Facile preparation of self-assembled hydrogel-like GdPO4*H2O nanorods

Of the methods employed in the preparation of one-dimensional lanthanide phosphate (LnPO(4)) nanorods/nanowires, such as GdPO(4), the hydrothermal method has been mainly used as a synthetic route. In this study, we report a facile low-temperature solution approach to prepare GdPO 4*H(2)O nanorods by simply refluxing GdCl(3) and KH(2)PO(4) for only 15 min at 88 degrees C, an approach that can easily be scaled up by increasing the reagent amounts. We observed a highly viscous macroscopic hydrogel-like material when we mixed as-prepared GdPO(4)*H(2)O nanomaterials with H(2)O. Hydrogels are an important class of biomaterials. Their building blocks, normally formed from protein-, peptide-, polymer-, and lipid-based materials, offer three-dimensional scaffolds for drug delivery, tissue engineering, and biosensors. Our preliminary results showed that GdPO(4)*H(2)O hydrogels could be used for encapsulation and drug release, and that they were biocompatible, acting as scaffolds to foster cell proliferation. These findings suggested that they might have biomedical uses. Our findings may lead to the creation of other inorganic nanomaterial-based hydrogels apart from the organic and biomolecular protein-, peptide-, polymer-, and lipid-based building blocks.     

Silk Fibroin-Based Biomaterials for Tissue Engineering Applications

Tissue engineering (TE) involves the combination of cells with scaffolding materials and appropriate growth factors in order to regenerate or replace damaged and degenerated tissues and organs. The scaffold materials serve as templates for tissue formation and play a vital role in TE. Among scaffold materials, silk fibroin (SF), a naturally occurring protein, has attracted great attention in TE applications due to its excellent mechanical properties, biodegradability, biocompatibility, and bio-absorbability. SF is usually dissolved in an aqueous solution and can be easily reconstituted into different forms, including films, mats, hydrogels, and sponges, through various fabrication techniques, including spin coating, electrospinning, freeze drying, and supercritical CO₂-assisted drying. Furthermore, to facilitate the fabrication of more complex SF-based scaffolds, high-precision techniques such as micro-patterning and bio-printing have been explored in recent years. These processes contribute to the diversity of surface area, mean pore size, porosity, and mechanical properties of different silk fibroin scaffolds and can be used in various TE applications to provide appropriate morphological and mechanical properties. This review introduces the physicochemical and mechanical properties of SF and looks into a range of SF-based scaffolds that have recently been developed. The typical applications of SF-based scaffolds for TE of bone, cartilage, teeth and mandible tissue, cartilage, skeletal muscle, and vascular tissue are highlighted and discussed followed by a discussion of issues to be addressed in future studies.     

Multi‐Level Logic Gate Operation Based on Amplified Aptasensor Performance

Conventional electronic circuits can perform multi‐level logic operations; however, this capability is rarely realized by biological logic gates. In addition, the question of how to close the gap between biomolecular computation and silicon‐based electrical circuitry is still a key issue in the bioelectronics field. Here we explore a novel split aptamer‐based multi‐level logic gate built from INHIBIT and AND gates that performs a net XOR analysis, with electrochemical signal as output. Based on the aptamer–target interaction and a novel concept of electrochemical rectification, a relayed charge transfer occurs upon target binding between aptamer‐linked redox probes and solution‐phase probes, which amplifies the sensor signal and facilitates a straightforward and reliable diagnosis. This work reveals a new route for the design of bioelectronic logic circuits that can realize multi‐level logic operation, which has the potential to simplify an otherwise complex diagnosis to a “yes” or “no” decision.     

Nanomaterial-based electrochemical biosensors

The unique properties of nanoscale materials offer excellent prospects for interfacing biological recognition events with electronic signal transduction and for designing a new generation of bioelectronic devices exhibiting novel functions. In this Highlight I address recent research that has led to powerful nanomaterial-based electrical biosensing devices and examine future prospects and challenges. New nanoparticle-based signal amplification and coding strategies for bioaffinity assays are discussed, along with carbon-nanotube molecular wires for achieving efficient electrical communication with redox enzyme and nanowire-based label-free DNA sensors.     

Metalated peptide fibers derived from a natural metal-binding peptide motif

Biological molecules serve as convenient scaffolds for the construction of nanoscopic architectures which can effectively interact with small molecules and metal complexes to extend their scope for nano(bio)technological applications. Metalloproteins possess natural metal ion binding motifs and the possibility of using these sequences to generate metalated peptide conjugates with defined metal ion coordination offers a facile entry into metalated supramolecular aggregates. This report describes the formation of metalated fibers from Cu-binding octarepeat motifs of the prion protein. Conjugate 1 effectively binds copper, silver, and manganese, leading to persistent length and thermally stable peptide fibers, which could be applied for molecular bioelectronic applications.     

Long-term storage of bionanodevices by freezing and lyophilization

Successful long-term storage of a "smart dust" device integrating biomolecular motors and complex protein assemblies has been demonstrated using freezing or lyophilization, which implies that fabrication and application can be separated even for complex bionanodevices.     

Surface patterning of silica nanostructures using bio-inspired templates and directed synthesis

Natural systems excel in directing the synthesis of inorganic materials for various functional purposes. One of the best-studied systems is silica synthesis, as occurs in diatoms and marine sponges. Various biological and synthetic polymers have been shown to template and catalyze silica formation from silicic acid precursors. Here, we describe the use of poly-L-lysine to promote the synthesis of silica in neutral, aqueous solution and when immobilized onto a silicon support structure under similar conditions. Either reagent jetting or conventional photolithography techniques can be used to pattern the templating polymer. Spots created by reagent jetting led to the creation of silica structures in the shape of a ring that may be a result of the spotting process. Photolithographically defined poly-L-lysine spots led to thin laminate structures after exposure to a dilute aqueous silicic acid solution. The laminate structures were nanostructured and highly interconnected. Photolithographic patterning of (3-aminopropyl)trimethoxysilane, a reagent that mimics the lysine functional group, led to similar silica coatings even though low-molecular-weight materials do not rapidly promote silica synthesis in solution. This result highlights the importance of functional-group arrangement for templating and promoting the synthesis of inorganic materials. The described surface-patterning techniques offer a route to integrate conventional silicon-patterning technologies with biologically based material synthesis. Such combined fabrication techniques enable controlled assembly over multiple length scales and an approach to understanding interfacial silica synthesis, as occurs in natural systems.     

Multi-focal multiphoton lithography

Multiphoton lithography (MPL) provides unparalleled capabilities for creating high-resolution, three-dimensional (3D) materials from a broad spectrum of building blocks and with few limitations on geometry, qualities that have been key to the design of chemically, mechanically, and biologically functional microforms. Unfortunately, the reliance of MPL on laser scanning limits the speed at which fabrication can be performed, making it impractical in many instances to produce large-scale, high-resolution objects such as complex micromachines, 3D microfluidics, etc. Previously, others have demonstrated the possibility of using multiple laser foci to simultaneously perform MPL at numerous sites in parallel, but use of a stage-scanning system to specify fabrication coordinates resulted in the production of identical features at each focal position. As a more general solution to the bottleneck problem, we demonstrate here the feasibility for performing multi-focal MPL using a dynamic mask to differentially modulate foci, an approach that enables each fabrication site to create independent (uncorrelated) features within a larger, integrated microform. In this proof-of-concept study, two simultaneously scanned foci produced the expected two-fold decrease in fabrication time, and this approach could be readily extended to many scanning foci by using a more powerful laser. Finally, we show that use of multiple foci in MPL can be exploited to assign heterogeneous properties (such as differential swelling) to micromaterials at distinct positions within a fabrication zone.     

Micropatterning Electrospun Scaffolds to Create Intrinsic Vascular Networks

Sufficient vascularization is critical to sustaining viable tissue‐engineered (TE) constructs after implantation. Despite significant progress, current approaches lack suturability, porosity, and biodegradability, which hinders rapid perfusion and remodeling in vivo. Consequently, TE vascular networks capable of direct anastomosis to host vasculature and immediate perfusion upon implantation still remain elusive. Here, a hybrid fabrication method is presented for micropatterning fibrous scaffolds that are suturable, porous, and biodegradable. Fused deposition modeling offers an inexpensive and automated approach to creating sacrificial templates with vascular‐like branching. By electrospinning around these poly(vinyl alcohol) templates and dissolving them in water, microvascular patterns were transferred to fibrous scaffolds. Results indicated that these scaffolds have sufficient suture retention strength to permit direct anastomosis in future studies. Vascularization of these scaffolds is demonstrated by in vitro endothelialization and perfusion.     

Crystalline molecular machines: function, phase order, dimensionality, and composition

The design of molecular machines is stimulated by the possibility of developing new materials with complex physicochemical and mechanical properties that are responsive to external stimuli. Condensed-phase matter with anisotropic molecular order and controlled dynamics, also defined as amphidynamic crystals, offers a promising platform for the design of bulk materials capable of performing such functions. Recent studies have shown that it is possible to engineer molecular crystals and extended solids with Brownian rotation about specific axes that can be interfaced with external fields, which may ultimately be used to design novel optoelectronic materials. Structure/function relationships of amphidynamic materials have been characterized, establishing the blueprints to further engineer sophisticated function. However, the synthesis of amphidynamic molecular machines composed of multiple "parts" is essential to realize increasingly complex behavior. Recent progress in amphidynamic multicomponent systems suggests that sophisticated functions similar to those of simple biomolecular machines may eventually be within reach.     

Surface crystallization of rapamycin on stents using a temperature induced process

Metallic drug eluting stents (DES) are usually prepared by coating with a drug-polymer matrix as a rate controlling diffusion barrier. However, coating materials may display numerous problems, thus carrier-free DES are desired, yet releasing drug over long period of time. For this, we are reporting a novel temperature induced (TI) crystallization process for coating rapamycin on stents. Rapamycin crystals with a defined morphology and target drug load were applied from supersaturated solution. This method enables fabrication of controllable and homogeneous crystalline coatings on stent scaffolds and allowing the drug to release for several weeks.     

Bioelectronic Interface Connecting Reversible Logic Gates Based on Enzyme and DNA Reactions

It is believed that connecting biomolecular computation elements in complex networks of communicating molecules may eventually lead to a biocomputer that can be used for diagnostics and/or the cure of physiological and genetic disorders. Here, a bioelectronic interface based on biomolecule‐modified electrodes has been designed to bridge reversible enzymatic logic gates with reversible DNA‐based logic gates. The enzyme‐based Fredkin gate with three input and three output signals was connected to the DNA‐based Feynman gate with two input and two output signals—both representing logically reversible computing elements. In the reversible Fredkin gate, the routing of two data signals between two output channels was controlled by the control signal (third channel). The two data output signals generated by the Fredkin gate were directed toward two electrochemical flow cells, responding to the output signals by releasing DNA molecules that serve as the input signals for the next Feynman logic gate based on the DNA reacting cascade, producing, in turn, two final output signals. The Feynman gate operated as the controlled NOT gate (CNOT), where one of the input channels controlled a NOT operation on another channel. Both logic gates represented a highly sophisticated combination of input‐controlled signal‐routing logic operations, resulting in redirecting chemical signals in different channels and performing orchestrated computing processes. The biomolecular reaction cascade responsible for the signal processing was realized by moving the solution from one reacting cell to another, including the reacting flow cells and electrochemical flow cells, which were organized in a specific network mimicking electronic computing circuitries. The designed system represents the first example of high complexity biocomputing processes integrating enzyme and DNA reactions and performing logically reversible signal processing.     

Three‐Dimensional Scaffolds of Carbonized Polyacrylonitrile for Bone Tissue Regeneration

Carbon‐based materials have been extensively studied for stem cell culture. However, difficulties associated with engineering pure carbon materials into 3D scaffolds have hampered applications in tissue engineering and regenerative medicine. Carbonized polyacrylonitrile (cPAN) could be a promising alternative, as cPAN is a highly ordered carbon isomorph that resembles the graphitic structure and can be easily processed into 3D scaffolds. Despite the notable features of cPAN, application of cPAN in tissue engineering and regenerative medicine have not been explored. This study, for the first time, demonstrates the fabrication of microporous 3D scaffolds of cPAN and excellent osteoinductivity of cPAN, suggesting utility of 3D cPAN scaffolds as synthetic bone graft materials. The combination of excellent processability and unique bioactive properties of cPAN may lead to future applications in orthopedic regenerative medicine.     

Supramolecular Nested Microbeads as Building Blocks for Macroscopic Self‐Healing Scaffolds

The ability to construct self‐healing scaffolds that are injectable and capable of forming a designed morphology offers the possibility to engineer sustainable materials. Herein, we introduce supramolecular nested microbeads that can be used as building blocks to construct macroscopic self‐healing scaffolds. The core–shell microbeads remain in an “inert” state owing to the isolation of a pair of complementary polymers in a form that can be stored as an aqueous suspension. An annealing process after injection effectively induces the re‐construction of the microbead units, leading to supramolecular gelation in a preconfigured shape. The resulting macroscopic scaffold is dynamically stable, displaying self‐recovery in a self‐healing electronic conductor. This strategy of using the supramolecular assembled nested microbeads as building blocks represents an alternative to injectable hydrogel systems, and shows promise in the field of structural biomaterials and flexible electronics.     

Charge transport in disordered films of non-redox proteins

Electrical conduction in solid state disordered multilayers of non-redox proteins is demonstrated by two-terminal transport experiments at the nanoscale and by scanning tunneling microscopy (STM/STS experiments). We also show that the conduction of the biomolecular films can be modulated by means of a gate field. These results may lead to the implementation of protein-based three-terminal nanodevices and open important new perspectives for a wide range of bioelectronic/biosensing applications.     

Recent progress in lactam-based polymer semiconductors for organic electronic devices

Numerous polymer semiconductor materials with alternating electron donor–electron acceptor (D–A) structures have attracted immense attention because they exhibit excellent semiconductor performance and solution processability. These materials can be used for the fabrication of various lightweight and flexible electronic devices. In this review, we provide a brief overview of the structural features and important properties of lactams whose performance can be enhanced by introducing an acceptor in the design of D–A-type polymer semiconductor materials. The focus is on polymer semiconductor materials with lactams in their structures, such as diketopyrrolo[3,4-c]pyrrole, naphthalene diimide, isoindigo, 2,2-bithiophene-3,3-dicarboximide, and thieno[3,4-c]pyrrole-4,6-dione. The recent advances made in the field in the last 3 years are discussed. In addition, the application of polymers for the fabrication of organic electronic devices and the progress in the field are discussed.     

丝素蛋白纤维及功能化材料的设计与构筑

随着环境污染、资源枯竭和医疗健康等问题的加剧,研发同时满足特定使用性能、安全性及可再生性的新型材料成为当前的发展趋势.而丝素蛋白材料正是以天然蚕丝为基本原材料,经一定的加工和功能化而形成的具有特殊结构、独特性能和广泛应用的生物质材料,近年来在生物医药、生物电子、智能传感等领域展现出巨大的应用潜力.本专论总结了丝素蛋白纤维及功能化材料的最新成果,结合本课题组相关工作,重点阐述了再生丝素蛋白纤维的仿生制备、生物医用支架的构筑与功能化、智能电子材料的设计以及天然多功能蚕丝及其构筑基元制备的研究进展,以期为高性能丝素蛋白材料的设计与构筑提供指导和借鉴.     

A modular approach toward functionalized three-dimensional macromolecules: from synthetic concepts to practical applications

A new strategy for the preparation of functional, multiarm star polymers via nitroxide-mediated "living" radical polymerization has been explored. The generality of this approach to the synthesis of three-dimensional macromolecular architectures allows for the construction of nanoscopically defined materials from a wide range of different homo, block, and random copolymers combining both apolar and polar vinylic repeat units. Functional groups can also be included along the backbone or as peripheral/chain end groups, thereby modulating the reactivity and polarity of defined portions of the stars. This modular approach to the synthesis of three-dimensional macromolecules permits the application of these tailored materials as multifunctional hosts for hydrogen bonding, nanoparticle formation, and as scaffolds for catalytic groups. Examples of applications of the functional stars in catalysis include their use in a Heck-type coupling as well as an enantioselective addition reaction.     

Elimination of aggregates of ferredoxin from its self-assembled monolayer on silicon substrate

The self-assembled ferredoxin monolayer onto the (100) surface of the silicon substrate was prepared and the nonspecifically adsorbed aggregates of ferredoxin on the substrate were successfully eliminated by using a zwitterionic surfactant, 3-[(3-cholamidopropyl) dimethylammonio]-1-propanesulfonate (CHAPS). The AFM image of the self-assembled ferredoxin monolayer on the silicon substrate treated with CHAPS clearly shows that the size of ferredoxin clusters is about 20–30 nm, which is on the order of an aggregate of about five ferredoxin molecules, whereas the size of ferredoxin aggregates on the substrate without CHAPS treatment was measured to be about 100–200 nm. Those results offer a useful method for the elimination of the nonspecific adsorption of proteins onto inorganic substrates, which has been a long-term problem in the fabrication of biomolecular electronic devices by the self-assembly technique.     

Understanding and Manipulating Inorganic Materials with Scanning Probe Microscopes

Scanning probe microscopies, such as scanning tunneling microscopy and atomic force microscopy, are uniquely powerful tools for probing the microscopic properties of surfaces. If these microscopies are used to study low-dimensional materials, from two-dimensional solids such as graphite to zero-dimensional nanostructures, it is possible to elucidate atomic-scale structural and electronic properties characteristic of the bulk of a material and not simply the surface. By combining such measurements with chemical synthesis or direct manipulation it is further possible to elucidate relationships between composition, structure, and physical properties, thus promoting an understanding of the chemical basis of material properties. This article illustrates that the combination of scanning probe microscopies and chemical synthesis has advanced our understanding of charge density waves, high-temperature superconductivity, and nanofabrication in low-dimensional materials. This new approach to studying materials has directly contributed to our knowledge of how metal dopants interact with charge density waves and elucidated the local crystal chemistry of complex copper oxides, microscopic details of the superconducting states in materials with a high superconducting transition I_c, and new approaches to the fabrication of multi-component nanostructures. Coupling scanning probe microscopy measurement and manipulation with chemical synthesis should provide an approach to understanding material properties and creating complex nanostructures in general.