The electrochemical Peltier heats of Fe(CN) 6 3− /Fe(CN) 6 4− system at 295.15 K

A specially designed thermo-electrochemical calorimeter was applied to measure the electrochemical Peltier heats (EPH) of Fe(CN) ₆ ^3?/4? system at 295.15 K. The curves of the electrode potential changes and temperature changes against time for Fe(CN) ₆ ^3?/4? couple with five groups of different concentrations were obtained under the condition of various constant-current polarizations. The EPH values for the considered electrode reaction are determined to be ?41.31, ?42.73, ?44.28, ?45.87, and ?46.65 kJ mol^?1 at the respective concentrations of 0.125, 0.175, 0.225, 0.275, and 0.300 mol dm^?3; and the EPH and the apparent enthalpy change corresponding to the infinite dilution to be ?37.42 and ?84.10 kJ mol^?1 at 295.15 K, respectively.     

Organoclays from alkaline-treated acid-activated clays

The cetyltrimethylammonium hydroxide (C16TMAOH) solution was proposed for the preparation of organoclays. Montmorillonite clay was acid activated at different acid/clay (a/c) (in mass) ratios, then treated with alkaline (sodium hydroxide) solution before being reacted with C16TMAOH solution. The acid activation caused a reduction in the number of cation exchange sites, and hence improved the exfoliation of the silicate sheets at higher pH values. The basal spacing increased significantly from 2.20 to 4.01 nm, and depended on the a/c ratios. The acid-activated clays with a/c ratios greater than 0.3 adsorbed significant amounts of C16TMA cations with a basal spacing of 4.01 nm compared with the non-acid-activated montmorillonite (2.51 nm). Meanwhile, the treatment of NaOH solution yielded clays with similar properties to that of the raw used clay. The XRF data, FT-IR, and ²⁹Si MAS-NMR techniques confirmed that the resulting amorphous silica during the acid activation was dissolved, and accompanied by a dramatical reduction in the surface areas. Similar amounts of C16TMA cations were adsorbed, i.e., close to 1 mmol g^?1, with a single basal spacing of 2.52 nm, independently of the treated acid-activated clays. The in-situ powder XRD studies revealed that an increase of the basal spacing to 4.20 nm was observed at intermediate temperatures ranging from 50 to 150 °C for organo-acid-activated clays with basal spacing of 4.01 nm, while a continuous decrease of the basal spacing was observed for organoclays with a basal spacing of 2.52 nm. At higher temperatures greater than 250 °C, the decomposition of the surfactant occurs, and the basal spacing decreases to a value of about 1.4 nm.     

Electrochemical myoglobin biosensor based on carbon ionic liquid electrode modified with Fe3O4@SiO2 microsphere

In this paper, a Fe₃O₄@SiO₂ core-shell structure microsphere was synthesized and used to investigate the direct electron transfer of myoglobin (Mb) with a 1-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) as the substrate electrode. The mixture of Mb and Fe₃O₄@SiO₂ microsphere could form an organic–inorganic composite, which was immobilized on the surface of CILE with a chitosan (CS) film. Cyclic voltammetric experiments indicated that a pair of well-defined quasi-reversible redox peaks appeared on CS/Mb-Fe₃O₄@SiO₂/CILE with the formal peak potential (E ^0′) located at ?0.31 V (vs. saturated calomel electrode), which was corresponded to the electroactive center of Mb heme Fe(III)/Fe(II) redox couples. Direct electrochemical behaviors of Mb in CS-Fe₃O₄@SiO₂ composite film were carefully investigated with the electrochemical parameters calculated. The CS/Mb-Fe₃O₄@SiO₂/CILE showed good electrocatalytic behaviors to the reduction of trichloroacetic acid in the concentration range from 0.2 to 11.0 mmol L^?1 with the detection limit of 0.18 mmol L^?1 (3σ). Based on CS/Mb-Fe₃O₄@SiO₂/CILE, a new third-generation reagentless electrochemical biosensor was constructed with higher sensitivity and reproducibility.     

Large Hexagonal Bi‐ and Trilayer Graphene Single Crystals with Varied Interlayer Rotations

Bi‐ and trilayer graphene have attracted intensive interest due to their rich electronic and optical properties, which are dependent on interlayer rotations. However, the synthesis of high‐quality large‐size bi‐ and trilayer graphene single crystals still remains a challenge. Here, the synthesis of 100 μm pyramid‐like hexagonal bi‐ and trilayer graphene single‐crystal domains on Cu foils using chemical vapor deposition is reported. The as‐produced graphene domains show almost exclusively either 0° or 30° interlayer rotations. Raman spectroscopy, transmission electron microscopy, and Fourier‐transformed infrared spectroscopy were used to demonstrate that bilayer graphene domains with 0° interlayer stacking angles were Bernal stacked. Based on first‐principle calculations, it is proposed that rotations originate from the graphene nucleation at the Cu step, which explains the origin of the interlayer rotations and agrees well with the experimental observations.     

Metal‐Free Aminosulfonylation of Aryldiazonium Tetrafluoroborates with DABCO⋅(SO2)2 and Hydrazines

The coupling of aryldiazonium tetrafluoroborates, DABCO?(SO₂)₂, and hydrazines under metal‐free conditions leads to the formation of aryl N‐aminosulfonamides. The reaction proceeds smoothly at room temperature and shows broad functional‐group tolerance. A radical process is proposed for this transformation.     

A Doping Technique that Suppresses Undesirable H2 Evolution Derived from Overall Water Splitting in the Highly Selective Photocatalytic Conversion of CO2 in and by Water

Photocatalytic conversion of CO₂ to reduction products, such as CO, HCOOH, HCHO, CH₃OH, and CH₄, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga₂O₃ photocatalysts exhibit high conversion of CO₂. Doping of Zn species into Ga₂O₃ suppresses the H₂ evolution derived from overall water splitting and, consequently, Zn‐doped, Ag‐modified Ga₂O₃ exhibits higher selectivity toward CO evolution than bare, Ag‐modified Ga₂O₃. We observed stoichiometric amounts of evolved O₂ together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO₂ introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO₂ on the catalyst surface.     

Chemical and Toxicological Investigations of a Previously Unknown Poisonous European Mushroom Tricholoma terreum

The established tradition of consuming and marketing wild mushrooms has focused attention on mycotoxicity, which has become a global issue. In the present study, we describe the toxins found in a previously unknown poisonous European mushroom Tricholoma terreum. Fifteen new triterpenoids terreolides A–F ( 1 – 6 ) and saponaceolides H–P ( 8 – 16 ) were isolated from the fruiting bodies of the toxic mushroom T. terreum. Terreolides A–C ( 1 – 3 ) possessed a unique 5/6/7 trioxaspiroketal system, whereas terreolides D–F ( 4 – 6 ) possessed an unprecedented carbon skeleton. Two abundant compounds in the mushroom, saponaceolide B ( 7 ) and saponaceolide M ( 13 ), displayed acute toxicity, with LD₅₀ values of 88.3 and 63.7 mg kg^?1 when administered orally in mice. Both compounds were found to increase serum creatine kinase levels in mice, indicating that T. terreum may be the cause of mushroom poisoning ultimately leading to rhabdomyolysis.     

AgI Microplate Monocrystals with Polar {0001} Facets: Spontaneous Photocarrier Separation and Enhanced Photocatalytic Activity

Elucidating the facet‐dependent photocatalytic activity of semiconductor photocatalysts is important in improving the overall efficiency of photocatalysis. Furthermore, combining facet control with selective deposition of oxidation and/or reduction cocatalysts on specific faces of semiconductor photocatalysts is potentially an effective strategy to synergistically optimize the functionality of photocatalysts. In the present study, high‐purity wurtzite‐type β‐AgI platelet microcrystals with polar {0001} facets were prepared by a facile polyvinylpyrrolidone‐assisted precipitation reaction. The polar‐faceted AgI microplates were used as archetypes to demonstrate preferential diametric migration (i.e., effective separation) of photogenerated electrons and holes along the c axis. Such vectorial electron–hole separation stems from the asymmetric surface structures, which give rise to distinct photoexcited reaction behaviors on the ±(0001) polar facets of wurtzite‐type semiconductors. Furthermore, on selective deposition of Ag and MnO_x (1.5<x<2) cocatalysts on the reductive (0001) and oxidative (000$\bar 1$ ) facets, respectively, photocatalytic activity of the AgI microplates in degrading organic pollutants was dramatically enhanced thanks to the broad light‐absorption range, strong dye‐adsorption ability, and effective spatial separation of photocarriers.     

In-situ synthesis,characterization and antimicrobial activity of viscose fiber loaded with silver nanoparticles

In order to broaden applications of viscose fiber, graft copolymerization of acrylic acid was conducted on its surface followed by in situ loading of Ag nanoparticles (Ag-NPs). The loading amount of Ag-NPs was affected by the concentrations of Ag⁺ and trisodium citrate, and their optimum concentrations were found to be 0.014 and 0.030 g/ml. The Ag-NP-loaded fibers presented a prolonged Ag release behavior in aqueous solution, of which the cumulative release was less than 5 % within 48 h. In addition, the viscose fibers showed good antimicrobial activity against S. aureus, and their consecutive antimicrobial activity was kept at more than 90 % after several washing cycles. Modified viscose fibers, therefore, offer a great opportunity for use as antimicrobial fabrics.