Multifunctional Natural and Synthetic Melanin for Bioelectronic Applications: A Review.

Emerging material interest in bioelectronic applications has highlighted natural melanin and its derivatives as promising alternatives to conventional synthetic conductors. These materials, traditionally noted for their adhesive, antioxidant, biocompatible, and biodegradable properties, have barely been used as conductors due to their extremely low electrical activities. However, recent studies have demonstrated good conductive properties in melanin materials that promote electronic-ionic hybrid charge transfer, attributed to the formation of an extended conjugated backbone. This review examines the multifunctional properties of melanin materials, focusing on their chemical and electrochemical synthesis and their resulting structure-property-function relationship. The wide range of bioelectronic applications will also be presented to highlight their importance and potential to expand into new design concepts for high-performance electronic functional materials. The review concludes by addressing the current challenges in utilizing melanin for biodegradable bioelectronics, providing a perspective on future developments.

Independent Heating Performances in the Sub-Zero Environment of MWCNT/PDMS Composite with Low Electron-Tunneling Energy.

The structural stability of various structures (railroads, bridges, buildings, etc.) is lowered due to freezing because of the decreasing outside temperature in winter. To prevent damage from freezing, a technology for de-icing has been developed using an electric-heating composite. For this purpose, a highly electrically conductive composite film with multi-wall carbon nanotubes (MWCNTs) uniformly dispersed in a polydimethylsiloxane (PDMS) matrix through a three-roll process was fabricated by shearing the MWCNT/PDMS paste, through a two-roll process. The electrical conductivity and the activation energy of the composite were 326.5 S/m and 8.0 meV at 5.82 Vol% of MWCNTs, respectively. The dependence of the electric-heating performance (heating rate and temperature change) on the applied voltage and environmental temperature (from -20 °C to 20 °C) was evaluated. The heating rate and effective-heat-transfer characteristics were observed to decrease as the applied voltage increased, while they showed the opposite tendency when the environmental temperature was at sub-zero temperatures. Nevertheless, the overall heating performance (heating rate and temperature change) was maintained with little significant difference in the considered external-temperature range. The unique heating behaviors can result from the low activation energy and the negative-temperature (T) coefficient of resistance (R) (NTCR, dR/dT < 0) of the MWCNT/PDMS composite.

Stimuli-responsive nanoparticle-nanofiber hybrids for drug delivery and photodynamic therapy.

Hybrid nanomaterials possess integrated multi-components to syncretize various properties and functions within a single entity. Owing to this synergistic effect, they promise efficient anti-cancer therapy. In line with this target, we produced stimuli-responsive nanoparticle-nanofiber hybrids (NNHs) via embedding photoresponsive natural melanin nanoparticles (MNPs) within a biocompatible polycaprolactone (PCL) nanofiber matrix. Electrospinning was performed to produce monolithic and core-shell structured NNHs using a single and a coaxial nozzle. The NNHs were upgraded to drug delivery systems by model hydrophilic drug-ampicillin (amp)-loading. The drug release results showed that monolithic PCL meshes displayed a burst release, whereas nanohybrid formation with MNPs improved the release profile toward Fickian diffusion. Core-shell NNH presented a more sustained drug release profile than its MNP-free replica and monolithic NNH because its encapsulating shell layer hindered the diffusion of the drug. The photodynamic therapy accompanied by UV-A-irradiation on monolithic and core-shell NNHs yielded up to 34 % and 37 % malignant melanoma cell death. Moreover, this study proved the potency of MNPs-enhanced NNHs in drug delivery and photodynamic therapy applications. Even so, more efforts should be concerted to unlock unknown features of the NNHs, which have the power to advance emerging areas, including but not limited to material science, biosensing, and theranostics.

Biodegradable bioelectronics for biomedical applications.

Biodegradable polymers have been widely used in tissue engineering with the potential to be replaced by regenerative tissue. While conventional bionic interfaces are designed to be implanted in living tissue and organs permanently, biocompatible and biodegradable electronic materials are now progressing a paradigm shift towards transient and regenerative bionic engineering. For example, biodegradable bioelectronics can monitor physiologies in a body, transiently rehabilitate disease symptoms, and seamlessly form regenerative interfaces from synthetic electronic devices to tissues by reducing inflammatory foreign-body responses. Conventional electronic materials have not readily been considered biodegradable. However, several strategies have been adopted for designing electroactive and biodegradable materials systems: (1) conductive materials blended with biodegradable components, (2) molecularly engineered conjugated polymers with biodegradable moieties, (3) naturally derived conjugated biopolymers, and (4) aqueously dissolvable metals with encapsulating layers. In this review, we endeavor to present the technical bridges from electrically active and biodegradable material systems to edible and biodegradable electronics as well as transient bioelectronics with pre-clinical bio-instrumental applications, including biodegradable sensors, neural and tissue engineering, and intelligent drug delivery systems.

Platelet-rich plasma loaded nerve guidance conduit as implantable biocompatible materials for recurrent laryngeal nerve regeneration.

Vocal cord paralysis caused by recurrent laryngeal nerve (RLN) injury during thyroidectomy results in hoarseness, aspiration, and dyspnea. We evaluated the usefulness of nerve guidance conduits (NGCs) constructed from an asymmetric polycaprolactone (PCL)/Pluronic F127 porous membrane and filled with platelet-rich plasma (PRP) for functional RLN regeneration. We evaluated the proliferation and migration of Schwann cells (SCs) after PRP treatment in vitro. For the in vivo study, rabbits were divided into a non-loaded NGC group and a PRP-loaded NGC group. The left RLNs were resected and interposed with the NGCs. Functional and histological examinations of the vocal cords were performed. SC proliferation and migration increased in a PRP dose-dependent manner, with the PRP increasing the levels of neurotrophic factors, myelin-associated glycoprotein, and ERK. In vivo, the PRP group showed significantly better vocal cord mobility and less vocalis muscle atrophy than the non-loaded NGC group. Histologically, the ingrowth of nerve endings occurred more rapidly in the PRP group, and acetylcholinesterase, neurofilament, and S-100 expression in neural endings were significantly higher in the PRP group. Furthermore, transmission electron microscopy showed that myelinated axons were more tightly packed in the PRP group. This study shows that PRP-loaded NGCs provide a favorable environment for neural regeneration and suggests that this technique has therapeutic potential for promoting RLN recovery.

Precisely tuned photonic properties of crystalline nanocellulose biocomposite coatings by gradually tailored nanoarchitectures.

Inspired by nature, we fabricated optically tuned bio-organic films of cellulose nanofibers (CNFs) and chitosan by precisely structuring layer-by-layer (LBL) assembly techniques. Directly extracted from tunicate, highly crystalline CNFs were deposited into gradual nanoporous structures, which dictates wave-like behaviors of optical transmittance and cyclic patterns of structural coloration. The optical transmittance of a glass substrate increased from 91% to 98.2% at a wavelength of 550 nm by reflectivity attenuation controls. The monochromic structural colors were discretely varied from orange to purple, seen only at a specific angle of the incident light, demonstrating visibly hidden security potential. Furthermore, we could modulate the coloration cycles by accelerating the LBL processes with polydopamine-coated CNFs. The 3D nanoporous structures of CNFs also provide synergies, including superhydophilic surface-driven antifogging properties. Our optically versatile biofilms made by all-natural CNFs and chitosan provide various potential applications, including solar cells, securities, and eco-friendly colors.

High crystallinity of tunicate cellulose nanofibers for high-performance engineering films.

Tunicate cellulose nanofibers (CNFs) have received widespread attention as renewable and eco-friendly engineering materials because of their high crystallinity and mechanical stiffness. Here, we report the effects of disintegration process conditions on structure-property relationships of tunicate CNFs. By varying the hydrolysis time, we could establish a correlation between crystallinity of the CNFs with linearity and stiffness, which produces different molecular ordering within their nanostructured films. Despite having identical raw materials, tensile strength and thermal conductivity of the resulting layered films varied widely, ranging from 95.6 to 205 MPa and from 1.08 to 2.37 W/mK respectively. Furthermore, nanolayered CNF films provided highly anisotropic thermal conductivities with an in- and through-plane ratio of 21.5. Our systematic investigations will provide general and practical strategies in tailoring material properties for emerging engineering applications, including flexible paper electronics, heat sink adhesives and biodegradable, implantable devices.

Electrically conducting polymers for bio-interfacing electronics: From neural and cardiac interfaces to bone and artificial tissue biomaterials.

Conductive polymers (CPs) are gaining considerable attention as materials for implantable bioelectronics due to their unique features such as electronic-ionic hybrid conductivity, mechanical softness, ease of chemical modification, as well as moderate biocompatibility. CPs have been utilized for a wide range of applications including neural engineering, regenerative medicine, multi-functional sensors and actuators. This review focuses on CP materials design for use in bio-interfacing electronics including composites, conductive hydrogels, and electrochemical deposition. We start by elaborating on the fundamental materials characteristics of CPs, including bio-electrochemical charge-transfer mechanisms, and contrast them with naturally derived CPs. We then present recent critical examples of the bioelectronic and biomedical applications of CPs, including neural recording and stimulation, tissue regeneration, stretchable electronics, and mechanical actuation. We conclude with a perspective of the current material challenges of CPs in bio-interfacing electronics.

Nanoarchitecturing of Natural Melanin Nanospheres by Layer-by-Layer Assembly: Macroscale Anti-inflammatory Conductive Coatings with Optoelectronic Tunability.

Natural melanins are biocompatible conductors with versatile functionalities. Here, we report fabrication of multifunctional poly(vinyl alcohol)/melanin nanocomposites by layer-by-layer (LBL) assembly using melanin nanoparticles (MNPs) directly extracted from sepia officinalis inks. The LBL assembly offers facile manipulation of nanotextures as well as nm-thickness control of the macroscale film by varying solvent qualities. The time-resolved absorption was monitored during the process and quantitatively studied by fractal dimension and lacunarity analysis. The capability of nanoarchitecturing provides confirmation of complete monolayer formation and leads to tunable iridescent reflective colors of the MNP films. In addition, the MNP films have durable electrochemical conductivities as evidenced by enhanced charge storage capacities for 1000 cycles. Moreover, the MNP covered ITO (indium tin oxide) substrates significantly reduced secretion of inflammatory cytokines, TNF-α, by raw 264.7 macrophage cells compared to bare ITO, by a factor of 5 and 1.8 with and without lipopolysaccharide endotoxins, respectively. These results highlight the optoelectronic device-level tunability along with the anti-inflammatory biocompatibility of the MNP LBL film. This combination of performance should make these films particularly interesting for bioelectronic device applications such as electroceuticals, artificial bionic organs, biosensors, and implantable devices.