Nucleobase-Interaction-Directed Biomimetic Supramolecular Self-Assembly

Abstract

Conspectus The design and fabrication of synthetic self-assembled systems that can mimic some biological features require exquisitely sophisticated components that make use of supramolecular interactions to attain enhanced structural and functional complexity. In nature, nucleobase interactions play a key role in biological functions in living organisms, including transcription and translation processes. Inspired by nature, scientists are progressively exploring nucleobase synthons to create a diverse range of functional systems with a plethora of nanostructures by virtue of molecular-recognition-directed assembly and flexible programmability of the base-pairing interactions. To that end, nucleobase-functionalized molecules and macromolecules are attracting great attention because of their versatile structures with smart and adaptive material properties such as stimuli responsiveness, interaction with external agents, and ability to repair structural defects. In this regard, a range of nucleobase-interaction-mediated hierarchical self-assembled systems have been developed to obtain biomimetic materials with unique properties. For example, a new “grafting to” strategy utilizing complementary nucleobase interactions has been demonstrated to temporarily control the functional group display on micellar surfaces. In a different approach, complementary nucleobase interactions have been explored to enable morphological transitions in functionalized diblock copolymer assembly. It has been demonstrated that complementary nucleobase interactions can drive the morphological transformation to produce highly anisotropic nanoparticles by controlling the assembly processes at multiple length scales. Furthermore, nucleobase-functionalized bottle brush polymers have been employed to generate stimuli-responsive hierarchical assembly. Finally, such interactions have been exploited to induce biomimetic segregation in polymer self-assembly, which has been employed as a template to synthesize polymers with narrow polydispersity. It is evident from these examples that the optimal design of molecular building blocks and precise positioning of the nucleobase functionality are essential for fabrication of complex supramolecular assemblies. While a considerable amount of research remains to be explored, our studies have demonstrated the potential of nucleobase-interaction-mediated supramolecular assembly to be a promising field of research enabling the development of biomimetic materials. This Account summarizes recent examples that employ nucleobase interactions to generate functional biomaterials by judicious design of the building blocks. We begin by discussing the molecular recognition properties of different nucleobases, followed by different strategies to employ nucleobase interactions in polymeric systems in order to achieve self-assembled nanomaterials with versatile properties. Moreover, some of their prospective biological/material applications such as enhanced drug encapsulation, superior adhesion,...

Matrix-Directed Mineralization for Bulk Structural Materials

“…To provide matrixes with tunable chemical compositions, more complex structures, and higher precision, we suggest different assembly techniques should be used synergistically. For example, because the self-assembly of biocompatible nanoparticles can be precisely controlled, , by using the nanoparticle self-assembly technique and 3D printing technique together, complex hierarchical structures could be constructed . There are plenty of combinations of assembly techniques yet to be investigated. − , …”

Nucleobase-containing polymer architectures controlled by supramolecular interactions: the key to achieve biomimetic platforms with various morphologies

“…26 These studies also showed that the obtained type of morphology can vary when some parameters including the pH or solvent type are changed. 26 Indeed, these parameters affected the H-bonds between nucleobases responsible for the self-assembly and in consequence the self-assembled morphology. The correlation between complementary H-bonds in nucleobase-containing copolymers and their morphology is still under investigation.…”

“…18 Similar to the vinylic monomers, the synthesis of cytosine and guanine containing nucleobase copolymers is very complex, and the number of examples of self-assembled architectures made from these polymers are in consequence very limited. 15,26,27 Since most of the examples of self-assembled nucleobase-containing copolymers concern adenine and/or thymine (uracil) derivatives, 26,28 the discussion of this section will focus on monomers containing these nucleobases prepared by SN reactions.…”

“…17,25 Professor O'Reilly performed pioneer works in the field of self-assembly in solution state of nucleobase-containing polymers prepared by RAFT. 26 In this context, a block topology was generally chosen in order to access an amphiphilic behavior. In this case the nucleobase-containing block was hydrophobic and was combined with a hydrophilic block mainly of poly(Nacryloylmorpholine).…”

Direct Detection of Hydrogen Bonds in Supramolecular Systems Using 1H-15N HMQC

“…[1][2][3] The interplay of multiple interactions, [4][5][6][7][8][9] configuration and conformational preference, 4,[10][11][12][13][14] alongside secondary electrostatic interactions [15][16][17] to tune hydrogen-bonding strength, 18,19 has furnished design rules for hydrogen-bonding motifs [20][21][22] and given rise to several that form strongly associated dimers that are widely employed in materials science. 21,23,24 Hydrogen-bonding can be inferred in the solid state using X-ray crystallography or neutron diffraction. [25][26][27][28] Solution-based techniques (UV/vis, NMR and IR) can qualitatively establish that molecular recognition takes place by changes in resonance or vibrational frequency, (e.g.…”