Resorcinol-formaldehyde semiconducting resins as precursors for carbon spheres toward electrocatalytic oxygen reduction.

The carbon spheres synthesized by pyrolysis of resorcinol-formaldehyde (RF) semiconducting resins exhibit enhanced activity for electrocatalytic oxygen reduction. The spheres consist of narrow reticulated carbon layers, which are derived from the donor-acceptor π-stacking interaction of the resins, and show high electron conductivity.

Nafion-Integrated Resorcinol-Formaldehyde Resin Photocatalysts for Solar Hydrogen Peroxide Production.

Photocatalytic generation of H2O2 from water and O2 is a promising strategy for liquid solar-fuel production. Previously reported powder photocatalysts promote a subsequent oxidative/reductive decomposition of the H2O2 generated, thereby producing low-H2O2-content solutions. This study reports that Nafion (Nf)-integrated resorcinol-formaldehyde (RF) semiconducting resin powders (RF@Nf), synthesized by polycondensation of resorcinol and formaldehyde with an Nf dispersion solution under high-temperature hydrothermal conditions, exhibit high photocatalytic activities and produce high-H2O2-content solutions. Nf acts as a surface stabilizer and suppresses the growth of RF resins. This generates small Nf-woven resin particles with large surface areas and efficiently catalyze water oxidation and O2 reduction. The Nf-woven resin surface, due to its hydrophobic nature, hinders the access of H2O2 and suppresses its subsequent decomposition. The simulated-sunlight irradiation of the resins in water under atmospheric pressure of O2 stably generates H2O2, producing high-H2O2-content solutions with more than 0.06 wt % H2O2 (16 mM).

Solar-Driven Generation of Hydrogen Peroxide on Phenol-Resorcinol-Formaldehyde Resin Photocatalysts.

Photocatalytic generation of H2O2 from water and O2 under sunlight is a promising artificial photosynthesis reaction to generate renewable fuel. We previously found that resorcinol-formaldehyde resin powders prepared with a high-temperature hydrothermal method become semiconductors comprising π-conjugated/π-stacked benzenoid-quinoid donor-acceptor resorcinol units and are active for photocatalytic H2O2 generation. Here, we have prepared phenol-resorcinol-formaldehyde resins with small amounts of phenol (∼5 mol % relative to resorcinol), which show enhanced photocatalytic activity. Incorporating phenol bearing a single -OH group in the resin matrices relaxes the restriction on the arrangement of the aromatic rings originating from the H-bonding interactions between the resorcinol -OH groups. This creates stronger donor-acceptor π-stacking and increases the electron conductivity of the resins. We have demonstrated that simulated sunlight illumination of the resins in water under an atmospheric pressure of O2 stably generated H2O2 with more than 0.9% solar-to-chemical conversion efficiency.

Preparation of Nanoscale Particles of Five Major Polymers as Potential Standards for the Study of Nanoplastics.

Nanoplastics are likely ubiquitous in the environment, and their potential toxic effects are a concern. However, quantitative information about the distribution of nanoplastics is still lacking, and toxicity tests are limited to a few select polymers because of the lack of appropriate standard materials, which should be nanoscale particles with standardizable morphologies, properties comparable to those of commercial polymers, and no impurities. Here, a precipitation-based method for preparing spherical nanoscale particles without the introduction of impurities is developed. The similarity of the molecular weight distributions, crystallinities, and thermal properties of five major polymers prepared using this method-low-density polyethylene, high-density polyethylene, polypropylene, polyvinyl chloride, and polystyrene-to those of commercial polymers indicate their potential for use as standard nanoplastic particles. This study provides a fundamental approach for the synthesis of standard nanoplastic particles that will facilitate quantification of the concentrations of nanoplastics in the environment and tests of their toxicity, which are required to assess the risks associated with exposure to them.

Polythiophene-Doped Resorcinol-Formaldehyde Resin Photocatalysts for Solar-to-Hydrogen Peroxide Energy Conversion.

The generation of hydrogen peroxide (H2O2) from water and dioxygen by sunlight-driven heterogeneous photocatalysis is a promising method for the artificial photosynthesis of a liquid solar fuel. We previously found that resorcinol-formaldehyde (RF) resin powders prepared by high-temperature hydrothermal synthesis act as highly active semiconductor photocatalysts for H2O2 generation. Herein, we report that RF resin powders doped with poly(3-hexylthiophene-2,5-diyl) (RF/P3HT) exhibit enhanced photocatalytic activities. The highly dispersed P3HT within the resin particles created charge transfer complexes with the conduction band of the resin via electron donation, facilitating efficient transfer of the photogenerated conduction band electrons through P3HT. This enhanced charge separation promoted efficient water oxidation and O2 reduction. The solar-to-chemical conversion efficiency for H2O2 generation on the RF/P3HT resin in water under simulated sunlight irradiation with atmospheric pressure of O2 was ∼1.0%, which is the highest efficiency reported for powder catalysts in artificial photosynthesis.

Photocatalytic Dinitrogen Reduction with Water on Boron-Doped Carbon Nitride Loaded with Nickel Phosphide Particles.

Photocatalytic N2 reduction with water by sunlight irradiation is a challenging issue toward sustainable energy society, but previously reported photocatalysts had suffered from low stability and low activity. We prepared a boron-doped carbon nitride (BCN) semiconductor powder loaded with nickel phosphide particles (Ni2P) as cocatalysts. The Ni2P/BCN catalyst, when photoirradiated in pure water by simulated sunlight under N2 flow, successfully produces NH3 at room temperature. The B doping leads to a positive shift of the valence band level and enhances water oxidation by the photoformed holes. The Ni2P particles efficiently receive the conduction band electrons of BCN, leading to enhanced charge separation of the photoformed hole and electron pairs, and behave as N2 reduction sites. Simulated sunlight irradiation of the catalyst in water stably generates NH3 with 0.010% solar-to-chemical conversion efficiency. This noble-metal-free system therefore shows a significant potential for N2 photofixation.

Solar-to-hydrogen peroxide energy conversion on resorcinol-formaldehyde resin photocatalysts prepared by acid-catalysed polycondensation.

The photocatalytic generation of hydrogen peroxide from water and dioxygen (H2O + 1/2O2 → H2O2, ΔG° = +117 kJ mol-1) under sunlight is a promising strategy for the artificial photosynthesis of a liquid fuel. We had previously found that resorcinol-formaldehyde (RF) resin powders prepared by the base-catalysed high-temperature hydrothermal method act as semiconductor photocatalysts for H2O2 generation. Herein, we report that RF resins prepared by the acid-catalysed high-temperature hydrothermal method (~523 K) using common acids at pH < 4 exhibit enhanced photocatalytic activity. The base- and acid-catalysed methods both produce methylene- and methine-bridged resins consisting of π-conjugated and π-stacked benzenoid-quinoid donor-acceptor resorcinol units. The acidic conditions result in the resins with a lower bandgap (1.7 eV) and higher conductivity because the lower-degree of crosslinking creates a strongly π-stacked architecture. The irradiation of the RF-acid resins with simulated sunlight in water with atmospheric-pressure O2 generates H2O2 at a solar-to-chemical conversion efficiency of 0.7%, which is the highest efficiency ever reported for powder catalysts used in artificial photosynthesis.

Resorcinol-formaldehyde resins as metal-free semiconductor photocatalysts for solar-to-hydrogen peroxide energy conversion.

Artificial photosynthesis is a critical challenge in moving towards a sustainable energy future. Photocatalytic generation of hydrogen peroxide from water and dioxygen (H2O + [Formula: see text]O2 → H2O2, ΔG° = 117 kJ mol-1) by sunlight is a promising strategy for artificial photosynthesis because H2O2 is a storable and transportable fuel that can be used directly for electricity generation. All previously reported powder photocatalysts, however, have suffered from low efficiency in H2O2 generation. Here we report that resorcinol-formaldehyde resins, widely used inexpensive polymers, act as efficient semiconductor photocatalysts to provide a new basis for H2O2 generation. Simple high-temperature hydrothermal synthesis (~523 K) produces low-bandgap resorcinol-formaldehyde resins comprising π-conjugated and π-stacked benzenoid-quinoid donor-acceptor resorcinol couples. The resins absorb broad-wavelength light up to 700 nm and catalyse water oxidation and O2 reduction by the photogenerated charges. Simulated sunlight irradiation of the resins stably generates H2O2 with more than 0.5% solar-to-chemical conversion efficiency. Therefore, this metal-free system shows significant potential as a new artificial photosynthesis system.

Room temperature carbon monoxide oxidation based on two-dimensional gold-loaded mesoporous iron oxide nanoflakes.

In this work, we fabricate a highly effective catalyst for carbon monoxide oxidation based on gold-loaded mesoporous maghemite nanoflakes which exhibit nearly 100% CO conversion and a very high specific activity of 8.41 molCO gAu-1 h-1 at room temperature. Such excellent catalytic activity is promoted by the synergistic cooperation of their high surface area, large pore volume, and mesoporous structure.

Gold nanoparticles supported on mesoporous iron oxide for enhanced CO oxidation reaction.

Herein, we report the synthesis of gold (Au)-loaded mesoporous iron oxide (Fe2O3) as a catalyst for both CO and NH3 oxidation. The mesoporous Fe2O3 is firstly prepared using polymeric micelles made of an asymmetric triblock copolymer poly(styrene-b-acrylic acid-b-ethylene glycol) (PS-b-PAA-b-PEG). Owing to its unique porous structure and large surface area (87.0 m2 g-1), the as-prepared mesoporous Fe2O3 can be loaded with a considerably higher amount of Au nanoparticles (Au NPs) (7.9 wt%) compared to the commercial Fe2O3 powder (0.8 wt%). Following the Au loading, the mesoporous Fe2O3 structure is still well-retained and Au NPs with varying sizes of 3-10 nm are dispersed throughout the mesoporous support. When evaluated for CO oxidation, the Au-loaded mesoporous Fe2O3 catalyst shows up to 20% higher CO conversion efficiency compared to the commercial Au/Fe2O3 catalyst, especially at lower temperatures (25-150 °C), suggesting the promising potential of this catalyst for low-temperature CO oxidation. Furthermore, the Au-loaded mesoporous Fe2O3 catalyst also displays a higher catalytic activity for NH3 oxidation with a respectable conversion efficiency of 37.4% compared to the commercial Au/Fe2O3 catalyst (15.6%) at 200 °C. The significant enhancement in the catalytic performance of the Au-loaded mesoporous Fe2O3 catalyst for both CO and NH3 oxidation may be attributed to the improved dispersion of the Au NPs and enhanced diffusivity of the reactant molecules due to the presence of mesopores and a higher oxygen activation rate contributed by the increased number of active sites, respectively.

Mesoporous Iron Oxide Synthesized Using Poly(styrene-b-acrylic acid-b-ethylene glycol) Block Copolymer Micelles as Templates for Colorimetric and Electrochemical Detection of Glucose.

Herein, we report the soft-templated preparation of mesoporous iron oxide using an asymmetric poly(styrene-b-acrylic acid-b-ethylene glycol) (PS-b-PAA-b-PEG) triblock copolymer. This polymer forms a micelle consisting of a PS core, a PAA shell, and a PEG corona in aqueous solutions, which can serve as a soft template. The mesoporous iron oxide obtained at an optimized calcination temperature of 400 °C exhibited an average pore diameter of 39 nm, with large specific surface area and pore volume of 86.9 m2 g-1 and 0.218 cm3 g-1, respectively. The as-prepared mesoporous iron oxide materials showed intrinsic peroxidase-like activities toward the catalytic oxidation of 3,3',5,5'-tertamethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). This mimetic feature was further exploited to develop a simple colorimetric (naked-eye) and electrochemical assay for the detection of glucose. Both our colorimetric (naked-eye and UV-vis) and electrochemical assays estimated the glucose concentration to be in the linear range from 1.0 µM to 100 µM with a detection limit of 1.0 µM. We envisage that our integrated detection platform for H2O2 and glucose will find a wide range of applications in developing various biosensors in the field of personalized medicine, food-safety detection, environmental-pollution control, and agro-biotechnology.

Porous nanozymes: the peroxidase-mimetic activity of mesoporous iron oxide for the colorimetric and electrochemical detection of global DNA methylation.

Nanomaterials (nanozymes) with peroxidase-mimetic activity have been widely used in biosensing platforms as low-cost, relatively stable and prevailing alternatives to natural enzymes. Herein, we report on the synthesis and application of the peroxidase-mimetic activity of mesoporous iron oxide (MIO) for the detection of global DNA methylation in colorectal cancer cell lines. The target DNA was extracted and denatured to get ssDNA followed by direct adsorption onto the surface of a bare screen-printed gold electrode (SPGE). A 5-methylcytosine antibody (5mC) functionalized nanomaterial (MIO-5mC) was then used to recognise the methylcytosine groups present on the SPGE. The MIO-5mC conjugates catalyse the TMB solution in the presence of hydrogen peroxide to give the colorimetric (i.e., naked-eye observation) and electrochemical detection of DNA methylation. The assay could successfully detect as low as 10% difference in the global DNA methylation level in synthetic samples and cell lines with good reproducibility and specificity (%RSD = <5%, for n = 3). This strategy avoids the use of natural enzyme horseradish peroxidase (HRP), traditional PCR based amplification and bisulfite treatment steps that are generally used in many conventional DNA methylation assays. We envisage that our assay could be a low-cost platform with great potential for genome-wide DNA methylation analysis in point-of-care applications.

Correction: Gold-loaded nanoporous iron oxide nanocubes: a novel dispersible capture agent for tumor-associated autoantibody analysis in serum.

Correction for 'Gold-loaded nanoporous iron oxide nanocubes: a novel dispersible capture agent for tumor-associated autoantibody analysis in serum' by Sharda Yadav et al., Nanoscale, 2017, 9, 8805-8814.

Gold-loaded nanoporous superparamagnetic nanocubes for catalytic signal amplification in detecting miRNA.

This paper reports the development of a nonenzymatic, amplification-free, and sensitive platform for the detection of microRNA based on a new class of electrocatalytically active superparamagnetic gold-loaded nanoporous iron oxide nanocubes (Au@NPFe2O3NC). The assay showed an excellent detection sensitivity down to 100 fM and specificity towards the analysis of miR-21 in cell lines and tissue samples derived from patients with oesophageal squamous-cell carcinoma (ESCC).

Gold-loaded nanoporous iron oxide nanocubes: a novel dispersible capture agent for tumor-associated autoantibody analysis in serum.

Autoantibodies are produced against tumor associated antigens (TAAs) long before the appearance of any symptoms and thus can serve as promising, non-invasive biomarkers for early diagnosis of cancer. Current conventional methods for autoantibody detection are highly invasive and mostly provide diagnosis in the later stages of cancer. Herein we report a new electrochemical method for early detection of p53 autoantibodies against colon cancer using a strategy that combines the strength of gold-loaded nanoporous iron oxide nanocube (Au@NPFe2O3NC)-based capture and purification while incorporating the inherent simplicity, inexpensive, and portable nature of the electrochemical and naked-eye colorimetric readouts. After the functionalisation of Au@NPFe2O3NC with p53 antigens, our method utilises a two-step strategy that involves (i) magnetic capture and isolation of autoantibodies using p53/Au@NPFe2O3NC as 'dispersible nanocapture agents' in serum samples and (ii) subsequent detection of autoantibodies through a peroxidase-catalyzed reaction on a commercially available disposable screen-printed electrode or naked-eye detection in an Eppendorf tube. This method has demonstrated a good sensitivity (LOD = 0.02 U mL-1) and reproducibility (relative standard deviation, %RSD = <5%, for n = 3) for detecting p53 autoantibodies in serum and has also been successfully applied to analyse a small cohort of clinical samples obtained from colorectal cancer. We believe that the highly inexpensive, rapid, sensitive, and specific nature of our assay could potentially aid in the development of an early diagnostic tool for cancer and related diseases.

How a replication origin and matrix attachment region accelerate gene amplification under replication stress in mammalian cells.

The gene amplification plays a critical role in the malignant transformation of mammalian cells. The most widespread method for amplifying a target gene in cell culture is the use of methotrexate (Mtx) treatment to amplify dihydrofolate reductase (Dhfr). Whereas, we found that a plasmid bearing both a mammalian origin of replication (initiation region; IR) and a matrix attachment region (MAR) was spontaneously amplified in mammalian cells. In this study, we attempted to uncover the underlying mechanism by which the IR/MAR sequence might accelerate Mtx induced Dhfr amplification. The plasmid containing the IR/MAR was extrachromosomally amplified, and then integrated at multiple chromosomal locations within individual cells, increasing the likelihood that the plasmid might be inserted into a chromosomal environment that permits high expression and further amplification. Efficient amplification of this plasmid alleviated the genotoxicity of Mtx. Clone-based cytogenetic and sequence analysis revealed that the plasmid was amplified in a chromosomal context by breakage-fusion-bridge cycles operating either at the plasmid repeat or at the flanking fragile site activated by Mtx. This mechanism explains how a circular molecule bearing IR/MAR sequences of chromosomal origin might be amplified under replication stress, and also provides insight into gene amplification in human cancer.

microRNA changes in the dorsal horn of the spinal cord of rats with chronic constriction injury: A TaqMan® Low Density Array study.

Elucidation of the mechanisms underlying neuropathic pain is expected to aid in the discovery and selection of effective therapeutic methods. Currently, microRNA (miRNA) is thought to play an important role in the development and maintenance of the nervous system. We, therefore, hypothesized that miRNAs are involved in neuropathic pain, and investigated this possibility by analyzing miRNA expression in the dorsal horn of the spinal cord in a chronic constriction injury (CCI) rat model using the TaqMan® Low Density Array (TLDA). Neuropathic pain model rats were produced by CCI induced by ligation of the sciatic nerve. The miRNA expression in the dorsal horn of the spinal cord was analyzed in Day 0 rats, with no sciatic nerve ligation or sham operation, Day 7 rats, examined 7 days after sciatic nerve ligation or sham operation, and Day 14 rats, examined 14 days after sciatic nerve ligation or sham operation using TLDA. In this study, 111 miRNAs were significantly regulated in CCI rats in both the Day 7 and Day 14 groups compared with sham rats in both groups. Of these 111, there were 75 miRNAs (67.6%) that had been analyzed in previous reports and 36 miRNAs (32.4%) related to the development of tumors of the nervous system and neurodegenerative diseases. Certain miRNAs were reported to be related to neuropathic pain; miR-500, -221 and -21. The expression levels of a large number of miRNAs in the dorsal horn of the spinal cord in CCI rats changed. These results provide a step toward elucidation of the mechanisms underlying neuropathic pain.

Adsorption of carbon dioxide and nitrogen on zeolite rho prepared by hydrothermal synthesis using 18-crown-6 ether.

Zeolite rho was prepared by hydrothermal synthesis using an 18-crown-6 ether (18C6) as a structure-directing agent, and the effects of the calcination temperature for removal of 18C6 on the physicochemical properties and CO(2)-adsorption properties were investigated. CO(2) adsorption on zeolite rho calcined at 150°C was lower than that on samples calcined at temperatures above 300°C. For samples calcined above 300°C, CO(2) adsorption increased with increasing calcination temperature up to 400°C. It is thought that the pore volume for adsorption of CO(2) increased as a result of 18C6 removal, resulting in increasing CO(2) adsorption. A decrease in CO(2) adsorption for calcination from 400°C to 500°C was observed. The particle size of zeolite rho increased with increasing 18C6 molar ratio. Particle sizes of 1.0-2.1 µm and 1.4-2.6 µm were found by field-emission scanning electron microscopy and dynamic light-scattering, respectively. The particle size is controlled in these regions by adjusting the 18C6 molar ratio. XRD showed that zeolite rho samples with 18C6 molar ratios of 0.25-1.5 had high crystallinity. The adsorbed amount of CO(2) is almost constant, at 3.4 mmol-CO(2)g(-1), regardless of the 18C6 molar ratio. However, CO(2) selectivity, which is the CO(2)/N(2) adsorption ratio, decreased. The amount of CO(2) adsorbed on zeolite rho is lower than that on zeolite NaX, but higher than that on SAPO-34. The CO(2)/N(2) adsorption ratio for zeolite rho was higher than those for SAPO-34 and zeolite NaX.

Crystallization process of zeolite rho prepared by hydrothermal synthesis using 18-crown-6 ether as organic template.

There are many viewpoints on the formation mechanisms for zeolites, but the details are not clear. An understanding of the elementary steps for their formation is important for the development of large-scale membranes and efficient manufacturing processes. In this study, the effects of silicon, aluminum, and the incorporation of 18-crown-6 (18C6) ether, on the formation of zeolite rho, using 18C6 as the structure directing agent (SDA) have been investigated by using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray fluorescence spectrometry (EDX), nuclear magnetic resonance spectroscopy (NMR), thermo gravimetric analysis (TGA), and the pH measurement. These results suggested that a zeolite rho has four synthesis steps; (1) 0-3 h, the dehydration and condensation reaction between the silica and alumina to form amorphous aluminosilicates; (2) 3-20 h, the particle growth and aggregation process for the amorphous aluminosilicates; (3) 20-48 h, the crystallization and crystal growth of zeolite rho, with the incorporation of 18C6; and (4) 48-96 h, gentle growth with an increase in Na/Si ratio and a change in rate for the bounding state between the silica- and the alumina-based species. We consider the above to reflect the four steps for the formation of zeolite rho.

Distribution of oil-degrading bacteria in coastal seawater, Toyama Bay, Japan.

Oil-degrading bacteria are considered to play an important role in the biodegradation of spilled or released oil in the sea. The distribution of indigenous oil-degrading bacteria in the coastal seawater of Toyama Bay, Japan, was examined. Surface seawater samples with or without oil film in fishing port were analyzed by denaturing gradient gel electrophoresis (DGGE) of the PCR-amplified V3 region of bacterial 16S rDNA. Sequence analysis revealed that several DGGE bands clearly detected only in samples with oil film corresponded to Cyanobacteria. Moreover, we cultured surface seawater samples with oil film in two different liquid culture media, a marine broth and an NSW medium; each culture contained 0.5% (w/v) C-heavy oil. Emulsification of the oil was observed at day 6 in the marine broth and day 9 in the NSW medium. Time-dependent changes of bacterial communities in those culture media were analyzed by DGGE. Interestingly, we found that Alcanivorax sp. became one of the dominant bacteria in each culture medium when emulsification of the oil began. Alcanivorax sp. is one of the well-known oil-degrading bacteria in seawater and is associated with the production of biosurfactants. These results suggest that Cyanobacteria and Alcanivorax play important roles in the bioremediation of oil-contaminated areas in Toyama Bay.