Rapid Printing and Patterning of Tough, Self-Healable, and Recyclable Hydrogel Thin-Films toward Flexible Sensing Devices.

Direct and rapid printing and surface patterning of hydrogel thin films are of great significance in the construction of advanced electronic devices, yet they are greatly underdeveloped due to the intrinsic contradiction between mechanical strength and self-healability as well as recyclability. Here, we present a universal and rapid slipping-directed route with a newly developed water-soluble star polymer hydrogel for direct and reproducible printing and patterning of freestanding functional thin films with precisely controlled thicknesses, components, and surface structures on a large scale. The resulting thin films combine the features of large transmittance (93%), tough mechanical strength (114 MPa), multiresponsive self-healability, recyclability, and remarkable multifunctionality. With the unique humidity-sensitive properties as motivation, diverse humidity-sensing devices including an actuating switch, a supercapacitive sensor, and a noncontact electronic skin are facilely constructed through the humidity-induced transverse, longitudinal, and patterning assembly techniques, respectively. The method presented here is universal and efficient in the fabrication and assembly of thin films with controlled configuration and functionality for advanced flexible electronics.

Reduction-Controlled Atomic Migration for Single Atom Alloy Library.

Picturing the atomic migration pathways of catalysts in a reactive atmosphere is of central significance for uncovering the underlying catalytic mechanisms and directing the design of high-performance catalysts. Here, we describe a reduction-controlled atomic migration pathway that converts nanoparticles to single atom alloys (SAAs), which has remained synthetically challenging in prior attempts due to the elusive mechanism. We achieved this by thermally treating the noble-metal nanoparticles M (M = Ru, Rh, Pd, Ag, Ir, Pt, and Au) on metal oxide (CuO) supports with H2/Ar. Atomic-level characterization revealed such conversion as the synergistic consequence of noble metal-promoted H2 dissociation and concomitant CuO reduction. The observed atomic migration pathway offers an understanding of the dynamic mechanisms study of nanomaterials formation and catalyst design.

Plant Cellulose Nanofiber-Derived Structural Material with High-Density Reversible Interaction Networks for Plastic Substitute.

Ubiquitous petrochemical-based plastics pose a potential threat to ecosystems. In response, bioderived and degradable polymeric materials are being developed, but their mechanical and thermal properties cannot compete with those of existing petrochemical-based plastics, especially those used as structural materials. Herein, we report a biodegradable plant cellulose nanofiber (CNF)-derived polymeric structural material with high-density reversible interaction networks between nanofibers, exhibiting mechanical and thermal properties better than those of existing petrochemical-based plastics. This all-green material has substantially improved flexural strength (∼300 MPa) and modulus (∼16 GPa) compared with those of existing petrochemical-based plastics. Its average thermal expansion coefficient is only 7 × 10-6 K-1, which is more than 10 times lower than those of petrochemical-based plastics, indicating its dimension is almost unchanged when heated, and thus, it has a thermal dimensional stability that is better than those of plastics. As a fully bioderived and degradable material, the all-green material offers a more sustainable high-performance alternative to petrochemical-based plastics.

Bio-Inspired Lotus-Fiber-like Spiral Hydrogel Bacterial Cellulose Fibers.

Hydrogel materials with high water content and good biocompatibility are drawing more and more attention now, especially for biomedical use. However, it still remains a challenge to construct hydrogel fibers with enough strength and toughness for practical applications. Herein, we report a bio-inspired lotus-fiber-mimetic spiral structure hydrogel bacterial cellulose fiber with high strength, high toughness, high stretchability, and energy dissipation, named biomimetic hydrogel fiber (BHF). The spiral-like structure endows BHF with excellent stretchability through plastic deformation and local failure, assisted by the breaking-reforming nature of the hydrogen bonding network among cellulose nanofibers. With the high strength, high stretchability, high energy dissipation, high hydrophilicity, porous structure, and excellent biocompatibility, BHF is a promising hydrogel fiber for biomedicine. The outstanding stretchability and energy dissipation of BHF allow it to absorb energy from the tissue deformation around a wound and effectively protect the wound from rupture, which makes BHF an ideal surgical suture.

Ultralight Multifunctional Carbon-Based Aerogels by Combining Graphene Oxide and Bacterial Cellulose.

Nanostructured carbon aerogels with outstanding physicochemical properties have exhibited great application potentials in widespread fields and therefore attracted extensive attentions recently. It is still a challenge so far to develop flexible and economical routes to fabricate high-performance nanocarbon aerogels, preferably based on renewable resources. Here, ultralight and multifunctional reduced graphene oxide/carbon nanofiber (RGO/CNF) aerogels are fabricated from graphene oxide and low-cost, industrially produced bacterial cellulose by a three-step process of freeze-casting, freeze-drying, and pyrolysis. The prepared RGO/CNF aerogel possesses a very low apparent density in the range of 0.7-10.2 mg cm-3 and a high porosity up to 99%, as well as a mechanically robust and electrically conductive 3D network structure, which makes it to be an excellent candidate as absorber for oil clean-up and an ideal platform for constructing flexible and stretchable conductors.

Bacterial Cellulose: A Robust Platform for Design of Three Dimensional Carbon-Based Functional Nanomaterials.

Three dimensional (3D) carbon nanomaterials exhibit great application potential in environmental protection, electrochemical energy storage and conversion, catalysis, polymer science, and advanced sensors fields. Current methods for preparing 3D carbon nanomaterials, for example, carbonization of organogels, chemical vapor deposition, and self-assembly of nanocarbon building blocks, inevitably involve some drawbacks, such as expensive and toxic precursors, complex equipment and technological requirements, and low production ability. From the viewpoint of practical application, it is highly desirable to develop a simple, cheap, and environmentally friendly way for fabricating 3D carbon nanomaterials in large scale. On the other hand, in order to extend the application scope and improve the performance of 3D carbon nanomaterials, we should explore efficient strategies to prepare diverse functional nanomaterials based on their 3D carbon structure. Recently, many researchers tend to fabricate high-performance 3D carbon-based nanomaterials from biomass, which is low cost, easy to obtain, and nontoxic to humans. Bacterial cellulose (BC), a typical biomass material, has long been used as the raw material of nata-de-coco (an indigenous dessert food of the Philippines). It consists of a polysaccharide with a ß-1,4-glycosidic linkage and has a interconnected 3D porous network structure. Interestingly, the network is made up of a random assembly of cellulose nanofibers, which have a high aspect ratio with a diameter of 20-100 nm. As a result, BC has a high specific surface area. Additionally, BC hydrogels can be produced on an industrial scale via a microbial fermentation process at a very low price. Thus, it can be an ideal platform for design of 3D carbon-based functional nanomaterials. Before our work, no systematic work and summary on this topic had been reported. This Account presents the concepts and strategies of our studies on BC in the past few years, that is, converting cheap biomass into high value-added 3D carbon nanomaterials and designing diverse functional materials on 3D carbon structure. We first briefly introduce the history, constituent, and microstructure features of BC and discuss its advantages as a raw material for preparing the CNF aerogels. Then, we summarize the methods and strategies for preparing various 3D carbon-based nanomaterials from BC. In addition, the potential applications of the developed CNF aerogel based functional materials are also highlighted in this Account, including stretchable conductors, oxygen reduction reaction catalysts, supercapacitors, lithium-ion battery, and oil cleanup. Finally, we give some prospects on the future challenges in this emerging research area of designing CNF aerogel based functional nanomaterials from BC.

Thermoresponsive poly(N-isopropylacrylamide)/graphene/Au nanocomposite hydrogel for water treatment by a laser-assisted approach.

The thermoresponsive poly(N-isopropylacrylamide)/graphene/Au multicomponent hydrogel is prepared by the simultaneous in-situ formation of Au nanoparticles and the reduction of graphene oxide, assisted by NIR laser irradiation of a prefabricated PNIPAM/GO hydrogel with auric acid precursor, showing great potential for water treatment owing to the excellent photothermal effect.

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.

Graphene-based macroscopic assemblies and architectures: an emerging material system.

Due to the outstanding physicochemical properties arising from its truly two-dimensional (2D) planar structure with a single-atom thickness, graphene exhibits great potential for use in sensors, catalysts, electrodes, and in biological applications, etc. With further developments in the theoretical understanding and assembly techniques, graphene should enable great changes both in scientific research and practical industrial applications. By the look of development, it is of fundamental and practical significance to translate the novel physical and chemical properties of individual graphene nanosheets into the macroscale by the assembly of graphene building blocks into macroscopic architectures with structural specialities and functional novelties. The combined features of a 2D planar structure and abundant functional groups of graphene oxide (GO) should provide great possibilities for the assembly of GO nanosheets into macroscopic architectures with different macroscaled shapes through various assembly techniques under different bonding interactions. Moreover, macroscopic graphene frameworks can be used as ideal scaffolds for the incorporation of functional materials to offset the shortage of pure graphene in the specific desired functionality. The advantages of light weight, supra-flexibility, large surface area, tough mechanical strength, and high electrical conductivity guarantee graphene-based architectures wide application fields. This critical review mainly addresses recent advances in the design and fabrication of graphene-based macroscopic assemblies and architectures and their potential applications. Herein, we first provide overviews of the functional macroscopic graphene materials from three aspects, i.e., 1D graphene fibers/ribbons, 2D graphene films/papers, 3D network-structured graphene monoliths, and their composite counterparts with either polymers or nano-objects. Then, we present the promising potential applications of graphene-based macroscopic assemblies in the fields of electronic and optoelectronic devices, sensors, electrochemical energy devices, and in water treatment. Last, the personal conclusions and perspectives for this intriguing field are given.

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 Young's 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.

Acquisition of structure-guiding and structure-forming properties during maturation from the pro-silicatein to the silicatein form.

Silicateins are the key enzymes involved in the enzymatic polycondensation of the inorganic scaffold of the skeletal elements of the siliceous sponges, the spicules. The gene encoding pro-silicatein is inserted into the pCold TF vector, comprising the gene for the bacterial trigger factor. This hybrid gene is expressed in Escherichia coli and the synthesized fusion protein is purified. The fusion protein is split into the single proteins with thrombin by cleavage of the linker sequence present between the two proteins. At 23 °C, the 87 kDa trigger factor-pro-silicatein fusion protein is cleaved to the 51 kDa trigger factor and the 35 kDa pro-silicatein. The cleavage process proceeds and results in the release of the 23 kDa mature silicatein, a process which very likely proceeds by autocatalysis. Almost in parallel with its formation, the mature enzyme precipitates as pure 23 kDa protein. When the precipitate is dissolved in an urea buffer, the solubilized protein displays its full enzymatic activity which is enhanced multi-fold in the presence of the silicatein interactor silintaphin-1 or of poly(ethylene glycol) (PEG). The biosilica product formed increases its compactness if silicatein is supplemented with silintaphin-1 or PEG. The elastic modulus of the silicatein-mediated biosilica product increases in parallel with the addition of silintaphin-1 and/or PEG from 17 MPa (silicatein) via 61 MPa (silicatein:silintaphin-1) to 101 MPa (silicatein:silintaphin-1 and PEG). These data show that the maturation process from the pro-silicatein state to the mature form is the crucial step during which silicatein acquires its structure-guiding and structure-forming properties.

Ultrastrong, Thermally Stable, and Food-Safe Seaweed-Based Structural Material for Tableware.

Widely used disposable plastic tableware is usually buried or directly discharged into the natural environment after using, which poses potential threats to the natural environment and human health. To solve this problem, nondegradable plastic tableware needs to be replaced by tableware composed of biodegradable structural materials with both food safety and the excellent mechanical and thermal properties. Here, a food-safe sargassum cellulose nanofiber (SCNF) is extracted from common seaweed in an efficient and low energy consuming way under mild reaction conditions. Then, by assembling the SCNF into a dense bulk material, a strong sargassum cellulose nanofiber structural material (SCNSM) with high strength (283 MPa) and high thermal stability (>160 °C) can be prepared. The SCNSM also possesses good machinability, which can be processed into tableware with different shapes, e.g., knives and forks. The overall performance of the SCNSM-based tableware is better than commercial plastic, wood-based, and poly(lactic acid) tableware, which shows great application potential in the tableware field.

Deformable hard tissue with high fatigue resistance in the hinge of bivalve Cristaria plicata.

The hinge of bivalve shells can sustain hundreds of thousands of repeating opening-and-closing valve motions throughout their lifetime. We studied the hierarchical design of the mineralized tissue in the hinge of the bivalve Cristaria plicata, which endows the tissue with deformability and fatigue resistance and consequently underlies the repeating motion capability. This folding fan-shaped tissue consists of radially aligned, brittle aragonite nanowires embedded in a resilient matrix and can translate external radial loads to circumferential deformation. The hard-soft complex microstructure can suppress stress concentration within the tissue. Coherent nanotwin boundaries along the longitudinal direction of the nanowires increase their resistance to bending fracture. The unusual biomineral, which exploits the inherent properties of each component through multiscale structural design, provides insights into the evolution of antifatigue structural materials.

Controlled assemblies of gold nanorods in PVA nanofiber matrix as flexible free-standing SERS substrates by electrospinning.

Under control: Controlled assemblies of gold nanorods in a poly(vinyl alcohol) (PVA) nanofiber matrix with tunable optical properties can be achieved by using electrospinning. The resultant assemblies can be used as substrates for surface-enhanced Raman spectroscopy (SERS). This work provides a facile way to control alignment of anisotropic nanostructures in a polymer nanofiber matrix and generates new assemblies with interesting properties.

Synthesis of multifunctional Ag@Au@phenol formaldehyde resin particles loaded with folic acids for photothermal therapy.

Multifunctional Ag@Au@ phenol formaldehyde resin (PFR) particles loaded with folic acids (FA) have been designed for killing tumor cells through photothermy conversion under the irradiation of near-infrared (NIR) light. Possessing the virtue of good fluorescence, low toxicity, and good targeting, the nanocomposite consists of an Ag core, an Au layer, a PFR shell, and folic acids on the PFR shell. The Ag@PFR core-shell structure can be prepared with a simple hydrothermal method after preheating. We then filled the PFR shell with a layer of Au by heating and modified the shell with polyelectrolyte to change its surface charge state. To capture tumor cells actively, FA molecules were attached onto the surface of the Ag@Au@PFR particles in the presence of 1-ethyl-3-(3-dimethly aminopropyl) carbodiimide (EDAC) and N-hydroxysuccinimide (NHS). Owing to the excellent property of Au NPs and Ag NPs as photothermal conversion agents, the Ag@Au@ PFR@FA particles can be utilized to kill tumor cells when exposed to NIR light.

Synthesis of Fe3O4@phenol formaldehyde resin core-shell nanospheres loaded with Au nanoparticles as magnetic FRET nanoprobes for detection of thiols in living cells.

A magnetic, sensitive, and selective fluorescence resonance energy transfer (FRET) probe for detection of thiols in living cells was designed and prepared. The FRET probe consists of an Fe(3)O(4) core, a green-luminescent phenol formaldehyde resin (PFR) shell, and Au nanoparticles (NPs) as FRET quenching agent on the surface of the PFR shell. The Fe(3)O(4) NPs were used as the core and coated with green-luminescent PFR nanoshells by a simple hydrothermal approach. Au NPs were then loaded onto the surface of the PFR shell by electric charge absorption between Fe(3)O(4)@PFR and Au NPs after modifying the Fe(3)O(4)@PFR nanocomposites with polymers to alter the charge of the PFR shell. Thus, a FRET probe can be designed on the basis of the quenching effect of Au NPs on the fluorescence of Fe(3)O(4)@PFR nanocomposites. This magnetic and sensitive FRET probe was used to detect three kinds of primary biological thiols (glutathione, homocysteine, and cysteine) in cells. Such a multifunctional fluorescent probe shows advantages of strong magnetism for sample separation, sensitive response for sample detection, and low toxicity without injury to cellular components.

Amorphous Precursor-Mediated Calcium Phosphate Coatings with Tunable Microstructures for Customized Bone Implants.

Calcium phosphate (CaP) is frequently used as coating for bone implants to promote osseointegration. However, commercial CaP coatings via plasma spraying display similar microstructures, and thus fail to provide specific implants according to different surgical conditions or skeletal bone sites. Herein, inspired by the formation of natural biominerals with various morphologies mediated by amorphous precursors, CaP coatings with tunable microstructures mediated by an amorphous metastable phase are fabricated. The microstructures of the coatings are precisely controlled by both polyaspartic acid and Mg2+ . The cell biological behaviors, including alkaline phosphatase activity, mineralization, and osteogenesis-related genes expression, on the CaP coatings with different microstructures, exhibit significant differences. Furthermore, in vivo experiments demonstrate the osseointegration in different types of rats and bones indeed favors different CaP coatings. This biomimetic strategy can be used to fabricate customized bone implants that can meet the specific requirements of various surgery conditions.

Anti-Swelling, Robust, and Adhesive Extracellular Matrix-Mimicking Hydrogel Used as Intraoral Dressing.

Due to the wet and dynamic environment of the oral cavity, the healing of intraoral wounds, such as tooth extraction wounds, requires stable and firm wound dressings. In clinical practice, cotton balls and gauzes, sponge plugs, or sutures are used to treat extraction wounds, but none of these means can continuously isolate the wound from the intraoral environment and facilitate ideal healing conditions. Herein, inspired by the natural extracellular matrix, a family of wound dressings is developed for intraoral wound repair. Infiltrating a ductile long-chain hydrogel network into a prefabricated, sturdy macromolecular meshwork and in situ crosslinking endowed the composite hydrogel with controllable swelling behaviors and robust mechanical properties. The macromolecular meshwork functioned as the backbone to support the composite and restricts the swelling of the long-chain hydrogel network. In vitro tests verified that this wound dressing can provide durable protection for intraoral wounds against complex irritations. Furthermore, accelerated wound healing occurred when the wound dressing is applied in vivo on a canine tooth extraction model, due to the effective reduction of acute inflammation. These results suggest that this family of bioinspired hydrogels has great potential for application as intraoral wound dressing.

Bioinspired crystallization of CaCO3 coatings on electrospun cellulose acetate fiber scaffolds and corresponding CaCO3 microtube networks.

This article describes the mineralization behavior of CaCO(3) crystals on electrospun cellulose acetate (CA) fibers by using poly(acrylic acid) (PAA) as a crystal growth modifier and further templating synthesis of CaCO(3) microtubes. Calcite film coatings composed of nanoneedles can form on the surfaces of CA fibers while maintaining the fibrous and macroporous structures if the concentration of PAA is in a suitable range. In the presence of a suitable concentration of PAA, the acidic PAA molecules will first adsorb onto the surface of CA fibers by the interaction between the OH moieties of CA and the carboxylic groups of PAA, and then the redundant carboxylic groups of PAA can ionically bind Ca(2+) ions on the surfaces of CA fibers, resulting in the local supersaturation of Ca(2+) ions on and near the fiber surface, which can induce the nucleation of CaCO(3) on the CA fibers instead of in bulk solution. Calcite microtube networks on the macroscale can be prepared by the removal of CA fibers after the CA@CaCO(3) composite is treated with acetone. When the CA fiber scaffold is immersed in CaCl(2) solution with an extended incubation time, the first deposited calcite coatings can act as secondary substrate, leading to the formation of smaller calcite mesocrystal fibers. The present work proves that inorganic crystal growth can occur even at an organic interface without the need for commensurability between the lattices of the organic and inorganic counterparts.