Hybrid Soft Nanomaterials Composed of DNA Microspheres and Supramolecular Nanostructures of Semi‐artificial Glycopeptides

Abstract

Aqueous hybrid soft nanomaterials consisting of plural supramolecular architectures with a high degree of segregation (orthogonal coexistence) and precise hierarchy at the nano‐ and microscales, which are reminiscent of complex biomolecular systems, have attracted increasing attention. Remarkable progress has been witnessed in the construction of DNA nanostructures obtained by rational sequence design and supramolecular nanostructures of peptide derivatives through self‐assembly under aqueous conditions. However, orthogonal self‐assembly of DNA nanostructures and supramolecular nanostructures of peptide derivatives in a single medium has not yet been explored in detail. In this study, DNA microspheres, which can be obtained from three single‐stranded DNAs, and three different supramolecular nanostructures (helical nanofibers, straight nanoribbons, and flowerlike microaggregates) of semi‐artificial glycopeptides were simultaneously constructed in a single medium by a simple thermal annealing process, which gives rise to hybrid soft nanomaterials. Fluorescence imaging with selective staining of each supramolecular nanostructure uncovered the orthogonal coexistence of these structures with only marginal impact on their morphology. Additionally, the biostimuli‐responsive degradation propensity of each supramolecular architecture is retained, and this may allow the construction of active soft nanomaterials exhibiting intelligent biofunctions.

Effect of side chain phenyl group on the self‐assembled morphology of dipeptide hydrazides

“…These obtained peptide hydrazides have shown higher self-assembly ability compared with their acid counterparts. [22][23][24][25][26][27][28][29] For example, the acid form Z-FF-OH (Figure 1) formed a hydrogel at a concentration higher than approximately 0.05 wt%, [13] whereas the hydrazide form Z-FF-NHNH 2 (Figure 1) showed limited aqueous solubility under similar conditions in our study, but was able to form fibrous nanostructures at lower concentrations. [22] Nevertheless, Z-FF-NHNH 2 was barely soluble in water.…”

“…For example, several groups reported that minimal derivations of C-termini, such as transformations from acid forms to ester forms, strengthen the ability for self-assembling. [20,21] On the other hand, we [22][23][24] and other researchers [25][26][27][28][29] have investigated the propensity for self-assembly of peptide derivatives bearing a hydrazide group at their C-terminal (peptide hydrazides), which can be easily synthesized from the corresponding ester derivatives or by solid phase synthesis with appropriate resins. These obtained peptide hydrazides have shown higher self-assembly ability compared with their acid counterparts.…”

Updating the use of nano-biosensors as promising devices for the diagnosis of coronavirus family members: A systematic review

“…Nanomaterials (NMs) less than 100 nm in size provide a greater surface volume, enhancing their intrinsic physicochemical properties and increasing their susceptibility to external influences when compared to the bulk material. Depending on NM composition, morphology, and size, these compounds may be used in very specialized applications, such as in special nanostructures made from iron or transition metals whose magnetic properties can be used for biosensing [30] , [38] , [39] , [40] .…”

One-Pot Construction of Multicomponent Supramolecular Materials Comprising Self-Sorted Supramolecular Architectures of DNA and Semi-Artificial Glycopeptides

“…, self-sorting behavior) even under multicomponent adverse conditions. − As such, self-sorting enables plural supramolecular architectures to retain their individual properties and functions as well as their individual and hierarchical structures even under complex conditions. In artificial systems, only several self-sorting pairs of synthetic self-assembling molecules have hitherto been reported. − Therein, the structural elucidation and in situ real-time imaging of self-sorted supramolecular architectures and their multistimuli responsiveness have been actively studied. For instance, van Esch and co-workers reported that otherwise unachievable one-pot tandem reactions can proceed with using self-sorted supramolecular nanofibers, each of which is tethered to a distinct catalytic group .…”

“…Very recently, we have exploited self-assembling DNAs and peptide derivatives as components to develop multicomponent supramolecular nanomaterials capable of exhibiting narcissistic self-sorting behavior (Figure ). The high-fidelity recognition based on the Watson–Crick base pairing and programmable sequences of DNAs allows the construction of a variety of DNA nanostructures with controlled shapes and sizes. − By contrast, diverse peptide-based nanostructures have been developed based on distinctive secondary structures, such as the α-helix and β-sheet, the driving forces of which are appreciably orthogonal to those of DNA nanostructures. − However, to the best of our knowledge, the studies on integrative self-sorted supramolecular nanostructures (ssSNs) composed of DNA nanostructures and peptide supramolecular nanostructures are few. − Previously, we found that three single-stranded DNAs capable of self-assembling into microspheres − (Figure C, the DNA microspheres are constructed by a three-dimensional (3D) network of three-way junction units) and semi-artificial glycopeptides (GPs) capable of constructing supramolecular nanostructures (Figure A) can give rise to hybrid soft nanomaterials with a high degree of segregation (orthogonal coexistence) of the two morphologically distinct supramolecular nanostructures through a simple thermal annealing-induced one-pot assembly process (Figure D_ii). These are considered as non-integrative ssSNs (Figure A).…”