Study on the Molecular Assembly Using Cholic Acid

胆酸分子组装的研究

• 批准号: 14540528
• 负责人: KOHMOTO Shigeo
• 金额: $ 2.3万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540528/
• 关键词: cholic acid; molecular recognition; tripodant; cholaphane; liquid crystal; deoxyribonucleoside; homooxacalixarene; ビシクロコーラファン; カプセル型分子; 配列制御; 水素結合; 分子集合体; ホスト-ゲスト

1)Molecular recognition by tripodant cholic acid derivatives : Tripodants prepared from three molecules of cholic acids with trimesic and cyclotriverahylene were investigated for recognition of deoxyribonucleosides and AZT The largest binding constant (5 x 10^5 M^<-1>) was obtained for dA using a methyl cholate tether in solid -liquid extraction. Weak binding (10^2 M^<-1>) was observed for AZT.2)X-ray structural determination of a bicyclocholaphane : X-ray structure of macrocycles containing steroidal moiety has hardly been reported. We succeeded to determined the X-ray structure of bicyclocholaphane which possessed P-helicity in its crystal structure, the cholic acid pillars were twisted., while it had two twisted diastereomeric forms in solution.3)Trial to prepare liquid crystalline cholic acid derivatives : In order to prepare dimeric type of liquid crystalline molecules of cholic acid derivatives, various kinds of cholate possessing long aryl and alkyl chains were prepared. Unlike cholesterol which is a flat steroid, we expected to have unique liquid crystalline properties from the L-shaped bent type steroids. However, they did not show liquid crystal phases yet.4)Preparation of a liquid crystalline molecule for molecular recognition: Self-assembled liquid crystal phases were prepared from homooxacalic[4]arene derivatives Its core part may behave as a potential molecular recognition site.

1)三脚架胆酸衍生物的分子识别：研究了由三个胆酸分子与均苯三甲酸和环三苯异丙乙烯制备的三脚架对脱氧核糖核苷和AZT的识别。<-1>在固液萃取中使用胆酸甲酯系链获得了dA的最大结合常数（5 × 10^5 M^）。观察到AZT的弱结合（10^2 M^<-1>）。2）双环胆甾烷的X-射线结构测定：含有甾体部分的大环化合物的X-射线结构几乎没有报道。我们成功地测定了双环胆甾烷的X-射线结构，其晶体结构具有P-螺旋性，胆酸柱是扭曲的。3）胆酸衍生物液晶的制备实验：为了制备胆酸衍生物的二聚型液晶分子，制备了各种具有长芳基和长烷基链的胆酸盐。不同于胆固醇是一种扁平的类固醇，我们期望从L形弯曲型类固醇中获得独特的液晶性质。4）用于分子识别的液晶分子的制备：由高氧杂[4]芳烃衍生物制备了自组装液晶相，其核心部分可能作为潜在的分子识别位点。

项目成果

K.Takatsuki, M.Yamamoto, S.Ohgushi, S.Kohmoto, K.Kishikawa, H.Yamashita: "A New Protecting Group '3',5'-O-sulfinyl for xylo-nucleosides. A Simple and Efficient Synthesis of 3'-amino-3'deoxyadenosine (a puromycin intermediate), 2,2'-anhydro-pyrimidine nucl

K.Takatsuki、M.Yamamoto、S.Ohgushi、S.Kohmoto、K.Kishikawa、H.Yamashita：“木核苷的新保护基 3,5-O-亚磺酰基。简单高效的合成

K.Kishikawa, N.Muramatsu, S.Kohmoto, K.Yamaguchi, M.Yamamoto: "Control of Molecular Aggregations by Doping in Mesophases : Transformation of Semectic C Phases Smectic CA Phases by Addition of Long Bent-Core Molecules Possessing a Central Strong Dipole."Ch

K.Kishikawa、N.Muramatsu、S.Kohmoto、K.Yamaguchi、M.Yamamoto：“通过中间相掺杂控制分子聚集：通过添加具有中心强的长弯核分子将近晶 C 相转变为近晶 CA 相”

S.Kohmoto, T.Noguchi, H.Masu, K.Kishikawa, M.Yamamoto, K.Yamaguchi: "Reaction-Phase-Selective Inter-and Intramolecular Photochemical Reaction of 2-Pyridone Derivatives."Ogr.Lett.. 6(5). 683-685 (2004)

S.Kohmoto、T.Noguchi、H.Masu、K.Kishikawa、M.Yamamoto、K.Yamaguchi：“2-吡啶酮衍生物的反应相选择性分子间和分子内光化学反应。”Ogr.Lett.. 6(

K.Kishikawa, N.Muramatsu, S.Kohmoto, K.Yamaguchi, M.Yamamoto: "Control of Molecular Aggregations by Doping in Mesophases : Transformation of Smectic C Phases to Smectic C_A Phases by Addition of Long Bent-Core Molecules Possessing a Central Strong Dipole"

K.Kishikawa、N.Muramatsu、S.Kohmoto、K.Yamaguchi、M.Yamamoto：“通过中间相掺杂控制分子聚集：通过添加具有中心的长弯核分子将近晶 C 相转变为近晶 C_A 相”

T.Kajitani, S.Kohmoto, M.Yamamoto, K.Kishikawa: "Generation of Stable Calamitc Liquid-Crystal Phases with Lateral Intermolecular Hydrogen Bonding."Chem.Mater.. (in press). (2004)

T.Kajitani、S.Kohmoto、M.Yamamoto、K.Kishikawa：“通过横向分子间氢键生成稳定的 Calamitc 液晶相。”Chem.Mater..（出版中）。