Li-Bo Mao

Synthetic nacre by predesigned matrix-directed mineralization

Making nacre shine in the lab Many of the materials that animals use to make shells and skeletons are built with brittle or soft molecules. They owe their amazing mechanical properties to their layered construction, which is a challenge for synthetic fabrication. Pearly nacre, for example, has proved challenging to make owing to its complex structure of aragonite crystals in an organic matrix. Using an assembly-and-mineralization approach, Mao et al. have managed to fabricate nacre in the laboratory (see the Perspective by Barthelat). First, a layered, three-dimensional chitosan matrix is made, within which aragonite nanocrystals are precipitated from a solution containing calcium bicarbonate. Science, this issue p. 107; see also p. 32 A consecutive assembly-and-mineralization process leads to synthetic nacre, which strongly resembles natural nacre. [Also see Perspective by Barthelat] Although biomimetic designs are expected to play a key role in exploring future structural materials, facile fabrication of bulk biomimetic materials under ambient conditions remains a major challenge. Here, we describe a mesoscale “assembly-and-mineralization” approach inspired by the natural process in mollusks to fabricate bulk synthetic nacre that highly resembles both the chemical composition and the hierarchical structure of natural nacre. The millimeter-thick synthetic nacre consists of alternating organic layers and aragonite platelet layers (91 weight percent) and exhibits good ultimate strength and fracture toughness. This predesigned matrix-directed mineralization method represents a rational strategy for the preparation of robust composite materials with hierarchically ordered structures, where various constituents are adaptable, including brittle and heat-labile materials.

Super-elastic and fatigue resistant carbon material with lamellar multi-arch microstructure.

Low-density compressible materials enable various applications but are often hindered by structure-derived fatigue failure, weak elasticity with slow recovery speed and large energy dissipation. Here we demonstrate a carbon material with microstructure-derived super-elasticity and high fatigue resistance achieved by designing a hierarchical lamellar architecture composed of thousands of microscale arches that serve as elastic units. The obtained monolithic carbon material can rebound a steel ball in spring-like fashion with fast recovery speed (∼580 mm s−1), and demonstrates complete recovery and small energy dissipation (∼0.2) in each compress-release cycle, even under 90% strain. Particularly, the material can maintain structural integrity after more than 106 cycles at 20% strain and 2.5 × 105 cycles at 50% strain. This structural material, although constructed using an intrinsically brittle carbon constituent, is simultaneously super-elastic, highly compressible and fatigue resistant to a degree even greater than that of previously reported compressible foams mainly made from more robust constituents.

Bioinspired, Ultrastrong, Highly Biocompatible, and Bioactive Natural Polymer/Graphene Oxide Nanocomposite Films

Tough and biocompatible nanocomposite films: A new type of bioinspired ultrastrong, highly biocompatible, and bioactive konjac glucomannan (KGM)/graphene oxide (GO) nanocomposite film is fabricated on a large scale by a simple solution-casting method. Such KGM-GO composite films exhibit much enhanced mechanical properties under the strong hydrogen-bonding interactions, showing great potential in the fields of tissue engineering and food package.

Mass production of bulk artificial nacre with excellent mechanical properties

Various methods have been exploited to replicate nacre features into artificial structural materials with impressive structural and mechanical similarity. However, it is still very challenging to produce nacre-mimetics in three-dimensional bulk form, especially for further scale-up. Herein, we demonstrate that large-sized, three-dimensional bulk artificial nacre with comprehensive mimicry of the hierarchical structures and the toughening mechanisms of natural nacre can be facilely fabricated via a bottom-up assembly process based on laminating pre-fabricated two-dimensional nacre-mimetic films. By optimizing the hierarchical architecture from molecular level to macroscopic level, the mechanical performance of the artificial nacre is superior to that of natural nacre and many engineering materials. This bottom-up strategy has no size restriction or fundamental barrier for further scale-up, and can be easily extended to other material systems, opening an avenue for mass production of high-performance bulk nacre-mimetic structural materials in an efficient and cost-effective way for practical applications.Artificial materials that replicate the mechanical properties of nacre represent important structural materials, but are difficult to produce in bulk. Here, the authors exploit the bottom-up assembly of 2D nacre-mimetic films to fabricate 3D bulk artificial nacre with an optimized architecture and excellent mechanical properties.

Micrometer-Thick Graphene Oxide-Layered Double Hydroxide Nacre-Inspired Coatings and Their Properties.

Robust, functional, and flame retardant coatings are attractive in various fields such as building construction, food packaging, electronics encapsulation, and so on. Here, strong, colorful, and fire-retardant micrometer-thick hybrid coatings are reported, which can be constructed via an enhanced layer-by-layer assembly of graphene oxide (GO) nanosheets and layered double hydroxide (LDH) nanoplatelets. The fabricated GO-LDH hybrid coatings show uniform nacre-like layered structures that endow them good mechanic properties with Youngs modulus of ≈ 18 GPa and hardness of ≈ 0.68 GPa. In addition, the GO-LDH hybrid coatings exhibit nacre-like iridescence and attractive flame retardancy as well due to their well-defined 2D microstructures. This kind of nacre-inspired GO-LDH hybrid thick coatings will be applied in various fields in future due to their high strength and multifunctionalities.

A shape-memory scaffold for macroscale assembly of functional nanoscale building blocks

A shape-memory chitosan scaffold (CSS) fabricated by an ice-templated method can be used as a versatile host matrix for self-assembly of a wide range of functional nanoscale building blocks, and thus it can produce a family of functional three-dimensional (3D) macroscale assemblies, which show promising practical application potential in various fields.

A designed multiscale hierarchical assembly process to produce artificial nacre-like freestanding hybrid films with tunable optical properties

In this work, we propose a multiscale hierarchical assembly process to realize the nacre-like layered structural arrangement of functional nanoparticles in a polymer matrix aiming to simultaneously achieve tensile strength enhancement and tunable optical properties in the hybrid materials. Through the designed fabrication route, functional nanoparticles (NPs) were firstly attached onto the surface of brick-like silicate-1 zeolite microcrystals as functional building blocks. Then, NP–zeolite functional microbricks were feasibly assembled with polyvinylalcohol (PVA) to form layered, functional hybrid films. Finally, a 50–100% tensile stress enhancement in the hybrid film is observed when compared to that of pure PVA film. Beside the tensile strength enhancement, the optical properties of the hybrid film can also be tuned by the incorporation of different functional nanoparticles. Our fabrication approach is an example of an alternative strategy to prepare strong hybrid materials with flexible tailoring of functionalities.

Ultrathin hybrid films of polyoxohydroxy clusters and proteins: layer-by-layer assembly and their optical and mechanical properties.

The hierarchical assembly of inorganic and organic building blocks is an efficient strategy to produce high-performance materials which has been demonstrated in various biomaterials. Here, we report a layer-by-layer (LBL) assembly method to fabricate ultrathin hybrid films from nanometer-scale ionic clusters and proteins. Two types of cationic clusters (hydrolyzed aluminum clusters and zirconium-glycine clusters) were assembled with negatively charged bovine serum albumin (BSA) protein to form high-quality hybrid films, due to their strong electrostatic interactions and hydrogen bonding. The obtained hybrid films were characterized by scanning electron microscope (SEM), UV-vis, Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF), and X-ray diffraction (XRD). The results demonstrated that the cluster-protein hybrid films exhibited structural homogeneity, relative transparency, and bright blue fluorescence. More importantly, these hybrid films displayed up to a 70% increase in hardness and up to a 100% increase in reduced Youngs modulus compared to the pure BSA film. These hybrid cluster-protein films could be potentially used as biomedical coatings in the future because of their good transparency and excellent mechanical properties.

Biomimetic mineralization of zein/calcium phosphate nanocomposite nanofibrous mats for bone tissue scaffolds

Biomimetic mineralization process has been extended to bio-inspired bone-like calcium phosphate coatings on biodegradable polymer substrates. The objective of the current work is to synthesize zein/calcium phosphate nanocomposite nanofibrous scaffolds by the biomimetic mineralization process for bone tissue engineering. After incubation in 10 times concentrated simulated body fluid for 2 hours, the surface of electrospun zein nanofibers was uniformly coated with plate-like calcium phosphate nanosheets which attach to fibers and preserve the fibrous morphology of electrospun zein fibers. The crystalline phases in the composite are hydroxyapatite and dicalcium phosphate dihydrate. The biological in vitro cell culture with adipose-derived stem cells demonstrated that mineralized electrospun zein scaffolds can improve specific biological functions like adhesion, spread and proliferation resulting from the retained fibrous morphology and bioactive environment provided by calcium phosphate minerals. This study has demonstrated that mineralization of electrospun zein fibers provides a simple platform to fabricate a new biomimetic scaffold for bone tissue engineering, which can recapitulate both the morphology of the extracellular matrix and the composition of the bone.

Seeded Mineralization Leads to Hierarchical CaCO3 Thin Coatings on Fibers for Oil/Water Separation Applications

Like their biogenic counterparts, synthetic minerals with hierarchical architectures should exhibit multiple structural functions, which nicely bridge the boundaries between engineering and functional materials. Nevertheless, design of bioinspired mineralization approaches to thin coatings with distinct micro/nanotextures remains challenging in the realm of materials chemistry. Herein, a general morphosynthetic method based on seeded mineralization was extended to achieve prismatic-type thin CaCO3 coatings on fibrous substrates for oil/water separation applications. Distinct micro/nanotextures of the overlayers could be obtained in mineralization processes in the presence of different soluble (bio)macromolecules. These hierarchical thin coatings therefore exhibit multiple structural functions including underwater superoleophobicity, ultralow adhesion force of oil in water, and comparable stiffness/strength to the prismatic-type biominerals found in mollusk shells. Moreover, this controllable approach could proceed on fibrous substrates to obtain robust thin coatings, so that a modified nylon mesh could be employed for oil/water separation driven by gravity. Our bioinspired approach based on seeded mineralization opens the door for the deposition of hierarchical mineralized thin coatings exhibiting multiple structural functions on planar and fibrous substrates. This bottom-up strategy could be readily extended for the syntheses of advanced thin coatings with a broad spectrum of engineering and functional constituents.