Study on the Rectification of Ionic Diode Based on Cross-Linked Nanocellulose Bipolar Membranes.

Nanocellulose-based membranes have attracted intense attention in bioelectronic devices due to their low cost, flexibility, biocompatibility, degradability, and sustainability. Herein, we demonstrate a flexible ionic diode using a cross-linked bipolar membrane fabricated from positively and negatively charged cellulose nanofibrils (CNFs). The rectified current originates from the asymmetric charge distribution, which can selectively determine the direction of ion transport inside the bipolar membrane. The mechanism of rectification was demonstrated by electrochemical impedance spectroscopy with voltage biases. The rectifying behavior of this kind of ionic diode was studied by using linear sweep voltammetry to obtain current-voltage characteristics and the time dependence of the current. In addition, the performance of cross-linked CNF diodes was investigated while changing parameters such as the thickness of the bipolar membranes, the scanning voltage range, and the scanning rate. A good long-term stability due to the high density cross-linking of the diode was shown in both current-voltage characteristics and the time dependence of current.

Scalable Paper Supercapacitors for Printed Wearable Electronics.

Printed paper-based electronics offers solutions to rising energy concerns by supplying flexible, environmentally friendly, low-cost infrastructure for portable and wearable electronics. Herein, we demonstrate a scalable spray-coating approach to fabricate tailored paper poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/cellulose nanofibril (CNF) electrodes for all-printed supercapacitors. Layer-by-layer spray deposition was used to achieve high-quality electrodes with optimized electrode thickness. The morphology of these electrodes was analyzed using advanced X-ray scattering methods, revealing that spray-coated electrodes have smaller agglomerations, resulting in a homogeneous film, ultimately suggesting a better electrode manufacturing method than drop-casting. The printed paper-based supercapacitors exhibit an areal capacitance of 9.1 mF/cm2, which provides enough energy to power electrochromic indicators. The measured equivalent series resistance (ESR) is as low as 0.3 Ω, due to improved contact and homogeneous electrodes. In addition, a demonstrator in the form of a self-powered wearable wristband is shown, where a large-area (90 cm2) supercapacitor is integrated with a flexible solar cell and charged by ambient indoor light. This demonstration shows the tremendous potential for sequential coating/printing methods in the scaling up of printed wearables and self-sustaining systems.

The effect of crosslinking on ion transport in nanocellulose-based membranes.

Ion selective membranes are at the heart of energy conversion and harvesting, water treatment, and biotechnologies. The currently available membranes are mostly based on expensive and non-biodegradable polymers. Here, we report a cation-selective and low-cost membrane prepared from renewable nanocellulose and 1,2,3,4-butanetetracarboxylic acid which simultaneously serves as crosslinker and source of anionic surface groups. Charge density and structure of the membranes are studied. By using different degrees of crosslinking, simultaneous control over both the nanochannel structure and surface charge concentration is achieved, which in turn determines the resulting ion transport properties. Increasing negative charge concentration via higher crosslinker content, the obtained ion conductivity reaches up to 8 mS/cm (0.1 M KCl). Optimal ion selectivity, also influenced by the solution pH, is achieved at 20 wt% crosslinker addition (with ion conductivity of 1.6 mS/cm). As regular ~1.4 nm nanochannels were formed at this composition, nanofluidic contribution to ion transport is likely.

In situ and non-cytotoxic cross-linking strategy for 3D printable biomaterials.

3D bioprinting allows the production of patient-specific tissue constructs with desired structural characteristics such as high resolution, controlled swelling degree, and controlled degradation behavior by mostly using hydrogels. Crosslinking of hydrogels is an essential parameter in bioprinting applications, which is beneficial for tuning structural specifications. In this study, gelatin-alginate-whey protein isolate based hydrogels have been used for 3D printing structures in a layer-by-layer fashion. These structures were cross-linked by the Amino Acid (monomer) Decorated and Light Underpinning Conjugation Approach (ANADOLUCA) method, which is a unique, non-invasive photosensitive cross-linking technique for protein-based mixtures. In that aim, hydrogel properties (e.g., printability, biocompatibility, rheologic and mechanical behavior) and cross-linking properties (e.g., swelling and degradation behavior) were studied. Results were compared with UV and ionic cross-linking techniques, which are the abundantly used techniques in such studies. The results showed that the ANADOLUCA method can be used for in situ cross-linking under mild conditions for the printing of bio-inks, and the proposed method can be used as an alternative for UV-based and chemical cross-linking techniques.

Ferritin based bionanocages as novel biomemory device concept.

Ferritin is an iron cage having protein, capable of extracting metal ions in their cages and a consequence of the electron transfer of metal ions in their cage by reduction and oxidation processes, electrochemical information storage devices can be designed. In this work, ferritin based protein biomemory substrate has been synthesized by using Amino Acid (monomer) Decorated and Light Underpinning Conjugation Approach (ANADOLUCA) method, which utilizes photosensitive electron transfer based microemulsion co-polymerization as nanobead form of ferritin. Protein substrate contains metal ions such as silver and copper or metal ion pairs namely, silver-copper (Janus bionanocage) and co-polymeric shell of the photosensitive crosslinker protein. The redox behavior of bionanocages differentiates electrochemical "writing" and "erase" states depending on these metal ions (silver or copper) or metal ion pairs. The bionanocages based biomemory substrates have been immobilized using graphene modified glassy carbon electrodes and the memory functions of ferritin based bionanocages have been confirmed by chronoamperometry (CA) and open circuit potential amperometry (OCPA). The stability and durability of multi-state memory devices represent promising properties for future bioelectronic information technologies.

A motion- and sound-activated, 3D-printed, chalcogenide-based triboelectric nanogenerator.

A multilayered triboelectric nanogenerator (MULTENG) that can be actuated by acoustic waves, vibration of a moving car, and tapping motion is built using a 3D-printing technique. The MULTENG can generate an open-circuit voltage of up to 396 V and a short-circuit current of up to 1.62 mA, and can power 38 LEDs. The layers of the triboelectric generator are made of polyetherimide nanopillars and chalcogenide core-shell nanofibers.