Thermal degradation of the flavonoid glycosides and hydrothermolysis of the triterpenoid-, steroid-, steroidal alkaloid-, cardenolide-, and flavonoid glycosides were studied. The latter cleavage reaction was applied to the structure determination of new triterpenoid glycosides and gangliosides. The useful products for structure elucidation and FD mass fragmentation analysis were obtained by means of thermal degradation of flavonoid glycosides. Hydrothermolysis of the above mentioned glycosides also afforded useful products, namely genuine aglycones, prosapogenins and oligosaccharides, which were not obtained easily by another methods. Furthermore, selective cleavage reaction of ester type glycosidic linkages using hydrothermolysis could be found out. The structures of sugar moiety of a lanostane-type triterpenoid pentaglycoside (67) isolated from the sea cucumber Pentacta australis, a gypsogenin 3,28-O-bisglycoside (69) from Gypsophila paniculata, and a ganglioside molecular species (75) from the starfish Asterias amurensis versicolor Sladen were characterized with the assistance of the effective cleavage reaction, hydrothermolysis.

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  本論文は，武満徹が（1930〜1996）が1973年に作曲したピアノ独奏曲である《フォー・アウェイ》を考察の対象とした。ティモシー・クーツィンは1988年の論文において，ピッチクラス・セット理論を用いることで，同曲の構造上の一貫性を見出そうと試みた。そのなかで彼は，(01)と(06)というふたつの音程が，作品全体に構造的な一貫性をもたらす点でとりわけ重要であることを強調している。本論文の第1節では，同曲で用いられる和音に関して三和音的な読みを行なう必要性を強調し，より古い時代の和声の語彙に立脚した代替的な分析の方針を提示した。続く節では，同曲の響きの構成方法に焦点を当て，ふたつのケースを考える必要性を示した。すなわち，(01)と(06)というふたつの音程そのものが前景化する場合と，これらが三和音的な響きの派生形の一部と考えられる場合である。第３節では，《フォー・アウェイ》が作曲された当時の時代状況と，武満がバリ島旅行について記したエッセイを検討した。武満は，《フォー・アウェイ》を作曲する直前にバリ島を訪れており，そこで聴いたバリ島の伝統音楽であるガムランから大きな影響を受けた。武満はガムランに，音階に基づく即興演奏の美しさを見出した。また，彼は，「自己」と「他者」との関係の上に立ち現れる音楽の在り方に感銘を受けた。武満は，この経験を通して，「音階」と「関係」とのあいだに概念上の相同性を見出した。《フォー・アウェイ》において武満はオクタトニック・スケールを用いることで異なる文化のあいだの相互関係を音楽的に表現していると考えられ，それゆえ，この音階は，同曲において特権的な位置にあることを示した。以上によって，武満の創作観と実作品との繋がりが明らかになった。

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To obtain the useful informations on the structure of minute amounts of natural glycosphingolipids, we have been developing the mass spectrometrical technique. In this time, we wish to report the usefulness of the CAD-MS/MS of [M+Na]^+ ions obtained in the (+)FABMS to the structure elucidation of the cerebrosides. First, the mechanism of the fragmentation of the [M+Na]^+ ions were discussed. The CAD-MS/MS spectra of [M+Na]^+ ions obtained in the (+)FABMS of the synthetic ceramides 1, 2, 3, and 4 were investigated (Fig. 1). No significant fragment ion was observed in the spectra of 3 and 4, on the other hand, the high intense fragment ions due to fission of the amide bond were detected in the spectra of 1 and 2 possessing 2'-OH group. It means that the conjugation of amide is spread by the neighboring 2'-OH group in 1 and 2 followed by the amide N atom becomes sp3-like, which is able to coordinate to Na^+, and therefore the amide linkage is easily cleaved by means of the formation of the five membered ring proposed as scheme 1. Next, the application of the method to the structure elucidation of the ceramide moiety of the glycosphingolipids were attempted. The prominent fragment ions originated by cleavage of amide bond were observed in CAD-MS/MS spectra of [M+Na]^+ ions appeared in the (+)FABMS of the cerebrosides 5 and 6 (Fig. 2), and which indicate that the method provide the useful information for the structures of the ceramide moieties of the cerebrosides possessing 2'-OH group without chemical degradation. Furthermore, the FAB-CAD-MS/MS method was applied to the cerebroside molecular species obtained from starfish, namely, the molecular mass and the fatty acid composition of the main constituents of the species are estimated without acid hydrolysis (Fig. 3). In addition, the method was proved to be applicable to the structure elucidation of lactosylceramide (Fig. 4).

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From the CHCl_3 soluble part of MeOH extractives of the body walls of marine mollusk, Aplysia kurodai, collected along the coast of Fukuoka, two isoprenoids, aplykurodin A(1) and B(2) and four halogenated terpenoids (3)-(6) were obtained. The structure of aplykurodin A(1) was determined on the basis of chemical and spectral data and X-ray crystallographic analysis. The absolute stereostructure of 1 was elucidated by means of the CD analysis. Aplykurodin B(2) is dehydrocompound of 1. The relative stereostructures of 3,4 and 5 were verified by comparison of their spectral data with those of the known compounds. The structure determination of 6 is in progress. To the author's knowledge, 1 and 2 are new isoprenoids which are presumed to be the related compounds of steroids. 3 and 5 are also new halogenated monoterpenoids.

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Our investigation on the chemistry of biologically active natural products during the last 40 years since 1953 are reviewed in this paper. The following subjects are discussed : I. photochemical relationship between rhodopsin and compounds related to areca alkaloid, II. furanoid diterpenoid constituents from dioscoreaceae plants and colombo root, III. field desorption and fast atom bombardment mass spectrometry of biologically active natural glycosides and glycosphingolipids, IV. investigation of biologically active marine natural products, 1) constituents of steroid glycoside sulfates from Asteroidea, 2) spine toxins from Acanthaster planci, 3) constituents of triterpenoid glycoside sulfates from Holothuroidea, 4) constituents of isoprenoids from Opisthobranchia and Octocorallia, 5) constituents of glycosphingolipids from Asteroidea.

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Glycosphingolipids (GSLs) are contained in the cell membranes, and have recently been implicated in many physiological functions. Gangliosides, sialic acid-containing GSLs, are especially enriched in brains and nervous tissues, and are involved in the regulation of many cellular events. Recently, a number of GSLs have been obtained from the marine invertebrates such as echinoderms, poriferans, and mollusks. We have also been researching the biologically active GSLs from the echinoderms for elucidating the structure-function relationships of GSLs, and for developing the novel medicinal resources. In this time, we conducted the isolation and characterization of biologically active GSLs from the sea cucumber Holothuria pervicax, and could obtain three cerebroside molecular species, HPC-1, HPC-2, HPC-3 from less polar fraction of the CHCl_3/MeOH extract of the whole bodies of H. pervicax, and three ganglioside molecular species, HPG-1, HPG-3, HPG-8 from the water-soluble lipid fraction. The structure of the GSLs were characterized on the basis of spectral (^1H-NMR, ^<13>C-NMR, ^1H-^1H COSY. HSQC, and positive ion FAB mass) and chemical (methanolysis and methylation analysis) evidences. Namely, HPC-1, HPC-2, and HPC-3 are sphingosine-type cerebroside, sphingosine-type cerebroside with 2-hydroxy fatty acid, and phytosphingosine-type cerebroside composed of 2-hydroxy fatty acid, respectively. On the other hand, HPG-1, HPG-3, and HPG-8 are ganglioside molecular species derived from the phytosphingosine-type cerebroside HPC-3. The sugar moieties of them are unique in respect of that the sialic acid directly bind to glucose of cerebroside, and that HPG-1 and HPG-3 possess tandem-type disialosyl oligosaccharide moieties. The gangliosides HPG-1, HPG-3, and HPG-8 shows neuritogenic activities toward the rat pheochromocytoma cell line PC12 cell at 10μg/ml in vitro.

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過去10年間に経験した原発性十二指腸癌10例について検討した.平均年齢65.7歳でやや女性に多かった.発生部位では乳頭上部癌が10例中8例と圧倒的に多かった.臨床症状では便潜血反応陽性を含む出血による症状がとくに留意すべき所見と思われた.存在診断, 質的診断は, 胃十二指腸造影, 十二指腸内視鏡生検で可能であるが, 他臓器原発の癌との鑑別, 浸潤範囲, 転移の有無, 手術適応の決定などには, CT, 超音波検査, 血管造影が有効であった.自験例は全例進行癌であり, リンパ節転移率は高く, 膵浸潤も高頻度にみられた.手術法は, 系統的リンパ節郭清を伴う膵頭十二指腸切除術を原則とすべきと考えられる.

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虫垂粘液嚢腫は比較的稀な疾患である.今回,われわれは嚢胞液中のCEAが極めて高値であった虫垂粘液嚢腫の1例を経験したので報告する.症例は74歳女性で,回盲部腫瘤の診断で当院入院となった.注腸検査,大腸内視鏡検査では盲腸の粘膜下腫瘍の所見を示し,腹部超音波, CT検査では回盲部に嚢胞性の腫瘤を認めた.虫垂粘液嚢腫の診断にて虫垂切除術を行った.虫垂は腫大し,大きさは7.0×4.0cmであった.嚢胞液中のCEAは62,577ng/mlと著明に上昇していた.病理所見では,虫垂嚢胞腺腫の診断であり,抗CEA抗体による免疫組織染色は陽性であった.

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Ganglioside GAA-7 (1) derived from the starfish Asterias amurensis versicolor showed neuritogenic and growth-inhibitory activities towards the mouse neuroblastoma cell line (Neuro2a). On the other hand, the structure of its oligosaccharide moiety is very unique, since 1 possesses two sialic acids which directly linked to the GalNAc residue. We are conducting the reconstitution of the biologically active ganglioside 1, and now report the synthetic studies of the demethyl compound (2) of 1. The strategy for the synthesis of 2 is shown in chart 1. 1 possesses the less available N-glycolyl type sialic acid (NeuGc), therefore we prepared the glycosyl donor of NeuGc 5 from the N-acetyl type sialic acid (NeuAc) in 6 steps. For examination of its donor property, 5 was glycosylated with two lactose derivatives 8 and 11. As a result, the NeuGc-containing oligosaccharides 12 and 13 were obtained in good yields. In the preparation of the asialotrisaccharide 6, three GalNAc donors, bromide, trichloro-acetimidate and thioglycoside were examined. As a result, the thioglycoside of GalNAc 7 gave the highest chemical yield and regioselectivity. For examination of the disialylation reaction, tetra O-acetyl lactose derivative 17 was prepared and glycosylated with the NeuGc donor 5 in CH_3CN in the presence of N-iodosuccinimide and trifluoromethanesulfonic acid. The disialylated lactose derivative 18 was obtained in 15% yield together with some monosialylated lactosides. The disialylation of the NeuGc donor 5 towards the asialooligosaccharide 6 was achieved to give 3 by one step in moderate chemical yield. Ceramide moiety was prepared from the cerebrosides derived from the starfish Acanthaster planci. The extracted cerebroside molecular species were hydrolyzed by the glycosidases (Charonia lampas), and the resultant ceramides were separated by flash chromatography to yield pure ceramide 21. The isolated ceramide 21 was easily converted to the synthetically useful ceramide 4. Glycosylation of the sialopentasaccharide 3 and the ceramide 4 thus obtained is in progress.

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1972年から1985年迄に29例の再僧帽弁置換術(ReMVR)を施行した。
ReMVRの早期死亡率は17.2% (5/29).遠隔期死亡率は10.3% (3/29)であつた。再手術の原因は, 機械弁では多岐に渡っているのに対し, 生体弁では1例のparavalvular leakageを除く15例がprimarytissue failureであった。摘出生体弁の病理組織は, 石灰化や線維組織の高度変性を認め, 術後6年以降に生体弁の再手術が増加してくる事から, 長期耐久性に問題があると思われる。現在使用しているSt. Jude Medical弁は最長生存6年で弁不全の発生は無く, 更に長期の耐久性に問題を残すものの, 僧帽弁位の第一選択弁として使用可能と考えている。

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To obtain the useful information on the structure of minute amounts of natural glycosphingolipids, we have been developing the mass spectrometrical technique. We have reported the usefulness of the CAD-MS/MS of [M+Na]^+ ions obtained in the (+)-FABMS to the structure elucidation of ceramide, cerebroside, and ceramide-lactoside, possessing α-hydroxy fatty acid in their ceramide part. On going our previous study, we attempted to apply this method to gangliosides from echinodermata by using gangliosides which have already been characterized in our laboratory. When (+)-FABMS of acanthaganglioside C (1) was measured, [M+Na]^+ ion was observed. However, in the FABMS/MS of [M+Na]^+ ion, the characteristic fragment ion originated in the fission of the amide bond was not observed (Fig. 3). As we have proposed, the fission of the amide bond would not occur without the formation of the stable five-membered chelate ring (Fig. 1). In order to reduce the effect of carboxyl group which must be disturbed the formation of the chelate ring, 1 was treated with DMSO-CH_3I to give methyl ester derivative acanthaganglioside C-ME (2). When (+)-FABMS/MS of 2 was measured, the highly intense and characteristic fragment ion, arisen from the fission of the amide bond of ceramide part, was observed (Fig. 4). In the FABMS/MS of AG-2 ME, methyl ester derivative of acanthaganglioside molecular species, each [M+Na]^+ ions provided the characteristic fragment ions with highly intense, too (Fig. 5). Furthermore, in the case of the disialoganglioside molecular species (LLG-3), too, this method could be applied (Fig. 7). The method must be very useful for the determination of ceramide structure of gangliosides possessing α-hydroxy fatty acyl moiety in their ceramide part. In addition, these methyl ester derivatives were useful for their NMR analysis. Usually, underivatized gangliosides from echinodermata give low resolutive NMR spectra. When their methyl ester derivatives were measured, the high resolutive spectra were obtained in the ^1H- and ^<13>C-NMR (Fig. 8).

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