A new sesquiterpene alcohol, C₁₅H₂₂O, m. p. 69-70°C, named occidol, has been isolated from the essential oil of the wood of Thuja occidentalis L. The structure (II) is proposed for occidol.

View full abstract

(1) Non acid-fast cells of an avian tubercle bacillus were easily lysed by lysozyme, whereas acid-fast cells could be digested by a successive attack of lysozyme followed by Sclerotinia-enzyme. Bacterical lysozyme, trypsin and pancreatin, however, had no synergistic action with lysozyme. The synergistic factor contained in the Sclerotinia-enzyme extract was assumed to be a certain polysaccharidase.
2) The release of a mucopolysaccharide from the cell-wall during incubation with lysozyme increased by previously heating the cells at about 60° for 10min. The effect of heat-treat-ment upon the sensitivity of cells to lysozyme, which was accompanied by a remarkable Nakamura effect, was concluded to be due to the activation of some autolytic enzymes.

View full abstract

1. In biochemical investigations on the lipaseformation of Sclerotinia fungus, the following facts were observed. i, The original strain Ss had an activity of oxidative fermentation while its mutant Sm had not such activity; the activity of the former seemed responsible for its. high activity of lipase formation in a laterperiod of culture. ii, During the lipase formation by washed mycelium of Ss at the expense of reserved fat maintaining its carbohydrate content at a constant level in the cell, the production of alcohol and oxalic acid were recognized and the RQ value exceeded 1.0. iii, Though bile salt and cyanide were inhibitory for the endogeneous respiration they were stimulatory for the fermentation of cellular carbohydrate and the lipase activity of washed mycelium was increased to some extent. iv, The extract of bran culture of Ss itself, remarkably promoted the lipase activity of washed mycelium along with increase of RQ value and had no influence on oxygen consumption. v, The washed mycelium of Ss harvested at a later period of culture was found to decompose oxalic acid into CO₂ and formic acid.
2. The lipase type of the following fungi was proved to be dividable into two groups; One is that of Scletotinia which can react additively on olive oil with either Rhizopus or pancreatic lipase which also has a high activity, on substrates other than glyceride such as Tween ann Span, and the other is that of Rhizopus which can not react additively with pancreatic lipase.
3. The fungal lipase was shown to have considerable activity in organic solvents such as ether or petroether.

View full abstract

Two enzymes which are concerned with maltose hydrolysis in molds, saccharogenic amylase and maltase, were fractionated by adsorption with calcium triphosphate and elution with potassiumdiphosphate and diammoniumphosphate solutions. Maltase was crystallized from diammoniumphosphate eluate by a method involving fractionation with ethanol and acetone, and the removal of salted-out inpuritics. It was found that the crystalline maltase hydrolyzes maltose and phenol-α-glucoside but methyl-α-glucoside is not appreciably hydrolyzed, while saccharogenic amylase is inactive toward the latter two substrates. Optimal pH of crystalline maltase is 3.4 and opt. temperature 50°C.

View full abstract

The first budding cycle of a bakers' yeast was synchronized with the aid of the method of starving pre-cultures. Immediately after inoculation for the synchronous culture, stimulation of endogenous respiration with 2, 4-dinitrophenol (DNP) was observed, which however, disappeared when budding cycle began. During the budding cycle, inhibition effects became more stronger as the bud forming proceeded. The substrates which were dissimilated stimulative by DNP were trehalose and acid-soluble glycogen. The former was more sensitive to the increase of the concentration of DNP and was consumed by 3×10^-4M of DNP almost wholly, whereas the latter contained a labile part which was dissimilated stimulatively at a low concentration (less than 6×10^-5M).

View full abstract

Degradation studies on pyoluteorin have been conducted. Alkali fusion of dechloro-O, O', N-methylpyoluteorin (II) afforded 1, 3-dimethoxybenzene and N-methylpyrrole-2'-carboxylic acid. Lithium aluminum hydride reduction of II gave 2, 6-dimethoxyphenyl-N-methyl-2'-pyrryl-methanol (VI) indicating that a carbonyl group is linked directly to both the benzene and the pyrrole ring. Further, chromic acid oxidation of II furnished N-methyl-2, 6-dimethoxybenzoylformamide (VII) which was also obtained from O, O', N-methylpyoluteorin (I). Alkaline hydrolysis of VII gave the corresponding keto acid which was then converted with hydrogen peroxide to 2, 6-dimethoxybenzoic acid (IX). In view of these results, pyoluteorin must have the constitution of 2'-(2, 6-dihydroxybenzoyl)-x, x'-dichloropyrrole.

View full abstract

(±)-Allethrolone-methylether (II), when first oxidized by ozone and then by potassium hypobromite, affords (±)-α-methoxysuccinic acid (V) through the intermediate keto acids (III) and (IV).

View full abstract

The oxidative degradations of the methyl-ethers of naturally derived pyrethrolone and cinerolone eventually afford (-)-α-methoxysuccinic acid. This chemical conversion without disturbance of the asymmetric centre concerned, establishes, beyond doubt, the absolute configuration of the asymmetric C₍₄₎ involved in (+)-pyrethrolone and (+)-cinerolone in the ultimate correlation between these alcohols and (-)-glyceraldehyde via the key intermediate, (-)-α-methoxysuccinic acid.

View full abstract

Coniferyl alcohol, 1-(4-hydroxy-3-methoxyphenyl)-propanediol-(1, 3) and 1-(4-hydroxy-3-methoxyphenyl)-propanediol-(1, 2) have been found to react with hydrogen sulfide. From the results of paper chromatography and U. V. spectra a portion of the sulfidation products obtained from the first and second compounds appear to be identical. Upon alkali treatment, these products readily yielded a double bond conjugated to aromatic nucleus. From the last-named compound, a crystalline compound was obtained and its structure is discussed here. In accordance with previous works, it was found that symplocosigenol and dehydrodi-isoeugenol do not react with hydrogen sulfide.

View full abstract

In order to establish the mechanism of occurrence of sunlight flavour of beer in continuation of the preceding paper, humulone, lupulone, and their analogues and degradation compounds, i.e., cohumulone, adhumulone, 5-acetyl-3-methylfilicinic acid including analogues, tetrahydrohumulone, hexahydrolupulone, humulinic acid and lupuloxinic acid, were tested for the occurrence of sunlight flavour of beer.
As a result, among the above-mentioned compounds, humulone, lupulone, cohumulone, adhumulone, tetrahydrohumulone and hexahydrolupulone were found to cause the sunlight flavour, but the other compounds did not cause typical sunlight flavour. This fact shows that some specific structural components seem requisite for the occurrence of sunlight flavour of beer.
It was also revealed that isomerization caused by boiling accelerates the occurrence of the sunlight flavour of beer. Finally, the result of the experiment conducted by the gas chromatographic procedure showed that any new component is not detected by the exposure of beer to sunlight but, two components somewhat increased.

View full abstract

The isolation and identification of phenolic components contained in cigarette smoke, produced in constant-volume continuous smoking by means of an artificial smoking device, have been studied. Phenol, m-cresol and guaiacol were isolated as 3, 5-dinitrobenzoates and identified by elementary analysis, mixed examination and infrared spectroscopy. Salicylaldehyde, 2, 5-dimethylphenol, m-ethylphenol and p-cresol were identified by paper chromatography of the phenylazobenzenesulfonic acid-dye derivatives. From the crude phenolic fraction, lauric acid was paperchromatographically identified and a paraffin (m.p. 64-66°) was isolated.

View full abstract

Free amino acids in the cigarette smoke, produced in constant-volume continuous smoking by the use of an artificial smoking-device, have been paper-chromatographically studied, and twelve amino acids, i.e., α-alanine, β-alanine, glycine, glutamic acid, glutamine, serine, γ-amino butyric acid, valine, leucine, aspartic acid, proline, and ornithine(?) were qualitatively identified. Besides these amino acids, the presence of the other two unidentified ninhydrin-positive substances was observed. The presence of ten amino acids, other than glutamic acid and glutamine, has not yet been reported in the literature concerning tobacco smoke.

View full abstract

Free amino acid contained in the smoke of seven different cigarettes, respectively made from a single variety of tobacco, have been quantitatively determined by paper chromatography and colorimetry. Fourteen amino acids (α-alanine, proline, glycine, glutamic acid, glutamine, β-alanine, serine, γ-amino butyric acid, aspartic acid, valine, leucine, ornithine, threonine, and phenylalanine) and three ninhydrin-positive substances were detected. Of these acids α-alanine was most abundant (10.5-268.2γ/1 cigt.) and proline (5.5-25.1γ), glycine (4.7-22.5γ), etc. followed in this order. In general, the smoke of sun-cured or bulk-sweated tobaccos contained more kinds and more amounts of amino acids than that of flue-cured tobaccos. In another experiment, it was found that about 15% of artificially added mono-sodium glutamate is transferred into cigarette smoke.

View full abstract

PGA mutase was crystallized in two forms. The activity of the crystalline enzyme was directly assayed by the polarimetric measure-ment, The optimum pH, the equilibrium constant at 25°C, and the Michaelis constant for the coenzyme were determined.
Among the compounds structurally related to the substrate, only phosphoryl enolpyruvate inhibited the enzyme. In relatively high concentrations various metallic ions showed inhibitory effects, but the SH-inhibitors had little effect. Moreover the chelating agents given in relatively high concentrations inhibited the enzyme. It is then discussed whether the mutase may be the metal enzyme or not. Fluoride inhibited the activity. However, this inhibition was prevented by the addition of EDTA or citrate, whose concentration was higher than that of fluoride. The mechanism of fluoride inhibition is discussed.

View full abstract

Crystalline PGA mutase was recognized as a heterogeneous protein by moving boundary electrophoresis and was then completely separated into each component by zone electrophoresis.
Among the six components obtained, five of them (I-V) had the PGA mutase activity, and the specific activity of component I was the highest and the others became lower in order. The differences among the properties of those components were also discussed.
As the components (I-V) had a small activity in the absence of the added coenzyme, it is considered that a small amount of the coenzyme combines with each component. Though fluoride inhibited the activity of each component, it could not inhibit its activity in the presence of chelating agents.

View full abstract

It has now been shown that Acetate A¹⁾ previously obtained by isomerizing ilexol acetate is nothing other than urs-13 (18)-en-3β-yl acetate prepared²⁾ from α-amyrin, furnishing conclusive evidence for its conversion into one of the compounds of the ursane series.
Isoilexol, oxidized with chromium trioxide at room temperature, afforded a ketone named isoilexone, C₃₀H₄₈O, m.p. 194-195°, [α]_??_+75.90° (c, 0.527), and oxidized with the same oxidant at 70-80°C, another ketone named isoilexenedione, C₃₀H₄₆O₂, m.p. 221-223°, [α]_??_+16.28° (c, 0.307).
Huang-Milon reduction of these ketones afforded one and the same deoxy compound named isoilexene, C₃₀H₅₀, m.p. 183-185°, [α]_??_+48.34° (c, 0.290), which might well be assumed to constitute a pair of optical antipodes with olean-13 (18)-ene, C₃₀H₅₀, m.p. 184-185°, [α]_??_-48.50° (c, 0.545).

View full abstract

Cell suspensions of Aerobacter aerogenes formed a remarkable amount of phenolsulphatase and dissimilate tyramine, provided a suitable primer was present with tyramine. As a primer, many carbon sources, especially, a mixture of amino acids could be considered useful. Several compounds such as glucose strongly inhibited not only the utilization of tyramine but also the phenolsulphatase synthesis of the cell suspensions containing tyramine and casein acid-hydrolyzate, while other compounds such as xylose either ineffective or only a little effective to both of the reactions. Therefore, the possibility that there might be a functional relationship between the ultilization of tyramine and the phenolsulphatase synthesis of Aerobacter aerogenes was considered.

View full abstract

Isohibalactone, the geometric isomer of hibalactone, was synthesized by the following route. Piperonylsuccinic acid anhydride was converted into thioethyl methyl ester ans was reduced to piperonylbutyrolactone by Raney nickel catalyst. Piperonylbutyrolactone was also prepared from piperonylsuccinic anhydride by the reduction with amalgamated aluminum. Condensation of piperonal with the lactone in the presence of potassium amide afforded α-(3, 4-methylenedioxy-phenyl-hydroxymethyl)-β-(3, 4-methylenedioxybenzyl)-butyrolactone, m.p. 151_??_2°C. Dehydration of the hydroxylactone with p-toluenesulfonic acid gave isohibalactone, m.p.156-6.5°C.

View full abstract

Petroleum ether extract of the heartwood of Cryptomeria japonica D. Don contains isodextropimaric acid, sugiol, xanthoperol, and a viscous resin. After saponification of the resin fraction, β-sitosterol, ferruginol, xanthoperol and an unknown compound are found to be present, showing the occurrence of these substances in states of chemical combination with other constituents. It has now been proposed that isodextropimaric acid is optically active.

View full abstract

During investigations conducted on the mode of degradation of ribonucleic acid by Microorganisms, it was found that one strain of Penicillium produces nucleoside-5'-monophosphates from ribonucleic acid. Identification of these nucleoside-5'-monophosphates was carried out by means of chromatography on anion exchange column, ultraviolet spectrophotometry, paper electrophoresis, and characteristic color reactions using orcinol, carbazole, and rosaniline. It is suggested that this strain contains 5'-phosphodiesterase (or 5'-phosphodiesterase system) which cleaves all of the 5'-phosphodiester linkages in ribonucleic acid thus giving rise to nucleoside-5'-monophosphates. It is a point of interest in this study to indicate the presence of 5'-phosphodiesterase for the first time in a common microorganism, as 5'-phosphodiesterase has been recognized only in somewhat particular materials such as snake venom.

View full abstract