Degradation of organic compounds on TiO<Subscript>2</Subscript> photocatalysts prepared by a hydrothermal method in the presence of NH<Subscript>4</Subscript>F

TiO₂ photocatalysts were synthesized by a hydrothermal method from tetraisopropyl orthotitanate (TPOT) in the presence of NH₄F with different NH₄F/Ti molar ratios (0, 0.25, and 1). The formation of a well-crystallized anatase phase of TiO₂ and the suppression of phase transition to rutile were observed, even at high calcination temperature, owing to the effects of NH₄F. The TiO₂ synthesized hydrothermally with NH₄F exhibited absorption with a shift to the longer wavelengths of the visible-light region. The hydrothermally synthesized TiO₂ with a moderate amount of NH₄F exhibited high photocatalytic activity for the degradation of alcohol diluted in water under both UV-light and visible-light irradiations.     

Construction of alpha-helix peptides with beta-cyclodextrin and dansyl units and their conformational and molecular sensing properties

In order to apply de novo peptide design to molecular sensing, we designed and synthesized a-helical peptides with beta-cyclodextrin (beta-CDx) as a binding site and a dansyl unit (Dns) as a fluorescence sensing site. The conformational and molecular sensing properties of the peptides with beta-CDx and Dns in various positions were investigated. Circular dichroism and fluorescence measurements revealed that beta-CDx and Dns form intramolecular complexes which depend on their positions in the peptides. In the 17 residual peptides named EK3 and EK3R, in which beta-CDx and Dns were introduced at the fourth and the eighth positions (EK3) or at the eighth and the fourth positions (EK3R), Dns was deeply included in the CDx cavity and formed a more stable self-inclusion complex with CDx than in the peptides EK6 and EK6R, in which these moieties were at the eighth and the fifteenth positions or at the fifteenth and the eighth positions, respectively. The stability of the self-inclusion complex between beta-CDx and Dns controlled the a-helix structure as well as the binding and sensing abilities for the exogenous guests. These results demonstrate the usefulness of peptide tertiary structure for arranging CDx and other functional units, and suggest that this approach is important in the development of a new type of CDx-based sensory system.     

Control of product selectivity by a styrene additive in ruthenium-catalyzed C-H arylation

A unique effect of styrene additive on product selectivity was observed for RuH(2)(CO)(PPh(3))(3)-catalyzed C-H arylation of acetophenone derivatives bearing two ortho C-H bonds. Without styrene, the C-H arylation with arylboronates gives diarylation products as the major products throughout the reaction, but the use of styrene as an additive switches the product selectivity and leads to selective formation of monoarylation products.     

The Effect of Lithium Doping in Solution-Processed Nickel Oxide Films for Perovskite Solar Cells

The effect of substitutional Li doping into NiO_x hole transporting layer (HTL) for use in inverted perovskite solar cells was systematically studied. Li doped NiO_x thin films with preferential crystal growth along the (111) plane were deposited using a simple solution-based process. Mott-Schottky analysis showed that hole carrier concentration (N_A) is doubled by Li doping. Utilizing 4 % Li in NiO_x improved the power conversion efficiency (PCE) of solar devices from 9.0 % to 12.6 %. Photoluminescence quenching investigations demonstrate better hole capturing properties of Li:NiO_x compared to that of NiO_x, leading to higher current densities by Li doping. The electrical conductivity of NiO_x is improved by Li doping. Further improvements of the device were made by using an additional ZnO layer onto PCBM, to remove shunt paths, leading to a PCE of 14.2 % and a fill factor of 0.72.     

Enhanced pearl-chain formation by electrokinetic interaction with the bottom surface of vessel

Counterions in an electric double layer (EDL) around a colloidal particle accumulate on one side of the EDL and are deficient on the other side under an electric field, resulting in an imbalance of ionic concentration in the EDL, that is to say, the ionic polarization of EDL. It is well known that the ionic polarization of EDL induces electric dipole moments whereby the alignments of colloidal particles (e.g., pearl chains) are formed under alternating electric fields. In this study, we focus on the effect of the frequency of applied electric fields (100 Hz-1 kHz) on the alignment of silica particles settling at the bottom of a silica glass vessel. In digital imaging analyses for pearl chains of silica particles, it is confirmed that surface distances between two neighboring particles decrease but the number of particles in a pearl chain increases as the frequency of the applied electric field is lowered from 1 kHz to 100 Hz. More interestingly, electrical conductance measurements suggest that the induced ionic polarization of EDL around silica particles at the bottom of the silica vessel is enhanced as the frequency is lowered from 1 kHz to 100 Hz, whereas the ionic polarization around isolated silica particles in uniform dispersions is alleviated by the relaxation of ionic concentration in the EDL as a result of the diffusion of counterions. This curious phenomenon can be explained by considering that the ionic polarization of EDL of silica particles at the bottom of a vessel is affected by the electro-osmosis of the silica surface at the bottom of the vessel.     

Deuterium isotope effect on the atomic orbital alignment dependence in the reaction of the oriented Ar (3P2) with CH3CN (CD3CN)

Atomic orbital alignment effect was observed for the CN (B2Sigma+) formation in the reaction of oriented Ar (3P2) with CH3CN (CD3CN). The relative cross-sections for each magnetic MJ' substrate in collision frame sigmaH|MJ'| for CH3CN and sigmaD|MJ'| for CD3CN, were determined to be sigmaH0:sigmaH|1|:sigmaH|2|:sigmaD0:sigmaD|1|:sigmaD|2| = 1.00:0.81:0.84:2.01:1.92:1.87. A significant atomic orbital alignment effect was observed. In addition, a notable deuterium isotope effect was observed on both the cross-section and the atomic orbital alignment effect.     

Dextran oxidized by a malaprade reaction shows main chain scission through a maillard reaction triggered by schiff base formation between aldehydes and amines

Although periodate‐oxidized dextran is widely used in biomedical applications, the degradation mechanism of oxidized dextran has not yet been elucidated. Herein, we propose a novel main chain scission mechanism of oxidized dextran triggered by reaction with amine. NMR analysis revealed four hemiacetal substructures during oxidation by periodate. Kinetic analysis showed that the degradation time constant of the C3‐removed substructure and increasing time constant of the reducing end protons are consistent with the decrease in molecular weight determined by gel permeation chromatography. A methylene group is generated at the same time constant of degradation, indicating that oxidized dextran degradation proceeds via a Maillard reaction. Oxidized dextran does not degrade in saline solution without reactive amine species. Thus, we conclude that oxidized dextran is degraded in the main chain via Schiff base formation through a Maillard reaction, depending on the oxidation ratio and amino acid concentration. These findings help to elucidate the reaction mechanism of polysaccharide degradation and develop novel biodegradable polysaccharide materials for biomedical applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2254–2260     

Synthesis and NMR study of 9′-substituted spiroindolinonaphthoxazine derivatives

A photochromic spiroindolinonaphthoxazine derivative, 1,3,3-trimethyl-9′-hydroxy-spiro[indoline-2,3′(3H)- naphtho[2,1-b][1,4]oxazine] 3 was synthesized by condensation of 1,2,3,3-tetramethylindolenium iodide 1 and l-nitroso-2,7-dihydroxynaphthalene 2 . Further, two new derivatives, 5 and 7 , were prepared in good yields by the reactions of 3 with the hexafluoropropene trimer 4 and 4-[perfluoro(2-isopropyl-1,3-dimethyl-1-butenyl)-oxybenzoyl chloride 6 , respectively. Their unique structural features and property are discussed based on ¹H-, ¹³C- and ¹⁹F nmr spectral data.     

Improving the design stresses of high density polyethylene pipes and vessels used in reverse osmosis desalination plants

Nanocomposite materials have been used on a wide scale in industrial and structural applications. The present work aims at studying the mechanical properties of high density polyethylene (HDPE) grade TR-401 hexene copolymer reinforced by montmorillonite nanoparticles (MMT), used to fabricate pipes and membranes vessels for reverse osmosis desalination plants. Different volume fractions and particle sizes of the MMT clay were used to investigate the effect of this filler on the mechanical properties of the produced composite. Mechanical properties tests were carried out and good improvements of the composite properties were obtained compared to the parent polymer. The test results showed a significant enhancement of the mechanical properties at low filler proportions. Pipe fabricated from these composites had many outstanding and desirable features. For example, by adding 4.75% MMT to the HDPE produced quality pipes and fittings with the highest design stress basis of any polyethylene. A significant increase in the modulus of elasticity observed, together with an unusual increase in the design stress, approved the HDPE/MMT composite for high pressure piping and membrane vessels used in reverse osmosis desalination plants.