Search

血管新生（既存の血管から新しい血管ネットワークが形成される現象）は通常、厳密に制御されているが、一旦この制御機構が崩壊すると、調節不能な血管新生（病的血管新生）が発生する。糖尿病網膜症における不可逆的な視野欠損や失明の原因は網膜に生じた病的血管新生である。そこで、糖尿病網膜症の病態・機序を解明するための一環として、増殖糖尿病網膜症（PDR）における硝子体中細胞外スーパーオキシドジスムターゼ（EC-SOD）の役割について検討した。硝子体中EC-SODおよび血管新生の主要因子である血管内皮細胞増殖因子（VEGF）濃度は、黄斑円孔患者に比べPDR患者で高値を示し、全患者において両者間に強い正の相関関係が認められた。そこで、EC-SODの役割を探索するため、in vitro血管新生モデルを用いてEC-SODの抗血管新生作用を検討した。EC-SODはVEGF誘発ヒト臍帯静脈血管内皮細胞（HUVEC）およびヒト網膜毛細血管内皮細胞増殖、およびHUVEC管腔形成を抑制した。以上より、EC-SODはPDR患者の硝子体内で上昇し、in vitroにおいて抗血管新生作用を有したことから、血管新生の病態において中心的な役割を担う可能性が示唆された。, Angiogenesis, in which new vessels are formed from existing vessels, is usually regulated strictly. However, once the regulated mechanism is ruptured, dysregulated angiogenesis (pathological neovascularization) is generated. In diabetic retinopathy (DR), retinal pathological neovascularization is leading causes of irreversible failing vision and blindness. Therefore, as part to clarify the mechanism of pathogenesis in DR, we investigated the role of intravitreal EC-SOD in proliferative diabetic retinopathy (PDR). The intravitreal concentrations of EC-SOD and vascular endothelial growth factor (VEGF), which is a major factor in angiogenesis, were significantly higher in PDR patients than in macular hole patients, and showed a positive correlation with each other (in the whole patients). Furthermore, to investigate possible roles of EC-SOD, we evaluated the angiostatic effect of EC-SOD using an in vitro angiogenesis model. EC-SOD significantly suppressed VEGF-induced cell proliferation in human umbilical vein endothelial cells (HUVECs) and human retinal microvascular endothelial cells, and in vitro tube formation in HUVECs. In conclusion, EC-SOD was increased in the vitreous body from PDR patients and had the angiostatic effects in vitro. Therefore, these results suggest that EC-SOD may play a pivotal role in the pathogenesis of angiogenesis.

不均一系触媒であるパラジウム炭素(Pd/C)は、反応後の除去が容易であり幅広い還元性官能基の接触水素化に汎用されているが、触媒活性が高く官能基選択的接触還元への適用は困難である。 したがって、Pd/Cを用いた官能基選択的接触還元反応の開発は、有機合成工程における有用な官能基変換法となるため重要である。著者らの研究室ではPd/C触媒条件下窒素性触媒毒を利用した官能基選択的接触還元反応を開発してきた。反応多様性の観点から、新しい官能基選択性を有する還元反応の開発は重要な研究課題である。今回著者らは硫黄化合物の添加による触媒活性の制御に関して詳細に検討した。その結果、ジフェニルスルフィド(Ph2S)の添加により、Pd/C触媒条件下容易に接触還元される芳香族カルボニル基、芳香族ハロゲン、芳香族シアノ基、ベンジルエステル及びN-Cbz保護基の共存下、オレフィン、アセチレン及びアジドの選択的還元が可能となった。, While Pd/C is one of the most useful catalysts for hydrogenation, the high catalyst activity of Pd/C causes difficulty in its application to chemoselective hydrogenation between different types of reducible functionalities. Therefore the development of a new chemoselective hydrogenation method using Pd/C is important, because it might become a useful tool for synthetic organic chemistry fields. We have developed a chemoselective hydrogenation method using nitrogenous catalyst poisons. In order to achieve further chemoselective hydrogenation using Pd/C, we investigated the use of sulfur catalyst poisons as a controller of the Pd/C catalyst activity. We found that the addition of Ph2S (diphenylsulfide) to the PoYC-catalyzed hydrogenation reaction mixture led to reasonable deactivation of the Pd/C activity. By the use of the Pd/C-Ph2S catalytic system, olefins, acetylenes, and azides could be selectively reduced in the coexistence of aromatic carbonyls, aromatic halides, cyano groups, benzyl esters, and N-Cbz (benzyloxycarbonyl) protecting groups. The present method is promising as a general and practical chemoselective hydrogenation process in synthetic organic chemistry.

代表的なメソポーラスシリカとして知られるTi-HMS, MCM-41そしてFSM-16を有機合成反応における反応促進剤として活用することを試みた。ルイス酸サイトを有するTi-HMSが接触還元条件下,選択的に水酸基の脱ベンジル化反応を加速することを見出した。 MCM-41が水酸基の保護基として知られるt-butyldimethylsilyl (TBS)基存在下,triethylsilyl (TES)基を選択的に脱保護できることを見出した。 FSM-16がα-ハイドロキシカルボン酸の酸化的光脱炭酸反応やアリールメチルハライドやアリールメチルアルコールの光酸化反応,スチレン類の酸化開裂反応等幾つかの光反応を促進することを見出した。, Ti-HMS, MCM-41 and FSM-16 which are typical hexagonal mesoporous silica, were investigated for use as a promoter for organic synthesis. Ti-HMS, which possesses Lewis acid sites, was found to accelerate deprotection of the benzyl group, which is a typical protecting group of the hydroxyl group, selectively under hydrogenolytic conditions. MCM-41 proved to deprotect the triethylsilyl (TES) group, which is a typical protecting group of hydroxyl group, selectively and easily in the presence of t-butyldimethylsilyl (TBS) group. FSM-16 was found to accelerate several photo-reactions such as oxidative photodecarboxylation of α-hydroxy carboxylic acid, oxidation of arylmethylhalides and arylmethylalcohols, and oxidative cleavage of styrenes.

DNAのヌクレオソーム単位での断片化はアポトーシスの特徴的変化の一つであるが,断片化の欠損するアポトーシスも報告されている。本研究では,アポトーシスの核変化誘導機序の解明のために,DNA断片化を伴わない細胞死におけるその欠損原因の解析を行った。(1)ヌクレオソーム単位でのDNA断片化欠損はネオカルチノスタチンにより誘導されたMolt-4細胞のアポトーシスにおいて認められた。この時,DNA断片化に必須であるとされているDNA fragmentation factor (DFF)はMolt-4細胞において正常に機能していたことから,DFFだけでDNA断片化の誘導を説明することはできないと考えられた。(2)イミダゾールによる細胞内酸性化はDNA断片化を抑制したが,細胞内pHの中性化により断片化誘導が認められた。このことはアポトーシスにおけるDNA断片化誘導には細胞内pHが中性付近に保持されることが必要であることを示唆する結果である。(3)亜鉛とノコギリヤシ果エキスは前立腺癌細胞株にヌクレオソーム単位でのDNA断片化を欠損した細胞死を誘導し,この時の細胞死のタイプは主としてネクローシスであった。これらの知見はアポトーシスの実行過程の解明に重要な情報を与える。, Oligonucleosomal DNA fragmentation is a hallmark of apoptosis, however the fragmentation does not always occur in apoptotic cell death. In the present study, we examined the cause of no oligonucleosomal DNA fragmentation in the cell death to clarify the ladder formation mechanism during apoptosis. (1) Oligonucleosomal DNA fragmentation was not observed in neocarzinostatin (NCS)-induced apoptotic Molt-4 cells. DNA fragmentation factor (DFF), which is essential for the apoptotic ladder formation, was found to be functionally expressed in these cells, suggesting that the DFF expression is not sufficient to induce the oligonucleosomal DNA fragmentation. (2) Intracellular acidification by imidazole inhibited the formation of oligonucleosomal DNA fragmentation and the neutralization in these cells induced DNA fragmentation. This result suggests that maintaining intracellular pH in the neutral range is essential for the induction of apoptotic DNA fragmentation. (3) Zinc and the extract from S. repens induced cell death, associated with no oligonucleosomal DNA fragmentation in prostatic cancer ceH lines. Zinc and the extract-treated cells exhibited mainly necrotic features. These findings provide important information about the execution phase of apoptosis.

近年,日本において医食同源,薬膳というものが注目を集めている。そこで日本における歴史的背景を明らかにし,その関わりと役割について考察を行った。日本の伝統的な行事や風習に深く関わりを持ってきた料理やお菓子の中に,現在の薬膳に繋がる一定の規則性を垣間見ることが出来た。この薬膳の考えは現代の自然志向にも対応しており,今後益々注目されるものと思われた。今後も薬膳に関する考察を通じて,食生活の面からの健康を考察する。, In recent years m Japan, "Ishoku-dougen" and "Yaku-zen" have attracted attention. In this paper the historical background in Japan was clarified and relation and the role were also considered. The same idea as the present "Yaku-zen" is able to be seen in the dish which brought relation to a traditional event and traditional customs of Japan. The idea of this "Yaku-zen" corresponds also to the present-day natural intention and it is thought that it would be observed increasingly from now on. I want to also consider health from the field of eating habits in consideration of "Yaku-zen".

活発な研究が行われているヘテロベンゼンのなかで,セレナベンゼンは未だ安定に単離されていなかったが,電子求引基によって安定化されたセレナベンゼンが,本研究で初めて空気中室温で安定に単離された。セレナベンゼンの反応を行い,化学的性質を解明するとともに,各種機器スペクトルデータ,X線結晶構造解析によりその構造を明らかにした。, The chemistry of heterobenzenes is one of the interesting research fields in heterocyclic chemistry and recently attention has been focused on them. Selenabenzenes with two electron-withdrawing groups (EWGs) at 2- and 6-positions 44a-c were synthesized from dihalides 25a, 25b and 25c' via 7 steps and isolated as stable compounds at room temperatwe. According to X-ray structual analysis of a benzoyl derivative 44c, the six membered ring containing a selenium atom was almost planar and the structure of the selenium atom was tetrahedral with four sp^3 hybridized orbitals.

ラット,ブタ,ヒトの肝臓からカルボキシルェステラーゼを精製し,その基質特異性などの諸性質を検討した。ラットからはcarboxylesterase pI 6.0とcarboxylesterase pI 6.2,ブタからはインドメタシン水解酵素,ヒトからはcarboxylesterase pI 5.3とcarboxylesterase pI 4.5を得た。これらの酵素のうちラット由来のcarboxylesterase pI 6.2のみがプランルカストに対して水解活性を示し,この基質特異性の差がヒトとラットでのプランルカストの代謝経路の違いの原因であると考えられた。プタ由来のインドメタシン水解酵素は,カルボキシルエステラーゼの一般的な基質であるα-naphthyl acetate に対して水解活性を示さず,アミノ酸配列の解析から新規の酵素であると考えられた。ヒト由来の2種類のカルボキシルエステラーゼの基質特異性は大きく異なっていた。これらの結果は,カルボキシルエステラーゼの種差および基質特異性の情報はエステル型およびアミド型薬物の代謝を理解する上で重要であることを示している。なお,本研究では基質特異性の検討を簡便かつ短時間に行うためにHPLCでの移動相の簡便な選択法の開発を行った。, Carboxylesterases designated as carboxylesterase pI 6.0 and pI 6.2,indomethacin hydrolyzing enzyme, and carboxylesterase pI 5.3 and pI 4.5 from the livers of rat, pig, and human, respectively, were purified to electrophoretic homogeneity by several stages of column chromatography. Some properties, especially the substrate specificity, of these esterases were clarified. Pranlukast was effectively hydrolyzed by carboxylesterase pI 6.2 from rat but not by another esterases, suggesting that the substrate specificity of carboxylesterases from rat and human reflects the difference in pranlukast metabolism between the two species. Indomethacin hydrolyzing enzyme from pig exhibited no catalytic activity for α-naphthylacetate, which is a typical substrate of carboxylesterases. Amino acid sequence analysis of this hydrolyzing enzyme revealed it to be a novel esterase. The substrate specificity of carboxylesterase pI 5.3 and pI 4.5 from human was observed to be quite different. These results imply that the differences in the substrate specificity of carboxylesterases between specics is helpful to understand the metabolism of ester- and amide-type drugs. In this study, a convenient method was developed to select the mobile phase to separate drugs commonly used in clinical therapy, using high-performance liquid chromatography (HPLC) , and applied to assay for the substrate specificity of carboxylesterases. Using this method, the time required for not only the setting of HPLC conditions, but also the analysis was shortened.

Melatoninおよびその関連化合物のtrifluoroacetyl(TFA)化反応によって生成する3,3-spirocyclicインドール誘導体の生成機構を考察した。Melatonin,melatonin-(N-acetyl)-d_3,serotonin類およびtryptamine類のTFA誘導体のマススペクトルの測定とその解析より,この特異的な誘導体化反応は側鎖にエノール化しうるN-acyl基をもつN-acyltryptamine類に共通して起こる閉環反応であることを明らかにした。そして,インドール骨格のN-TFA化による3位の活性化と側鎖のN-acyl基のエノール化を経てspirocyclic構造生成に至るmelatoninのTFA誘導体反応の生成機構が提唱された。, The trifluoroacetylation (TFA) mechanism of melatonin was extensively discussed on the basis of mass spectral data for the TFA derivatives of melatonin, melatonin-(N-acetyl)-d_3,serotonins, and tryptamines. It has been demonstrated that 3,3-spirocyclic indole derivatives are commonly generated in the TFA reactions of N-acyltryptamines of the enolic form. We have proposed a mechanism where the specific cyclization reaction involving the spirocyclic structure proceeds by virtue of activation of the 3-position of the indole moiety induced by TFA of the N atom in the moiety and enolation of the N-acyl group.

1977年にベロ細胞傷害性の毒素を産生する大腸菌の存在が報告され, 1982年に米国でベロ毒素産生大腸菌(VTEC)による食中毒が発生してこの菌のヒトにおける病原性が確認された。その後, 世界各地でこの菌による食中毒が報告され, 最近ではその散発的あるいは集団発生が日本各地で報告されている。腸管出血性大腸菌ともいわれるこの菌による感染症の症状としては出血性の下痢と, 続発する溶血性尿毒症症候群および中枢神経系異常が挙げられる。VTECによる発症の過程は, 1)大腸菌が腸管壁に付着し, コロニーを形成して増殖する, 2)ベロ毒素を産生・遊離する, ついで, 3)ベロ毒素が局所的に腸管上皮細胞を傷害し, 全身的には腎細胞傷害, 溶血, 中枢神経系障害を引き起こすの各ステップがある。さらに, 腸管ではattaching and effacing lesionといわれる腸管上皮細胞の病変が観察され, これにはベロ毒素以外にいくつかの因子が関与する。本稿では主としてVTECのビルレンスに関する因子について最近の知見を紹介する。, Verotoxin-producing Escherichia coli (VTEC) was first reported in 1977,and was recognized as a human pathogen in 1982 by an outbreak of the disease in the USA. Thereafter, the food-borne diseases by the bacteria, enterohemorrhagic E.coli, have been reported in many countries. The VTEC infection is responsible for a heterogeneous group of diseases, including diarrhea, hemorrhagic colitis, homolytic uremic syndrome, and central nervous system abnormalities. The process for the development of the complex diseases is considered as follows; 1) adherence of the bacteria to intestinal mucosa, and enteric colonization, 2) production and release of verotoxin, 3) local injury of intestinal epithelial cells, and causing systemic disorders such as hemolytic uremic syndrome and central nervous system complications. In the present paper, we review the literature concerning VTEC, and its virulence factor in particular.

In order to substantiate the hypothesis that the μ-, δ-, or κ-opioid receptor Affinity of opioid peptides can be elicited by an amino-terminus tyrosine residue and the 4th phenylalanine aromatic ring lying in the proper spatial disposition, a series of simple peptide-mimic tyrosine esters, in which tyrosine is linked to aromatic ring separated by a variety of methylene spacers, were prepared and evaluated by in vitro radioligand receptor assay. Compounds having the 6 or 7 methylene spacers were more potent in opioid receptor affinity than those having fewer or more methylene spacers. The N-monomethyl- and N, N-dimethyltyrosine congeners were more potent than the corresponding tyrosine esters. The order of the receptor type selectivity of these compounds was μ>>δ>κ.

ヤナギマツタケAgrocybe cylindracea及びベニテングダケAmanita muscariaから得た直鎖状(1→3)-α-D-グルカン(AG-AL及びAM-APP)のカルボキシメチル化誘導体(AG-AL-CMS, AG-AL-CM1及びAM-APP-CM)中のカルボキシメチル基の分布, 並びにそれらカルボキシメチル化多糖類の免疫調節作用について紹介する。Α-D-グルカン(AG-AL及びAM-APP)はマウスにおけるSarcoma180固型腫瘍に対し殆んど抗腫瘍作用をホさないが, そのカルボキシメチル化誘導体(水溶性のAG-AL-CMS及びAM-APP-CM, ゼラチン様のAG-AL-CMI)は顕著な抗腫瘍活性が認められた。カルボキシメチル化誘導体(AG-AL-CMS, AG-AL-CM1及びAM-APP-CM)中のカルボキシメチル基の置換度と置換位置は我々が開発した方法によって決定された。その方法はこれらカルボキシメチル基のヒドロキシエチル基への還元によって生成するヒドロキシエチル化多糖の加水分解, 及びその加水分解物の還元アセチル化によって得られるアルジトールアセテート並びに1,2-ethylene-D-glucose誘導体のGC-MS分析によって行われる。これらの置換基はカルボキシメチル化(1→3)-α-D-グルカンと(1→3)-β-D-グルカンとの間で特徴的な分布パターンを示した。これらカルボキシメチル化グルカン類(AG-AL-CMS, AG-AL-CM1及びAM-APP-CM)の免疫調節作用は腫瘍免疫に重要な役割を演ずるマウス腹腔マクロファージを用いて評価された。腹腔滲出細胞中のマクロファージの割合はカルボキシメチル化(1→3)-α-D-グルカン投与後50%以上の増加が認められた。カルボキシメチル化(1→3)-α-D-グルカン類はスーパーオキシドアニオン, 一酸化窒素, 腫瘍壊死因子等の産生能, グルコース消費能及び酸性ホスファターゼ活性能等においてカルボキシメチル化直鎖状(1→3)-β-D-グルカン(CMPS)よりもマクロファージに対する高い活性能を示した。これらカルボキシメチル化α-D-グルカン類はマウス血清中において腫瘍退縮因子の誘導が見出されるが, この因子の誘導活性はカルボキシメチル化β-D-グルカンの場合よりも弱いものである。AG-AL-CMS, AG-AL-CM1及びAM-APP-CMの網内系貪食能はCMPSのそれと同等の値が認められた。我々が既に報告したCMPSとマイトマイシンC結合体の抗腫瘍活性に関する研究を基にして, これらカルボキシメチル化(1→3)-α-D-グルカン類は薬物送達システムにおける高分子担体としての有用性が期待される。, This review deals with the distribution of carboxymethyl groups in the carboxymethylated derivatives(AG-AL-CMS, AG-AL-CMI and AM-APP-CM) of linear (l-3)- α -D-glucans(AG-AL and AM-APP) from Agrocybe cylindracea and Amanita muscaria, and also the immunomodulating activities of their carboxymethylated polysaccharides. These carboxymethylated derivatives(water-soluble AG-AL-CMS and AM-APP-CM, gelatinous AG-AL-CMI) possessed potent antitumor activity against the solid form of Sarcoma 180 in mice, although the native D-glucans(AG-AL and AM-APP) had little effect on the tumor. The degree and location of the substitution of the carboxymethyl groups in the carboxymethylated derivatives(AG-AL-CMS, AG-AL-CMI and AM-APP-CM) were determined by our previously developed method. The procedure involves the reduction of the carboxymethyl groups to hydroxyethyl groups, hydrolysis of the resulting hydroxyethyl polysaccharide and GC-MS analysis of the hydrolysate as the alditol acetates and l , 2-ethylene-D-glucose derivatives. These substituents exhibited a characteristic distribution pattern between carboxymethylated (1→3)- α -D-glucan and (1→3)-βD-glucan. Immunomodulating activities of the carboxymethylated glucans(AG-AL-CMS, AG-AL-CMI and AM-APP-CM) were evaluated with murine peritoneal macrophages playing an important role in tumor immunity. The ratio of macrophages in peritoneal exudate cells increased more than 50% after the administration of the carboxymethylated (l-3)- α -D-glucans. The carboxymethylated (1→3)- α -D-glucans indicated higher potentiating activities for macrophages than carboxymethylated linear (1→3)-β-D-glucan(CMPS) in the potency of products of superoxide anion, nitric oxide, tumor necrosis factor, the amount of glucose consumption, and the activation of acid phosphatase. The carboxymethylated α -D-glucans are found to induce the tumor regressing factor in mouse serum, although the ability of the induction of this factor is weaker than that of the carboxymethylated β-D-glucan. The reticuloendothelial system-potentiating activation of AG-AL-CMS, AG-AL-CMI and AM-APP-CM was similar to that of CMPS. We suggest from our work on the antitumor activity of the conjugate of mitomycin C with CMPS that the carboxymethylated (1→3)- α -D-glucans could also be a useful polymer for a carrier in a drug delivery system.

The present study was carried out to examine the effects of Maharishi Amrit Kalash 4 (MAK-4) and 5 (MAK-5) on non-specific immunological mechanisms in mice. Mice aged 4 weeks were divided into 3 groups : a no treatment group (control), MAK-4 treated group (MAK-4 group) and MAK-5 treated group (MAK-5 group). The MAK-4 and MAK-5 were given p.o. at a dose of 50 mg/kg per day for 8 weeks. The following results were obtained : 1. MAK-4 and MAK-5 did not affect the body weight gain and food consumption of the mice. 2. The acid phosphatase (APH) and lactate dehydrogenase (LDH) activities of peritoneal macrophages (Mφ) in the MAK-4 and MAK-5 groups increased significantly compared to the control group. 3. Concanavalin A (Con A) induced cell proliferation in the spleen was high in the MAK-4 and MAK-5 groups. These results suggested that MAK-4 and MAK-5 has a stimulatory effect on Mφ because of the increases in the APH and LDH activities in the peritoneal Mφ of mice. MAK-4 and MAK-5 also intensified the T-cell function represented by Con A-induced splenocyte proliferation.

Nicotinic acetylcholine receptor (AChR) is a multisubunit membrane glycoprotein which functions as a ligand-triggered cation channel. Receptors from electric tissues and skeletal muscle have a molecular weight of approximately 290,000 as a monomer and are composed of four types of polypeptide chains which assemble into a heterologous α_2βγδ pentamer. We determined the carbohydrate structure of Torpedo AChR, which was the first determination for neurotransmitter receptors. About 70 % of the oligosaccharides of the AChR were of the high mannose-type, Man_9GlcNAc_2 and Man_8GlcNAc_2. These two types of oligosaccharides were distributed in all the subunits. The remaining were various kinds of complex-type oligosaccharides, existing mainly in the γ and δ subunits. The α and β subunits had only one carbohydrate chain each, while the γ and δ subunits had two and three carbohydrate chains, respectively. These glycosylation sites were identified by sequencing glycopeptides obtained by lectin-affinity chromatography. The participation of oligosaccharides in ligand-binding of AChR was examined using a newly developed binding assay. The sialic acids and high mannose-type oligosaccharides on AChR were found to be unnecessary for its ligand binding. Next we found that the β and δ subunits of Torpedo AChR were phosphorylated on their tyrosine residues. The level of the phosphorylation was enhanced by incubating the AChR-rich membrane fraction with cholinergic ligands. This suggests that cholinergic agonists physiologically regulate phosphorylation on tyrosine in vivo, which might be included in the desensitization mechanism of the receptor. We also examined the spatial relation of proteins surrounding AChR using Torpedo AChR-rich membrane fraction. Bifunctional crosslinkers revealed an intimate relation among the AChR γ subunit, 43-kD protein, and dystrophin. Finally, we found neurotoxin-binding activities in the su-pernatant fraction obtained by ultracentrifugation of a homogenate of the electric organ, which usually does not contain AChR. This new activity was different in nature from AChR, and could function as a regulator or a modulator for AChR function.

ヒト胎盤およびブタ水晶体と筋肉から精製したアルドース還元酵素に及ぼす加水分解型および縮合型タンニンの阻害を比較した。ガロタンニンは他のタンニンより強くこれらの酵素を阻害し, このうち1,2,3,4,6-penta-O-galloyl-β-D-glucose(PGG)が最も低いIC_値(60-70nM)を示した。PGGはアルコール脱水素酵素, アルデヒド還元酵素, カルボニル還元酵素に対して低度の阻害しか示さなかった。PGGによるアルドース還元酵素の阻害様式はカルボニル基質に対して混合型であったが, 活性化剤である硫酸イオン存在下では不拮抗型となった。, The inhibitory effects of various hydrolyzable and condensed tannins for aldose reductases of human placenta, pig lens and pig muscle were examined and compared. Gallotannins inhibited these enzymes much more than other tannins with 1,2,3,4,6-penta-O-galloyl-β-D-glucose (PGG) showing the lowest IC_ values (60-70 nM). PGG had low inhibitory effect on aldehyde reductase, carbonyl reductase and alcohol dehydrogenase. The inhibition of aldose reductase by PGG was of the mixed type with respect to the carbonyl substrate, but the inhibition was found to be uncompetitive when assaying enzyme activity in the presence of sulfate ions, an activator of the enzyme.

A 1,4-sigmatropic rearrangement of 10-alkyl and 10-aryl-9-phenyl-10-thiaanthracenes is described. 10-(4-Methoxyphenyl)-9-phenyl-10-thiaanthracene generated by proton abstraction of 10-(4-methoxyphenyl)-9-phenylthioxanthenium perchlorate (1a) with bases such as sodium dimsylate, sodium methoxide, sodium hydride, and Grignard reagent underwent 1,4-rearrangement to afford 9-(4-methoxyphenyl)-9-phenylthioxanthene (2a) in high yield. The deprotonation of 1a with organolithiums such as phenyllithium or methyllithium afforded 9,9-diphenylthioxanthene ( 3 ) or 9-methyl-9-phenylthioxanthene (2d) via ligand-exchanged thiaanthracene intermediates generated in situ, along with 2a. Other 10-alkyl or 10-aryl-9-phenylthiaanthracenes generated from the corresponding thioxanthenium salts (1b-g) by treatment with base also decomposed thermally to give 1,4-rearranged products 2b-g in good yield. These 1,4-rearrangements were found to be intramolecular 1,4-sigmatropic rearrangements by cross over experiments.

メタクリル酸(MAA)とそのn-アルキルエステル類(RMA)との共重合反応性を調べた結果, ベンゼン中の反応においてRMAのアルキル鎖の増長に伴うモノマー反応性比の大きな変化が認められたが, カルボソ酸中の反応においてはその変化は僅かであった。モノマー反応性比に対するアルキル鎖長の影響およびその溶媒効果の特徴, さらに重合成長反応性に対する水素結合の影響についての分子軌道計算結果を用いた摂動エネルギーによる評価より, モノマー反応性比に対するn-アルキル鎖の立体的影響は小さいこと, また, 実験結果におけるモノマー反応性比の変化は主として反応溶液中におけるMAAの水素結合会合平衡の影響によることが示された。, The effect of the alkyl group on copolymerization of methacrylic acid(MAA)with its n-alkyl esters (RMA) was investigated. The monomer reactivity ratios largely varied with alkyl group length in reactions in benzene. This effect was not so great in reactions in carboxylic acids. The steric effects of alkyl groups on copolymerization would thus appear slight and variations in the reactivity ratio to possibly be due to variations in the hydrogen-bonding equilibria of MAA. The effects of the hydrogen bond on propagation reactivity were also discussed by perturbation energy based on quantum chemical calculations.

高速液体クロマトグラフィーのための誘導体化反応が, カルボキシル基, カルボニル基(ケトン, アルデヒド, α-ケト酸を含む), 水酸基(アルコール, フェノール・カテコールを含む), チオール基, アミノ基(アミン, アミノ酸, ポリアミンを含む), その他及び光学異性体に分類して記述されている。, Description of derivatization reactions for high-performance liquid chromatography classified as carboxylic compounds, carbonyl compounds (including ketones, aldehydes and α-keto acids), hydroxy compounds (including alcohols, phenols and catechols), thiols, amines (including amines, amino acids and polyamines) and others as well as enantiomers is presented.

近年, ジヒドロジオール脱水素酵素は発癌性芳香族炭化水素の解毒酵素として注目されてきた。一方, 本酵素はナフタレンやベンゼンの代謝的活性化に関与していると考えられている。本酵素は哺乳動物組織に広く分布するが, 多くの組織で多型として存在し, 単離された酵素の性質は動物種または組織によって異なる。本稿では, 哺乳動物組織におけるジヒドロジオール脱水素酵素の多様性および異物と生体内物質代謝における役割について述べる。, Dihydrodiol dehydrogenase has recently attracted attention as an inactivating enzyme of carcinogenic polycyclic aromatic hydrocarbons. The enzyme is thought to be involved in the metabolic activation of naphthalene and benzene. It is ubiquitously distributed in mammalian tissues where it is in various forms. There are marked species or tissue differences in the features of this enzyme. This review directs attention to the various forms of dihydrodiol dehydrogenase in mammalian tissues and its roles in the metabolism of xenobiotics and endogenous compounds.

〓花(菌 : Cordyceps cicadae)虫体部の熱水抽出液より多糖CI-3L(〔α〕D+24.8゜)を単離した。CI-3LはD-mannose, D-gaIactose, D-glucoseがモル比, 1.0 : 1.0 : 0.3で構成され, 少量のタンパク質を含んでいた。CI-3Lは分子量が約32,000であり, コンカナバリンAに親和性がある。メチル化分析, スミス分解, 段階的加水分解, ^C-NMRスペクトルの結果は次のことを示した。本多糖は主として, 1→6結合のα-D-mannopyranose残基の主鎖並びに1→2結合のα-D-mannopyranose残基と1→2結合のβ-D-galactofuranose残基の側鎖から構成される。CI-3Lは虫体部から単離した他のgalacto(gluco)mannan類と類似した構造であるが, 比旋光度, 分子量, 及び結合様式の割合において異なっていた。, A polysaccharide CI-3L (Ca)D+24.8゜) was isolated from the hot-water extract of the insect-body portion of Chan hua (fungus : Cordyceps cicadae). It was found to consist of D-mannose, D-galactose and D-glucose in the molar ratio of 1.0 : 1.0 : 0.3,and contain a small amount of protein. CI-3L has a molecular weight of about 32,000,and affinity for concanavalin A. The results of methylation analysis, Smith degradation, stepwise hydrolysis and ^C-NMR spectroscopy indicated that the polysaccharide was composed primarily of a main chain of (1→6)-linked α-D-mannopyranosyl residues, and side chains of (l→2)-linked α-D-mannopyranosyl and ( I→2)-linked β-D-galactofuranosyl residues. CI-3L is similar in structure to other galacto (gluco) mannans of the insect-body portion, but differs in specific rotation, molecular weight, and proportions of linkage modes.

近年, 癌の光力学療法(PDT)が注目され, 精力的な研究が広範に進められている。現在, PDTの臨床試験に用いられている光増感剤としては, ヘマトポルフィリン誘導体(Hpd)が挙げられる。しかしながら, このHpdは, 高い組織透過性を有する600nm以上の可視光に対して弱い吸収を示すにとどまり, さらにHpd中の活性成分が腫瘍組織に取り込まれる割合は, 正常組織に比べてけた外れに大きいわけではない。したがって, より効果的なPDTを実施するにあたり, 適用される光増感剤としては, 組織透過性の高い赤色光領域に強い吸収を持ち, 腫瘍組織に対して高い選択性および親和性を具備するものが望まれる。このような理由で, 最近, 多種多様な新しい光増感剤が登場してきた。なかでも, メソ置換ポルフィリン, クロリン誘導体, バクテリオクロリンおよびフタロシアニンが, PDTにおける第二世代光増感剤として注目を集めている。, There is currently worldwide activity in the development of a photodynamic therapy (PDT) for cancer. The sensitizer currently used in clinical trials of PDT for cancer consists of a mixture of hematoporphyrin derivatives (Hpd). Hpd, however, absorbs only weakly above 600nm where light exhibits the deepest penetration into tissues. Furthermore, the uptake by the tumour of the active component in Hpd is only marginally higher than that by most normal tissues. Thus it has been evident for some time that the effectiveness of PDT could be enhanced by the use of photosensitizers that absorb more strongly towards the red end of the light spectrum and are more selectively retained by neoplastic tissues. For these reasons, several new classes of photosensitizers for PDT have been suggested over the past few years. Among them, substituted porphyrins, chlorin analogs, bacteriochlorins, and phtalocyanines have received increasing attention as a second- gereration photosensitizer in PDT.

クロレラ藻体(Chlorella pyrenoidosa)より単離した二種の多糖CP-I([α]^_D+22.1゜)とCP-II([α]^_D+63.5゜)は, ゲル濾過で均一なパターン, そしてガラス繊維濾紙電気泳動で単一なスポットを示した。分子量はゲル濾過によって, CP-I, 38000;CP-II, 2800と推定された。CP-Iではglucose, fucose, rhamnose, galactose, mannoseが8.8 : 4.8 : 1.8 : 1.5 : 1.0のモル比で, そしてCP-IIではglucose, galactose, rhamnose, mannoseが18.3 : 4.7 : 3.0 : 1.0のモル比で構成されていた。メチル化分析, スミス分解, 及び^C-NMRの結果から, CP-IIは, 主としてα1→4結合のD-glucopyranose残基, 1→4,6結合のD-gIucopyranoseの分岐糖, 及び1→2,4結合のL-rhamnopyranose分岐糖よりなり, そして少量の1→2結合のD-mannopyranose(1→3結合のD-glucopyranose)残基と共に, 非還元末端のD-galacto-, D-gluco(manno)pyranose残基からなることが示された。両多糖はcarbon-clearance法において有意な細網内皮系賦活作用を示した。, Two polysaccharides, CP- I ([α]^_D+22.1゜ ) and CP-II ( [a]^_D +63.5゜), isolated from Chlorella cells (Chlorella pyrenoidosa), showed homogeneous patterns on gel filtration, and one spot on glass-fiber electrophoresis. The molecular weights were estimated by gel filtration to be 38000 for CP- I and 2800 for CP- II ・ CP- I was composed of glucose, fucose, rhamnose, galactose and mannose in the molar ratios of 8.8 : 4.8 : 1.8 : 1.5 : 1.0,and CP-ll was composed of glucose, galactose, rhamnose and mannose in the molar ratios of 18.3 : 4.7 : 3.0 : 1.0. The results of methylation analysis, Smith degradation and^C-NMR spectroscopy indicated that CP-II was chiefly composed of α(1→4) linked D-glucopyranosyl residues, branched, (1→4,6) Iinked D-glucopyranosyl and (1→2,4) Iinked L-rhamnopyranosyl residues, and contained non-reducing terminal, D-galacto- and D-gluco (manno) pyranosyl residues, together with small amounts of (l→2) Iinked D-mannopyranosyl ((1→3) Iinked D-glucopyranosyl) residues. Both polysaccharides showed reticuloendothelial system-potentiating activity in a carbon-clearance test.

We have carried out the molecular orbital calculations supported by the modified MNDO methods (MNDO/H, Modified MNDO and Am1) to study the self-associations of formic acid, 2-pyridone and its tautomer, 2-pyridinol. The greater self-association energy of 2-pyridone than that of 2-pyridinol was shown in all the methods. The calculated self-association energies of formic acid and 2-pyridone by the MNDO/H method were well compatible with the experimental values. However, the difference in energy between two tautomers of 2-pyridone was too small to reproduce the experimentally known values. On the other hand, it was found that the Modified MNDO method was invalid for the doubly hydrogen-bonded systems. The AM1 method have been shown to give a proper account of the tautomeric features of 2-pyridone, although the calculated energies of hydrogen-bonding were only about a half the experimental values.

Lactaldehyde reductase activity of pig kidney extract was potently inhibited by aldehyde reductase inhibitors such as barbital and diphenic acid. The lactaldehyde reductase and aldehyde reductase activities from this tissue were co-purified to apparent homogeneity, and co-migrated on isoelectric focusing and Sephadex G-100 filtration. These two enzymatic activities in the crude extract were almost completely immunoprecipitated by an antibody against the purified reductase. The results indicate that lactaldehyde reductase in pig kidney is identical to aldehyde reductase.

ヨウ素滴定によるホルマリン中のホルムアルデヒドの定量において, 試薬の添加順序を守ることは極めて重要である。ホルムアルデヒドはアルカリ性条件下, 次亜ヨウ素酸イオンによってギ酸に酸化されるが, この反応は, アルカリ性下における次亜ヨウ素酸イオンのヨウ素酸イオンヘの速やかな移行との競い合いである。従って, 試薬の正しい添加順序に従わないと, 測定値の定量性は失われる。, It is very important that the proper order of reagent addition should be followed in the determination of formaldehyde in formalin by iodometry. Formaldehyde is oxidized to formic acid by hypoiodate ions in an alkaline medium. This reaction competes with the rapid transfer of hypoiodate ions to iodate ions in this medium. Quantitative determination is thus not possible when the right order of reagent is not followed.

肺がんによる死亡者数は増加傾向にあり、新たな治療標的の同定と治療法の開発が必要である。これまでに著者らは、細胞間接着を構成するクローディン-2 が正常肺組織に発現しないが、腺がん組織に高発現することを見出している。肺腺がん細胞におけるクローディン-2 の発現をノックダウンすると細胞増殖能が低下したため、クローディン-2 による細胞増殖の調節機構を検討した。また、クローディン-2 が肺腺がんの治療標的になると考えられたため、クローディン-2発現を抑制する化合物を探索した。その結果、増殖期の細胞においてクローディン-2 は核内とタイトジャンクションに分布し、細胞周期調節因子のZO-1 associated nucleic acid binding protein（ZONAB）と結合することを解明した。クローディン-2 の発現をノックダウンすると、ZONAB の発現量が低下してG1 期の細胞の割合が増加した。クローディン-2 の核移行機序を検討し、208 番目のセリン残基のリン酸化が一部関与することを突き止めた。また、クローディン-2 指向性ペプチドがタイトジャンクションから細胞質内へのクローディン-2 の移行を介してネクローシスによる細胞死を誘導することを発見した。クローディン-2 はクラスリン依存性エンドサイトーシスによって細胞質内へ移行し、リソソームで分解された。フラボノイドのケルセチンはクローディン-2 の転写活性を低下させず、miR-16 マイクロRNA の発現誘導を介してクローディン-2 mRNA 量の安定性を低下させ、その発現量を低下させた。クローディン-2 を起点とするがん化機構の解明とその阻害剤の探索は、肺腺がんの新たな治療法の開発につながると期待できる。, The mortality associated with lung cancer has been increasing; consequently, novel therapeutic targets need to beidentified and novel therapeutic methods need to be developed. We recently reported that claudin-2, a component of the tight junction(TJ), was expressed in human lung adenocarcinoma, whereas it was absent from normal lung tissues. Knockdown of claudin-2 inlung adenocarcinoma cells decreased their proliferation. Therefore, we examined the mechanism underlying the regulation of cellproliferation by claudin-2. Moreover, we sought out compounds that can decrease claudin-2 expression. We found that claudin-2 wasdistributed both in the nucleus and in the TJ in proliferating cells and was bound with the ZO-1 associated nucleic acid binding(ZONAB) protein, which controls cell-cycle regulator expression. shRNA-mediated knockdown of claudin-2 decreased ZONABexpression and increased the proportion of cells in the G1 phase of the cell cycle. Moreover, we examined the nuclear trafficking ofclaudin-2 and found that this trafficking was regulated in part by the phosphorylation of claudin-2 at Ser208. The short peptide,DFYSP, whose sequence mimics the second extracellular loop of claudin-2, caused claudin-2 to be trafficked from the TJ to cytosol,increased lysosomal degradation of claudin-2, and induced necrotic cell death. Transport of claudin-2 to the cytosol was mediated viaa clathrin-dependent endocytosis pathway. Quercetin, a flavonoid, decreased claudin-2 expression through the induction of miR-16and a decrease in the stability of claudin-2 mRNA, although it did not inhibit the transcriptional activity of the claudin-2 gene. Theclarification of the involvement of claudin-2 in the molecular mechanism underlying carcinogenesis and the identification ofclaudin-2 inhibitors will lead to the development of novel agents for the treatment of lung adenocarcinoma.

ジアシルグリセロールキナーゼ (DGK) はジアシルグリセロールをリン酸化し、ホスファチジン酸へと変換する酵素である。現在までに哺乳類において10 種類のアイソフォームが同定されており、脳において強く発現していることが知られている。DGKβ はI 型に分類されるDGK アイソフォームであり、マウス脳においては、嗅球、皮質、海馬、線条体において特に強く発現している。しかしながら、その機能については不明な点が多いため、DGKβ 欠損マウスを用いて表現型解析を行った。DGKβ 欠損マウスでは、躁病様の表現型が認められ、これら表現型は既存の躁病治療薬で改善されることが明らかとなった。また、DGKβ 欠損マウスは多動性に加えて注意欠損様の行動が認められ、注意欠陥多動性障害(ADHD) 治療薬メチルフェニデートは注意欠損様の行動を改善することが示唆された。さらに、DGKβ 欠損マウスに痙攣誘発薬を投与したところ、痙攣行動の増悪が認められ、その一因に海馬における抑制性神経細胞の減少が考えられる。以上の結果より、DGKβ の欠損が躁病をはじめとする様々な疾患に関与している可能性およびこれら疾患の病態解明・治療薬探索にDGKβ 欠損マウスが有用であると考えられる。, Diacylglycerol kinase (DGK) is an enzyme that converts diacylglycerol to phosphatidic acid. To date, ten isoforms ofDGKs have been identified in mammals, and it is reported that DGKs is strongly expressed in the brain. DGKβ, a type of DGK, isexpressed in the olfactory bulb, cortex, hippocampus, and striatum. The roles of DGKβ are still unknown. We generated the DGKβknockout (KO) mice and investigated the phenotypes of DGKβ KO mice. DGKβ KO mice showed mania-like behaviors such ashyperactivity and reduced anxiety. These mania-like behaviors were ameliorated after commonly used medication for mania wereadministered. Furthermore, DGKβ KO mice showed attention-deficit behavior, which was ameliorated by treatment withmethylphenidate. Furthermore, DGKβ KO mice showed increased seizure sensitivity due to the decreased numbers of depressorneurons in the hippocampus. These results suggest that deficit of DGKβ is involved in various neurological diseases including mania,and DGKβ KO mice would be useful to elucidate the pathogenesis and find the therapeutic targets in these disorders of the centralnervous system.

わたし達の目は、日常的に太陽の紫外線や酸素などの影響を受けている。加えて、スマートフォンやパソコンなど電子端末機器の普及が進む現代社会において、目に関するトラブルの増加が懸念される。視機能の維持は我々のQOLに大きく関わるため、薬剤による治療や進行の抑制とともに、食品の機能性による予防も重要である。健康食品素材として広く利用されるビルベリーは、ブルーベリーの近縁種にあたる果実であり、果皮および果実内部にポリフェノールの一種であるアントシアニン色素を多く含んでいる。ビルベリー由来アントシアニンが目に与える機能性としては、in vitroおよびin vivo 試験において、網膜神経節細胞保護作用や光刺激に対する網膜視細胞保護作用、血管新生抑制作用、網膜炎症の軽減による視機能低下抑制作用などが報告されている。一方で、ヒト臨床試験の報告が少ないことが課題とされていたが、2015 年4 月より新たな食品表示基準として機能性表示食品制度が施行されたことにより、ヒト臨床試験の報告が増えてきている。ビルベリーエキスに含まれるアントシアニン（以下、ビルベリー由来アントシアニン）においても新たな報告がなされている。ビルベリー由来アントシアニンを健常人が接種することで得られる機能性として、物の遠近を見る近見視力や毛様体筋の緊張状態、眼精疲労の客観的指標であるフリッカー値、および目の疲労感の主観的指標であるvisual analogue scale（VAS）スコアや自覚症状アンケートにおいて、プラセボ接種群と比較して有意な改善が示されている。そのため、機能性表示食品として、目のピント調節力を改善すること、目の疲労感を和らげることが表示されている。今後もさらにヒト臨床試験が実施されることで、新たな機能性が明らかになることが予想される。, Eyes are organs, which protrude outside the body, exposed to ultraviolet rays from the sun and oxygen. Furthermore, thedisorders of the eyes have increased due to the widespread use of electronic terminal equipment, such as smartphones and personalcomputers. Visual function is very important for our quality of life. Prevention of diseases by using drugs and beneficial food-derivedsubstances is important. Bilberry, which is a species related to blueberry, contains large amounts of anthocyanin in the peel and fruit.The beneficial effects of anthocyanins derived from bilberry on eye health, such as their protective effects on retinal ganglion cellsagainst oxidative stress and on photoreceptor cells against light-induced damage, inhibitory effect against angiogenesis, andinhibitory effect on visual function decline by reducing inflammation in the retina, have been reported from in vitro and in vivostudies. However, few human clinical trials on the intake of anthocyanins derived from bilberry are present. In Japan, the new systemof functional display of foods started from April 2015, thereby resulting in some new results from human clinical trials with asupplement containing anthocyanins derived from bilberry. The beneficial effects of anthocyanins derived from bilberry in humanshave been reported including improvement of factors such as near visual acuity, tension of the ciliary body, flicker fusion frequencyindicative of eye strain, and visual analogue scale (VAS) score or subjective symptoms evaluation using questionnaires compared toplacebo. The beneficial effects of anthocyanins derived from bilberry have also been indicated in the improvement of eye focusingand reduction of eye fatigue. In the future, new beneficial functions related to eye health may emerge by conducting further humanclinical trials with bilberry.

2-Pyridone互変異性平衡の分子軌道法による研究の変遷を紹介する。溶液中でpyridone formが圧倒的濃度を占めるという実験結果を基に, 確実視されていたpyridone formのより大きな安定性は, 当時主流的な計算法であったπ一電子分子軌道論によって再現され, 理論的にも支持が得られていた。しかし, 1973年のP.Beakによる''2-pyridone formと2-pyridinolformとの間には, 本質的なエネルギ」差がない"という実測値の論文報告を契機に, 両互変異性体間のエネルギー差の縮小に向って, 再び分子軌道法による研究が再燃し, 全原子価電子を扱う半経験的分子軌道法による計算結果が多数報告された。そして1980年代に入りようやく, 高度な非経験的分子軌道法(ab initio 法)によってその実測値が再現きれるようになった。さらに, pyridone互変異性平衡に与える置換基効果の分子軌道法による研究の一端にも言及する。, The molecular orbital (MO) studies on tautomeric 2-pyridone have been reviewed : The greater stability of the pyridone form which was widely believed based on the experimental fact that the tautomeric equilibrium lies far to the pyridone form in solution had theoretically been reproduced by π-SCF MO calculations. However, in 1973,P. Beak has reported the experimental observation that there is no significant difference in fundamental stabilities of the tautomers in the gas phase. Since then, the efforts have been made for minimizing the difference in such stabilities by semiempirical MO calculations. And, it is not until the early 1980's that the precise energy difference has been reproduced by sophisticated ab initio calculations. Further, the MO studies of the substituent effect on the tautomeric equilibrium have also been introduced.

各種漢方製剤と西洋薬との併用では, ステロイド剤の場合がもっとも多く, 併用によりステロイド剤の使用量が減少すると同時に, その副作用が軽減される。また難治性の疾患にも, 漢方製剤との併用が西洋薬の効能増強と同時に副作用が軽減される臨床例が数多く報告されている。漢方製剤と西洋薬とを併用することにより, 相互の欠点を補ない, 相乗的な効果をあげることは中国における「中西医合作」の初歩的な成果といえる。, Recently western drugs have been sometimes taken with Chinese medicines to expect their protective effect on toxic side effects of the drugs. In the case of steroidal medicaments, the effect combined with Chinese medicines frequently results in decrease in their dose and diminishing the side effects. The combined effect has also applied to a remedy for intractable diseases, and can be expected to bring on further new protective and potential effects.

Pentafluorophenylhydrazine(PFPH)とO-(2,3,4,5,6-pentafluorobenzyl)-hydroxyl-amine(PFBOA)は水溶性低分子カルボニル化合物のガスクロマトグラフィー(GC)用縮合試薬としてすぐれた性質を有している。カルボニル化合物とPFPHあるいはPFBOAとの縮合反応は室温で速やかに進行し, 生成物は有機溶媒に容易に抽出され, 過剰の試薬は簡単に除去できる。誘導体は有機溶媒中で安定であり, 高い揮発性を有するため低温でのGC分離が可能であり, また電子捕捉検出器に高感度である。縮合反応によりsyn-, anti-異性体を形成するため2っのピークを与えるカルボニル化合物もある。PFPHに比べPFBOAの方がすぐれており, 誘導体化が短時間で進行し, 揮発性がより高いという利点,を持つ。PFPHとPFBOAはカルボニル化合物の微量分析に用いられている。, Pentafluorophenylhydrazine(PFPH) and O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBOA) have been found to be excellent as a derivatizing agent in the gas chromatographic (GC) determination of low-molecular-weight carbonyl compounds in aqueous solution. The reaction of carbonyl compounds with PFPH or PFBOA proceeds readily at room temperature to yield derivatives extractable from the agueous solution with organic solvents, and the complete removal of the unreacted reagent is easily achieved. The resulting derivatives are stable in organic solvents and very volatile, and therefore the GC separation can be carried out at low temperatures. Also, the derivatives are extremely sensitive towards the electron capture detector. Some carbonyl compounds react with PFPH or PFBOA to show two peaks corresponding to syn- and anti- isomers resulting from condensation reactions with them. The utility of PFBOA is compared with that of PFPH. The formaton of the PFBOA-derivatives is much more easily achieved than that of the corresponding PFPH-derivatives. The PFBOA-derivatives are also much more volatile than the corresponding PFPH-derivatives, and therefore the GC separation can be carried out at lower temperature. PFPH and PFBOA have been applied to the micro-determination of various kinds of carbonyl compounds.

世界中には約50種のStephania属植物が知られているが, 中国にはそのうち約30種が分布している。Stephania属は, Staphania, BotryodisciaおよびTuberiphaniaの3亜属より成り, Tuberiphania亜属はきらに, Tuberiphania群とTranscostula群に分類される。Tuberiphania群がらは, 約30種のアルカロイドが単離されており, 特にtetrahydropalmatineはこの群のみに見い出されるにすぎない。また数多くの研究から2つの群の相違は, Tuberiphania群には, Transcostula群より単離されているbisbenzylisoquinolineアルカロイドが含まれていない事であることが示されている。また著者らは, Tuberiphania群がら, dehydroaporphine型のdehydrostephanineとhasbanane型のrunanineの2種の新アルカロイドを見い出した。本論文では, stephania属植物の化学分類について考察した。, There are about fifty species of Stephania plants (Menispermaceae) in all over the world, and thirty species are found in China. Genus Stephania is divided into three subgenus : Stephania, Botryodiscia and Tuberiphania. Subgenus Tuberiphania is also divided into Tuberiphania and Transcostula groups. About thirty alkaloids have been isolated from Tuberiphania group. The studies on chemical constituents deal with the difference of Tuberiphania and Transcostula groups as the following ; the former group does not contain bisbenzyliosquinoline alkaloid, while the latter group contains these compounds. Authors have reported the isolation and confirmation of two new alkaloids, dehydrostephanine as dehydroaporphine type and runanine as hasbanane type. In this paper, we describe the chemotaxonomy of Stephania plants.

クララ属(Genus Sophora)はマメ科, ソラマメ亜科では比較的原始的な植物群で, ルピン型アルカロイドの他に種々のフラボノイドを生合成することで知られており, 今日までに100種近い化合物が単離されそれらの構造が決定, 報告されている。本稿ではフラボノイド化合物を中心に75種の化合物を生合成的な各段階で分類し, 種, 系および節とフラボノイドの酸化様式と置換基の関連について論ずる。クララ属の化学分類を構築するにはフラボノイド化合物は有用なtaxonomic markerであり, 今後の研究でフラボノイドの存在と分布が更に明らかにされることが必要である。, The genus Sophora is rather primitive taxon in the subfamily Faboideae (Leguminosae) and known to biosynthesize the varied flavonoid compounds as well as lupine alkaloids. Upto the present about 100 compounds were isolated and the structures determined were reported. In this paper, 75 compounds related with flavonoid are surveyed according to their biosynthetic stages, and the correlation of species, series and sections with oxygenation patterns and substituents is reviewed. The present survey suggests that the contained flavonoids are useful taxonomic markers, and will contribute to the establishment of chemotaxonomy on the genus Sophora after further accumulation of data on their occurrences and distributions.

和サンキライおよびサンキライの水性エキスについて, その抗アレルギー作用が検討された。抗アレルギー作用の試験は, マウスの耳を用いるpassive cutaneous anaphylaxis法で行われた。その結果, 和サンキライは50mg/kg以上の投与によって, サンキライは100mg/kg以上の投与によって, 共に抗アレルギー作用を有することが明らかとなった。, A study was carried out to examine the effects of Smilax china L..and Smilax glabra L.. On Type I allergic reaction. The aqueous extracts of them were administered into abdominal cavities of mice and the anti-allergic activities were evaluated by 48-hr homologous passive cutaneous anaphylaxis elicited in ears of mice. As a result, the reactions were suppressed by the administrations of more than 50 mg/kg of Smilax china L..and more than 100 mg/kg of Smilax glabra L.., respectively.

ヨードチンキのヨウ素酸滴定による定量は分析化学の学生実習において, 良い実習テーマの1つである。第十改正日本薬局方に収載されている定量法ではその操作中に濃塩酸(約12規定)50mlと水20mlを別々に加えることになっている。しかし, 学生達の健康面からしても, 比較的大量の濃塩酸を使用することはあまり推奨できることではない。この報告では, この定量法操作を改善するために, ヨードチンキのヨウ素酸滴定の正確さに対する塩酸濃度の影響について研究した。その結果, 塩酸2～3規定程度の薄い溶液中でもこの定量的な反応は円滑に進行することがわかった。従って結果としてこの定量法では直接濃塩酸を使用する代わりに6規定の塩酸(70ml)を使用することが, その取扱い易さから考えてもこの定量法操作に適していると考えられる。, Quantitative analysis of iodo tincture is accepted as one of the good examples for the student experiments in the course of analytical chemistry. The J. P. X. employs 50ml of the ca. 12 N HCI and 20 ml of water in the analytical procedure. Since the treatment of the concentrated HCI is not so recommended from the viewpoint of student health, in this report, the influence of hydrochloric acid concentrations upon the titration accuracy in iodatimetry of iodo tincture has been studied in order to improve this analytical procedure. The results have indicated that the quantitative reaction proceeds smoothly even in the solution containing 2-3 N HCl, so that, as a result, the use of 6 N hydrochloric acid (70ml) instead of ca. 12 N HCI is possible in the prescription of the above analysis for more easy handling of the hydrochloric acid.

数種の3-aryl-6-methylpyridazino〔4,5-e〕1,2,4-triazine-5(6H)-one誘導体を4,5-dichloro-2-methyl-3(2H)-pyrdazinoneより3工程で合成し, それらの除草作用を試験した。その結果3-phenyl, 3-(2-substituted phenyl)および3-(2,4-dichlorophenyl)体は種々の雑草に対し高い除草作用を示すのみならず, イネ, トウモロコシ, コムギ, ダイズなどの主要作物の生育は阻害しないという選択的な作用があることを見出した。さらに酸素電極法による光合成阻害作用の検定も行った。, From 4,5-dichloro-2-methyl-3 (2H)-pyridazinone, a series of 3-aryl-6-methylpyridazino [4,5-e]-1 , 2,4-triazin-5 (6H)-ones were prepared in three steps and tested for herbicidal activities. Among them, 3-phenyl, 3-(2-substituted phenyl), and 3-(2,4 dichlorophenyl) derivatives were found to show not only a broad herbicidal spectrum against several weeds, but selective activities to such crops as rice, corn, wheat, and soybean. In addition, their activities as photosynthesis inhibitors were evaluated by a oxygen electrode method.

中国葯科大学, 広西壮族自治区中医葯研究所および中国科学院武漢植物研究所の三ケ所から交換〓葉標本として送られた約160点の標本を新エングラーの分類系に従い収録した。, About 160 herbarium specimens send as exchange species from three Chinese facilities for research (Chinese Pharmaceutical University, Guangxi Institute of Traditional Medical and Pharmaceutical Sciences, and Wuhan Institute of Botany Academia Sinica) were recorded according to the new Engler's classification.

非水系の酸化及び還元ポーラログラムの第1及び第2波の物理的意味を分子軌道法と熱力学的考察により明瞭にした。この取り扱いを光励起状態に拡張することにより励起状態の酸化, 還元電位を評価した。この結果と電子スペクトル理論を結び付けることにより, 酸化-還元電位と電子スペクトルの関係を数式化した。またこの表式を拡張することにより, 電子スペクトルに対する置換基効果を置換基定数で記述することに初めて成功した。そしてこれらの理論的考察は実験的に証明された。一方, QSARの基礎研究も展開し, pK_aと分配定数を同時を求める方法, 重回帰分析の偶然相関を除くのに主成分分析を用いる方法, 及び立体効果や薬物一受容体相互作用能を記述する新しいパラメータを設定した。最後に内部フロー型電解ESR装置を製作し, 不安定ラジカルの分子間相互作用やコンフォメーションの研究に応用した。, In this review article we have newly given the physical meaning of oxidation-reduction potentials for both the first and second waves and at both the ground and excited states using the Born-Haber-type thermodynamic energy cycle and SCFMO calculation. Combining the above treatments with the theory of electronic spectra we have derived the general equations for describing the mutual relation between oxidation-reduction potentials and electronic spectra. These kinds of equations have led to the other formulas, by which we have first succeeded in describing the substituent effect on electronic spectra by means of substituent constants. The equations mentioned above were carefully checked by various kinds of experiments. Secondly we have extended our work to the basic study of QSAR. New methods were presented for evaluating partition coefficient and pK_a simultaneously. To reduce the chance correlation among descriptors in the multiple regression analysis (MRA) the usefulness of the combination of principal component analysis and MRA was verified. Also, we have discussed new descriptors scaled for steric effect and drug-receptor interaction on the ground of molecular electronic states. Finally we have reported the new flow type in situ electrolysis cell for recording ESR and cyclic voltammograms of unstable free radicals at various temperature. ESR spectra thus obtained were applied for interpreting the molecular conformations and molecular interactions of free radicals.

中国薬科大学,広西壮族自治区中医薬研究所および中国科学院武漢植物研究所の三ヶ所に交換〓葉標本として岐阜薬科大学から送った約180点の標本を収録した。, The species names of about 180 herbarium specimens which were sent to thre research institutions in China (Chinese Pharmaceutical University, Guangxi Insitute of Traditional Medical and Pharamceutical Sciences, and Wuhan Institute of Botany Academia Sinica) from Gifu Pharmaceutical University on the basis of Agreement are enumerated in this document.