An investigation of functionalized chitosan and alginate multilayer conformal nanocoating on mouse beta cell spheroids as a model for pancreatic islet transplantation.

Multilayer conformal coatings have been shown to provide a nanoscale barrier between cells and their environment with adequate stability, while regulating the diffusion of nutrition and waste across the cell membrane. The coating method aims to minimize capsule thickness and implant volume while reducing the need for immunosuppressive drugs, making it a promising approach for islet cell encapsulation in clinical islet transplantation for the treatment of Type 1 diabetes. This study introduces an immunoprotective nanocoating obtained through electrostatic interaction between quaternized phosphocholine-chitosan (PC-QCH) and tetrahydropyran triazole phenyl-alginate (TZ-AL) onto mouse ß-cell spheroids. First, successful synthesis of the proposed polyelectrolytes was confirmed with physico-chemical characterization. A coating with an average thickness of 540 nm was obtained with self-assembly of 4-bilayers of PC-QCH/TZ-AL onto MIN6 ß-cell spheroids. Surface coating of spheroids did not affect cell viability, metabolic activity, or insulin secretion, when compared to non-coated spheroids. The exposure of the polyelectrolytes to THP-1 monocyte-derived macrophages lead to a reduced level of TNF-α secretion and exposure of coated spheroids to RAW264.7 macrophages showed a decreasing trend in the secretion of TNF-α and IL-6. In addition, coated spheroids were able to establish normoglycemia when implanted into diabetic NOD-SCID mice, demonstrating in vivo biocompatibility and cellular function. These results demonstrate the ability of the PC-QCH/TZ-AL conformal coating to mitigate pro-inflammatory responses from macrophages, and thus can be a promising candidate towards nanoencapsulation for cell-based therapy, particularly in type 1 diabetes, where the insulin secreting ß-cells are subjected to inflammation and immune cell attack.

Nanopatterning Induced Si Doping in Amorphous Ga2O3 for Enhanced Electrical Properties and Ultra-Fast Photodetection.

Ga2O3 has emerged as a promising material for the wide-bandgap industry aiming at devices beyond the limits of conventional silicon. Amorphous Ga2O3 is widely being used for flexible electronics, but suffers from very high resistivity. Conventional methods of doping like ion implantation require high temperatures post-processing, thereby limiting their use. Herein, an unconventional method of doping Ga2O3 films with Si, thereby enhancing its electrical properties, is reported. Ion-beam sputtering (500 eV Ar+) is utilized to nanopattern SiO2-coated Si substrate leaving the topmost part rich in elemental Si. This helps in enhancing the carrier conduction by increasing n-type doping of the subsequently coated 5 nm amorphous Ga2O3 films, corroborated by room-temperature resistivity measurement and valence band spectra, respectively, while the nanopatterns formed help in better light management. Finally, as proof of concept, metal-semiconductor-metal (MSM) photoconductor devices fabricated on doped, rippled films show superior properties with responsivity increasing from 6 to 433 mA W-1 while having fast detection speeds of 861 µs/710 µs (rise/fall time) as opposed to non-rippled devices (377 ms/392 ms). The results demonstrate a facile, cost-effective, and large-area method to dope amorphous Ga2O3 films in a bottom-up approach which may be employed for increasing the electrical conductivity of other amorphous oxide semiconductors as well.

Acoustofluidics-Assisted Coating of Microparticles.

Microparticles have been applied in many areas, ranging from drug delivery, diagnostics, cosmetics, personal care, and the food industry to chemical and catalytic reactions, sensing, and environmental remediation. Coating further provides additional functionality to the microparticles, such as controlled release, surface modification, bio-fouling resistance, stability, protection, etc. In this study, the conformal coating of microparticles with a positively charged polyelectrolyte (polyallylamine hydrochloride, PAH) by utilizing an acoustofluidic microchip was proposed and demonstrated. The multiple laminar streams, including the PAH solution, were formed inside the microchannel, and, under the traveling surface acoustic wave, the microparticles traversed through the streams, where they were coated with PAH. The results showed that the coating of microparticles can be achieved in a rapid fashion via a microfluidic approach compared to that obtained by the batch method. Moreover, the zeta potentials of the microparticles coated via the microfluidic approach were more uniform. For the unfunctionalized microparticles, the charge reversal occurred after coating, and the zeta potential increased as the width of the microchannel or the concentration of the PAH solution increased. As for the carboxylate-conjugated microparticles, the charge reversal again occurred after coating; however, the magnitudes of the zeta potentials were similar when using the microchannels with different widths or different concentrations of PAH solution.

Nanothin Conformal Coating with Poly(N-vinylpyrrolidone) and Tannic Acid (PVPON/TA) Preserves Murine and Human Pancreatic Islets Function.

Beta cell replacement therapies can restore glycemic control to select individuals living with type 1 diabetes. However, the obligation of lifelong immunosuppression restricts cell therapies from replacing exogenous insulin administration. Encapsulation strategies can reduce the inherent adaptive immune response; however, few are successfully translated into clinical testing. Herein, we evaluated if the conformal coating of islets with poly(N-vinylpyrrolidone) (PVPON) and tannic acid (TA) (PVPON/TA) could preserve murine and human islet function while conferring islet allograft protection. In vitro function was evaluated using static glucose-stimulated insulin secretion, oxygen consumption rates, and islet membrane integrity. In vivo function was evaluated by transplanting human islets into diabetic immunodeficient B6.129S7-Rag1tm1Mom/J (Rag-/-) mice. The immunoprotective capacity of the PVPON/TA-coating was assessed by transplanting BALB/c islets into diabetic C57BL/6 mice. Graft function was evaluated by non-fasting blood glucose measurements and glucose tolerance testing. Both coated and non-coated murine and human islets exhibited indistinguishable in vitro potency. PVPON/TA-coated and control human islets were able to restore euglycemia post-transplant. The PVPON/TA-coating as monotherapy and adjuvant to systemic immunosuppression reduced intragraft inflammation and delayed murine allograft rejection. This study demonstrates that PVPON/TA-coated islets may be clinically relevant as they retain their in vitro and in vivo function while modulating post-transplant immune responses.

Pd-conformally coated, one-end-embedded gold nanowire percolation network for intrinsically stretchable, epidermal tattoo fuel cell.

Soft, conformal and wearable epidermal fuel cells may offer promising energy solutions to power next-generation on-skin electronics on-demand anytime anywhere. However, it is non-trivial to design intrinsically stretchable electrode in order to maintain the fuel cell performance under real-world and dynamic mechanical deformations. Here, we present a tattoo-like epidermal fuel cell based on Pd conformally-coated, one-end-embedded percolation gold nanowire (EP-AuNW/EP-AuPdNW) networks, which are in essence the combination of in-plane percolation conductivity and out-plane anisotropic conductivity. Both EP-AuNW and EP-AuPdNW are intrinsically stretchable conductors for anode and cathode in fuel cell. Compared to non-conformal counterparts, a 6-times greater power density was achieved for conformal system. Importantly, EP-NW based fuel cell can function under various mechanical deformations including stretching, compression, bending, and twisting; the power density showed negligible changes to the tensile strain up to ∼50% and could maintain its 75% performance even under 80% strain. Furthermore, a dragon-tattoo epidermal fuel cell was fabricated, demonstrating on-demand power generation with real-world ethanol sources.

Graphene Metamaterial 3D Conformal Coating for Enhanced Light Harvesting.

Silicon (Si) photovoltaic devices present possible avenues for overcoming global energy and environmental challenges. The high reflection and surface recombination losses caused by the Si interface and its nanofabrication process are the main hurdles for pursuing a high energy conversion efficiency. However, recent advances have demonstrated great success in improving device performance via proper Si interface modification with the optical and electrical features of two-dimensional (2D) materials. Firmly integrating large-area 2D materials with 3D Si nanostructures with no gap in between, which is essential for optimizing device performance, has rarely been achieved by any technique due to the complex 3D morphology of the nanostructures. Here we propose the concept of a 3D conformal coating of graphene metamaterials, in which the 2D graphene layers perfectly adapt to the 3D Si curvatures, leading to a universal 20% optical reflection decrease and a 60% surface passivation improvement. In a further application of this metamaterial 3D conformal coating methodology to standard Si solar cells, an overall 23% enhancement of the solar energy conversion efficiency is achieved. The 3D conformal coating strategy could be readily extended to various optoelectronic and semiconductor device systems with peculiar performance, offering a pathway for highly efficient energy-harvesting and storage solutions.

Polyacrylonitrile-Polyvinyl Alcohol-Based Composite Gel-Polymer Electrolyte for All-Solid-State Lithium-Ion Batteries.

The three-dimensional (3D) structure of batteries nowadays obtains a lot of attention because it provides the electrodes a vast surface area to accommodate and employ more active material, resulting in a notable increase in areal capacity. However, the integration of polymer electrolytes to complicated three-dimensional structures without defects is appealing. This paper presents the creation of a flawless conformal coating for a distinctive 3D-structured NiO/Ni anode using a simple thermal oxidation technique and a polymer electrolyte consisting of three layers of PAN-(PAN-PVA)-PVA with the addition of Al2O3 nanoparticles as nanofillers. Such a composition with a unique combination of polymers demonstrated superior electrode performance. PAN in the polymer matrix provides mechanical stability and corrosion resistance, while PVA contributes to excellent ionic conductivity. As a result, NiO/Ni@PAN-(PAN-PVA)-PVA with 0.5 wt% Al2O3 NPs configuration demonstrated enhanced cycling stability and superior electrochemical performance, reaching 546 mAh g-1 at a 0.1 C rate.

Electric current-assisted manipulation of liquid metals using a stylus at micro-and nano-scales.

A novel methodology, based on wetting and electromigration, for transporting liquid metal, over long distances, at micro-and nano-scale using a stylus is reported. The mechanism is analogous to a dropper that uses 'suction and release' actions to 'collect and dispense' liquid. In our methodology, a stylus coated with a thin metal film acts like the dropper that collects liquid metal from a reservoir upon application of an electric current, holds the liquid metal via wetting while carrying the liquid metal over large distances away from the reservoir and drops it on the target location by reversing the direction of electric current. Essentially, the working principle of the technique relies on the directionality of electromigration force and adhesive force due to wetting. The working of the technique is demonstrated by using an Au-coated Si micropillar as the stylus, liquid Ga as the liquid metal to be transported, and a Kleindiek-based position micro-manipulator to traverse the stylus from the liquid reservoir to the target location. For demonstrating the potential applications, the technique is utilized for closing a micro-gap by dispensing a minuscule amount of liquid Ga and conformally coating the desired segment of the patterned thin films with liquid Ga. This study confirms the promising potential of the developed technique for reversible, controlled manipulation of liquid metal at small length scales.

Prolongation of graft survival via layer-by-layer assembly of collagen and immunosuppressive particles on pancreatic islets.

Pancreatic islet transplantation holds great potential as a curative therapy for treating type 1 diabetes. However, the need for lifelong systemic immunosuppression with inevitable side effects is an obstacle to clinical success. Here we devised a strategy for the site-specific delivery of an immunosuppressant (tacrolimus) using layer-by-layer assembly of polymeric particles and collagen on the islet surface. This approach aims to provide a continuous and sustained supply of tacrolimus in the vicinity of transplanted cells while avoiding systemic drug exposure. The dose and release rate of tacrolimus can be tunable to achieve therapeutic windows by varying layer-by-layer construction and chemistry of polymers. Transplanting 400 IEQ of pancreatic islets coated with particles containing ∼3 µg of TAC per recipient provided controlled drug release and rectified diabetes for up to 5 months in a xenogeneic rodent model of type 1 diabetes. We anticipate that the findings of this study will be found useful by those developing local immunomodulation strategies aimed at improving the outcomes and safety of cell therapies for curing type 1 diabetes.

Green and multifunctional chitosan-based conformal coating as a controlled release platform for fruit preservation.

Food waste caused by the decay of perishable foods is a serious global issue. However, traditional preservative materials don't perform well in preventing food decay. Here, a green and multifunctional conformal coating is prepared by the hydrogen-bonding interactions among chitosan, nano-humic acid and curcumin, which is different from traditional preservative films obtained by solution blending. Thanks to the formation of hydrogen-bonding network, the surface roughness of the coating increased from 9.43 nm to 33.3 nm, which makes it more matches with the micro/nano structure of the fruit surface and obtains a good coating effect for various fruits. Furthermore, this coating shows distinctive mechanical properties (the tensile strength of 31.4 MPa), antioxidant and antibacterial activities (the inhibition zone ≥5 mm), and can be used to control the long-term release (up to 38 days) of natural preservative onto fruit surfaces. Through the demonstration of four perishable fruits, the coating can keep freshness and appearance at least 9 days longer than the uncoated samples, confirming the universal effectiveness of the coating in preventing fruit decay. This coating is easy to produce and use, washable, degradable, and makes from cheap or waste renewable biomaterials, which does not cause additional health and environmental concerns.

Direct Contraction Force Measurements of Engineered Cardiac Tissue Constructs With Inotropic Drug Exposure.

Contractility is one of the most crucial functions of the heart because it is directly related to the maintenance of blood perfusion throughout the body. Both increase and decrease in contractility may cause fatal consequences. Therefore, drug discovery would benefit greatly from reliable testing of candidate molecule effects on contractility capacity. In this study, we further developed a dual-axis piezoelectric force sensor together with our human cell-based vascularized cardiac tissue constructs for cardiac contraction force measurements. The capability to detect drug-induced inotropic effects was tested with a set of known positive and negative inotropic compounds of isoprenaline, milrinone, omecamtiv mecarbil, propranolol, or verapamil in different concentrations. Both positive and negative inotropic effects were measurable, showing that our cardiac contraction force measurement system including a piezoelectric cantilever sensor and a human cell-based cardiac tissue constructs has the potential to be used for testing of inotropic drug effects.

Toward Highly Stable Anode for Secondary Batteries: Employing TiO2 Shell as Elastic Buffering Marix for FeOx Nanoparticles.

Transition metal oxides are considered promising anode materials for next-generation lithium-ion and sodium-ion batteries (LIBs and SIBs) because of their high theoretical capacities; however, their practical application is limited by the detrimental large volume expansion that occurs upon cycling. In this work, a rationally designed TiO2 @Fe@FeOx nanocomposite encapsulated by a TiO2 shell with unique core-shell structure is synthesized and exhibits outstanding electrochemical performance as an anode in LIBs and SIBs. The nanocomposite exhibits a reversible capacity of 619.2 mAh g-1 at 1 A g-1 with a coulombic efficiency over 99.5% after 1000 cycles when used as a LIB anode. The nanocomposite also exhibits superior sodium storage performance (267 mAh g-1 at 50 mA g-1 , capacity retention of 65.4% after 1000 cycles at 200 mA g-1 ). The TiO2 shell serves as a strong conformal layer and soft matrix that can tolerate the volume expansion and maintain the structural integrity of the anode during discharging and charging. Moreover, the open active diffusion channels of the shell contribute to high ion diffusivity and improved ionic, and electronic diffusion. These findings indicate that adoption of TiO2 coating is an effective strategy to optimize the electrochemical performance of transition metal oxide anode materials.

Silver Nanowire Networks: Ways to Enhance Their Physical Properties and Stability.

Silver nanowire (AgNW) networks have been intensively investigated in recent years. Thanks to their attractive physical properties in terms of optical transparency and electrical conductivity, as well as their mechanical performance, AgNW networks are promising transparent electrodes (TE) for several devices, such as solar cells, transparent heaters, touch screens or light-emitting devices. However, morphological instabilities, low adhesion to the substrate, surface roughness and ageing issues may limit their broader use and need to be tackled for a successful performance and long working lifetime. The aim of the present work is to highlight efficient strategies to optimize the physical properties of AgNW networks. In order to situate our work in relation to existing literature, we briefly reported recent studies which investigated physical properties of AgNW networks. First, we investigated the optimization of optical transparency and electrical conductivity by comparing two types of AgNWs with different morphologies, including PVP layer and AgNW dimensions. In addition, their response to thermal treatment was deeply investigated. Then, zinc oxide (ZnO) and tin oxide (SnO2) protective films deposited by Atmospheric Pressure Spatial Atomic Layer Deposition (AP-SALD) were compared for one type of AgNW. We clearly demonstrated that coating AgNW networks with these thin oxide layers is an efficient approach to enhance the morphological stability of AgNWs when subjected to thermal stress. Finally, we discussed the main future challenges linked with AgNW networks optimization processes.

Strong Coupling Between Plasmons and Molecular Excitons in Metal-Organic Frameworks.

This Letter describes strong coupling of densely packed molecular emitters in metal-organic frameworks (MOFs) and plasmonic nanoparticle (NP) lattices. Porphyrin-derived ligands with small transition dipole moments in an ordered MOF film were grown on Ag NP arrays. Angle-resolved optical measurements of the MOF-NP lattice system showed the formation of a polariton that is lower in energy and does not cross the uncoupled MOF Q1 band. Modeling predicted the upper polariton energy and a calculated Rabi splitting of 110 meV. The coupling strength was systematically controlled by detuning the plasmon energy by changing the refractive index of the solvents infiltrating the MOF pores. Through transient absorption spectroscopy, we found that the lower polariton decays quickly at shorter time scales (<500 ps) and slowly at longer times because of energy transfer from the upper polariton. This hybrid system demonstrates how MOFs can function as an accessible excitonic material for polariton chemistry.

Insulative Ion-Conducting Lithium Selenide as the Artificial Solid-Electrolyte Interface Enabling Heavy-Duty Lithium Metal Operations.

The deployment of Li metal batteries has been significantly tethered by uncontrollable lithium dendrite growth, especially in heavy-duty operations. Herein, we implement an in situ surface transformation tactic exploiting the vapor-phase solid-gas reaction to construct an artificial solid-electrolyte interphase (SEI) of Li2Se on Li metal anodes. The conformal Li2Se layer with high ionic diffusivity but poor electron conductivity effectively restrains the Li/Li+ redox conversion to the Li/Li2Se interface, and further renders a smooth and chunky Li deposition through homogenized Li+ flux and promoted redox kinetics. Consequently, the as-fabricated Li@Li2Se electrodes demonstrate superb cycling stability in symmetric cells at both high capacity and current density. The merits of inhibited dendrite growth and side reactions on the stabilized Li@Li2Se anode are further manifested in Li-O2 batteries, greatly extending the cycling stability and energy efficiency.

Controlled Release Utilizing Initiated Chemical Vapor Deposited (iCVD) of Polymeric Nanolayers.

This review will focus on the controlled release of pharmaceuticals and other organic molecules utilizing polymeric nanolayers grown by initiated chemical vapor deposited (iCVD). The iCVD layers are able conform to the geometry of the underlying substrate, facilitating release from one- and two-dimensional nanostructures with high surface area. The reactors for iCVD film growth can be customized for specific substrate geometries and scaled to large overall dimensions. The absence of surface tension in vapor deposition processes allows the synthesis of pinhole-free layers, even for iCVD layers <10 nm thick. Such ultrathin layers also provide rapid transport of the drug across the polymeric layer. The mild conditions of the iCVD process avoid damage to the drug which is being encapsulated. Smart release is enabled by iCVD hydrogels which are responsive to pH, temperature, or light. Biodegradable iCVD layers have also be demonstrated for drug release.

Conformal Coating of Powder by Initiated Chemical Vapor Deposition on Vibrating Substrate.

Encapsulation of pharmaceutical powders within thin functional polymer films is a powerful and versatile method to modify drug release properties. Conformal coating over the complete surface of the particle via chemical vapor deposition techniques is a challenging task due to the compromised gas-solid contact. In this study, an initiated chemical vapor deposition reactor was adapted with speakers and vibration of particles was achieved by playing AC/DC's song "Thunderstruck" to overcome the above-mentioned problem. To show the possibilities of this method, two types of powder of very different particle sizes were chosen, magnesium citrate (3-10 µm, cohesive powder) and aspirin (100-500 µm, good flowability), and coated with poly-ethylene-glycol-di-methacrylate. The release curve of coated magnesium citrate powder was retarded compared to uncoated powder. However, neither changing the thickness coating nor vibrating the powder during the deposition had influence on the release parameters, indicating, that cohesive powders cannot be coated conformally. The release of coated aspirin was as well retarded as compared to uncoated aspirin, especially in the case of the powder that vibrated during deposition. We attribute the enhancement of the retarded release to the formation of a conformal coating on the aspirin powder.

Vertically-Aligned Multi-Walled Carbon Nano Tube Pillars with Various Diameters under Compression: Pristine and NbTiN Coated.

In this paper, the compressive stress of pristine and coated vertically-aligned (VA) multi-walled (MW) carbon nanotube (CNT) pillars were investigated using flat-punch nano-indentation. VA-MWCNT pillars of various diameters (30-150 µm) grown by low-pressure chemical vapor deposition on silicon wafer. A conformal brittle coating of niobium-titanium-nitride with high superconductivity temperature was deposited on the VA-MWCNT pillars using atomic layer deposition. The coating together with the pillars could form a superconductive vertical interconnect. The indentation tests showed foam-like behavior of pristine CNTs and ceramic-like fracture of conformal coated CNTs. The compressive strength and the elastic modulus for pristine CNTs could be divided into three regimes of linear elastic, oscillatory plateau, and exponential densification. The elastic modulus of pristine CNTs increased for a smaller pillar diameter. The response of the coated VA-MWCNTs depended on the diffusion depth of the coating in the pillar and their elastic modulus increased with pillar diameter due to the higher sidewall area. Tuning the material properties by conformal coating on various diameter pillars enhanced the mechanical performance and the vertical interconnect access (via) reliability. The results could be useful for quantum computing applications that require high-density superconducting vertical interconnects and reliable operation at reduced temperatures.

Promoting Dendrimer Self-Assembly Enhances Covalent Layer-by-Layer Encapsulation of Pancreatic Islets.

For type 1 diabetics, islet transplantation can induce beneficial outcomes, including insulin independence and improved glycemic control. The long-term function of the grafted tissue, however, is challenged by host inflammatory and immune responses. Cell encapsulation can decrease detrimental host responses to the foreign implant, but standard microencapsulation imparts large transplant volumes and impaired metabolite and nutrient diffusion. To mitigate these effects, we developed an efficient covalent Layer-by-Layer (cLbL) approach for live-cell nanoencapsulation, based on oppositely charged hyperbranched polymers functionalized with complementary Staudinger ligation groups. Reliance on cationic polymers for cLbL, however, is problematic due to their poor biocompatibility. Herein, we incorporated the additional feature of supramolecular self-assembly of the dendritic polymers to enhance layer uniformity and decrease net polymer charge. Functionalization of poly (amino amide) (PAMAM) with triethoxysilane decreased polymer charge without compromising the uniformity and stability of resulting nanoscale islet coatings. Encapsulated pancreatic rat islets were viable and functional. The implantation of cLbL islets into diabetic mice resulted in stable normoglycemia, at equivalent dosage and efficiency as uncoated islets, with no observable alterations in cellular engraftment or foreign body responses. By balancing multi-functionality and self-assembly, nano-scale and stable covalent layer-by-layer polymeric coatings could be efficiently generated onto cellular organoids, presenting a highly adaptable platform for broad use in cellular transplantation.

Stabilizing Metallic Iron Nanoparticles by Conformal Graphitic Carbon Coating for High-Rate Anode in Ni-Fe Batteries.

Nickel-iron (Ni-Fe) batteries are promising candidates for large-scale energy storage due to their high safety and low cost. However, their power density and cycling efficiency remain limited by the poor kinetics of the Fe anode. Herein, we report high-performance Fe anodes based on active Fe nanoparticles conformally coated with carbon shells, which were synthesized from low-cost precursors using a scalable process. Such core-shell structured C-Fe anodes offer high electrochemical activity and stability. Specifically, a high specific capacity of 208 mAh g-1 at a current density of 1 A g-1 (based on the total weight of Fe and C) and a capacity retention of 93% after 2000 cycles at 4 A g-1 can be achieved. When coupled with a Ni cathode, such a full cell battery can deliver a high energy density of 101.0 Wh kg-1 at power density of 0.81 kW kg-1 and 51.6 Wh kg-1 at 8.2 kW kg-1 (based on the mass of the electrode materials), among the best energy and power performance among Ni-Fe batteries reported results. Thus, this work may provide an effective and scalable route toward high-performance anodes for high-power and long-life Ni-Fe batteries.