Fabrication of 3D Ordered Structures with Multiple Materials via Macroscopic Supramolecular Assembly

Abstract

Integration of diverse materials into 3D ordered structures is urgently required for advanced manufacture owing to increase in demand for high-performance products. Most additive manufacturing techniques mainly focus on simply combining different equipment, while interfacial binding of distinctive materials remains a fundamental problem. Increasing studies on macroscopic supramolecular assembly (MSA) have revealed efficient interfacial interactions based on multivalency of supramolecular interactions facilitated by a "flexible spacing coating." To demonstrate facile fabrication of 3D heterogeneous ordered structures, the combination of MSA and magnetic field-assisted alignment has been developed as a new methodology for in situ integration of a wide range of materials, including elastomer, resin, plastics, metal, and quartz glass, with modulus ranging from tens of MPa to over 70 GPa. Assembly of single material, coassembly of two to four distinctive materials, and 3D alignment of "bridge-like" and "cross-stacked" heterogeneous structures are demonstrated. This methodology has provided a new solution to mild and efficient assembly of multiple materials at the macroscopic scale, which holds promise for advanced fabrication in fields of tissue engineering, electronic devices, and actuators. Additive manufacture, especially three dimentional (3D) printing, is a revolutionary concept with applications in diverse fields. [1-4] Owing to the increase in demand for differently processed materials with multiple functions for advanced applications such as tissue engineering, the research of additive manufacture is facing new challenges of integrating multicomponents into one entity with high-performance or desired functions. [5,6] For example, ex situ cell growth and tissue formation require complex 3D microenvironments consisting of

Elastic-Modulus-Dependent Macroscopic Supramolecular Assembly of Poly(dimethylsiloxane) for Understanding Fast Interfacial Adhesion

“…Our previously reported elastic-modulus-dependent MSA rule , indicates that flexible surfaces are requisite to realize MSA of macroscopic building blocks by improving the molecular mobility of supramolecular groups for multivalency. Even though the method of inducing external flexible spacing coatings is effective in increasing the surface flexibility of hard materials for MSA, , the strategy of directly tailoring the intrinsic bulk properties of building block materials (e.g., elastic modulus), which has not been reported yet, holds promise to simplify the design and fabrication of MSA building blocks. As a typical elastomer with a tunable elastic modulus in the processing, PDMS provides the feasibility to demonstrate the above strategy.…”

“…To date, the first strategy of postmodifying a thick "flexible spacing coating" beneath supramolecular groups has been proven effective to facilitate MSA of hard building blocks such as glass, plastics, metal, etc. 18,19 However, there are no reports on the second strategy of adjusting intrinsic properties (e.g. elastic modulus) of nonhydrogel bulk materials for MSA, which may provide processing convenience in cases of diverse polymer materials by avoiding inducing thick coatings.…”

“…We have shown that MSA is not applicable when the elastic modulus of the hydrogel building blocks increases to a critical value (e.g., 2.5 MPa for a host/guest interactive system). , Accordingly, possible strategies to realize MSA of nonhydrogel hard materials may be increasing the surface flexibility by either (1) inducing external compliant coatings or (2) reducing the modulus of the bulk materials that are used as building blocks. To date, the first strategy of postmodifying a thick “flexible spacing coating” beneath supramolecular groups has been proven effective to facilitate MSA of hard building blocks such as glass, plastics, metal, etc. , However, there are no reports on the second strategy of adjusting intrinsic properties (e.g. elastic modulus) of nonhydrogel bulk materials for MSA, which may provide processing convenience in cases of diverse polymer materials by avoiding inducing thick coatings.…”

Macroscopic Supramolecular Assembly Strategy to Construct 3D Biocompatible Microenvironments with Site-Selective Cell Adhesion

“…The macroscopic supramolecular assembly (MSA) is a new concept with the focus on mild noncovalent interactions between surfaces with a dimension larger than 10 μm, − which may provide solutions to building such 3D scaffolds based on the idea of modular assembly. With an MSA process, multiple materials including metals, resins and hydrogels have been built into 3D ordered structures, − whose geometry can be well adjusted. Especially, the obtained 3D structures have interconnected pores at the cellular level, indicating the feasibility of forming scaffolds for cell migration and efficient nutrition/waste exchange during metabolic processes.…”

Supramolecular Chirality Suppresses Molecular Chirality: Selective Chiral Recognition in Hierarchically Coassembled Pyridine–Benzimidazole Conjugates with Precise ee% Detection

“…Moreover, developing an advanced protocol to rationally design and prepare coassembled chiral systems where multiple constituents are participating is rather challenging. Unlike single self-assembly systems, multiple constituent systems benefit chirality control at hierarchical levels, enabling the diversified synthesis of soft materials via noncovalent combinations between constituents, to achieve specific and unprecedented functions. − Nevertheless, advancing binary coassemblies to ternary systems has recently been hard to realize, and programmable synthesis of chiral nanoarchitectures between ternary coassemblies is also limited.…”