Construction of Enantioselective Photochromic System Controlled by Chirality of the Reaction-Field

反应场手性控制的对映选择性光致变色体系的构建

基本信息

批准号：
14540503
负责人：
YOKOYAMA Yayoi
金额：
$ 2.3万
依托单位：
Tokyo Kasei Gakuin 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 2004
项目状态：
已结题

项目摘要

DNA- quaternary ammonium ion complex(DNA-QAIC) was obtained by the addition of dimethyldioctadecylammoniun salt to DNA, according to the procedures previously reported. We have clarified that DNA-QAIC can be the transparent matrices of photochromic reactions.The stretched films of DNA-quaternary ammonium ion complex (DNA-QAIC) incorporating diarylethene exhibited large reversible change in optical rotation by its photochromic reactions.Diarylethenes show similar conversion ratio to their colored form in solution, regardless of the presence or absence of the hydroxyl groups in their structure. The diarylethenes showed lower reactivity in DNA-QAIC film or in organic solvents like chloroform in the presence of DNA-QAIC, than in solution without DNA-QAIC. The diarylethene with hydroxyl groups at 2-positions of the benzothiophene rings, that is 1,2-bis(2-hydroxymethyl-3-benzothienyl)hexafluorocyclopentene, showed no coloration when it is dissolved in chloroform together with DNA-QAIC. It is … More because the conformation of the diarylethene was fixed to a non-cyclizable parallel conformation. It was suggested that the diarylethene molecules were partly intercalated between the DNA base pairs.It is well-known that amioanthracene can intercalate between DNA base pairs. The diarylethene with an aminoanthracene intercalated at the anthracene moiety between the DNA base pairs in solution. As the result, fluorescence property changed to some extent, although the photochromic reaction was observed.Although the photochromic reaction were not detected for the powder of spiropyran, the powder of DNA-QAIC incorporating spiropyran showed thermally reversible photochrimism. In this case, the spiropyran in the powder were considered to be intercalating into the DNA-QAIC, and DNA-QAIC can be the transparent matrices of photochromic reactions. The thermal decoloration reactions of spiropyrans in DNA-QAIC films was slower, and the absorbance at the photo-thermo-stationary state was smaller than those in polystyrene films. The structure and the motion of spiropyrans doped in the DNA-QAIC films were restricted, so that it was difficult to change to the corresponding merocyanine form. Less

根据之前报道的方法，将二甲基双十八烷基铵盐加入到DNA中得到DNA-季铵离子复合物（DNA-QAIC）。我们已经阐明DNA-QAIC可以作为光致变色反应的透明基质。DNA的拉伸薄膜。 -掺入二芳基乙烯的季铵离子络合物（DNA-QAIC）通过其光致变色反应显示出旋光度的大可逆变化。二芳基乙烯表现出类似的无论其结构中是否存在羟基，二芳基乙烯在 DNA-QAIC 膜中或在 DNA-QAIC 存在的有机溶剂（如氯仿）中表现出比在溶液中更低的反应性。没有DNA-QAIC，二芳基乙烯在苯并噻吩环的2位上具有羟基，即1,2-双(2-羟甲基-3-苯并噻吩基)六氟环戊烯与DNA-QAIC一起溶解在氯仿中时没有显示出颜色，这是因为二芳基乙烯的构象被固定为不可环化的平行构象。有人认为二芳基乙烯分子部分插入DNA碱基对之间。众所周知，氨基蒽可以插入DNA碱基对之间。将二芳基乙烯与氨基蒽插入到溶液中DNA碱基对之间的蒽部分中，尽管观察到光致变色反应，但荧光性质发生了一定程度的改变。虽然螺吡喃粉末没有检测到光致变色反应。，掺入螺吡喃的DNA-QAIC粉末表现出热可逆光致变色性。在这种情况下，粉末中的螺吡喃被认为是嵌入到DNA-QAIC中的。 DNA-QAIC和DNA-QAIC可以作为光致变色反应的透明基质，DNA-QAIC薄膜中螺吡喃的热脱色反应较慢，光热稳定状态下的吸光度比聚苯乙烯薄膜小。 DNA-QAIC薄膜中掺杂的螺吡喃结构和运动受到限制，难以转变为相应的部花青形式。