Continuous hydrolysis of olive oil by lipase in microporous hydrophobic membrane bioreactor

Continuous hydrolysis of olive oil byCandida cylindracea’s lipase was studied in a microporous hydrophobic membrane bioreactor. Olive oil and buffer solution, fed continuously through two compartments partitioned by membrane, caused reaction at the interface of lipase-adsorbed membrane and buffer solution. Fatty acid was obtained in a single phase without being mixed with components of other phases. At all mean residence times, countercurrent flow mode was superior to cocurrent one. The lipase was adsorbed onto the membrane, and its adsorption was suggested to be partially specific from the experiments with enzymes having various levels of purity. The percent hydrolysis depended hyperbolically on the interfacial enzyme concentration. The hydrolysis seemed to be limited by diffusion of fat or fatty acid through the micropores of the membrane at higher interfacial enzyme concentrations. The lipase was stabilized significantly by glycerol added to the buffer solution. Satisfactory performance of the membrane bioreactor was obtained in a longterm continuous operation which lasted for 24 days by feeding buffer-glycerol (18.0%) solution over the adsorbed lipase. The operational half-life of the adsorbed enzyme was 15 days at 40 C.     

Quality-Assurance Technology in Japan

A survey of the state of SQA in Japan finds that the situation is much like, but slightly different than, that in the US.     

Activity measurement of the constituents in molten Fe–B and Fe–B–C alloys

The distribution ratios of Fe and B between molten Fe–B alloy and molten Ag were measured at temperatures between 1573 and 1923 K. Also, distribution ratios of Fe and B between molten Fe–B–C_satd. alloys and molten Ag were measured at 1873 K. It was found that the excess Gibbs free energy of mixing in molten Fe–B and Fe–B–C alloys can be expressed by utilizing the Redlich–Kister polynomial. The activity curves of the elements in molten Fe–B alloy and Fe–B–C alloy were estimated.     

Application of the solid polymer electrolyte (SPE) method to organic electrochemistry—III. Kolbe type reactions on Pt-SPE

The feasibility of a solid polymer electrolyte (SPE) method for Kolbe type reactions was investigated by using Pt-SPE composed with Nafion 415 and platinum. The Kolbe reaction of acetic acid proceeded effectively on one side and both sides Pt-SPE composites. The lower current efficiency was observed on the latter than on the former. Neat acetic acid could also be electrolysed on both sides SPE though the cell voltage was fairly high.A methanolic solution of monomethyl adipate was electrolysed to give dimethyl sebacate on both sides Pt-SPE according to the Brown-Walker reaction. The current efficiency and the terminal voltage increased with the concentration of monomethyl adipate. Pt-SPE behaved as an active electrode of a high roughness factor, eg about 6, for the Kolbe reaction of acetate.     

Polymerization via zwitterion 25. Alternating copolymerizations of cyclic acyl phosphorite and phosphite with vinyl monomers having an electron withdrawing group

Summary Spontaneous copolymerizations of cyclic acyl phosphonite (SPO) and phosphite (SPI) with an electron-deficient vinyl monomer such as methyl acrylate (MA), methyl vinyl ketone (MVK), and acrolein (AL), gave the corresponding alternating copolymers. These copolymerizations took place without added initiator and proceeded through zwitterion intermediates. Copolymer structures 1a, 1b, 2 and 3 have been established, all of which were derived in a regiospecific manner of ambident anions. The scheme of the copolymerizations is presented.     

Cationic ring-opening polymerization of 2-phenyl-1,3,6,2-trioxaphosphocane

Summary The ring-opening polymerization of 2-phenyl-1,3,-6,2-trioxaphosphocane (4), an eight-membered cyclic phosphonite, has been investigated. Cationic initiators of PhCH₂-Cl and MeOTf gave polymers, whereas anionic and radical initiators did not yield polymer. The structure of polymer was examined by IR, ¹H, ³¹P, and ³¹C NMR spectroscopy of polymers and elemental analysis as well as the alkaline hydrolysis products. The polymer consisted of two different units, i.e., the major part is the normal phosphinate structure 5 and the minor part is the isomerized unit 6 in 7% with PhCH₂Cl initiation and in 34% with MeOTf initiator. The difference in nature of propagating species from these two initiators are discussed in connection with their reactivities.On leave from the Institute of Chemistry, Academia Sinica, Beijing, China     

Catalysis of gasification of coal-derived cokes and chars

Calcium is the most important in-situ catalyst for gasification of US coal chars in O₂, CO₂ and H₂O. It is a poor catalyst for gasification of chars by H₂. Potassium and sodium added to low-rank coals by ion exchange and high-rank coals by impregnation are excellent catalysts for char gasification in O₂, CO₂ and H₂O. Carbon monoxide inhibits catalysis of the CH₂O reaction by calcium, potassium and sodium; H₂ inhibits catalysis by calcium. Thus injection of synthesis gas into the gasifier will inhibit the CH₂O reaction. Iron is not an important catalyst for the gasification of chars in O₂, CO₂ and H₂O, because it is invariably in the oxidized state. Carbon monoxide disproportionates to deposit carbon from a dry synthesis gas mixture (3 vol H₂ + 1 vol CO) over potassium-, sodium- and iron-loaded lignite char and a raw bituminous coal char, high in pyrite, at 1123 K and 0.1 MPa pressure. The carbon is highly reactive, with the injection of 2.7 kPa H₂O to the synthesis gas resulting in net carbon gasification. The effect of traces of sulphur in the gas stream on catalysis of gasification or carbon-forming reactions by calcium, potassium, or sodium is not well understood at present. Traces of sulphur do, however, inhibit catalysis by iron.     

A radical scavenging reaction of α-tocopherol with methyl radical

To study a radical scavenging reaction of α-tocopherol, it was reacted with methyl radical in dimethyl sulfoxide. Two main products, a geminal dimethyl cyclohexadienone and methyl ether of α-tocopherol, were obtained and these structures were determined by¹³C nuclear magnetic resonance spectroscopy. The radical methylation data of α-tocopherol suggested that a delocalized radical species would be an intermediate. TMIG-RI No. 3.     

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.     

Copolymerization of ethanesultam with 2-methyl-2-oxazoline

Summary This paper describes the so-called No Catalyst Copolymerization between dioxo-1,1-thiazetidine-1,2(Ethanesultam; ESm) and 2-methyl-2-oxazoline. The copolymerization took place without any added initiator to produce copolymers of MeOZO and ESm. The structure of the copolymer was determined by the IR and NMR spectra, elemental analysis, as well as by the result of an alkaline hydrolysis of the copolymer. The reaction scheme of the copolymerization via zwitterion mechanism (Eq 3–5) was proposed.