Catalytic Friedel–Crafts Acylation of Heteroaromatics

Catalytic Friedel–Crafts acylation of heteroaromatics has been achieved using metal triflates as catalysts. While conventional Friedel–Crafts acylation often requires the use of more than stoichiometric amounts of aluminum chloride, metal triflates such as tin(II) triflate, scandium triflate, and gallium triflate, etc. have enabled efficient acylation reactions by catalytic use.     

Growth of High-Quality Pb((Zn1/3Nb2/3)0.91Ti0.09)O3 Single Crystals by Excess ZnO Addition

A high-quality single crystal of Pb((Zn_1/3Nb_2/3)_0.91Ti_0.09)O₃ (PZNT 91/9), 40 mm in diameter and 20 mm in length, was successfully grown using the solution Bridgman method with a slight excess amount of ZnO. High-quality wafers were sliced from the light-brown single crystal. No PbO inclusions or opaque areas were observed in the transparent wafers. An array probe for echocardiography was constructed with the single-crystal wafer, and its superior performance was demonstrated.     

Dynamic Fracture Characterization of Al2O3 and SiCw/Al2O3

The dynamic stress intensity factors, which were determined with newly developed bar impact facilities and a new data reduction procedure, for an Al₂O₃ ceramic and 29 vol% SiC_w/Al₂O₃ composite were virtually identical, thus indicating that the short SiC whiskers were ineffective under dynamic fracture. SEM studies revealed five distinct fracture morphologies with increased percentage area of transgranular fracture in both materials with rapid crack propagation. Also, the high dynamic stress intensity factor caused multiple microscopic crack planes to form and then join as the crack advanced.     

Preparation and properties of negatively charged ultrafiltration membrane: Photografted sodium styrene sulfonate onto brominated polyacrylonitrile membrane

Charged ultrafiltration membranes were prepared by photografting sodium styrene sulfonate onto photosensitive polyacrylonitrile membrane containing bromine atoms. The degree of the photografting was characterized by contact angles of air or n-octane in water and FTIR spectra for the negatively charged membrane. Permeations of dextran and dextransulfate through the negatively charged membranes were studied by ultrafiltration in the aqueous solutions of both solutes. With an increase of photoirradiation, the permeability of the solutes decreased. Also, an electrostatic repulsion of the solute and the membrane was confirmed by direct comparison between the permeability of the solutes, dextran, and dextransulfate, each having similar molecular size.     

Regiospecific analysis by ethanolysis of oil with immobilized <Emphasis Type="Italic">Candida antarctica</Emphasis> lipase

A mixture of oil/ethanol (1∶3, w/w) was shaken at 30°C with 4% immobilized Candida antarctica lipase by weight of the reaction mixture. The reaction regiospecifically converted FA at the 1- and 3-positions to FA ethyl esters, and the lipase acted on C₁₄−C₂₄ FA to a similar degree. The content of 2-MAG reached a maximum after 4 h; the content was 28–29 mol% based on the total amount of FA in the reaction mixture at 59–69% ethanolysis. Only 2-MAG were present in the reaction mixture during the first 4 h, and 1(3)-MAG were detected after 7 h. After removal of ethanol from the 4-h reaction mixture by evaporation, 2-MAG were fractionated by silica gel column chromatography. The contents of FA in the 2-MAG obtained by ethanolysis of several oils coincided well with FA compositions at the 2-position, which was analyzed by Grignard degradation. It was shown that ethanolysis of oil with C. antarctica lipase can be applied to analysis of FA composition at the 2-position in TAG.     

Chemospecific ring-opening polymerization of α-methylenemacrolides

α-Methylenemacrolides having various groups, such as aromatic, ether, and amine, were enzymatically, anionically, and radically polymerized. The polymerization with the lipase catalyst successfully afforded polymers only through the ring-opening process, whereas the vinyl polymerizations selectively proceeded by using anionic and radical initiators. The polyesters obtained by the enzymatic polymerization have a polymerizable methacrylic methylene group in the main-chain, in addition to the aromatic and polar groups, and were further radically polymerized to quantitatively produce a cross-linked polymer gel.     

Synthetic potential of molluscan sulfatases for the library synthesis of regioselectively O-sulfonated D-galacto-sugars

The substrate specificities of three molluscan sulfatases (E.C. 3.1.6.1; snail, abalone, and limpet origins) were investigated with assorted p-nitrophenyl (pNP) di-O-sulfonated beta-D-galactopyranosides and beta-lactosides [3,6-SO(3) Gal (1), 3',6'-SO(3) Lac (2), 4, 6SO(3) Gal (3), 2,6-SO(3) Gal (4), 3,4-SO(3) Gal (5), and 3,6-SO(3) GalNAc (6); Ac, acetyl; Gal, galactose; Lac, lactose] together with mono-O-sulfonated beta-D-galactopyranoside [pNP 3SO(3)-Gal (7)] and tri-O-sulfonated alpha-D-galactopyranoside [2,3,6-SO(3)-alpha-Gal (11)]. Some notable differences between the substrate specificity of the three sulfatases were disclosed; snail sulfatase hydrolyzed the 3O- and 2O-sulfo groups of 1 and 4, respectively, to afford 6SO(3) Gal (9) in high yields, while the abalone enzyme did not act on 4. Only the limpet enzyme could cleave the 3O-sulfo groups of 7 to give pNP beta-galactoside. In contrast, every enzyme could utilize 11 as a good substrate to afford a mixture of 6SO(3)-alpha-Gal (13) and 2,6-SO(3) alpha-Gal (12). None of the enzymes could cleave the O-sulfo groups of 5 and 6, which indicates that a primary 6O-sulfo group tends to promote the enzymatic hydrolysis of O-sulfo groups at the secondary positions.     

Pore structure of carbons coated on ceramic particles

Pore structure of carbon coated on ceramic particles by carbonization of precursor in a powder mixture at 900 °C was studied by focusing on the effects of substrate ceramics (MgO, TiO₂ and various phases of Al₂O₃) and of carbon precursor (poly(vinyl alcohol) (PVA), poly(ethylene terephthalate) (PET) and hydroxyl propyl cellulose (HPC)). By dissolving substrate MgO particles, carbon coated was found to have a high BET surface area, more than 1000 m²/g, which was almost the same as the value estimated from apparent surface area measured on carbon-coated MgO particles under the assumption of zero surface area of the substrate. The carbon separated was found to be rich in micropores from the analyses by DFT method and α_s plot. The dependence of the BET surface area on the amount of carbon coated on TiO₂ with a high surface area was the same for three carbon precursors, although the carbon yields from the precursors were slightly different. Porous Al₂O₃ substrates, γ-Al₂O₃as-received and that formed from Al(OH)₃ during carbonization, gave a high BET surface area, but dense Al₂O₃, α-Al₂O₃, gave a low surface area.     

Critical temperature for production of MAG by esterification of different FA with glycerol using <Emphasis Type="Italic">Penicillium camembertii</Emphasis> lipase

Production of MAG by a lipase-catalyzed reaction is known to be effective at low temperature. This phenomenon can be explained by assuming that synthesized MAG are excluded from the reaction system because MAG, which have low m.p., are solidified at low temperatures. Consequently, MAG are efficiently accumulated and do not serve as the precursor of DAG. If this hypothesis is correct, the critical temperature for MAG production, defined as the highest temperature at which DAG synthesis is repressed, should depend on the m.p. of the MAG. Esterification of FFA with glycerol using Candida rugosa, Rhizopus oryzae, and Penicillium camembertii lipases produced MAG efficiently at low temperatures. However, Candida lipase showed very low esterification activity at high temperatures (>20°C), and Rhizopus lipase produced not only MAG but also DAG even at low temperatures. Meanwhile, P. camembertii lipase catalyzed synthesis of MAG only from FFA and glycerol at low temperatures, although the enzyme catalyzed synthesis of DAG from MAG in addition to synthesis of MAG at high temperatures. We thus studied the effect of temperature on esterification of C₁₀−C₁₈ FFA with glycerol using Penicillium lipase as a catalyst and determined the critical temperatures for production of MAG. The critical temperature for production of each MAG showed a linear correlation with m.p. of the MAG, which supported the hypothesis. In addition, because the m.p. of MAG are estimated from that of the constituent FA, the optimal temperature for production of MAG can be predicted from the m.p. of the FFA used as a substrate.     

Preparation of micron-scale monodisperse oil-in-water microspheres by microchannel emulsification

Micron-scale monodisperse oil-in-water (O/W) micropheres (MS) were prepared using a novel microchannel (MC) emulsification technique. The characteristics of the MS preparation and the O/W-MS prepared were studied. Soybean oil and medium-chain triacyglycerol (MCT) were used as the disprrsed phase, and physiological saline was used as the continuous phase. Silicon MC with 1 to 3μm-equivalent channel diameters were employed. A novel MC module was devised to easily recover the O/W-MS prepared. The effects of the channel shape on the behavior of MS formation, on the MS size, and on the distribution were investigated. An MC with a terrace at the MC outlet stably yielded micron-scale monodisperse O/W-MS; the MS had diameters of about 5 μm, and their coefficients of variation were below 9%. Monodisperse food-grade O/W-MS with diameters of about 4 μm could be obtained by using polyglycerol fatty acid ester as the surfactant. The size and size distribution of the recovered O/W-MS remained almost constant over 60 d, demonstrating their long-term stability.