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.

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.

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.

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.

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 [...].

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.

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.

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.

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.

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.

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.

High-performance portable graphene field-effect transistor device for detecting Gram-positive and -negative bacteria.

Current techniques for Gram-typing and for diagnosing a pathogen at the early infection stage rely on Gram stains, cultures, Enzyme linked immunosorbent assay (ELISA), polymerase chain reaction (PCR), and gene microarrays, which are labor-intensive and time-consuming approaches. In addition, a delayed or imprecise diagnosis of clinical pathogenic bacteria leads to a life-threatening emergency or overuse of antibiotics and a high-rate occurrence of antimicrobial-resistance microbes. Herein, we report high-performance antibiotics (as bioprobes) conjugated graphene micropattern field-effect transistors (ABX-GMFETs) to facilitate on-site Gram-typing and help in the detection of the presence or absence of Gram-negative and -positive bacteria in the samples. The ABX-GMFET platform, which consists of recognition probes and GM transistors conjugated with novel interfacing chemical compounds, was integrated into the microfluidics to minimize the required human intervention and facilitate automation. The mechanism of binding of ABX-GMFET was based on a charge or chemical moiety interaction between the bioprobes and target bacteria. Subsequently, ABX-GMFETs exhibited unprecedented high sensitivity with a limit of detection (LOD) of 100 CFU/mL (1-9 CFU/mL), real-time target specificity.

Anomalous restoration of sp2 hybridization in graphene functionalization.

The functionalization of nanocarbon materials such as graphene has attracted considerable attention over the past decades. In this work, we designed and synthesized a unique N-heterocyclic carbene compound with a pyrene tail group (NHCp) to investigate how carbene species can be used for the functionalization of graphene. Although the carbene moiety of NHCp has the ability to covalently bond to graphene, the pyrene tail can noncovalently interact with graphene and allows monitoring its surrounding microenvironment. The major characteristics of the resulting nanohybrids were highly dependent on the type of graphene and the NHCp-to-graphene weight ratio. Importantly, despite the covalent functionalization of graphene, an anomalous decrease in the intensity of the Raman D peak and improved conductivity were observed for the nanohybrids. It was found that the covalent bond of NHCp to the graphene edge may allow the hybridization of their orbitals, which affects electronic energy levels and alters the double resonance process that originates the D peak at the edge defect. Importantly, the NHCp compound can act as a π acceptor (not just as a σ donor) via the NHCp-graphene covalent bridge. This is the first report showing that the concept of π-backdonation can be realized in two-dimensional materials, such as graphene, and rationally designed carbene molecules can functionalize graphene without losing their beneficial sp2 hybridization characteristics.

Electrical monitoring of photoisomerization of block copolymers intercalated into graphene sheets.

Insulating polymers have received little attention in electronic applications. Here, we synthesize a photoresponsive, amphiphilic block copolymer (PEO-b-PVBO) and further control the chain growth of the block segment (PVBO) to obtain different degrees of polymerization (DPs). The benzylidene oxazolone moiety in PEO-b-PVBO facilitated chain-conformational changes due to photoisomerization under visible/ultraviolet (UV) light illumination. Intercalation of the photoresponsive but electrically insulating PEO-b-PVBO into graphene sheets enabled electrical monitoring of the conformational change of the block copolymer at the molecular level. The current change at the microampere level was proportional to the DP of PVBO, demonstrating that the PEO-b-PVBO-intercalated graphene nanohybrid (PGNH) can be used in UV sensors. Additionally, discrete signals at the nanoampere level were separated from the first derivative of the time-dependent current using the fast Fourier transform (FFT). Analysis of the harmonic frequencies using the FFT revealed that the PGNH afforded sawtooth-type current flow mediated by Coulomb blockade oscillation.

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.

Multifunctional Role of MoS2 in Preparation of Composite Hydrogels: Radical Initiation and Cross-Linking.

This paper describes the multifunctional effect of molybdenum disulfide (MoS2) that enables the rapid and accessible preparation of nanocomposite hydrogels via a bottom-up design. The MoS2 nanoplatelet forms radical species through a redox reaction with persulfate under aqueous conditions while initiating the polymerization of acrylic monomers and providing noncovalent cross-linking points without requiring external stimuli or extra cross-linkers, leading to the formation of hydrogels that are in situ embedded with inorganic flakes. Furthermore, the addition of MoS2 could induce more rigid and elastic networks compared to those in control hydrogels using a typical cross-linker at the same level; for example, 0.08 wt % MoS2 resulted in a composite hydrogel of which the elastic modulus was 2.5 times greater than that from a hydrogel using N,N'-methylenebis(acrylamide) as the showing phase transition during polymerization. The composite hydrogels are self-healable, taking advantage of reversible physical cross-links. Thus, two cut hydrogel strips could be readily rejoined by heating at 70 °C, and the resulting whole strip showed mechanical strength similar to that of the pristine sample before it was cut. This synthetic approach would give way to the modular design of MoS2-containing composite hydrogels.

Zero reduction luminescence of aqueous-phase alloy core/shell quantum dots via rapid ambient-condition ligand exchange.

Quantum dots (QDs) have been widely studied as promising materials for various applications because of their outstanding photoluminescence (PL). Although ligand exchange methods for QDs have been developed over two decades, the PL quantum yield (QY) of aqueous phase QDs is still lower than that of their organic phase and the mechanism of quenching has not been clearly understood. In this study, we demonstrate for the first time that 3-mercaptopropionic-capped CdZnSeS/ZnS core/shell QDs obtained via ligand exchange in a ternary solvent system containing chloroform/water/dimethyl sulfoxide can enable the fast phase transfer and zero reduction of PL under ambient condition. The new solvent system allows the ligand-exchanged QDs to exhibit enhanced QYs up to 8.1% of that of the organic-phase QDs. Based on both theoretical calculation and experiment, it was found that control over the physical/chemical perturbation between the organic/aqueous phases by choosing appropriate solvents for the ligand exchange process is very important to preserve the optical properties of QDs. We believe that our new technologies and theoretical knowledge offer opportunities for the future design and optimization of highly stable and highly luminescent aqueous-phase QDs for various applications.

Correction: Pine cone mold: a toolbox for fabricating unique metal/carbon nanohybrid electrocatalysts.

Correction for 'Pine cone mold: a toolbox for fabricating unique metal/carbon nanohybrid electrocatalysts' by Hyunwoo Han et al., Nanoscale, 2019, DOI: 10.1039/c9nr06794a.

Pine cone mold: a toolbox for fabricating unique metal/carbon nanohybrid electrocatalysts.

Nature presents delicate and complex materials systems beyond those fathomable by humans, and therefore, extensive effort has been made to utilize or mimic bio-materials and bio-systems in various fields. Biomass, an inexhaustible natural materials source, can also present good opportunities for the development of unprecedented, advanced materials and processing systems. Herein, we demonstrate the use of pine cones as a biomass mold for creating new and useful metal/carbon nanohybrids (MCNHs). The inherent water-induced folding actuation of the cone scales allows the casting of an aqueous solution of a single metal precursor or a binary metal mixture into the cone mold by simply immersing the cone in the solution. The cone actively absorbs aqueous-phase metal precursors through the bract scales and the precursor ions introduced into the cone are anchored to the functional groups of the interior tissues of the cone. Subsequent heat treatment successfully led to the formation of unique MCNHs. Iron, manganese, and cobalt were employed as model metals, binary mixtures of which were also cast into the cone mold to create further versatile MCNHs. Nanoparticulate metals were formed on the carbon supports, where the size, size distribution, and crystallinity of the nanoparticles were highly dependent on the identity of the single-component precursor and the combination of precursors. Consequently, the electrochemical activity of the MCNHs also depended on which metal precursors were cast into the cone mold. The MCNH prepared from the mixture of iron and manganese precursors (MFeMnCNH) showed the best electrochemical activity. As model applications, MFeMnCNH was applied to electrode materials for electrochemical charge storage and the oxygen evolution reaction. An electrochemical capacitor cell based on the MFeMnCNH electrodes showed excellent performance with energy densities of 38.7-54.2 W h kg-1 at power densities of 16 000-160 kW kg-1. In addition, MFeMnCNH demonstrated a low overpotential of 464 mV and fast kinetics with a Tafel slope of 64.6 mV dec-1 as an electrocatalyst for the oxygen evolution reaction in 1.0 M KOH. These results substantiate that pine cones as a biomass mold show great promise for creating versatile MCNHs through further combination of various precursors.