Janus porous biomaterials are gaining increasing attention and there are considerable efforts to develop simple, rapid, and scalable methods capable of tuning micro‐ and macro‐structures. Here, a single‐step electro‐fabrication method to create a Janus porous film by the electrodeposition of the amino‐polysaccharide chitosan is reported. Specifically, a Janus structure emerges spontaneously when electrodeposition is performed at sub‐ambient temperature (0–5 °C). Sub‐ambient temperature electrodeposition experiments show that: a Janus microstructure emerges (potentially as the result of a subtle alteration of the intermolecular interactions responsible for self‐assembly); important microstructural features (pore size, porosity, and thicknesses) can be tuned by conditions; and this method is readily scalable (vs serial printing) and can yield complex tubular structures with Janus faces. In vitro studies demonstrate anisotropic cell guidance, and in vivo studies using a rat calvarial defect model further confirm the beneficial features of such Janus porous film for guided bone regeneration. In summary, these results further demonstrate that electro‐fabrication provides a simple and scalable platform technology for the controlled functional structures of soft matter for applications in regenerative medicine.
Janus films with controlled pore structures can be particularly important in diverse applications. There remains a challenge for simple, rapid, and scalable fabrication methods to control Janus balance (JB) including the thickness of the individual face as well as porosity and pore size. Here the electrofabrication of a porous Janus film with controlled Janus balance from aminopolysaccharide chitosan under the salt effect is reported. Sequential deposition of chitosan under programmable salt environment and electrochemical conditions enables construction of Janus films with precisely controlled Janus balance. Bioactive partially soluble calcium phosphate (CaP) salts can also generate porous structure in Janus film. It is specifically reported that a chitosan/hydroxyl apatite (HAp) composite Janus film can serve as an effective scaffold for guided bone regeneration. The dense layer functions to provide mechanical support and serves as a barrier for fibrous connective tissue penetration. The porous composite layer functions to provide the microenvironment for osteogenesis. In vivo studies using a rat calvarial defect model confirm the beneficial features of this Janus composite for guided bone regeneration. These results suggest the potential of electrofabrication as a simple and scalable platform technology to tune the self‐organization of soft matter for a range of emerging applications.
more » « less- NSF-PAR ID:
- 10461466
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 29
- Issue:
- 18
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Abstract Porous carbon materials have increasingly drawn interest for applications ranging from supercapacitive energy storage to bioengineering. However, a simple and scalable fabrication process of such materials, employing low‐cost chemical compounds without sacrificing morphological and chemical control, remains lacking. Here, a novel, rapid, continuous bottom‐up strategy for synthesizing structurally tunable porous carbon network films on insulating and conductive substrates is reported. By employing rapid thermal annealing (RTA) of a commercial polyacrylonitrile‐based blend, simultaneous phase separation and thermal crosslinking are induced, effectively freezing the structure. Subsequent burning of degradable components generates a porous carbon framework ( ≈ 360 to 700 nm) doped with nitrogen and oxygen atoms. Introducing a boron‐containing reagent in the precursor solution enables boron doping and pore size reduction as small as 20 nm, enhancing materials' performance. The direct fabrication of micro‐supercapacitors on stainless steel substrates is demonstrated, achieving an areal capacitance of 12.7 mF cm−2at 50 mV s−1, with ≈98% retention after 10 000 charge/discharge cycles. The benefit of boron doping is further highlighted for wound healing applications. Because RTA is already an established industrial method, this platform directly facilitates the synthesis of functional porous heteroatom‐doped carbon structures using commercial polymers and dopants for various applications.
-
more » « less
Abstract The inferior water vapor permeability and water resistance properties are the major challenges that hindered the development of chitosan‐CNF composites for packaging applications. In this study, the chitosan‐CNF composite films were prepared with in situ crosslinking of citric acid (CA) to reduce the percent water uptake (WU) and water vapor permeability (WVP). The composite films were produced by the solvent casting method with 10%, 15%, and 20% CNF as a reinforcement, 20%, 25%, and 30% CA as a crosslinker, and 20% glycerol as a plasticizer. The Fourier transform infrared (FTIR) spectra of composite films with a peak at 1710 cm−1confirmed the effective crosslinking of citric acid on the chitosan‐CNF matrix. The crosslinked composite films exhibited the lowest WU of 39% and WVP of 9.99 × 10−7g/Pa s m2with reduced light transmittance due to CNF reinforcement. The scanning electron microscopy (SEM) study showed the smooth surface morphology of composite films. The CA crosslinking slightly decreased the tensile strength of composite films. However, the composite film with optimal CNF and CA concentration (25% and 20%, respectively) exhibited comparable tensile strength with other synthetic and biopolymer composites and can be used as a potential biopolymer composite for packaging applications.
-
Electrochemical separation processes are undergoing a renaissance as the range of applications continues to expand because they offer opportunities for increased energy efficiency and sustainability in comparison to conventional separation technologies. Existing platforms such as electrodialysis and electrodeionization (EDI) are seeing significant improvement and are currently being deployed for treating a diverse set of liquid streams ( e.g. , water and wastewater treatment, organic acid separation, etc. ). In addition, the relatively low inherent electricity requirement for electrochemical separations could potentially be satisfied through integration with sustainable sources of renewable energy. In order to achieve a truly sustainable electrochemical separations process, it is paramount to improve the energy efficiency of electrochemical separations by minimizing all sources of resistances within these units. This work reports of a new class of symmetric and asymmetric Janus bipolar resin wafers (RWs) that augment the spacer channel ionic conductivity in EDI while having the additional functionality of splitting water into protons and hydroxide ions. The latter attribute is important in niche applications that require pH modulation such as silica and organic acid removal from liquid streams. The Janus bipolar RWs were devised from single ion-conducting RWs that were interfaced together to create an intimate polycation–polyanion junction. Interestingly, the conductivity of the single ion-conducting RWs at low salt concentrations was observed to be dependent on the ionic mobilities of the counterions that the RW was transferring. Using single ion-conducting RWs to construct Janus bipolar RWs enabled the incorporation of a water-splitting catalyst (aluminum hydroxide nanoparticles) into the porous ion-exchange resin bed. To the best of our knowledge, this is the first time a water dissociation catalyst has been implemented in the ion-exchange resin bed for EDI. The water dissociation catalyst in bipolar junctions pre-polarizes water making it easier to split into hydronium and hydroxide ion charge carriers under applied electric fields via the second Wien effect. The new molecularly layered Janus RWs demonstrate both satisfactory water-splitting and salt removal in bench scale EDI setups and these materials may improve, or even supplant, existing bipolar membrane electrodialysis units that currently necessitate large electrolyte feed concentrations.more » « less
-
more » « less
Abstract The fabrication and characterization of the first magnetoelectric sensors utilizing arrays of Janus magnetoelectric composite nanowires composed of barium titanate and cobalt ferrite are presented. By utilizing magnetoelectric nanowires suspended across electrodes above the substrate, substrate clamping is reduced when compared to layered thin-film architectures; this results in enhanced magnetoelectric coupling. Janus magnetoelectric nanowires are fabricated by sol–gel electrospinning, and their length is controlled through the electrospinning and calcination conditions. Using a directed nanomanufacturing approach, the nanowires are then assembled onto pre-patterned metal electrodes on a silicon substrate using dielectrophoresis. Using this process, functional magnetic field sensors are formed by connecting many nanowires in parallel. The observed magnetic field sensitivity from the parallel array of nanowires is 0.514 ± .027 mV Oe−1at 1 kHz, which translates to a magnetoelectric coefficient of 514 ± 27 mV cm−1 Oe−1.
