Layered β-ZrNBr Nitro-Halide as Multifunctional Photocatalyst for Water Splitting and CO2 Reduction

Developing mixed-anion semiconductors for solar fuel production has inspired extensive interest, but the nitrohalide-based photocatalyst is still in shortage. Here we report a layered nitro-halide β-ZrNBr with a narrow band gap of ca. 2.3 eV and low defect density to exhibit multifunctionalities for photocatalytic water reduction, water oxidation and CO₂ reduction under visible-light irradiation. As confirmed by the results of electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, the formation of anion vacancies in the nitro-halide photocatalyst was inhibited due to its relatively high formation energy. Furthermore, performance of β-ZrNBr can be effectively promoted by a simple exfoliation into nanosheets to shorten the carrier transfer distance as well as to promote charge separation. Our work extends the territory of functional photocatalysts into the nitro-halide, which opens a new avenue for fabricating efficient artificial photosynthesis.     

Rapid spectrophotometric determination of iron in natural waters with 4-(2-thiazolylazo)-6-chlororesorcinol

4-(2-Thiazolylazo)-6-chlororesorcinol reacts sensitively with iron(II) to form a water-soluble brown complex which has a characteristic absorption at 741 nm. By utilizing this absorption, rapid and selective spectrophotometric determination of iron has been developed. The absorbance is constant at pH 8.7 to 10.9 and Beer's law holds up to 1.8 ppm of iron, with a molar absorptivity of 3.13 × 10⁴ liters mol^?1 cm^?1. Many types of ions are tolerable and the method has been applied successfully to the determination of iron in river waters.     

Study of VUV emission and γ-ray responses of Nd:BaF2 scintillaotor

Nd³⁺ 1%, 5% and 10% doped BaF₂ single crystals were grown by the micro-pulling down method. Photoluminescence properties, including excitation and emission spectra and luminescence decay were measured under synchrotron radiation excitation at the Superlumi station in HASYLAB at DESY (Hamburg, Germany). The Nd³⁺ related 5d-4f emission lines peaking around 180 nm, 230 nm, and 260 nm, identified as the 5d–⁴I_j, 5d–⁴F_j, and 5d–²G_j transitions, were observed under 140–168 nm excitation. In photoluminescence decay under the 160 nm excitation, the dominant component decay time is about 12, 2.5 and 1.2 ns for Nd³⁺ 1%, 5% and 10% concentration, respectively. The decay time shortening is explained by the concentration quenching effect. Transmittance of Nd1% sample is about 80% for wavelengths above 185 nm. Finally, gamma-ray responses, non-proportionality and energy resolution of Nd1% sample were compared with the undoped BaF₂ scintillator. The light yield of the Nd1%:BaF₂ is about 93% of that of undoped BaF₂. ^©2009 Elsevier Ltd. All rights reserved.     

Bioelectrocatalytic endpoint assays based on steady-state diffusion current at microelectrode array

Highly reproducible bioelectrocatalytic endpoint assays are described. The method is based on a complete redox conversion of a substrate to a redox mediator with a corresponding redox enzyme and an amperometric detection of the reduced mediator on a diffusionally independent microelectrode array. The current reaches a steady state within a few seconds and is proportional to the number of the integrated microelectrodes. The method has successfully been applied to histamine detection at micro-molar level and glucose detection at milli-molar level.     

Regulated Incorporation of Two Different Metal Ions into Programmed Sites in a Duplex by DNA Polymerase Catalyzed Primer Extension

Metal‐mediated base pairs formed by the coordination of metal ions to natural or artificial bases impart unique chemical and physical properties to nucleic acids and have attracted considerable interest in the field of nanodevices. Ag^I ions were found to mediate DNA polymerase catalyzed primer extension through the formation of a C–Ag^I–T base pair, as well as the previously reported C–Ag^I–A base pair. The comparative susceptibility of dNTPs to Ag^I‐mediated enzymatic incorporation into the site opposite cytosine in the template was shown to be dATP>dTTP?dCTP. Furthermore, two kinds of metal ions, Ag^I and Hg^II, selectively mediate the incorporation of thymidine 5′‐triphosphate into sites opposite cytosine and thymine in the template, respectively. In other words, the regulated incorporation of different metal ions into programmed sites in the duplex by DNA polymerase was successfully achieved.     

A Novel Type of Luciferin from the Siberian Luminous Earthworm Fridericia heliota: Structure Elucidation by Spectral Studies and Total Synthesis

The structure elucidation and synthesis of the luciferin from the recently discovered luminous earthworm Fridericia heliota is reported. This luciferin is a key component of a novel ATP‐dependent bioluminescence system. UV, fluorescence, NMR, and HRMS spectroscopy studies were performed on 0.005 mg of the isolated substance and revealed four isomeric structures that conform to spectral data. These isomers were chemically synthesized and one of them was found to produce light when reacted with a protein extract from F. heliota. The novel luciferin was found to have an unusual extensively modified peptidic nature, thus implying an unprecedented mechanism of action.     

Alkylamines‐intercalated α‐zirconium phosphate as latent thermal anionic initiators

The reaction of glycidyl phenyl ether (GPE) with 1‐aminoalkanes‐intercalated α‐zirconium phosphate (α‐ZrP·1‐aminoalkane): 1‐aminoalkanes 1‐aminopropane (α‐ZrP·Pr), 1‐aminobutane (α‐ZrP·Bu), 1‐aminooctane (α‐ZrP·Oct), and 1‐aminohexadecane (α‐ZrP·Hed) was carried out at varying temperatures for 1 h periods. Reaction progress was not observed until the reactants were heated to 80 °C or above. On increasing the temperature, the conversion factors increased such that, at 140 °C, conversions of 62% (α‐ZrP·Pr), 60% (α‐ZrP·Bu), 67% (α‐ZrP·Oct), and 64% (α‐ZrP·Hed) were obtained. The thermal stabilities as latent initiators were tested: GPEs reacted with α‐ZrP·Pr, α‐ZrP·Bu, and α‐ZrP·Oct at 40 °C for 360 h achieved conversions of 83, 55, and 59%, respectively. In contrast, the reaction in the presence of α‐ZrP·Hed did not proceed at 40 °C. The order of the thermal stability of GPE in the presence of α‐ZrP·1‐aminoalkane intercalation compounds was: α‐ZrP·Hed > α‐ZrP·Bu ≈ α‐ZrP·Oct > α‐ZrP·Pr. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1854–1861