Organocatalytic Enantioselective Decarboxylative Addition of Malonic Acids Half Thioesters to Isatins

The organocatalytic enantioselective decarboxylative addition of malonic acids half thioesters to isatins using a squaramide catalyst afforded the products with high enantioselectivity. These products are key intermediates in the synthesis of 3‐substituted 3‐hydroxy‐2‐oxindole derivatives. The first enantioselective synthesis of (−)‐flustraminol B has been accomplished.     

Direct Enantioselective Three‐Component Kabachnik–Fields Reaction Catalyzed by Chiral Bis(imidazoline)‐Zinc(II) Catalysts

A direct three‐component reaction of aldehydes, amines and diaryl phosphites was catalyzed by a zinc(II) complex of 1,3‐bis(imidazolin‐2‐ly)pyridine (pybim) giving the corresponding α‐aminophosphonates in good yield with good enantioselectivity. The reaction was applied to a wide variety of aromatic aldehydes to give products with excellent yields (up to 99%) and enantiomeric excesses (up to 93% ee).     

Performances of metal fluoride added carbon anodes with pre-electrolysis for electrolytic synthesis of NF3

Metal fluoride added carbon anodes treated by pre-electrolysis were investigated for electrolytic production of nitrogen trifluoride (NF₃) in molten NH₄F·KF·4HF at 100 °C. The conditions for pre-electrolysis were first optimized using a graphite sheet anode as a model anode. The formation of fluorine-graphite intercalation compounds (fluorine-GICs) with semi-covalent C–F bonds, (C_xF)_n, on the MgF₂ and CaF₂ added carbon anode surface was accelerated by pre-electrolysis at potentials less than 4.0 V. Critical current densities (CCD) on the MgF₂ added carbon anodes pre-electrolyzed under various conditions were determined, and the highest CCD was 290 mA cm⁻² obtained for that pre-electrolyzed at 3.5 V for 500 C cm⁻². This anode was successfully used in the electrolysis at 100 mA cm⁻² for 290 h and the maximum NF₃ current efficiency was 55%. From these results, it was concluded that the metal fluoride added carbon anode treated by pre-electrolysis has a high potential for electrolytic production of NF₃ at higher current density.     

Fabrication and Pore Size Control of Large-Pore Mesoporous Silica Particles through a Solvent Evaporation Process

Large-pore mesoporous silica particles were synthesized through a solvent evaporation process using hydrophobic fumed silica particles and tetraethyl orthosilicate (TEOS) as silica sources. The solvent evaporation of an ethanol solution of fumed silica particles, TEOS, HCl and triblock copolymer (F127) resulted in mesoporous silica particles with pores with sizes of about 7 nm. In addition, the interplanar spacing of the mesoporous silica particles can be controlled by changing the solvent evaporation temperatures.     

Photocatalytic decomposition of gaseous HCHO over a titanium dioxide film formed on a hydrophobic PET sheet

BACKGROUND: The authors (Chem Eng J 148, 234 (2009)) previously demonstrated the excellent performance of a photocatalytic reactor with a parallel array of nine light sources. To enhance the possibility of practical application of this reactor, the present work explores the use of a PET (polyethylene terephthalate) sheet as a new cheap material to support TiO₂, as an alternative to glass tubes. A method of coating the hydrophobic PET sheet with a TiO₂ film using an aqueous coating solution is investigated and the performance of the TiO₂‐PET sheet prepared evaluated. RESULTS: The affinity of the coating solution for the PET sheet is greatly enhanced by addition of 0.01% (w/w) nonionic surfactant (polyoxyethylene lauryl ether). A relatively uniform thin TiO₂ film is formed on the entire surface of the PET sheet by applying the coating solution to the PET sheet and drying it at 100 °C. Decomposition experiments of gaseous HCHO indicate that the photocatalytic activity, although initially low, is increased with repeated use. This is because surfactant molecules added interfere initially with the decomposition of HCHO. After their decomposition, the TiO₂–PET sheet decomposes HCHO at almost the same rate as does the TiO₂–glass tube. CONCLUSION: The photocatalytic reactor with a parallel array of nine light sources can utilize a PET sheet as TiO₂ support with a reduction in material cost. Copyright © 2011 Society of Chemical Industry     

High oleic acid oil suppresses lung tumorigenesis in mice through the modulation of extracellular signal-regulated kinase cascade

This study was undertaken to estimate the effect of dietary high oleic acid oil (OA) on 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK)-induced lung tumorigenesis in mice. Diet containing 10% oil was fed to mice through experimental periods. On day 30 after NNK injection (100 mg/kg body weight, i.p.), the treatment increased the level of prostaglandin E₂ (PGE₂) as well as proliferating cell nuclear antigen, a marker of cell proliferation in a high linoleic acid oil (LA)-fed group but not in an OA-fed group. The NNK treatment also induced the activation of an extracellular signal-regulated kinase (Erk) cascade (Erk, Mek and Raf-1) in an LA-fed group. On the other hand, OA feeding abolished the NNK-induced activation of the Erk cascade. In conjugation with these events, OA feeding reduced lung tumor incidence and tumor multiplicity (percentage of mice with tumors) in mice compared with LA feeding at the 20th experimental week. These results suggest that OA suppresses lung tumorigenesis and that this suppression is correlated with the inhibition of PGE₂ production and inactivation of the Erk cascade.     

Syndiotactic‐specific radical polymerization of N‐isopropylacrylamide in toluene at low temperatures in the presence of silyl alcohols

The radical polymerization of N‐isopropylacrylamide was carried out in toluene at low temperatures in the presence of silyl alcohols, such as triethylsilanol. Poly(N‐isopropylacrylamide) with a racemo dyad content of 75% was obtained at ? 80 °C with a 4:1 triethylsilanol to monomer ratio loading. NMR analysis suggests that the mechanism for syndiotactic induction, in the presence of silyl alcohols, may be similar to that observed with alkyl alcohols. In this case, a 1:2 complex formation, via hydrogen bonding interactions, leads to the induction of syndiotactic specificity. Copyright © 2012 Society of Chemical Industry     

EFFECTS OF OPERATIONAL CONDITIONS ON DRYING CHARACTERISTICS IN CLOSED SUPERHEATED STEAM DRYING

The effects of operational conditions on the drying performance in closed superheated steam drying were examined theoretically and experimentally. The vapor generated from the sample was circulated in the drying chamber. In the theoretical analysis, the replacement of air with vapor in drying chamber and the convective vapor transfer in sample were considered. At the start of drying, the drying chamber was filled with air. As the drying proceeded, the air was replaced with the vapor generated from sample. The calculated results explained the characteristics of experimental data. The pore diameter of sample had little effect on the drying characteristics. During the internal evaporation period, the evaporation occurred in the narrow zone, which moved from the surface to the bottom of sample. The convective vapor transfer in sample had a significant influence on the drying performance. The excess increments in temperature and velocity of drying gas hardly contributed to shortening the drying time.     

Preparation and properties of biocomposites composed of sorbitol‐based epoxy resin,pyrogallol–vanillin calixarene,and wood flour

The reaction of pyrogallol (PG) and vanillin (VN), both of which are derived from plant resources, in the presence of p‐toluenesulfonic acid gave PG–VN calixarene (PGVNC) mainly composed of guaiacyl pyrogallol[4]arene. After sorbitol polyglycidyl ether (SPE) was mixed with PGVNC in tetrahydrofuran at an optimized epoxy/hydroxy ratio 1/2.65, the obtained SPE/PGVNC solution was mixed with wood flour (WF), prepolymerized at 150°C, and subsequently compressed at 190°C for 3 h to give SPE–PGVNC/WF biocomposites with WF content 0–20 wt%. The tan δ peak temperature of SPE–PGVNC was 148.1°C, which was much higher than that of the SPE cured with petroleum‐based phenol novolac (SPE–PN) at an optimized epoxy/hydroxy ratio 1/1. Although tan δ peak temperature slightly decreased with increasing WF content, the storage moduli of the SPE–PGVNC/WF biocomposites in the rubbery state at more than 150°C were much higher than those of SPE–PGVNC and SPE–PN. Also, the tensile modulus and strength for SPE–PGVNC/WF increased with increasing WF content. Field emission‐scanning electron microscopy analysis of the biocomposites revealed that WF is tightly incorporated into the crosslinked epoxy resins. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Bactericidal effect of cationic hydrogels prepared from hydrophilic polymers

This study investigated whether hydrogels comprising hydrophilic cationic polymers have similar bactericidal effects. Bacteria were seeded on hydrogels and agar and their viability was assessed with time. Cationic hydrogels displayed bactericidal effects upon long-term bacterial contact. Furthermore, we assessed the areal density of cationic monomer unit of the cationic hydrogels, water content, and the initial elastic modulus. We examined correlations between each factor and bacterial death ratios; consequently, the bacterial death ratios were strongly correlated with the areal density of cationic hydrogel monomers. Elastic energy (W_el) generated at the cytomembrane ion-binding region and the cationic hydrogel and the cytomembrane interfacial energy (W_f) were estimated; consequently, W_el exceeded W_f at higher contact areas. The cationic hydrogel may extract cytomembranes with a reasonable adsorption area. Therefore, cationic hydrogels may be used as probes for ultrasonic echo to sterilize medical equipment.