A strain of Macrosporium porri Elliott, when grown at 25° on 2% glucose solution of stone-leek decoction, gives rise to a hitherto undescribed pigment to which the name “macrosporin” is proposed. Optimum cultural condition for the production of the pigment and the method of its isolation are described here. Macrosporin, C₁₆H₁₂O₅, crystallizes as orange-yellow rhombic and melts at 300-302° with decomposition. General properties of macrosporin, its diacetate, m. p. 209-210°, and trimethylether, m. p. 260-261°, are described. Macrosporin is recognized to be a hydroxyanthraquinone derivative from the results of elementary analysis, molecular weight determination, and ultra-violet and infra-red spectra.

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The geometrical configuration of αδ-dimethylsorbic acid, an important intermediate in our successful total synthesis of chrysanthemum-dicarboxylic acid, is confirmed to be trans by the ultra-violet and infra-red absorptions and also by the dissociation constant of αδ-dimethyl-Δα-hexenoic acid derived from the parent αδ-dimethylsorbic acid by semi-hydrogenation over a palladium catalyst. Thus, the trans-configuration of this acid, previously deduced on a theoretical basis, is free from any experimental defect, and thence, the trans-configuration of the side-chain double-bond of the naturally derived chrysanthemum-dicarboxylic acid follows from the method of synthesis from trans-αδ-dimethylsorbic acid. This method of assignment may, in general, be applicable to the α-alkyl substituted conjugated diene carboxylic acids.

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1) The protease from the cultural filtrate of Ps. myxogenes sp. was purified and crystal-lized in a needle-like form with a high yield (0.5-0.9g of the once recrystallized ones from 5 liters of broth).
2) The crystalline protease was found to be homogeneous in nature, with electrophoresis at pH 8.07, and the i. e. p. was pH 5.5-6.0. For ultraviolet absorption spectrum, the maximum was observed at 275mμ and the minimum at 250 mμ. The M. W. has been confirmed to be about 77, 000 by the diffusion method. It showed a typical protein reac-tion in elementary analysis or by composition of amino acids.
3) By heat-treatment, the crystalline pro-tease was found to be stable up to 50°C and was inactivated rapidly over 58°C. At 58°C the enzyme was greatly protected by metal ions such as Ca, Mg, Mn or Co, but these ions did not show any protective action over 64°C. The enzyme was found to be unstable below pH 4.0, but stable between pH 5.5 to 10.0.
4) Enzymatic action of the crystalline protease was inhibited by the heavy metal ions such as Fe⁺⁺⁺, Fe⁺⁺, Hg⁺⁺, Cu⁺⁺, Ag⁺, Pb⁺⁺ or Zn⁺⁺. The high concentration of HCN, cystein or phenyl-hydrazine lowered the enzymatic action, but it was not affected by the low concentration. Enzymatic activity was not altered by EDTA-treatment, there-fore, it is concluded that Ca has no relation to enzymatic activity.

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The mold acylase has been purified by precipitation of the enzyme-rivanol complex and elution from the complex, together with fractionation with ammonium sulfate and acetone.
The mold acylase appears to be specifically activated by Co⁺⁺ ion and inactivated by Mn⁺⁺ and Hg⁺⁺ ions as well as by EDTA.
The enzyme activity inhibited by EDTA was restored to its original level with the addition of the cobaltous ion.
This research was aided by a grant from the Ajinomoto Company.

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Three racemates of pyrethidic (chrysanthemumdicarboxylic) acid were synthesized by various routes including schemes (2), (3), (4) and (5); thus, the total syntheses of three of the possible four racemates were attained. The stereochemical configurations for these racemates were tentatively assigned although no definite evidence was available. d-trans-Pyrethidic acid, naturally occurring chrysanthemumdicarboxylic acid, was also synthesized via scheme (2)

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1. Investigations were carried out on the formation of γ-pyrone derivatives, i.e. comenic acid, rubiginic acid and rubiginol from thirty kinds of carbohydrates, and fifteen kinds of organic acid. Gluconoacetobacter liq. was formed only from glucose, gluconate and 2-keto-gluconate.
2. Intact cells oxidized glucose, gluconate and 2-ketogluconate with carbon dioxide evolution, but in the presence of DNP (2×10^-3M) evolution of carbon dioxide was not observed, and 1.5, 1.0 and 0.5 moles of oxygen were consumed per mole of glucose, gluconate and 2-ketogluconate, respectively. Dried cells and cell-free extracts also showed the same oxidative pattern as intact cells in the presence of DNP.
3. Oxidation of glucose, gluconate and 2-ketogluconate by dried cells proceeded in phthalate buffer and was not affected by phosphate. Sodium fluoride (5×10^-2M) did not inhibit the oxidation of glucose.
4. Intact cells oxidized glucose, gluconate and 2-ketogluconate and formed the same oxidative products, i.e. the three γ-pyrone derivatives, and glycolic and tartronic acid.
5. As the oxidative product of Ca-2-keto-gluconate by dried cells, Ca-2, 5-diketo-gluconate was isolated and identified. Glu-conoacetobacter liq., formed the same oxidative products as described above from Ca-2, 5-diketogluconate.
6. The chemical pathway of glucose degradation by Gluconoacetobacter liq. was discussed and the most presumable pathway involving the formation of γ-pyrone deriva-tives was given.

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The presumption that some carbohydrates contained in the Virginia tobacco leaf converge to some furfural compounds in the stage of steam distillation was proved to be correct. The content of furfural compounds in the ether extractive-fraction was proved very much small in comparison with that in the essential oil. From the steam distillated essential oil, 5-hy-droxymethylfurfural and acetone were newly isolated and identified. Besides these results, the presence of C₆-aldehyde was also estimated.

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The constituents and contents of the carbonyl compounds, contained in the essential oil of Virginia tobacco leaves, were compared before and after redrying and aging. In the course of the redrying and aging stage, furfural, isobutyraldehyde and the estimated C₆-al-dehyde decreased, while, on the contrary, 5-hydroxymethylfurfural and 5-methylfurfural increased. Acetone is the only constituent that has been found after redrying and aging.

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Pantothenate synthesis from pantoate and β-alanine by Escherichia coli extracts was studied as a model synthesis of the peptide bond. It was found as the evidence for occurence of pantoyl-carboxyl activation that a significant quantity of pantoic acid hydroxamate was formed in the reaction mixture containing pantoate and ATP. Formation of pantothenate and development of hydroxamate color from activated pantoate were increased under the anaerobical conditions. Inhibition by -SH reagents and reversal of inhibition by thiol com-pounds are indicative of the evidence for involvement of -SH enzyme in pantothenate syn-thesis and pantoate activation. In view of these results, pantoate activation is formulated as shown in the following two-step reaction:
(1) HS-E+AMP_??_PP_??_PP_??_S•E+AMP
(2) PP_??_S•E+C₅H₁₁O₂•COO^-_??_C₅H₁₁O₂•CO_??_S•E+PP.

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(1) Fatty acids in essential oils of tea leaves (four kinds of essential oils previously reported, are represented as C-(l), W-(1), C-(2) and W-(2)) and green tea were iden-tified by paper chromatography.
(i) Acetic, propionic, n-butyric, isobutyric, isovaleric and caproic acid were found in C-(1) and W-(1). These acids have been reported by Takei et al.
(ii) Caprylic acid was found in W-(1), W-(2) and in the essential oil of green tea, but not in C-(l) and C-(2).
(iii) Formic acid was found in C-(1), W-(1) and W-(2). The presence of this acid in fresh tea-leaves has not been reported previously.
(2) Palmitic acid was obtained in a pure form from C-(1) and W-(1), by standing at -24°_??_-26°C.

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The synthetic procedure for the preparation of DL-tryptophan, reported by Warner and Moe has been investigated. In the Michael-type condensation between acrolein and ethyl acetamidomalonate, a number of organic and inorganic basic substances were employed and their catalytic activity was studied. Anion exchange resins were found to be a convenient catalyst for the reaction. γ-Acetamido-γ, γ-dicarbethoxybutyraldehyde, a product of the above reaction, was obtained as phenylhydrazone, and the Fischer indole synthesis, that is, the conversion of the phenylhydrazone into ethyl α-acetamido-α-carbethoxy-β-(3-indole)-propionate, was successfully carried out by employing cation exchange resins as a catalyst. Subsequent hydrolysis and decarboxylation of the indole derivative gave DL-tryptophan in a good yield.

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To find out a convenient method for the resolution of DL-tryptophan, asymmetric synthesis of acyl L-tryptophan anilides, and asymmetric hydrolysis of DL-tryptophan esters and DL-tryptophan amide were investigated. As a result, the enzymatic hydrolysis of DL-tryptophan amide was found to be an advantageous procedure for the resolution of DL-tryptophan.

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