for self-organization into hierarchical structures. This class of materials offers a variety of novel and exciting potential applications. This review draws together recent advances in supramolecular gels with an emphasis on their proposed uses as optoelectronic, energy, biomedical, and biological materials. Additional special topics reviewed include environmental remediation, participation in synthesis procedures, and other industrial uses. The examples presented here demonstrate unique benefits of supramolecular gels, including tunability, processability, and self-healing capability, enabling a new approach to solve engineering challenges.
The self-assembly of amphiphilic small molecules in water leads to nanostructures with customizable structure-property relationships arising from their tunable chemistries. Characterization of these assemblies is generally limited to their static...
Self-assembly of small amphiphilic molecules in water can lead to nanostructures of varying geometries with pristine internal molecular organization. Here we introduce a photoswitchable aramid amphiphile (AA), designed to exhibit extensive hydrogen bonding and robust mechanical properties upon self-assembly, while containing a vinylnitrile group for photoinduced cis−trans isomerization. We demonstrate spontaneous self-assembly of the vinylnitrile-containing AA in water to form nanoribbons. Upon UV irradiation, trans-to-cis isomerizations occur concomitantly with a morphological transition from nanoribbons to nanotubes. The nanotube structure persists in water for over six months, stabilized by strong and collective intermolecular interactions. We demonstrate that the nanoribbonto-nanotube transition is reversible upon heating and that switching between states can be achieved repeatedly. Finally, we use electron microscopy to capture the transition and propose mechanisms for nanoribbon-to-nanotube rearrangement and vice versa. The stability and switchability of photoresponsive AA nanostructures make them viable for a range of future applications.
Strongly interacting amphiphilic molecules self-assemble in water. The flexibility of the amphiphiles and their head group repulsion mediate their nanostructure geometry.
Throughout the fields of biomedical imaging, materials analysis, and routine chemical analysis, it is desirable to have a toolkit of molecules that can allow noninvasive/remote chemical sensing with minimal sample preparation. Here, we describe the photophysical properties involved in photoacoustic (PA) measurements and present a detailed analysis of the requirements and complications involved in PA sensing. We report the use of nitrazine yellow (NY) as a well-behaved PA pH reporter molecule. Both the basic and acidic forms of NY are photoacoustically well-behaved and allow for rapid and noninvasive measurement of pH in either transparent or turbid media. We also find that the serum protein-bound form of NY is photoacoustically well-behaved and should permit applications in noninvasive 3D imaging (e.g., the lymphatic system).
Self-assembly of small molecules in water provides a powerful route to nanostructures with pristine molecular organization and small dimensions (<10 nm). Such assemblies represent emerging high surface area nanomaterials, customizable for biomedical and energy applications. However, to exploit self-assembly, the constituent molecules must be sufficiently amphiphilic and satisfy prescribed packing criteria, dramatically limiting the range of surface chemistries achievable. Here, we design supramolecular nanoribbons that contain: (1) inert and stable internal domains, and (2) sacrificial surface groups that are thermally labile, and we demonstrate complete thermal decomposition of the nanoribbon surfaces. After heating, the remainder of each constituent molecule is kinetically trapped, nanoribbon morphology and internal organization are maintained, and the nanoribbons are fully hydrophobic. This approach represents a pathway to form nanostructures that circumvent amphiphilicity and packing parameter constraints and generates structures that are not achievable by self-assembly alone, nor top-down approaches, broadening the utility of molecular nanomaterials for new targets.
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