A Photoaddressable Liquid Crystalline Phase Transition in Graphene Oxide Nanocomposites

The multifunctionality of graphene has the potential to unlock important developments in nanocomposite science. However, the manipulation of graphene without interfering with its unique properties and while controlling its spatial organization remains challenging. Here, the formation of a photoaddressable liquid crystalline (LC) solution through the stabilization of graphene oxide (GO) with photocleavable brushes is described. The LC behavior leads to the thermodynamic entrapment of GO into low aspect ratio domains that fail to display the properties typically predicted for graphene nanocomposites. The morphology and structural and electronic performance of these nanocomposites are regenerated through the brush cleavage, which controls the phase transition of the LC phase. These results show that kinetic control of graphene assembly can be an attractive tool toward the dynamic regulation of processable sol states and structured percolated networks for rational composite manufacturing.     

All‐Cellulose‐Based Quasi‐Solid‐State Sodium‐Ion Hybrid Capacitors Enabled by Structural Hierarchy

Na‐ion hybrid capacitors consisting of battery‐type anodes and capacitor‐style cathodes are attracting increasing attention on account of the abundance of sodium‐based resources as well as the potential to bridge the gap between batteries (high energy) and supercapacitors (high power). Herein, hierarchically structured carbon materials inspired by multiscale building units of cellulose from nature are assembled with cellulose‐based gel electrolytes into Na‐ion capacitors. Nonporous hard carbon anodes are obtained through the direct thermal pyrolysis of cellulose nanocrystals. Nitrogen‐doped carbon cathodes with a coral‐like hierarchically porous architecture are prepared via hydrothermal carbonization and activation of cellulose microfibrils. The reversible charge capacity of the anode is 256.9 mAh g^?1 when operating at 0.1 A g^?1 from 0 to 1.5 V versus Na⁺/Na, and the discharge capacitance of cathodes tested within 1.5 to 4.2 V versus Na⁺/Na is 212.4 F g^?1 at 0.1 A g^?1. Utilizing Na⁺ and ClO₄^? as charge carriers, the energy density of the full Na‐ion capacitor with two asymmetric carbon electrodes can reach 181 Wh kg^?1 at 250 W kg^?1, which is one of the highest energy devices reported until now. Combined with macrocellulose‐based gel electrolytes, all‐cellulose‐based quasi‐solid‐state devices are demonstrated possessing additional advantages in terms of overall sustainability.     

Design of Two‐Stage Class AB CMOS Buffers: A Systematic Approach

A systematic approach for the design of two‐stage class AB CMOS unity‐gain buffers is proposed. It is based on the inclusion of a class AB operation to class A Miller amplifier topologies in unity‐gain negative feedback by a simple technique that does not modify quiescent currents, supply requirements, noise performance, or static power. Three design examples are fabricated in a 0.5 µm CMOS process. Measurement results show slew rate improvement factors of approximately 100 for the class AB buffers versus their class A counterparts for the same quiescent power consumption (< 200 µW).     

Deconstructing the Effects of Matrix Elasticity and Geometry in Mesenchymal Stem Cell Lineage Commitment

A wide variety of environmental factors including physical and biochemical signals are responsible for stem cell behavior and function. In particular, matrix elasticity and cell shape have been shown to determine stem cell function, yet little is known about the interplay between how these physical cues control cell differentiation. For the first time, by using ultraviolet (UV) lithography to pattern poly(ethylene) glycol (PEG) hydrogels, it is possible to manufacture microenvironments capable of parsing the effects of matrix elasticity, cell shape, and cell size in order to explore the relationship between matrix elasticity and cell shape in mesenchymal stem cell (MSC) lineage commitment. These data show that cells cultured on 1000 μm² circles, squares, and rectangles are primarily adipogenic lineage regardless of matrix elasticity, while cells cultured on 2500 and 5000 μm² shapes more heavily depend on shape and elasticity for lineage specification. It is further characterized how modifying the cell cytoskeleton through pharmacological inhibitors can modify cell behavior. By showing MSC lineage commitment relationships due to physical signals, this study highlights the importance of cell shape and matrix elasticity in further understanding stem cell behavior for future tissue engineering strategies.     

Insulator‐Conductor Type Transitions in Graphene‐Modified Silver Nanowire Networks: A Route to Inexpensive Transparent Conductors

Silver nanowire coatings are an attractive alternative to indium tin oxide for producing transparent conductors. To fabricate coatings with low sheet resistance required for touchscreen displays, a multi‐layer network of silver nanowires must be produced that may not be cost effective. This problem is counteracted here by modifying the electrical properties of an ultra‐low‐density nanowire network through local deposition of conducting graphene platelets. Unlike other solution‐processed materials, such as graphene oxide, our pristine graphene is free of oxygen functional groups, resulting in it being electrically conducting without the need for further chemical treatment. Graphene adsorption at inter‐wire junctions as well as graphene connecting adjacent wires contributes to a marked enhancement in electrical properties. Using our approach, the amount of nanowires needed to produce viable transparent electrodes could be more than 50 times less than the equivalent pristine high density nanowire networks, thus having major commercial implications. Using a laser ablation process, it is shown that the resulting films can be patterned into individual electrode structures, which is a pre‐requisite to touchscreen sensor fabrication.     

The Effect of Alkyl Spacers on the Mixed Ionic-Electronic Conduction Properties of N-Type Polymers

Conjugated polymers with mixed ionic and electronic transport are essential for developing the complexity and function of electrochemical devices. Current n-type materials have a narrow scope and low performance compared with their p-type counterparts, requiring new molecular design strategies. This work presents two naphthalene diimide-bithiophene (NDI-T2) copolymers functionalized with hybrid alkyl-glycol side chains, where the naphthalene diimide unit is segregated from the ethylene glycol (EG) units within the side chain by an alkyl spacer. Introduction of hydrophobic propyl and hexyl spacers is investigated as a strategy to minimize detrimental swelling close to the conjugated backbone and balance the mixed conduction properties of n-type materials in aqueous electrolytes. It is found that both polymers functionalized with alkyl spacers outperform their analogue bearing EG-only side chains in organic electrochemical transistors (OECTs). The presence of the alkyl spacers also leads to remarkable stability in OECTs, with no decrease in the ON current after 2 h of operation. Through this versatile side chain modification, this work provides a greater understanding of the structure-property relationships required for n-type OECT materials operating in aqueous media.     

A Bio-Conjugated Fullerene as a Subcellular-Targeted and Multifaceted Phototheranostic Agent

Fullerenes are candidates for theranostic applications because of their high photodynamic activity and intrinsic multimodal imaging contrast. However, fullerenes suffer from low solubility in aqueous media, poor biocompatibility, cell toxicity, and a tendency to aggregate. C₇₀@lysozyme is introduced herein as a novel bioconjugate that is harmless to a cellular environment, yet is also photoactive and has excellent optical and optoacoustic contrast for tracking cellular uptake and intracellular localization. The formation, water-solubility, photoactivity, and unperturbed structure of C₇₀@lysozyme are confirmed using UV-visible and 2D ¹H, ¹⁵N NMR spectroscopy. The excellent imaging contrast of C₇₀@lysozyme in optoacoustic and third harmonic generation microscopy is exploited to monitor its uptake in HeLa cells and lysosomal trafficking. Last, the photoactivity of C₇₀@lysozyme and its ability to initiate cell death by means of singlet oxygen (¹O₂) production upon exposure to low levels of white light irradiation is demonstrated. This study introduces C₇₀@lysozyme and other fullerene-protein conjugates as potential candidates for theranostic applications.     

Dependence of Photocurrent Enhancements in Quantum Dot (QD)‐Sensitized MoS2 Devices on MoS2 Film Properties

This report demonstrates highly efficient nonradiative energy transfer (NRET) from alloyed CdSeS/ZnS semiconductor nanocrystal quantum dots (QDs) to MoS₂ films of varying layer thicknesses, including pristine monolayers, mixed monolayer/bilayer, polycrystalline bilayers, and bulk‐like thicknesses, with NRET efficiencies of over 90%. Large‐area MoS₂ films are grown on Si/SiO₂ substrates by chemical vapor deposition. Despite the ultrahigh NRET efficiencies there is no distinct increase in the MoS₂ photoluminescence intensity. However, by studying the optoelectronic properties of the MoS₂ devices before and after adding the QD sensitizing layer photocurrent enhancements as large as ≈14‐fold for pristine monolayer devices are observed, with enhancements on the order of ≈2‐fold for MoS₂ devices of mixed monolayer and bilayer thicknesses. For the polycrystalline bilayer and bulk‐like MoS₂ devices there is almost no increase in the photocurrent after adding the QDs. Industrially scalable techniques are specifically utilized to fabricate the samples studied in this report, demonstrating the viability of this hybrid structure for commercial photodetector or light harvesting applications.     

Hydroxyapatite Modified with Carbon‐Nanotube‐Reinforced Poly(methyl methacrylate): A Nanocomposite Material for Biomedical Applications

The paper reports on a freeze‐granulation technique to prepare a novel nanocomposite of poly(methyl methacrylate) (PMMA)‐modified hydroxyapatite (HA) with multiwalled carbon nanotubes (MWCNTs) as reinforcement for a new generation biomedical bone cement and implant coatings. By using this technique it is possible to increase material homogeneity and also enhance the dispersion of MWCNTs in the composite matrix. The phase composition and the surface morphology of the nanocomposite material were studied using X‐ray diffraction, field‐emission scanning electron microscopy, and micro‐Raman spectroscopy. Additionally, nanomechanical properties of different concentrations of MWCNT‐reinforced nanocomposite were performed by a nanoindentation technique, which indicates that a concentration of 0.1 wt % MWCNTs in the PMMA/HA nanocomposite material gives the best mechanical properties.     

Superparamagnetic Ag@Co‐Nanocomposites on Granulated Cation Exchange Polymeric Matrices with Enhanced Antibacterial Activity for the Environmentally Safe Purification of Water

Cation exchange polymeric matrices are widely used in water treatment protocols to reduce the mineral content of hard waters, even for human consumption. However, they are not antibacterial and flowing bacteria can be trapped in their structures and proliferate, thus acting as microbial contamination sources. Here, Ag@Co‐nanoparticles (Ag@Co‐NPs) with a low‐cost superparamagnetic Co⁰‐core and an antibacterial Ag‐shell are synthesized on granulated cation exchange polymeric matrices under soft reaction conditions. The presence of these NPs provides the final nanocomposite (NC) with additional functionalities (superparamagnetism and antibacterial activity) making it ideal for water purification applications. Ag@Co‐NPs are synthesized in situ on four cation exchange polymeric matrices containing either strong (sulfonic) or weak (carboxylic) acid functional groups homogeneously distributed (C‐type) or concentrated on an external shell (SST‐type) by the intermatrix synthesis (IMS) method. The NCs are characterized (metal content, NP size and distribution, metal oxidative state, and metal release) and evaluated for water purification applications.