Advances in the Use of Conducting Polymers for Healthcare Monitoring.

Conducting polymers (CPs) are an innovative class of materials recognized for their high flexibility and biocompatibility, making them an ideal choice for health monitoring applications that require flexibility. They are active in their design. Advances in fabrication technology allow the incorporation of CPs at various levels, by combining diverse CPs monomers with metal particles, 2D materials, carbon nanomaterials, and copolymers through the process of polymerization and mixing. This method produces materials with unique physicochemical properties and is highly customizable. In particular, the development of CPs with expanded surface area and high conductivity has significantly improved the performance of the sensors, providing high sensitivity and flexibility and expanding the range of available options. However, due to the morphological diversity of new materials and thus the variety of characteristics that can be synthesized by combining CPs and other types of functionalities, choosing the right combination for a sensor application is difficult but becomes important. This review focuses on classifying the role of CP and highlights recent advances in sensor design, especially in the field of healthcare monitoring. It also synthesizes the sensing mechanisms and evaluates the performance of CPs on electrochemical surfaces and in the sensor design. Furthermore, the applications that can be revolutionized by CPs will be discussed in detail.

Physically Exfoliating 2D Materials: A Versatile Combination of Different Materials into a Layered Structure.

Improving the properties of the existing two-dimensional (2D) materials is a major concern for many researchers today. Synergistic coupling of single-phase 2D material species with secondary functional materials has resulted in 2D nanohybrids with significantly enhanced properties beyond the sum of their individual components. In particular, nanohybrids created by alternatingly integrating different material species in the confined 2D nanometer regime have the potential to meet the needs of a wide variety of applications, particularly the many important energy-related applications that are of interest. However, scaling up production of 2D nanohybrids is still challenging, which is a major barrier to their practical application. Delamination and exfoliation by physical means separate the weakly bound 2D nanosheets into kinetically stable single- or few-layers. Herein, we provide a concise overview of recent achievements in the physical exfoliation-based fabrication of 2D nanohybrids featuring controlled heterolayered structures. Several strategies to efficiently produce heterolayered 2D nanohybrids in large quantities are described, such as (i) coexfoliation of different 2D species, (ii) aqueous-phase synthesis, and (iii) gas-phase synthesis. The versatility of the 2D nanohybrids was also illustrated by remarkable research examples, especially in energy-related applications.

Polymer Nanomaterials in Biomedicine.

Polymer nanomaterials have emerged as a promising class of materials within the field of biomedicine, owing to their unique physical, chemical, and biological properties [...].

All-Gas-Phase Synthesis of Heterolayered Two-Dimensional Nanohybrids Decorated with Metallic Nanocatalysts for Water Splitting.

Herein, a sequential gas-phase process involving air jet milling followed by chemical vapor deposition (CVD), is demonstrated to be an efficient strategy for the fabrication of heterolayered 2D nanohybrids (2DNHs) decorated with nanocatalysts. Tens of grams of the nanohybrids, which is a substantial quantity at the laboratory scale, are produced in the absence of solvents and water, and without the need for an extra purification procedure. Air jet milling enables the development of binary/ternary heterolayered structures consisting of graphene, WSe2 , and/or MoS2 via the gas-phase co-exfoliation of their bulk counterparts. Based on the X-ray photoelectron and Raman spectroscopy data, the heterolayers of the 2DNHs exert chemical and electronic effects on each other, while diminishing the interactions between same-component layers. Moreover, the electrochemically active surface area increases by >190% and the charge transfer resistance decreases by >35%. CVD is performed to introduce Pt and Ru nanoparticles with diameters of a few nanometers as additional electrocatalysts into the 2DNHs. The nanocatalyst-decorated 2DNHs show excellent performance for the production of hydrogen and oxygen gases in water-splitting cells. Notably, the proposed all-gas-phase processes allow for the large-scale production of functional 2DNHs with minimal negative environmental impact, which is crucial for the commercialization of nanomaterials.

Nanoparticulate Photoluminescent Probes for Bioimaging: Small Molecules and Polymers.

Recent interest in research on photoluminescent molecules due to their unique properties has played an important role in advancing the bioimaging field. In particular, small molecules and organic dots as probes have great potential for the achievement of bioimaging because of their desirable properties. In this review, we provide an introduction of probes consisting of fluorescent small molecules and polymers that emit light across the ultraviolet and near-infrared wavelength ranges, along with a brief summary of the most recent techniques for bioimaging. Since photoluminescence probes emitting light in different ranges have different goals and targets, their respective strategies also differ. Diverse and novel strategies using photoluminescence probes against targets have gradually been introduced in the related literature. Among recent papers (published within the last 5 years) on the topic, we here concentrate on the photophysical properties and strategies for the design of molecular probes, with key examples of in vivo photoluminescence research for practical applications. More in-depth studies on these probes will provide key insights into how to control the molecular structure and size/shape of organic probes for expanded bioimaging research and applications.

Surfactant-in-Polymer Templating for Fabrication of Carbon Nanofibers with Controlled Interior Substructures: Designing Versatile Materials for Energy Applications.

A simple, scalable, surfactant-in-polymer templating approach is demonstrated to create controlled long-range secondary substructures in a primary structure. A metal bis(2-ethylhexyl) sulfosuccinate (MAOT) as the surfactant is shown to be capable of serving as a sacrificial template and metal precursor in carbon nanofibers. The low interfacial tension and controllable dimensions of the MAOT are maintained in the solid-phase polymer, even during electrospinning and heat-treatment processes, allowing for the long-range uniform formation of substructures in the nanofibers. The MAOT content is found to be a critical parameter for tailoring the diameter of the nanofibers and their textural properties, such as size and volume of interior pores. The metal counterion species in the MAOT determine the introduction of metallic phases in the nanofiber interior. The incorporation of MAOT with Na as the counterion into the polymer phase leads to the formation of a built-in pore structure in the nanofibers. In contrast, MAOT with Fe as a counterion generates unique iron-in-pore substructures in the nanofibers (FeCNFs). The FeCNFs exhibit outstanding charge storage and water splitting performances. As a result, the MAOT-in-polymer templating approach can be extended to combinations of various metal precursors and thus create desirable functionalities for different target applications.

Exfoliation of 2D Materials for Energy and Environmental Applications.

The fascinating properties of single-layer graphene isolated by mechanical exfoliation have inspired extensive research efforts toward two-dimensional (2D) materials. Layered compounds serve as precursors for atomically thin 2D materials (briefly, 2D nanomaterials) owing to their strong intraplane chemical bonding but weak interplane van der Waals interactions. There are newly emerging 2D materials beyond graphene, and it is becoming increasingly important to develop cost-effective, scalable methods for producing 2D nanomaterials with controlled microstructures and properties. The variety of developed synthetic techniques can be categorized into two classes: bottom-up and top-down approaches. Of top-down approaches, the exfoliation of bulk 2D materials into single or few layers is the most common. This review highlights chemical and physical exfoliation methods that allow for the production of 2D nanomaterials in large quantities. In addition, remarkable examples of utilizing exfoliated 2D nanomaterials in energy and environmental applications are introduced.

Combining SWNT and Graphene in Polymer Nanofibers: A Route to Unique Carbon Precursors for Electrochemical Capacitor Electrodes.

It is important to fabricate nanostructured architectures comprised of functional components for a wide variety of applications because precise structural control in the nanometer regime can yield unprecedented, fascinating properties. Owing to their well-defined microstructural characteristics, it has been popular to use carbon nanospecies, such as nanotubes and graphene, in fabricating nanocomposites and nanohybrids. Nevertheless, it still remains hard to control and manipulate nanospecies for specific applications, thus preventing their commercialization. Herein, first, we report unique one-dimensional nanoarchitectures with meso-/macropores, consisting of single-walled nanotubes (SWNTs), graphene, and polyacrylonitrile, in which poly(vinyl alcohol) was employed as a dispersing agent and sacrificial porogen. One-dimensional SWNTs and two-dimensional graphene pieces were combined in the confined interior space of electrospun nanofibers, which led to unique microstructural characteristics such as enhanced ordering of SWNTs, graphene pieces, and polymer chains in the nanofiber interior. Next, the SWNT/graphene-in-polymer nanofiber (SGPNF) structures were converted into carbonized products (SGCNFs) with effective porosity and tunable electrochemical properties. Similar to SGPNFs, the microstructural and electrical properties of the SGCNFs depended on the incorporated amount of SWNT and graphene. At higher SWNT content, the mesopore volume proportion and specific discharge capacitance of the SGCNFs increased by max. 63 and 598%, respectively. The SGCNFs showed strong potential as a high-performance electrode material for electrochemical capacitors (max. capacitance: nonactivated ∼390 F g-1 and activated ∼750 F g-1). Flexible, all solid-state capacitor cells based on SGCNFs were also successfully demonstrated as a model application. The SGCNFs can be further functionalized by various methods, which will impart attractive properties for extended applications.

An Ultrasensitive, Selective, Multiplexed Superbioelectronic Nose That Mimics the Human Sense of Smell.

Human sensory-mimicking systems, such as electronic brains, tongues, skin, and ears, have been promoted for use in improving social welfare. However, no significant achievements have been made in mimicking the human nose due to the complexity of olfactory sensory neurons. Combinational coding of human olfactory receptors (hORs) is essential for odorant discrimination in mixtures, and the development of hOR-combined multiplexed systems has progressed slowly. Here, we report the first demonstration of an artificial multiplexed superbioelectronic nose (MSB-nose) that mimics the human olfactory sensory system, leading to high-performance odorant discriminatory ability in mixtures. Specifically, portable MSB-noses were constructed using highly uniform graphene micropatterns (GMs) that were conjugated with two different hORs, which were employed as transducers in a liquid-ion gated field-effect transistor (FET). Field-induced signals from the MSB-nose were monitored and provided high sensitivity and selectivity toward target odorants (minimum detectable level: 0.1 fM). More importantly, the potential of the MSB-nose as a tool to encode hOR combinations was demonstrated using principal component analysis.

Real-time detection of metal ions using conjugated polymer composite papers.

Cellulose, a natural polymeric material, has widespread technical applications because of its inherent structural rigidity and high surface area. As a conjugated polymer, polypyrrole shows practical potential for a diverse and promising range of future technologies. Here, we demonstrate a strategy for the real-time detection and removal of metal ions with polypyrrole/cellulose (PPCL) composite papers in solution. Simply, the conjugated polymer papers had different chemical/physical properties by applying different potentials to them, which resulted in differentiable response patterns and adsorption efficiencies for individual metal ions. First, large-area PPCL papers with a diameter of 5 cm were readily obtained via vapor deposition polymerization. The papers exhibited both mechanical flexibility and robustness, in which polypyrrole retained its redox property perfectly. The ability of the PPCL papers to recognize metal ions was examined in static and flow cells, in which real-time current change was monitored at five different applied potentials (+1, +0.5, 0, -0.5, and -1 V vs. Ag/AgCl). Distinguishable signals in the PPCL paper responses were observed for individual metal ions through principal component analysis. Particularly, the PPCL papers yielded unique signatures for three metal ions, Hg(ii), Ag(i), and Cr(iii), even in a real sample, groundwater. The sorption of metal ions by PPCL papers was examined in the flow system. The PPCL papers had a greatly superior adsorption efficiency for Hg(ii) compared to that of the other metal ions. With the strong demand for the development of inexpensive, flexible, light-weight, and environmentally friendly devices, the fascinating characteristics of these PPCL papers are likely to provide good opportunities for low-cost paper-based flexible or wearable devices.

Conducting polymer-based nanohybrid transducers: a potential route to high sensitivity and selectivity sensors.

The development of novel sensing materials provides good opportunities to realize previously unachievable sensor performance. In this review, conducting polymer-based nanohybrids are highlighted as innovative transducers for high-performance chemical and biological sensing devices. Synthetic strategies of the nanohybrids are categorized into four groups: (1) impregnation, followed by reduction; (2) concurrent redox reactions; (3) electrochemical deposition; (4) seeding approach. Nanocale hybridization of conducting polymers with inorganic components can lead to improved sorption, catalytic reaction and/or transport behavior of the material systems. The nanohybrids have thus been used to detect nerve agents, toxic gases, volatile organic compounds, glucose, dopamine, and DNA. Given further advances in nanohybrids synthesis, it is expected that sensor technology will also evolve, especially in terms of sensitivity and selectivity.

CoFe2O4 modified bentonite-based mixed matrix loose nanofiltration membranes for effective wastewater treatment.

Mixed-matrix membranes (MMMs) with an ideal polymer/hydrophilic flux enhancer interface considerably recuperates the separation and purification performance of membrane. In this direction, a novel CoFe2O4 functionalized natural clay-bentonite (CoFe2O4@BT) material as a compatible flux enhancer was synthesized for preparation of mixed matrix based in polyethersulfone (PES) matrix. Here, the influences of CoFe2O4@BT on the morphology and performance of the MMMs membranes were systematically investigated using various analytical techniques. Meanwhile, the water flux and sepration eficiency of the CoFe2O4@BT-PES membranes significantly enhanced due to the incorporation of CoFe2O4@BT that altered hydrophilicity, pore and surface characteristic features. The water flux as well as separation efficiency range up to 95%, 94.69%, 94.16% of Congo red (CR), Crystal violet (CV), and humic acid (HA) respectively. Meanwhile, the fouling parameters demonstrated that the CoFe2O4@BT-PES membranes exhibited better antifouling property in the long term experiment comparing with commercial polyamide membrane. CoFe2O4@BT material incorporated membranes showed less decline ratio and a better recovery ratio. The high rejection of dyes with a high permeation flux of the newly designed membranes indicated an amazing possibility for dye purification. In this study, a potential dye mechanism for composite membranes impacted by synthetic CoFe2O4@BT was also put forth. Within the context of application considerations for environmental protection, new materials stock in membranes show good potential for the separation of different organic contaminants.

Fabrication of graphene sheets intercalated with manganese oxide/carbon nanofibers: toward high-capacity energy storage.

Herein, 3D nanohybrid architectures consisting of MnO(x) nanocrystals, carbon nanofibers (CNFs), and graphene sheets are fabricated. MnO(x) -decorated CNFs (MCNFs) with diameters of about 50 nm are readily obtained via single-nozzle co-electrospinning, followed by heat treatment. The MCNFs are then intercalated between graphene sheets, yielding the ternary nanohybrid MCNF/reduced graphene oxide (RGO). This straightforward synthesis process readily affords product on a scale of tens of grams. The ultrathin CNFs, which might be a promising alternative to carbon nanotubes (CNTs), overcome the low electrical conductivity of the excellent pseudocapacitive component, MnO(x) . Furthermore, the graphene sheets separated by the MCNFs boost the electrochemical performance of the nanohybrid electrodes. These nanohybrid electrodes exhibit enhanced specific capacitances compared with a sheet electrode fabricated of MCNF-only or RGO-only. Evidently, the RGO sheet acts as a conductive channel inside the nanohybrid, while the intercalated MCNFs increase the efficiency of the ion and charge transfer in the nanohybrid. The proposed nanohybrid architectures are expected to lay the foundation for the design and fabrication of high-performance electrodes.

Multidimensional conducting polymer nanotubes for ultrasensitive chemical nerve agent sensing.

Tailoring the morphology of materials in the nanometer regime is vital to realizing enhanced device performance. Here, we demonstrate flexible nerve agent sensors, based on hydroxylated poly(3,4-ethylenedioxythiophene) (PEDOT) nanotubes (HPNTs) with surface substructures such as nanonodules (NNs) and nanorods (NRs). The surface substructures can be grown on a nanofiber surface by controlling critical synthetic conditions during vapor deposition polymerization (VDP) on the polymer nanotemplate, leading to the formation of multidimensional conducting polymer nanostructures. Hydroxyl groups are found to interact with the nerve agents. Representatively, the sensing response of dimethyl methylphosphonate (DMMP) as a simulant for sarin is highly sensitive and reversible from the aligned nanotubes. The minimum detection limit is as low as 10 ppt. Additionally, the sensor had excellent mechanical bendability and durability.

Rapid and Direct Liquid-Phase Synthesis of Luminescent Metal Halide Superlattices.

The crystallization of nanocrystal building blocks into artificial superlattices has emerged as an efficient approach for tailoring the nanoscale properties and functionalities of novel devices. To date, ordered arrays of colloidal metal halide nanocrystals have mainly been achieved by using post-synthetic strategies. Here, a rapid and direct liquid-phase synthesis is presented to achieve a highly robust crystallization of luminescent metal halide nanocrystals into perfect face-centered-cubic (FCC) superlattices on the micrometer scale. The continuous growth of individual nanocrystals is observed within the superlattice, followed by the disassembly of the superlattices into individually dispersed nanocrystals owing to the highly repulsive interparticle interactions induced by large nanocrystals. Transmission electron microscopy characterization reveals that owing to an increase in solvent entropy, the structure of the superlattices transforms from FCC to hexagonal close-packed (HCP) and the nanocrystals disassemble. The FCC superlattice exhibits a single and slightly redshifted emission, due to the reabsorption-free property of the building block units. Compared to individual nanocrystals, the superlattices have three times higher quantum yield with improved environmental stability, making them ideal for use as ultrabright blue-light emitters. This study is expected to facilitate the creation of metamaterials with ordered nanocrystal structures and their practical applications.

Controlled Growth of Perovskite Nanocrystals on Nanotubes via a Nanoseeding Intermediate Stage: Toward Novel Optoelectronic Applications.

CsPbBr3 perovskite nanocrystals (CNCs) were densely anchored on multiwalled carbon nanotubes (MWNTs) via a nanoseeding intermediate stage, in which lead-based nuclei are formed on the nanotube surface. After the formation of the intermediate, a cesium precursor was added to promote the growth of CNCs from the surface nuclei and to thereby obtain CNC-decorated MWNT nanohybrids (CMNHs). The morphology and properties of the CMNHs were determined by the reaction temperature employed during their synthesis. Importantly, the use of MWNTs promoted the formation of larger CNCs that emitted intense green light and modified the electronic structure and bandgap energy of the CNCs. Consequently, the CMNHs could function as optoelectronic transducers and exhibit a "turn-on" photocurrent response when exposed to UV light of narrow specific-range wavelengths. In a novel approach for preventing counterfeit products, the CMNHs were used as a light-emitting black ink to create quick-response codes with fake pixels.

Label-free, single protein detection on a near-infrared fluorescent single-walled carbon nanotube/protein microarray fabricated by cell-free synthesis.

Excessive sample volumes continue to be a major limitation in the analysis of protein-protein interactions, motivating the search for label-free detection methods of greater sensitivity. Herein, we report the first chemical approach for selective protein recognition using fluorescent single-walled carbon nanotubes (SWNTs) enabling label-free microarrays capable of single protein detection. Hexahistidine-tagged capture proteins directly expressed by cell-free synthesis on SWNT/chitosan microarray are bound to a Ni(2+) chelated by Nα,Nα-bis(carboxymethyl)-L-lysine grafted to chitosan surrounding the SWNT. The Ni(2+) acts as a proximity quencher with the Ni(2+)/SWNT distance altered upon docking of analyte proteins. This ability to discern single protein binding events decreases the apparent detection limit from 100 nM, for the ensemble average, to 10 pM for an observation time of 600 s. This first use of cell-free synthesis to functionalize a nanosensor extends this method to a virtually infinite number of capture proteins. To demonstrate this, the SWNT microarrays are used to analyze a network of 1156 protein-protein interactions in the staurosporine-induced apoptosis of SH-SY5Y cells, confirming literature predictions.

Controllable Physical Synergized Triboelectricity, Shape Memory, Self-Healing, and Optical Sensing with Rollable Form Factor by Zn cluster.

To build devices offering users comfortable experience, it is important to focus on form factor and multifunctionality. In this study, for the first time, multifunctional Zn clusters with shape memory, self-healing, triboelectricity, and optical sensing synergized with rollable form factor are designed and fabricated by coordinating COO- and Zn2+ . As pore forming agent, Zn clusters produce hierarchical porous structure depending on Zn amount. Zn clusters are applied as message transmitters and charge containers in optical sensing and corona charge injection, respectively. Moreover, Zn clusters in PVB-COO-Zn serve as positive tribomaterial due to Zn ion doping effect, increasing the output performance as the Zn amount reaches 20 wt%. In addition, injecting positive charge into PVB-COO-Zn 20 lead to more than 24 times increase in output performance compared to those of non-porous structures. The reversibility of Zn clusters endows shape memory and self-healing, synergized with the rollable form factor. The rollability is implemented using the long alkyl chain and the energy absorption of porous structure, providing damage resistance. The advancements in this work provide opportunities for multifunctional and unique applications (shape memory rotating-triboelectric nanogenerator, rollable self-healing touchpad, hidden tag) synergized with rollability that accomplishes working in broadened condition in near future.

Fire-Safe Polymer Composites: Flame-Retardant Effect of Nanofillers.

Currently, polymers are competing with metals and ceramics to realize various material characteristics, including mechanical and electrical properties. However, most polymers consist of organic matter, making them vulnerable to flames and high-temperature conditions. In addition, the combustion of polymers consisting of different types of organic matter results in various gaseous hazards. Therefore, to minimize the fire damage, there has been a significant demand for developing polymers that are fire resistant or flame retardant. From this viewpoint, it is crucial to design and synthesize thermally stable polymers that are less likely to decompose into combustible gaseous species under high-temperature conditions. Flame retardants can also be introduced to further reinforce the fire performance of polymers. In this review, the combustion process of organic matter, types of flame retardants, and common flammability testing methods are reviewed. Furthermore, the latest research trends in the use of versatile nanofillers to enhance the fire performance of polymeric materials are discussed with an emphasis on their underlying action, advantages, and disadvantages.

Morphology-Dependent Ambient-Condition Growth of Perovskite Nanocrystals for Enhanced Stability in Photoconversion Device.

CsPbBr3 perovskite nanocrystals with two different dimensionalities were synthesized at different temperatures and then integrated as optoelectronic transducers into transistor-type photoconversion devices. Postsynthesis transformation was observed for two-dimensional (2D) nanoplatelets, while the transformation was rarely found in 3D nanocubes. At ambient temperature and pressure, neighboring nanoplatelets made facet-to-facet contact and then fused into larger 2D nanoplatelets (2-5 times) without defects. The coalescence of 2D nanoplatelets at the ambient condition lowered the density of defects at the surface of the nanocrystals and thus could facilitate effective and stable photoconversion behavior in the nanocrystal film integrated into the device. Consequently, the ambient-condition aging of 2D nanoplatelets on device substrate led to 3 times higher retention in photoconversion performance. Importantly, these results provide a new concept of how perovskite nanocrystals can be integrated into a device for enhanced stability in device performance.