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(1) ソテツ種子の胚乳のリボヌクレアーぜを水抽出,硫安塩析,連続3回のDEAE-セルロースカラムクロマトグラフィーにより,高純度に精製した. (2) この酵素は至適pH 4.7であり,PH 3～11の間では比較的安定であるが,pH 4.7で65°C以上の加熱で急激に失活し,90°ではほとんど完全に失活する. (3) この酵素は,食塩の0.1～0.15Mで最も活性が強いが,0.4Mでも余り阻害されない.2価の金属イオンでは,10-3MのHg2+で強く阻害され,Pb2+もやや阻害的に作用するが,Mg2+,Ca2+,Mn2+,Zn2+ではほとんど影響されない. (4) この酵素は,リボ核酸に作用してヌクレオシド2',3'-環状リン酸を生ずるが,その場合,プリン系2',3'-環状リン酸エステルの方がピリミジン系のそれよりも生産が早い.

From the tissues of the silkworm several nucleolytic enzymes were detected. Among these, acid ribonuclease (RNase) and alkaline nuclease were dominant. The optimal pH values for these are 5·3 and 10·3, respectively. An acid deoxyribonuclease (DNase), optimally active at pH 5, was also found in the tissues of the insect. Changes of activity were investigated of the acid RNase and the alkaline nuclease through the whole life cycle of the silkworm. The former remains very active during each step of development. By contrast, the latter exists at higher levels only during the feeding period, and then drops abruptly to an almost undetectable level at the initiation of spinning. The acid DNase activity showed a peak 3 days after pupation. The acid RNase and DNase showed a wide distribution in the tissues of the silkworm, whereas the alkaline nuclease is restricted to the gut juice and to the gut.

リボヌクンオシド-3´(2´), 5´-ジ燐酸のカラムクロマトグラフによる分析法を確立した.これによって, 5´-末端燐酸基および3´-末端水酸基を有するオリゴリボヌクンオチドの両側末端および内部残基の分離同定が常法化された.さらに,より簡便な2次元濾紙クロマトグラフ法が同じ目的のために考案された.

C-Alkylations of some N-acetonyl- and N-phenacylamides were effected with alkyl halides by means of sodium ethoxide in ethanol or potassium amide in liquid ammonia. The present paper deals with its scope and structural limitation for these alkylation reactions.

(1) ソテツ花粉細胞を破壊することなく種々の塩類溶液に浸漬するとPMaseやRNaseが溶出されるが,シュクロースやグルコースなどの非電解溶媒では溶出されないことを見出した.食塩による最適溶出濃度は0.5Mであり,その濃度では花粉から酵素は急速に溶出された. (2) 酢酸亜鉛は0.5M食塩の存在下でもRNaseの溶出をさまたげたが, PMaseは溶出させた.その作用が亜鉛イオンによるものかどうか明らかにできなかった. (3) 酢酸ナトリウムによって花粉から溶出したRNaseをDEAE-セルロースカラムクロマトグラフィー,セファデックスG-100によるゲル濾過によって部分精製を行なった.得られたRNase画分は収率37%であり, PMaseは0.03%以下にまで除去された. (4) 精製されたRNaseは,至適pHが5.7付近にあって, RNAを分解してヌクレオシド2', 3'-環状リン酸および3'-モノヌクレオチドを生じた.

2:1 styrene-polysulfone was subjected to an alkaline degradation with potassium tert-butoxide in dimethylsulfoxide at 50°C. A random and not an unzipping degradation was operating throughout the decomposition and β-phenylbutyrophenone and other materials were obtained as the products, indicating dimeric and head to tail sequences are dominating in the polymer chain. NMR spectrometry was also undertaken to get a further information on the chain constitution, where repeating (StStSO2) sequence is believed to be the principal part of the polymer chain as compared to the NMR spectra of polystyrene, poly-α-methyl-styrene, and the high styrene containing styrene-polysulfone. 2:1 Styrol-Polysulfone wurden in Dimethylsulfoxid mit Kalium-tert.-butylat bei 50°C einem alkalischen Abbau unterworfen. Dieser vollzog sich statistisch und nicht nach einem Reisverschlusmechanismus. β-Phenylbutyrophenon und andere Reaktionsprodukte weisen auf dimere Kopf-Schwanz-Sequenzen als dominierend in der Kette hin. Auch NMR-Spektrometrie wurde angewendet, um eine weitere Information uber den Kettenaufbau zu erhalten. Es wird angenommen, das (StStSO2)-Sequenzen den Hauptanteil der Kettenabfolgen bilden, wie ein Vergleich mit den NMR-Spektren von Polystyrol, Poly-α-methylstyrol und styrolreichem Styrolpolysulfon ergibt.

Catalytic hydrogenations of both series of the compounds, N-arylmethylene-1-acylamino-1-arylmethylamines and hydroamides, over Raney nickel catalyst were examined under both conditions, in the presence of formamide and in the absence of it. While under the latter condition either of the hydrogenations proceeded to give secondary amine at least as one of the principal reduction products, under the former condition resulted in the predominant formation of N-formylated priomary amine. In correlation with the previously reported azomethine-formamide hydrogenation the reaction paths for the hydrogenations influenced by formamide were revealed to be of involving intermediates, azomethine, aldimine, and N-arylmethylene-1-formamido-1-arylmethylamine (in the case with hydroamides).

Porphyrin-metal compounds were extracted from various crude oils, and porphyrin aggregate was prepared through de-metallization procedure of the compounds. Absorption and fluorescent spectra were measured on both the extracted salts and the aggregate. Peaks of complex salts of porphyrin with vanadium or nickel were clearly found in almost all absorption curves. Fluorescent bands were not found in the spectra of metal salts, while the spectrum of free porphyrin aggregate showed a fluorescent band at 625mμ.Since the content of non-extracted vanadium in the distillate was negligible small, the analysis of vanadium in the distillate should be carried out by measuring the intensity of absorption band on complex salt of porphyrin with vanadium. Optimum conditions of the procedures were examined, and the result showed that the analysis was possible within the standard tolerance of 1-5% and total time of 20min. Actual results conducted on FCC plant control were given.

Treatments of β-chlorovinylaldehydes with zinc powder in ethanol selectively remove the β-chlorine atom to give the α, β-unsaturated aldehydes. However, the same treatments in nitrogen atmosphere and, preferably, by using the activated zinc powder lowered remark ably the yield of the α, β-unsaturated aldehydes and give the reductive dimer, 1, 2-di-(1-alkenyl) ethylene glycol, as major product.

1. For the purpose of studying intracellular electrolyte metabolism in patients with congestive heart failure and the effect of digitalis on them, sodium and potassium concentrations in erythrocytes in twenty-one patients with compensated heart disease or chronic congestive heart failure were measured. In 13 patients of these subjects, sodium and potassium concentrations in erythrocytes before and during administration of digitalis were measured. At the same time, sodium, potassium and aldosterone excretion in urine and venous pressure were estimated. 2. For determination of normal ranges of red cell Na, K concentrations by the method applied in the present study, 9 normal blood samples were obtained from healthy physicians and nurses. Their means and standard deviations are given next. Sodium concentration in serum is 143.8±2.88mEq/L. Potassium concentration in serum is 4.29±0.29mEq/L. Sodium concentration in red cells is 12.0±1.45mEq/L. Potassium concentration in red cells is 99.3±3.72mEq/L. 3. Sodium and potassium concentrations in serum and red cells before the onset of treatment in patients with congestive heart failure. i) Sodium concentration in serum was significantly decreased, whereas that in red cells was kept in almost normal range. ii) Potassium concentration in red cells was significantly increased along with the clinical grades of heart failure, whereas that in serum was kept in almost normal range. 4. Influence of digitalization on serum and red cell sodium and potassium concentrations in patients with congestive heart failure. i) Sodium concentrations in red cells in 9 of 10 patients were increased, whereas those in serum in 8 of 10 patients were not changed. ii) Potassium concentrations in red cells in all 10 patients were decreased to the normal range; on the other hand those in serum in 5 patients were increased, 3 were decreased and 2 were not changed. 5. One of the influences of therapeutic dose of digitalis on red cell electrolytes may be due to the direct effect of digitalis on erythrocytes (particularly on their membranes) especially in the early stadium of its administration, but during the late stadium with its maintenance dose, there may be some indirect effects due to haemodynamic improvement of congestive heart failure.

An accurate method for estimating light hydrocarbons in crude oil was developed. Since in conventional procedure of analysis some loss of C1 and C2 was inevitable, we made and used a hermetically sealed sampler. By comparing gas chromatography with fractional distillation for practical merits, it was concluded that the former was more adequate for analytical method; therefore, the former was applied.The chromatograph was equipped with a prefractionating system for cutting out light fraction of crude oil. The analysis was composed of two steps; at first n-pentane in crude oil was determined by using blended 1-pentene as internal standard; and secondly, other C1-C5 components were analysed with sealed sample by using n-pentene as standard. The accuracy and precision of this method were more excellent as compared with usual methods.

Catalytic hydrogenation of some azomethines, such as N-benzylideneaniline, N-benzylidenebenzylamine, and N- (4-methoxybenzylidene) phenethylamine in the presence of amide was examined under high pressure of hydrogen. The reaction resulted in conversion, ArCH=NR+2R'CONH2+H2→ArCHNHCOR'+RNHCOR'+NH3, particularly in excellent yields with formamide. With regard to this reaction path, it was recognized that the initiating essential reaction between azomethine and formamide would be the reaction, ArCH=NR+HCONH2→ArCH=NH+RNHCHO (NH3 acts as a catalyst), which was demonstrated by using N-benzylidene-4-sulfonamidobenzylamine as azomethine. Based on this reaction, the whole pathway for the above hydrogenation reaction was proposed. Mechanism for hydrogenation reaction of nitriles, oximes, and ammoniaaldehyde mixtures in the presence of formamide was also suggested.

Thermal reactions of the representative azomethines of N-benzylidene type with the reagents, trimethylammonium formate given by 5HCO-2H·2N (CH3)3, ammonium formate and formamide, were examined in order to elucidate distinctions among them. The reduction and oxidation coureses as to the formate reaction and the formamide reaction were definitely distinguished from each other ; in the former reaction saturation of the azomethine double bond is induced by ixidation of formic acid to carbon dioxide and in the latter reaction reductive cleavage at the double bond, induced by self-oxidation of the azomethine, leads to the formation of the cleaved N-formylated primary amines. Elucidation on the mechanistic paths as to both of the essential reactions was investigated. Particularly, the pathways of the very complicated formamide reaction were declared to be of involving aldimine, hydroamide, N-arylmethylene-1-formamido-1-arylmethylamine and N, N'-arylmethylenebisformamide as major or minor intermediates.