Macrosphelides from Antarctic fungus Pseudogymnoascus sp. (strain SF-7351) and their neuroprotective effects on BV2 and HT22 cells.

Strategies for reducing inflammation in neurodegenerative diseases have attracted increasing attention. Herein, we discovered and evaluated the neuroprotective potential of fungal metabolites isolated from the Antarctic fungus Pseudogymnoascus sp. (strain SF-7351). The chemical investigation of the EtOAc extract of the fungal strain isolate revealed a novel naturally occurring epi-macrosphelide J (1), a novel secondary metabolite macrosphelide N (2), and three known compounds, namely macrosphelide A (3), macrosphelide B (4), and macrosphelide J (5). Their structures were established unambiguously using spectroscopic methods, such as one-dimensional and two-dimensional nuclear magnetic resonance (1D and 2D-NMR) spectroscopy, high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), and gauge-including atomic orbital (GIAO) NMR chemical shift calculations, with the support of the advanced statistical method DP4+. Among the isolated metabolites, the absolute configuration of epi-macrosphelide J (1) was further confirmed using single-crystal X-ray diffraction analysis. The neuroprotective effects of the isolated metabolites were evaluated in lipopolysaccharide (LPS)-induced BV2 and glutamate-stimulated HT22 cells. Only macrosphelide B (4) displayed substantial protective effects in both BV2 and HT22 cells. Molecular mechanisms underlying this activity were investigated using western blotting and molecular docking studies. Macrosphelide B (4) inhibited the inflammatory response by reducing the nuclear translocation of NF-κB (p65) in LPS-induced BV2 cells and induced the Nrf2/HO-1 signaling pathway in both BV2 and HT22 cells. The neuroprotective effect of macrosphelide B (4) is related to the interaction between Keap1 and p65. These results suggest that macrosphelide B (4), present in the fungus Pseudogymnoascus sp. (strain SF-7351), may serve as a candidate for the treatment of neurodegenerative diseases.

Magnetic Iron Oxide Nanoneedles with Hierarchical Structure for Controllable Catalytic Activity of 4-Nitrophenol Reduction.

Catalyst systems with high catalytic activity and sustainability are highly desirable. Here, we report a design for catalytic composites with a hierarchical structure in which polydopamine (PD), multi-metallic nanocatalysts and iron oxide nanoneedles are successively deposited on a magnetic core. PD layers with various thicknesses are coated onto the magnetic core and serve as a template by which to take up multi-metallic nanocatalysts such as Au, Ag and Pt nanoparticles. The iron oxide nanoneedles act as spacers, preventing the nanocomposite from aggregating and increasing the surface area of the composite. The distinctive structures of the controllable template, the multi-metallic catalysts and needle-like layers enable the rapid migration of reactive ionic species and enhance catalytic ability via the synergistic effect of the multi-metallic nanocatalysts and iron oxide nanoneedles. Moreover, due to the strong magnetic property of the catalytic nanocomposites, they can be easily recovered with an external magnet and reused. Our hierarchical nanocomposites for recyclable nanocatalysts provide a new design concept for highly efficient catalysts.

Clinical and Prognostic Values of TRPM7 in Colon and Rectal Cancers.

Background and Objectives: Transient receptor potential melastatin 7 (TRPM7) is a unique channel protein, and functionally responsible for transportation of calcium and magnesium. Physiologically, the TRPM7 channel is involved in homeostasis of calcium and magnesium, and cell survival. TRPM7 expression is up-regulated in many cancers as malignant behaviors of cancer cells, and its deficiency suppresses their growth. Materials and Methods: In this study, we aimed to analyze clinical and prognostic characteristics of TRPM7 expression in colorectal cancers (CRC) using The Cancer Genome Atlas. Results: High expression of TRPM7 was observed in younger patients with rectal cancer (p = 0.0002). By quantitative correlation analysis, TRPM7 was negatively correlated with age (R = −0.239, p = 0.003) and p53 (R = −0.240, p = 0.002). Furthermore, it was positively correlated with APC expression (R = 0.534, p < 0.001) and KRAS expression (R = 0.319, p < 0.001). In colon cancer, there were no variables that showed a significant correlation with TRPM7. Survival analysis found that TRPM7 expression did not have any prognostic value in colon and rectal cancers. Conclusions: Our study highlights that TRPM7 expression in CRC, particularly in rectal cancer, may be a potential marker. Future studies are needed to provide deeper insights into the role of TRPM7 in rectal cancer.

Nanostructured Materials for Water Purification: Adsorption of Heavy Metal Ions and Organic Dyes.

Chemical water pollution poses a threat to human beings and ecological systems. The purification of water to remove toxic organic and inorganic pollutants is essential for a safe society and a clean environment. Adsorption-based water treatment is considered one of the most effective and economic technologies designed to remove toxic substances. In this article, we review the recent progress in the field of nanostructured materials used for water purification, particularly those used for the adsorption of heavy metal ions and organic dyes. This review includes a range of nanostructured materials such as metal-based nanoparticles, polymer-based nanomaterials, carbon nanomaterials, bio-mass materials, and other types of nanostructured materials. Finally, the current challenges in the fields of adsorption of toxic materials using nanostructured materials are briefly discussed.

Efficient and additive-free synthesis of morphology variant iron oxyhydroxide nanostructures for phosphate adsorption application.

Iron oxyhydroxide (FeOOH) nanostructures of different shapes were successfully synthesized on flexible textile cloth of polyester using a novel and simple technique based on hydrolysis method. The technique used herein is newly designed specifically to improve the efficiency in terms of energy, simplicity and cost involved in large scale synthesis of nanostructured thin films. Additionally, the morphology of nano-sized iron oxyhydroxide could be tuned into different shapes through variation in the type of precursors used for synthesis. The uniformity and adhesion of the depositions were also found to be excellent as examined by qualitative techniques. The as-deposited samples exhibited monoclinic and orthorhombic structures of FeOOH. A significant variation in the shape of as-deposited FeOOH nanostructures with change in precursor was observed through morphological studies, which displayed lance-shaped, rounded clusters and rod-like growth features in different cases. The nanocrystalline FeOOH can be directly applied to attract and trap phosphate from water reservoirs, thus contributing to environmental solutions. The proposed technique can also be utilized to deposit larger areas, which could be suitable for practical applications.

2D and 3D Bulk Materials for Environmental Remediation: Air Filtration and Oil/Water Separation.

Air and water pollution pose an enormous threat to human health and ecosystems. In particular, particulate matter (PM) and oily wastewater can cause serious environmental and health concerns. Thus, controlling PM and oily wastewater has been a great challenge. Various techniques have been reported to effectively remove PM particles and purify oily wastewater. In this article, we provide a review of the recent advancements in air filtration and oil/water separation using two- and three-dimensional (2D and 3D) bulk materials. Our review covers the advantages, characteristics, limitations, and challenges of air filters and oil/water separators using 2D and 3D bulk materials. In each section, we present representative works in detail and describe the concepts, backgrounds, employed materials, fabrication methods, and characteristics of 2D and 3D bulk material-based air filters and oil/water separators. Finally, the challenges, technical problems, and future research directions are briefly discussed for each section.

Elucidation of an intrinsic parameter for evaluating the electrical quality of graphene flakes.

A test method for evaluating the quality of graphene flakes, such as reduced graphene oxide (rGO) and graphene nanopowder (GNP), was developed in this study. The pelletizer was selected for a sampling tool, which enables us to formulate the flake sample as a measurable sample. Various parameters were measured from the pelletized sample in order to elucidate the best parameter for representing the quality of the graphene flakes in terms of their electrical properties. Based on the analysis of 4-probe measurement data on the pelletized sample, the best intrinsic parameter is volume resistivity (or volume conductivity) rather than resistivity (or conductivity). Additionally, the possible modification of a sample before and after the pressurization was investigated by electron microscopy and Raman spectroscopy. No significant modification was observed. The volume conductivity in the two types of the graphene was different from their individual conductivities by one order of magnitude. Based on the results of X-ray photoelectron spectroscopy and Raman spectroscopy measurements, the volume conductivity of the graphene flake samples was governed by the oxygen content in the sample. Our achievements will promote the effective use of powder-type graphene products for further applications.

One-pot synthesis of layered double hydroxide hollow nanospheres with ultrafast removal efficiency for heavy metal ions and organic contaminants.

Herein, Mg/Fe layered double hydroxide (MF-LDH) hollow nanospheres were successfully prepared by a one-step thermal method. After the thermal treatment of MF-LDH nanospheres at 400 °C, the MF-LDH was converted into the corresponding oxide, Mg/Fe layered double oxide (MF-LDO), which maintained the hollow nanosphere structure. The MF-LDO hollow nanospheres exhibited excellent adsorption efficiency for both As(V) and Cr(VI), showing 99% removal within 5 min and providing maximum removal capacities of 178.6 mg g-1 [As(VI)] and 148.7 mg g-1 [Cr(VI)]. Moreover, it met the maximum contaminant level requirements recommended by World Health Organization (WHO); 10 ppm for As(V) and 50 ppm for Cr(VI) in 10 and 20 min, respectively. Furthermore, Au nanoparticles were successfully introduced in the MF-LDO hollow nanospheres, and the products showed a conversion rate of 100% for the reduction of 4-nitrophenol into 4-aminophenol within 5 min. It is believed that these excellent and versatile abilities integrated with a facile synthetic strategy will facilitate the practical application of this material in cost-effective wastewater purification.

Polyelectrolyte Brush-Grafted Polydopamine-Based Catalysts with Enhanced Catalytic Activity and Stability.

Three types of surface treatments, namely, polyethyleneimine (PEI) coating, short PEI (S-PEI) grafting, and long PEI (L-PEI) grafting, were performed on polydopamine (Pdop)-based catalysts to enhance their catalytic activity and stability. Brush-grafted catalysts were prepared by the stepwise synthesis of Au and short (or long) PEI brushes on Pdop particles (PdopP/Au/S- or L-PEI grafting). PEI-coated Pdop-based catalysts (PdopP/Au/PEI coating) were also prepared as non-brush-grafted catalysts. Among the surface-treated PdopP/Au catalysts, the brush-grafted catalysts (S-PEI and L-PEI grafting) exhibited excellent and stable catalytic performance because the brush grafting enabled the protection of the catalysts against harsh conditions, effective transfer of reactants to the catalysts, and confinement of reactants around the catalysts. The brush-grafted catalysts could also more effectively decompose larger dyes than the non-brush-grafted catalysts. The process-to-effectiveness of PEI coating is the best because the release of Pdop from PdopP/Au was moderately inhibited by the presence of only one layer of PEI coating on the PdopP/Au. Thus, this approach could be an alternative method to enhance the stability of PdopP/Au catalysts.

Cube sugar-like sponge/polymer brush composites for portable and user-friendly heavy metal ion adsorbents.

Portable, non-toxic, and user-friendly sponge composites decorated with polyelectrolyte (PE) brushes were developed for the fast and efficient removal of heavy metal ions from waste water or drinking water. The polyacrylamide (PAM) and polyacrylic acid (PAA) brushes were grafted onto the sponge via "grafting-from" polymerization. For the polyethyleneimine (PEI) brush, "grafting-to" polymerization was used. A polydopamine (Pdop) layer was first coated on the sponge. Then, PEI was grafted onto the Pdop-coated sponge via a Michael addition reaction. The PEI-grafted sponge exhibited the best adsorption capacity and the fastest reaction rate of all the brushes due to the numerous adsorption sites of the PEI. The adsorption performance of two different PEI-grafted sponges depended on the molecular weight (MW) of the PEI. Simply by being dipped into a glass of water, non-toxic PEI-grafted sponge instantly removed the low concentration heavy metal ions, demonstrating a practical application for individual users.

Diterpenoids from the Roots of Euphorbia fischeriana with Inhibitory Effects on Nitric Oxide Production.

Bioactivity-guided isolation of a methanolic extract of Euphorbia fischeriana led to the isolation of four new abietane-type diterpenoids, fischeriolides A-D (1-4), together with 11 known diterpenoids. Their structures were elucidated based on the interpretation of 1D and 2D NMR spectroscopic and HRESIMS data. The absolute configuration of compound 3 was determined by single-crystal X-ray diffraction analysis and electronic circular dichroism methods. Compounds 5-9 exhibited inhibitory effects on LPS-induced nitric oxide production in RAW 264.7 macrophages with IC50 values in the range 4.9-12.6 µM.

Polyelectrolyte-mediated hierarchical mesoporous calcium silicates: a platform for drug delivery carrier with ultrahigh loading capacity and controlled release behavior.

We have developed a facile method for the poly(allylamine hydrochloride) (PAH)-assisted synthesis of mesoporous calcium silicate hydrates (PAH-CS) with a large specific surface area (BET = 348.4 m2 g-1) and pore volume (Vp = 1.42 cm3 g-1). Tetraethyl orthosilicate (TEOS) was employed as a silicon source, which was rapidly hydrolyzed and reacted with the amine groups of PAH to form spherical SiO2 nanoparticles (PAH-Si). Subsequently, Ca2+ ions reacted with the silicate anions produced during the dissolution of SiO2 in basic media, leading to the formation of the highly porous 3D networks of PAH-CS that were synthesized only under optimized reaction conditions. The PAH-CS containing an excess of Ca2+ and NH3 + enriched the surfaces with a very high cationic charge (ζ = +65.66 mV)and resulted in an extremely high loading capacity for anionic drugs and proteins. Ibuprofen (IBU) and FITC-labeled bovine albumin (FITC-Albumin) were chosen as a model drug and model protein, respectively, to test the loading and delivery efficiencies of the PAH-CS carriers. The ultrahigh drug loading capacities (DLC) and their release patterns were investigated under controlled pH conditions. Strikingly, the highest DLC reported to date (IBU or FITC-Albumin/carrier (3.35 g or 1 g g-1) was achieved in this work. The PAH-CS had no cytotoxic effect on osteoblast-like MC3T3-E1 cell lines evaluated by the LDH (Lactate dehydrogenase) assay in supernatant medium. Furthermore, the PAH-CS carriers could be entirely transformed to hydroxyapatite after releasing the drug in simulated body fluid (SBF), indicating good bioactivity and biodegradability of the PAH-CS carriers.

Polyelectrolyte-triggered transformation of various types of AgBr microstructures into AgBr nanophotocatalysts with a single shape and size.

AgBr nanostructures with unified shapes and sizes were prepared using simple polyelectrolyte (PE) coatings on various AgBr microstructures that were prepared by mixing silver precursors with hexadecyltrimethylammonium bromide (CTAB) under controlled conditions. The AgBr microstructures (plates, rods, and wires), regardless of initial structures or sizes, transformed into cubic AgBr nanoparticles (CNPs) after only three PE coatings. The electrostatic interactions between the PEs and the CTAB in the AgBr microstructures are the crucial factors that control the shapes and sizes of the AgBr microstructures. During the PE coating, the AgBr microstructures were transformed and rearranged into AgBr CNPs with favorable catalytic faces that enhanced the photocatalytic activity. The size- and shape-controlled AgBr CNPs showed excellent photocatalytic performance for the degradation of methylene orange (MO) dyes under visible-light irradiation without deterioration even after multiple uses.

Controlled etching of internal and external structures of SiO2 nanoparticles using hydrogen bond of polyelectrolytes.

We have demonstrated a novel strategy for the synthesis of mesoporous silica nanoparticles (MSNPs) using a surfactant-free method under ambient conditions. By the simple addition of an amine-based polymer (polyethylenimine; PEI) with a high molecular weight to a silica nanoparticle (SNP) solution, two types of MSNPs, including rambutan-like MSNPs (R-MSNPs) and hollow MSNPs (H-MSNPs), were produced. The structural changes of the MSNPs were systematically studied using various reaction conditions (reaction time, molar ratio and molecular weight of PEI, etc.) and were observed using electron microscopic techniques. The formation mechanisms of both MSNPs were carefully investigated using XPS, Raman, and IR spectroscopies. Because the synthesized MSNPs are highly porous materials that contain internal organic/inorganic networks, we investigated the removal/adsorption properties of these MSNPs with respect to pollutants toward possible future use in environmental remediation applications. The H-MSNPs exhibited better environmental remediation capabilities relative to the R-MSNPs because PEI is present between the cobweb-like internal structures of the H-MSNPs, thereby providing a significant number of reaction sites for the adsorption of pollutants. The approach presented here can also be used as a direct method for the preparation of intraconnected networks within the substructures.

Rattle-type hierarchical particles containing multilevel cores (Ag@AgCl@SiO2 and Au/Ag@AgCl@SiO2) as versatile catalysts.

A protocol for the synthesis of rattle-type core@shell particles containing Ag@AgCl or Au/Ag@AgCl core structures was developed, and the use of these particles as catalysts for the decomposition of toxic materials was demonstrated. A monometallic Ag or bimetallic Au/Ag core was incorporated into the interior of SiO2 capsules via controlled heat treatment of metal nanoparticle/SiO2-coated polymer particles, resulting in the formation of rattle-type core@shell structures. By appropriate treatments, it was possible to transform the Ag or Au/Ag core into multilevel cores (Ag@AgCl or Au/Ag@AgCl) within the SiO2 capsules (Ag@AgCl@SiO2 or Au/Ag@AgCl@SiO2). This method for the synthesis of rattle-type core@shell particles is useful for further introducing AgCl fused with plasmonic materials into the capsule structures. The rattle-type core@shell structures were used as photocatalysts for the decomposition of organic pollutants such as methyl orange. Furthermore, these nanocatalysts containing semiconductors such as AgCl were also applied toward the reduction of nitrophenol (NPh) to aminophenol (APh). The Ag@AgCl@SiO2 or Au/Ag@AgCl@SiO2 catalysts showed excellent catalytic properties in the decomposition of toxic substances in terms of their activity and reusability.

Evolution of AgX nanowires into Ag derivative nano/microtubes for highly efficient visible-light photocatalysts.

Our study proposes a novel strategy for the synthesis of Ag derivatives (AgX@Ag (X = Cl and Br) or Ag nano/microtubes) using the controlled chemical reduction or electron-beam irradiation of AgX nanowires (NWs), which are formed from the controlled dewetting of a AgX thin film on colloidal particles. The size of the AgX@Ag and Ag nano/microtubes can be controlled using the AgCl NWs as templates and varying the concentration of NaX. By controlling the concentration of NaBr, heterojunction-structured AgCl/AgBr NWs (H-AgCl/AgBr NWs) can be produced from the AgCl NWs due to a partial ion-exchange reaction (low concentration), and the AgBr NWs produced after a complete ion-exchange reaction between Cl- and Br- are further grown into micrometer-sized AgBr wires (high concentration). The resulting AgX NWs can be transformed into corresponding AgX@Ag or Ag nano/microtubes via a controlled chemical or physical method. The AgX derivatives (AgX@Ag nanotubes (NTs) and AgX NWs) are tested as visible-light-induced photocatalysts for decomposition of methyl orange. The AgX@Ag NTs exhibit the best photocatalytic activities due to the advantages of the core@shell structure, allowing multiple reflections of visible light within the interior cavity, providing a well-defined and clean Ag/AgX interface, and preventing direct adsorption of pollutants on AgX because of the shell structure. These advantages allow AgX@Ag NTs to maintain high catalytic performance even after multiple uses. The approach can also be used as a direct method for preparing Ag nano/microtubes with a tailored size and as a new method for incorporating a AgX NW core into a Ag nano/microtube shell. Our approach is useful for synthesizing various types of one-dimensional heterostructured NWs or metal NTs with controlled structures and properties.

(E)-1-(3,5-Di-meth-oxy-phen-yl)-3-(3-meth-oxy-phen-yl)prop-2-en-1-one.

In the title mol-ecule, C18H18O4, the C=C bond of the central enone group adopts a trans conformation. The relative conformation of the C=O and C=C bonds is s-cisoid. The dihedral angle between the planes of the benzene rings is 29.49 (12)°. In the crystal, weak C-H⋯O hydrogen bonds link the mol-ecules into chains along [010].

Bis(µ-4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylato-κ(2)O:O')bis[aqua(4,4''-di-fluoro-1,1':3',1''-terphenyl-2'-carboxyl-ato-κO)(pyridine-κN)cobalt(II)] diethyl ether disolvate.

The structure of the title compound, [Co(2)(C(19)H(11)F(2)O(2))(4)(C(5)H(5)N)(2)(H(2)O)(2)]·2C(4)H(10)O, comprises two Co(II) atoms in a distorted square pyramidal coordination environment, straddling a crystallographic inversion center with a Co⋯Co separation of 3.1923 (15) Å. Each Co(2+) cation is coordinated by three O atoms of three 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxyl-ate ligands, one water O atom and one pyridine N atom, forming a CoO(4)N polyhedron. Strong intra-molecular O-H⋯O hydrogen bonds are observed between terminal metal-bound carboxyl-ate groups and water O atoms.

Metal ion-enriched polyelectrolyte complexes and their utilization in multilayer assembly and catalytic nanocomposite films.

The mixing of Ag ion-doped poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAA) produced Ag ion-doped polyelectrolyte complex particles (PECs) in solution. Positively charged Ag ion-doped PECs (Ag ion PECs) with a spherical shape were deposited alternatively with PAA to form a multilayer assembly. The multilayered film containing Ag ion PECs was reduced to generate a composite nanostructure. Metal nanoparticle (NP)-enriched nanocomposite films were formed by an additional process of the postadsorption of precursors on PECs within the nanocomposite films, which resulted in the enhancement of the catalytic and electrical properties of the composite films. Because the films contain PECs that are responsive to changes in pH and most of the NPs are embedded in the PECs, interesting catalytic properties, which are unexpected in a particle-type catalyst, were observed upon pH changes. As a result of the reversible structural changes of the films and the immobilization of the NPs within the films, the film-type catalysts showed enhanced performance and stability during catalytic reactions under various pH conditions, compared to particle-type catalysts.

Dichloridobis(2-phenyl-pyridine-κN)zinc(II).

In the title compound, [ZnCl(2)(C(11)H(9)N)(2)], the Zn(2+) cation lies on a twofold axis and is coordinated by two Cl(-) anions and the N atoms of two 2-phenyl-pyridine ligands, forming a ZnN(2)Cl(2) polyhedron with a slightly distorted tetra-hedral coordination geometry. The dihedral angle between the phenyl ring and the metal-bound pyridine ring is 50.3 (4)° for each 2-phenyl-pyridine ligand. This arranges the phenyl ring from one ligand in the complex above the pyridine ring of the other resulting in an intra-molecular π-π inter-action, with a centroid-centroid distance of 3.6796 (17) Å. Weak C-H⋯Cl hydrogen bonds stabilize the crystal packing, linking mol-ecules into chains along the c axis.