Development and Optimization of Water-Soluble Double-Walled Carbon Nanotubes by Effective Surface Treatment of Inner Walls.

Carbon nanotubes are a significant class of nanomaterials with distinctive properties that have led to their application in a variety of fields, such as polymer composites, medicine, electronics, and material science. However, their nonpolar nature and insolubility in polar solvents limit their applications. To address this issue, highly functionalized and water-soluble double-walled carbon nanotubes (DWNTs) were developed by selectively oxidizing the inner walls of the DWNTs using oleum and nitric acid. The impact of reaction time on the chemical functionalization of DWNTs was investigated under two different reaction durations of 2 and 24 h. The presence of highly oxygenated functional groups resulted in high water solubility, which was confirmed by high- and low-frequency Raman spectroscopy, high-resolution transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) method, and optical spectroscopy. The conductivity of highly water-soluble W-DWNTs (24 h) was 122.65 × 102 S cm-1. After annealing for 12 h at 140 °C, the W-DWNTs retained 72% of their conductivity (88.79 × 102 S cm-1).

Boron-Doped Activated Carbon Supports for Cobalt-Catalyzed Oxygen Evolution in Alkaline Electrolyte.

Activated carbons (ACs) are the most widely used and attractive support materials for electrocatalytic applications because of their significant surface areas, high electrical conductivities, and moderate affinities toward supported metal catalysts. However, the corrosive behavior of ACs at oxidative potentials causes an inevitable reduction in the active surface area of supported catalysts, resulting in the continuous deterioration of their electrocatalytic performance. Therefore, the introduction of corrosion-resistant durable catalyst supports is essential for sustainable and efficient electrocatalysis. Here, we modified ACs to obtain different boron (B)-doped structures via doping-temperature controls to investigate the corrosion resistance of B-doped ACs. With increasing doping temperature, the B-doped ACs exhibited a decreased defect density and enhanced crystallinity owing to the accelerating dopant-induced graphitization. We found that the substitution of B atoms into the carbon lattice improved the structural integrity of the carbon structure, and cyclic voltammetry (CV) tests suggested that the highly B-substituted structures caused electrochemical surface passivation against carbon corrosion. Moreover, B-doped ACs significantly contributed to the increase in loading mass of cobalt (Co)-based catalyst on them and the electrochemical durability toward the oxygen evolution reaction as catalyst-support hybrid. The B22 (B-doped AC obtained at a 2200 °C B-doping temperature)-supported Co catalyst with the lowest oxidation current exhibited a voltage change of 32 mV at a current density of 10 mA/cm2 (ΔEj=10) after 10,000 cycles, which was a factor of ∼7 higher cycle durability and stability than that of the conventional IrO2 catalyst (ΔEj=10 = 205 mV). Here, we propose that surface engineering by B-doping to improve the structural integrity of ACs is an attractive method for designing durable electrocatalytic support materials.

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.

Microgels based on 0D-3D carbon materials: Synthetic techniques, properties, applications, and challenges.

Microgels are three-dimensional (3D) colloidal hydrogel particles with outstanding features such as biocompatibility, good mechanical properties, tunable sizes from submicrometer to tens of nanometers, and large surface areas. Because of these unique qualities, microgels have been widely used in various applications. Carbon-based materials (CMs) with various dimensions (0-3D) have recently been investigated as promising candidates for the design and fabrication of microgels because of their large surface area, excellent conductivity, unique chemical stability, and low cost. Here, we provide a critical review of the specific characteristics of CMs that are being incorporated into microgels, as well as the state-of-the art applications of CM-microgels in pollutant adsorption and photodegradation, H2 evoluation, CO2 capture, soil conditioners, water retention, drug delivery, cell encapsulation, and tissue engineering. Advanced preparation techniques for CM-microgel systems are also summarized and discussed. Finally, challenges related to the low colloidal stability of CM-microgels and development strategies are examined. This review shows that CM-microgels have the potential to be widely used in various practical applications.

Erratum: Anharmonicity and Universal Response of Linear Carbon Chain Mechanical Properties under Hydrostatic Pressure [Phys. Rev. Lett. 125, 105501 (2020)].

This corrects the article DOI: 10.1103/PhysRevLett.125.105501.

Erratum: Anharmonicity and Universal Response of Linear Carbon Chain Mechanical Properties under Hydrostatic Pressure [Phys. Rev. Lett. 125, 105501 (2020)].

This corrects the article DOI: 10.1103/PhysRevLett.125.105501.

Boron-Doped Edges as Active Sites for Water Adsorption in Activated Carbons.

Investigating the surface properties of heteroatom-doped carbon materials is essential because these versatile materials have found use in a variety of energy and environmental applications; an understanding of these properties would also lead to an improved appreciation of the direct interaction between the reactant and the functionalized surface. Herein, we explore the effect of boron (B) doping on the surface properties of activated carbon (AC) materials based on their water adsorption behavior and oxygen reduction reaction. In the high-temperature B doping process, B-doped AC materials at 1400 °C exhibit an open pore structure with B-O bonds, whereas at a temperature of 1600 °C, a nonporous structure containing a large amount of B-C bonds prevails. The B-O species act as active sites for water adsorption on the carbon surface. On the basis of the isothermal adsorption heat, we suggest that B atoms are present at the pore openings and on the surfaces. The B-O moieties at the open edges improve the electrocatalytic activity, whereas the B-C bonds at the closed edges decrease the electrocatalytic activity because of the stable structure of these bonds. Our findings provide new evidence for the electrocatalytic properties associated with the structure of B-doped edges.

Hierarchical Design of Functional, Fibrous, and Microporous Polymer Monoliths for the Molecular Recognition of Diethylstilbestrol.

This paper demonstrates the hierarchical design of functional, fibrous polymer monoliths. The monoliths are composed of conjugated microporous polymers that not only are embedded with heteroatoms but also feature fibrous yet compressible structures due to the in situ self-assembly process that occurs during the polymerization process. Therefore, the doped nitrogen atoms can allow the growth of zeolitic imidazolate framework (ZIF) nanocrystals, which causes the homogeneous encapsulation of individual fibers. The resulting hybrid monoliths exhibit enhanced physical properties as well as catalytic activity, allowing the formation of an additional coating layer via a thiol-epoxy reaction. The deliberate inclusion of template molecules during the reaction forms molecularly imprinted sites on the fibers to afford functional monoliths. As a proof of concept, the hierarchically designed materials are able to show effective recognition properties toward diethylstilbestrol, an endocrine disruptor, taking advantage of the binding sites that selectively capture the analyte molecules and the fibrous morphology that increases the accessibility of these binding sites. We envisage that the incorporation of various heteroatoms or nanocrystals will bring about the bespoke design of advanced monoliths with autonomous functions, leading to smart textile systems.

Thermodynamics of Linear Carbon Chains.

Linear carbon chains (LCCs) are one-dimensional materials with unique properties, including high Debye temperatures and restricted selection rules for phonon interactions. Consequently, their Raman C-band frequency's temperature dependence is a probe to their thermal properties, which are well described within the Debye formalism even at room temperatures. Therefore, with the basis on a semiempirical approach we show how to use the C band to evaluate the LCCs' internal energy, heat capacity, coefficient of thermal expansion, thermal strain, and Grüneisen parameter, providing universal relations for these quantities in terms of the number of carbons atoms and the temperature.

Vertically and Horizontally Drawing Formation of Graphite Pencil Electrodes on Paper by Frictional Sliding for a Disposable and Foldable Electronic Device.

The objective of this study is to fabricate an electrode by frictional sliding caused by a rough paper surface. The pressure exerted during drawing induces adsorption of the graphite particles by the rough paper and simultaneously reduces the surface roughness of the paper electrode. Repetitive drawing in one-way direction reduced the roughness of the paper surface, decreasing the grain boundaries of graphite. This increases the electron pathway at the electrode, thus reducing the resistance to less than 50 Ω. At the same time, repetitive drawing could confirm that unstable errors caused by the hand could help converge within a certain margin of error. We quantified the relationship between pressure and resistance when drawing on the electrode using a pencil hardness tester. In addition, the electrodes formed by repeated drawing generated a new surface grain and boundary, parallel to the drawing direction, and changed the electrode characteristics with respect to the drawing direction. The grain boundary difference based on the drawing direction was measured via a heating test of the foldable device, a sound pressure level, and laser scattering vibrometer measurements of a linear speaker. The fabricated graphite electrodes can be used in disposable foldable paper electronics because they are prepared using inexpensive materials.

Carbon Nanomaterials as Versatile Platforms for Biosensing Applications.

A biosensor is defined as a measuring system that includes a biological receptor unit with distinctive specificities toward target analytes. Such analytes include a wide range of biological origins such as DNAs of bacteria or viruses, or proteins generated from an immune system of infected or contaminated living organisms. They further include simple molecules such as glucose, ions, and vitamins. One of the major challenges in biosensor development is achieving efficient signal capture of biological recognition-transduction events. Carbon nanomaterials (CNs) are promising candidates to improve the sensitivity of biosensors while attaining low detection limits owing to their capability of immobilizing large quantities of bioreceptor units at a reduced volume, and they can also act as a transduction element. In addition, CNs can be adapted to functionalization and conjugation with organic compounds or metallic nanoparticles; the creation of surface functional groups offers new properties (e.g., physical, chemical, mechanical, electrical, and optical properties) to the nanomaterials. Because of these intriguing features, CNs have been extensively employed in biosensor applications. In particular, carbon nanotubes (CNTs), nanodiamonds, graphene, and fullerenes serve as scaffolds for the immobilization of biomolecules at their surface and are also used as transducers for the conversion of signals associated with the recognition of biological analytes. Herein, we provide a comprehensive review on the synthesis of CNs and their potential application to biosensors. In addition, we discuss the efforts to improve the mechanical and electrical properties of biosensors by combining different CNs.

Anharmonicity and Universal Response of Linear Carbon Chain Mechanical Properties under Hydrostatic Pressure.

Isolated linear carbon chains (LCCs) encapsulated by multiwalled carbon nanotubes are studied under hydrostatic pressure (P) via resonance Raman scattering. The LCCs' spectroscopic signature C band around 1850 cm^{-1} softens linearly with increasing P. A simple anharmonic force-constant model not only describes such softening but also shows that the LCCs' Young's modulus (E), Grüneisen parameter (γ), and strain (ϵ) follow universal P^{-1} and P^{2} laws, respectively. In particular, γ also presents a unified behavior for all LCCs. To the best of our knowledge, these are the first results reported on such isolated systems and the first work to explore universal P-dependent responses for LCCs' E, ϵ, and γ.

Influenza-Host Interplay and Strategies for Universal Vaccine Development.

Influenza is an annual epidemic and an occasional pandemic caused by pathogens that are responsible for infectious respiratory disease. Humans are highly susceptible to the infection mediated by influenza A viruses (IAV). The entry of the virus is mediated by the influenza virus hemagglutinin (HA) glycoprotein that binds to the cellular sialic acid receptors and facilitates the fusion of the viral membrane with the endosomal membrane. During IAV infection, virus-derived pathogen-associated molecular patterns (PAMPs) are recognized by host intracellular specific sensors including toll-like receptors (TLRs), C-type lectin receptors, retinoic acid-inducible gene-I (RIG-I)-like receptors (RLRs), and nucleotide-binding oligomerization domain (NOD)-like receptors (NLRs) either on the cell surface or intracellularly in endosomes. Herein, we comprehensively review the current knowledge available on the entry of the influenza virus into host cells and the molecular details of the influenza virus-host interface. We also highlight certain strategies for the development of universal influenza vaccines.

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.

Quantifying Carbon Edge Sites on Depressing Hydrogen Evolution Reaction Activity.

To understand the effect of microstructural characteristics of carbon materials on their electrochemical or electrocatalytic performance, an in-depth study of the edges in carbon materials should be carried out. In this study, catalytically grown platelet-type carbon nanofibers (CNFs) with fully exposed edges were physically and chemically passivated to clarify the relationship between the edge density and the hydrogen evolution reaction (HER) activity. Due to the aligned structure along the fiber axis, the edges on the outer surface of the CNFs were easily modified without using a complex process. The edges on the surface of the CNFs were inactivated by sequentially forming single, double, and multiple loops as the heat treatment temperatures increased. The number of edges within the CNFs was quantitatively measured using temperature-programmed desorption (TPD) up to 1800 °C. The surviving edges on the surface of thermally treated CNFs were identified by chemical functionalization via an amination reaction. We identified a close relationship between the HER activity and the edge density. When evaluating the electrochemical and electrocatalytic activity of carbon materials, it is important to know the portion of the edge surface area with respect to the total surface area and edge ratio.

The Use of Electrospun Organic and Carbon Nanofibers in Bone Regeneration.

There has been an increasing amount of research on regenerative medicine for the treatment of bone defects. Scaffolds are needed for the formation of new bone, and various scaffolding materials have been evaluated for bone regeneration. Materials with pores that allow cells to differentiate into osteocytes are preferred in scaffolds for bone regeneration, and porous materials and fibers are well suited for this application. Electrospinning is an effective method for producing a nanosized fiber by applying a high voltage to the needle tip containing a polymer solution. The use of electrospun nanofibers is being studied in the medical field, and its use as a scaffold for bone regeneration therapy has become a topic of growing interest. In this review, we will introduce the potential use of electrospun nanofiber as a scaffold for bone regenerative medicine with a focus on carbon nanofibers produced by the electrospinning method.

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.

Carbon fibers for treatment of cancer metastasis in bone.

When cancer metastasizes to bone, the resulting pain and functional disorders due to bone destruction adversely affect the patient's quality of life. We have developed a new cancer metastasis control system consisting of anticancer agents conjugated to carbon fibers (CFs), which are nonbiodegradable, carriers of a wide variety of molecules with extremely high affinity for bone. In the evaluation of cancer suppression effects on Walker 256 cancer cells, cisplatin (CDDP)-conjugated CFs (CF-CDDP) were found to be as effective in cancer suppression as CDDP. In the evaluation of the cancer suppression effects of local injection in the rat model of tibial cancer bone metastasis, similar cancer suppression was noted in the CF-CDDP group and CDDP group; however, blood Pt concentrations were significantly lower in the CF-CDDP group. Experiments with CDDP and CF-CDDP injected into bone actually destroyed by cancer metastases revealed the presence of significantly more newly formed bone tissue with the administration of CF-CDDP. Local administration of CF-CDDP is expected to become the first therapy to suppress cancer growth with low prevalence of adverse reactions, and to repair bone damaged by metastasis.

Polymer wrapping-induced dispersion of single walled carbon nanotubes in ethylene glycol under mild sonication.

SWCNTs were individually dispersed in ethylne glycol (EG) via mild bath-type sonication using quaternized poly(furfuryl methacrylate)-co-(2-(dimethylamino)ethyl methacrylate) p(FMA-co-QDMAEMA) as a dispersing agent. QDMAEMA, which has alkyl groups, was more favorable to the dispersion ability of single walled carbon nanotubes (SWCNTs). The dispersion mechanism of SWCNTs in EG via helical wrapping of polymer chains along their sidewalls was suggested based on transmission electron microscopic observation.