微生物酵素処理によって得られたsoybean 11 S globulinの乳化特性

The hydrolysate coagulum produce by hydrolyzing soybean 11S globulin with enzymatic treatment at 65℃, pH 6.1 for 30 min was found to have a desirable taste. On the other hand, hydrolysates that have hardly bitter taste were obtained by hydrolyzing the soybean 11S globulin with 1N hydrochloric acid for a period of over 2 hours at 65℃. The emulsion stability(ES) and emulsion capacity(EC) of the hydrolysates of soybean 11S globulin at pH 6.1 were superior to those of acid-treated soybean 11S globulin. When the quantity of the enzyme was 0.03 units, the values of the emulsifying properties of the hydrolysates increased constantly with the reaction time, and the reproducibility of the values was very high.pH6.1，65℃で酵素反応を30分行う事で11Ｓglobulinの加水分解により得られた分解物であるcoagulumの味は好ましいものであった．一方，１Ｎ-HClを用いて11Ｓglobulinを65°Cで２時間以上反応させたところ，加水分解物は常に強い苦みを持っていた．pH6.1での酵素による加水分解物の乳化安定性（ES）および乳化力（EA）は酸処理したsoybean11Ｓglobulinの加水分解物のそれより優れていた．酵素量が0.03unitの時，加水分解物の乳化特性の値は一定に増加し，また，値の再現性は常に高かった

不斉合成における最近の手法と考察(総説)

Some asymmetric syntheses were presented here and discussed briefly including NADH model reactions, phase transfer-catalyzed asymmetric epoxidation, enantiotopic group-selective hydrolysis of a malonic anhydride with alkoxide anion, intramolecular acid-catalyzed lactonizations, catalytic asymmetric Diels-Alder synthesis, asymmetric aldol condensation, chiral homoallyl alcohol synthesis, asymmetric addition of diethylzinc to aldehyde, kinetic resolution of racemic hydroperoxides and binaphthol by lipas, and lipase-catalyzed enantiotopic group differentiation of 2-O-benzylglycerol and 2-alkylpropanediol

オリーブに含まれるオリーブアナアキゾウムシ摂食刺激物質β-sitostery-D-glucoside

The olive weevil [Dyscerus perforatus (ROELOFS); Coleopetera; Curculionidae] is a native species in Japan and now the most serious pest of the olive trees. Originally, this weevil seemed to colonise Ligustrum japonicum Thumb. and L. obtusifolium Sieb. et Zucc, both of which belong to the same oleacea family as olive. However, when olive trees were introduced to Japan in 1908, the weevils immediately attacked the plants and soon preferred them to the former hosts. Unlike in the former hosts, where the weevils live in a low population density, it is extraordinary high in the case of olive trees and the subsequent assault becomes seriously damaging for the host plant. During the course of our study on the relationship between olive trees and olive weevils, we came to be interested in the possible chemical constituents that are responsible for host selection and attraction of the olive weevil to this plant. Previously, we reported that a secoiridoid gluconside, oleuropein, and some lignans, (-)-olivil and (+)-l-acetoxypinoresinol, from the olive tree stimulated the feeding habit of the weevil. In this study, we found a steroidal glucoside as another feeding stimulant component in the olive tree. Here, we describe the isolation, characterization and activity of this feeding stimulant.オリーブアナアキゾウムシは，モクセイ科のオリーブに多数寄生し甚大な被害を与えるため，オリーブ栽培上の深刻な問題となっている．我々は，これまでオリーブのメタノール抽出物から，オリーブアナアキゾウムシの摂食刺激成分として，雌雄に活性を示すセコイリドイド配糖体1種と，雌に特異的に活性を持つ2種のリグナン類を得た．さらに今回，同じメタノール抽出物から，活性物質としてステロイド配糖体であるβ-sitosteryl-D-glucosideを得た．この成分は雌雄に対してほぼ同等の摂食刺激活性を示した

An Endonuclease Excising 8-Oxo-2'-deoxyguanosine in Regenerating Rat Liver

Oxidative DNA damage is generated in every tissue in the body, and is mainly excised by glycosylases. However, endonucleases and exonucleases are suggested as being present in tissues, since oxidized nucleosides such as thymidine glycol and 8-Oxo-2'-deoxyguanosine are detected in urine. For this reason, we studied repair enzymes induced in regenerating rat liver, and detected an enzyme cleaves phosphodiester bonds on the 5'side of 8-oxo-2'-deoxyguanosine nucleotides in DNA. The coexistence of this enzyme and phosphodiesterase II results in the release of 8-oxo-2'-deoxyguanosine monophosphate from calf thymus DNA enriched with 8-oxoguanine by γ-ray irradiation. This enzyme is found in regenerating rat liver, but not in normal rat liver. The enzyme may have a specific connection to DNA replication.DNA酸化傷害は身体中のあらゆる細胞で発生し，主にグリコシラーゼ類によって除去されている．しかし，チミジングリコールや8-オキソ-2’-デオキシグアノシンのような酸化ヌクレオシドも尿中に排泄されてきて検出されるので，エンドヌクレアーゼとエキソヌクレアーゼが組織中に存在することが示唆される．本研究は複製が活発に行われる再生肝を用いて，エンドヌクレアーゼ活性を持つ修復酵素をホスホセルロースカラムによって分離して検出することを試みた．その結果，再生肝中にDNA中の8-オキソ-2’-デオキシグアノシンヌクレオシドの5’側のホスホジエステル結合を切断する活性があることが判明した．本酵素とホスホジエステラーゼを共存させると，γ-線を照射して8-オキソグアニンを豊富に含む子ウシ胸腺DNAから，8-オキソ-2’-デオキシグアノシンが放出された．本酵素はラット再生肝では認められたが，通常のラット肝では認められなかった．本酵素は，DNA複製と特異的に関連しているのかもしれない

ケニア産キク科薬用植物Vernonia hindiiに含まれる生物活性物質

A novel stigmastane-type steroid glucoside glucoside has been isolated from the aerial parts of Vernonia hindii.The structure was elucidated by spectroscopic methods.The compound exhibitewd lettuce seedling growth inhibitory activity.熱帯・砂漠など特殊な環境に自生する植物には、生物活性2次代謝物質を含むものが多く、古くから民間伝承薬や天然殺虫剤として使用されてきた。しかし、まだ十分に調査・研究されていない植物も残されている。本研究では、ケニアに自生するキク科薬物植物のVernonia hindiiに含まれる活性物質の単離と構造解明を行い、その生物活性を調べた。植物生長制御試験を指標としてV . hindiiのメタノール抽出物を文画・精製した結果、新規の化学構造をもつ植物生長抑制物質を単離した。さらに、種々の分析機器を用いて化学構造を解析し、stigmastan型のステロイド配糖体であると決定した。この化合物は100μg / discでコントロールと比べ、24％まっでレタスの生長を抑制した

多価不飽和脂肪酸を２位に結合するホスファチジルコリンの炭素アナローグの合成

Carbon analogues of Phosphatidylcholines having linoleic or arachidonic acid at the 2-position were synthesized. The synthetic route involves conversion of the polyunsaturated fatty acid iodination. The derivatives were converted to diols by LiAIH4 reduction and submitted to lipase-catalyzed monostearoylation in isopropylether. The mono-ester was converted to phoshatidylcholines by the usual phosphodiester synthesis.自然界に広く存在するホスフォリパーゼA2はグリセロリン脂質の2位のエステル結合を選択的に切断する酵素であり,消化,アラキドン酸カスケードの起動,リン脂質過酸化物の代謝等,生理作用に広く関わっている。本研究ではホスフォリパーゼA2の基質ミメテイックとしてホスファチジルコリンの2位エステル結合が炭素-炭素結合に置き換わった化合物をアラキドン酸とステアリン酸を出発原料としてリパーゼ触媒によるアシル化反応及び有機化学反応によって合成した

Reactions of 1-stearoyl-2-(13'-oxo-9',11'-tridecadienoyl)-sn-glycero-3-phosphocholine with amino acids and peptides and its differential generation from hydroperoxides of 1-stearoyl-2-&alph;-linolenoyl-sn -glycero-3-phosphocholine and

Phosphatidylcholines (PCs) bearing various kinds of aldehydic acyl chains at the sn-2 position have been detected in atherosclerotic tissues. However, 1-acyl-2-(13'-oxo-9',11'-tridecadienoyl)-sn-glycero-3-phosphocholine and other a,b,g,d-unsaturated aldehyde PCs have not. To determine whether this might be due to their high chemical reactivity with biomolecules, we investigated the reactions of 1-stearoyl-2-(13'-oxo-9',11'-tridecadienoyl)-sn-glycero-3-phosphocholine (OTDA-PC, where OTDA refers to the oxo-tridecadienoyl moiety) with nucleophilic amino acids and peptides by means of electrospray mass spectroscopy. OTDA-PC formed Michael adducts with lysine, arginine, histidine, hippuryl lysine and hippuryl arginine, but was surprisingly unreactive with cysteine or glutathione. When 1-stearoyl-2-(13'-hydroperoxy-9'Z,11'E,15'Z-octadecatrienoyl)-sn-glycero-3-phosphocholine (PC-LNA-OOH, where LNA-OOH denotes the linolenic acid hydroperoxide moiety)　was decomposed in the presence of the reactive lysine, OTDA-PC was still detected as a major product. However, OTDA-PC could not be detected when 1-stearoyl-2-(13'-hydroperoxy-9'Z,11'E-octadecadienoyl)-sn-glycero-3-phosphocholine (PC-LA-OOH, where LA-OOH refers to linoleic acid hydroperoxide) was decomposed in the presence or absence of lysine.  Since linoleic acid is the major polyunsaturated fatty acid in atherosclerotic tissues, these results indicate that formation of OTDA-PC in only minor amounts in such tissues may explain its not having been detected in them. Surprisingly, 1-stearoyl-2-(9'-oxononanoyl)-sn-glycero-3-phosphocholine was the major aldehydic product of the decomposition of PC-LA-OOH under anaerobic conditions. KEY WORDS: Lipid oxidation, Bioactive phospholipid aldehydes (core aldehydes), Michael addition  Bull. Chem. Soc. Ethiop. 2008, 22(2), 269-276.&#160

A Synthesis Phosphatidylinositol Bearing Arachildonic acid

Phosphatidylinositol bearing arachidonoyl group at sn-2 position was synthesized through preparation of protected myo-inositol, chemoenzymatic synthesis of an optically active lysophosphatidylcholine, introduction of an optically active sn-2 hydroxyl group, phospholipase D-assisted synthesis of a phosphatidic acid, and trisopropylbenzene sulfonylchloride assisted eaterification of the acid with the protected myo-inositol; as a final step.ホスファチジルイノシトールは，細胞外からのシグナルが細胞膜中の特異的受容体に結合する事により遊離される情報伝達物質の前駆体である．一般にそのグリセロール骨格のsn-２位には高度不飽和脂肪酸が，特にアラキドン酸が結合していることが知られている．本研究では，そのようなアラキドン酸結合ホスファチジルイノシトールの簡便な合成法を酵素的，化学的手法を用いる事により位置選択的に合成する事に成功した

Production of Functionally Deficient Dendritic Cells from HTLV-I-Infected Monocytes: Implications for the Dendritic Cell Defect in Adult T Cell Leukemia

AbstractAdult T cell leukemia (ATL) is induced by an infection with human T lymphotropic virus type I (HTLV-I) and is accompanied by immunodeficiency. Monocyte-derived immature dendritic cells (DCs) donated by 11 ATL patients were suppressed in the ability to take up fluorescein isothiocyanate (FITC)–dextran and were down-regulated in the expression of CD1a and CD86 antigens (Ags). Monocytes from the patients showed impaired expression of CD14 and HLA-DR Ags. These results suggest intrinsic abnormalities of monocytes and a defect of DC maturation in ATL patients. Therefore, we examined the influence of HTLV-I infection of monocytes on their differentiation to DCs. Monocytes obtained from healthy donors were susceptible to HTLV-I infection in vitro. HTLV-I-infected monocytes were down-regulated in the expression of CD14 Ags, and immature DCs obtained from them expressed CD1a poorly and were impaired in the ability to take up FITC–dextran. Mature DCs differentiated from these cells could not stimulate autologous CD4+ T cell or CD8+ T cell proliferation, even after being secondarily pulsed with HTLV-I at an immature DC stage. These results suggest that HTLV-I-infected monocytes cannot properly differentiate to DCs and that this might be one of the important mechanisms producing dysfunctional DCs in ATL patients

Sn-1位に多価不飽和脂肪酸を結合する2-0-methoxyethoxymethylglycerolの立体配置決定

A correlation of optical rotation, optical purity and configuration of the asymmetric center was done for 2-0-methoxyethoxymethylglycerol bearing polyunsaturated fatty acyl group at sn-1 position. This compound was enzymatically prepared and is an important starting material for the syntheses of optical active glycerophospholipids naving polyunwaturated fatty acyl groups.自然界に広く存在し，重要な生理機能を担っている多価不飽和脂肪酸結合リン脂質の化学的合成に必要な出発原料としての2-0-methoxyethoxymethylglycerolの立体配置と光学純度を，立体配置・光学純度既知の物質に化学的に誘導し，それらの比旋光度をお互いに比較する事により決定した