Studies on Chemical Functions of Novel Redox Coenzymes

在本研究项目中，新的redox coenzymes的物理化学性质和化学功能，如PQQ （焦罗喹啉酮）、细菌胺脱氢酶的TTQ （色氨酸）和Tyr-Cys （酪氨酸和半胱氨酸二聚体）的半乳糖氧化酶已被解释。Followings is the summary of the results. PQQ项目·关于quinoprotein methanol脱氢酶的模型研究已经被携带到通过添加-elimination机制发现的甲醇氧化复合物PQQ过程。钙离子在甲基氧化物中的催化作用也得到了证实。通过对钙离子的氧化对减少的PQQ的氧化进行了研究，分子氧进行了调查。碱性有机媒体中Coenzyme PQQ的电化学行为已经被解释了。苯甲基酒精的光化学氧化被Coenzyme PQQ的三重兴奋状态证明了这一点。光化学还原反应 ... More Coenzyme PQQ和相关的O-quinones已在细节中进行了调查。新型补充剂-用O-喹酮衍生物的氮烷离子的循环反应已经发现，通过电荷转移复合体进行电子转移。TTQ项目-TTQ模型研究-TTQ辅酶酶中含有胺脱氢酶的胺被证明是为了澄清胺氧化机理。TTQ辅因子在甲基脱氢酶中的电静态环境已被使用TTQ模型化合物进行了调查。合成、物理化学性质和氨基氧化反应中的indolequinone衍生物作为一种新型有机协同剂的模型化合物TTQ的胺脱氢酶已经被调查过了. Try-Cys项目·用于半乳糖氧化酶的活动站点模型已经被开发出来，以便在新有机协同剂中遮蔽光对三醚组的电子效应的作用。Galactose氧化酶的活性站点模型已被开发为按顺序研究铜（II）的物理化学性质和反应性的复合体的苯氧基物种。Less（低）

In this research project, the physicochemical properties and chemical functions of novel redox coenzymes such as PQQ (pyrroloquinolinequinone) of bacterial alcohol and glucose dehydrogenases, TTQ (tryptophan tryptophylquinone) of bacterial amine dehydrogenases, and Tyr-Cys (a dimer of tyrosine and cysteine) of galactose oxidase have been explored. Followings are the summary of the results.PQQ Project・Model studies on quinoprotein methanol dehydrogenase has been carried out to find that the oxidation of methanol by calcium complex of coenzyme PQQ proceeds via addition-elimination mechanism. The catalytic role of calcium ion on the methanol oxidation has been also explored.・Catalysis by calcium ion on the reoxidation of reduced PQQ by molecular oxygen has been investigated.・Electrochemical behavior of coenzyme PQQ in aprotic organic media has been explored.・Photochemical oxidation of benzyl alcohols by the triplet excited state of coenzyme PQQ has been explored.・Photochemical redox react … More ions of coenzyme PQQ and related o-quinones have been investigated in detail.・Novel addition-cyclization reaction of nitroalkane anions with o-quinone derivatives has been found to proceed via electron transfer in the charge-transfer complexes.・TTQ Project・Model studies of TTQ-containing amine dehydrogenases has been performed to clarify the amine oxidation mechanism by TTQ coenzyme.・Electrostatic environment of the TTQ cofactor in methylamine dehydrogenase has been investigated by using TTQ model compounds.・Synthesis, physicochemical properties, and amine-oxidation reaction ofindolequinone derivatives as model compounds of novel organic cofactor TTQ of amine dehydrogenases have been investigated.Try-Cys Project・Active site models for galactose oxidase have been developed in order to shed light on the electronic effect of the thioether group in the novel organic cofactor.・Active site models for galactose oxidase have been developed in order to study the physicochemical properties and reactivities of copper (II) complex of the phenoxyl radical species of the novel organic cofactor. Less