Hydrophobic Interaction of Chromophoresin Visual Pigment Formation

1. 合成了5,6-二氢-、7,8-二氢-、-和3,4-脱氢视网膜的疏水相互作用。视网膜类似物与载脂蛋白色素的形成导致了β -离子环周围松散的疏水相互作用的完成。无β -离子环的视网膜类似物的视蛋白位移3,7-十二戊烯醛的视蛋白位移为1400 cm^<-1>，小于-1,2400 cm^<-1>.3。s -顺式锁定的视网膜类似物与天然视网膜色素形成相同，而s -反式锁定的类似物则不形成色素。3,7- ddp与载脂蛋白色素区域的光异构化可产生11-顺式异构体，而3,7- ddt的选择性不高，为43%。含8,18-甲醇-和乙醇视网膜色素的视网膜色素类似物的β -波段较强，呈负α -波段，而α -波段为正α -波段。测定全反式11-甲基视网膜的构象为10,12-二- s -顺式。这些类似物与载脂蛋白色素的光异构反应产生相应的11-顺式异构体，其区域选择性超过90%。

1. Hydrophobic Interaction around beta-IononeRing of Chromophores5,6-Dihydro-, 7,8-dihydro-, alpha-, and 3,4-dehydroretinals were synthesized Pigment formation of the retinal analogs with aporetinochrome resulted in apparent completion with loose hydrophobic interaction around the beta-ionone ring.2. Opsin Shifts of Retinal Analogs without beta-Ionone RingThe opsin shift of the structurely linear analog, 3,7-dodecapentaenal showed 1400 cm^<-1> smaller value of the neative one, 2400 cm^<-1>.3. The Conformation of Retinochrome Chromophore in 6S-BondWith 6S-cis locked retinal analog, the pigment were formed as in native retinochrome formation, while 6S-trans locked analog gave no pigment.4. Regiospecific Photoisomerization of Retinal AnalogsPhotoisomerization of 3,7-DDP with aporetinochrome regiospecifically gave 11-cis typed isomer, whereas 3,7-DDT did not show the high selectivity, 43%.5. CD Spectra of 6S-Cis Locked Retinal AnalogsThe retinochrome analogs with 8,18-methano- and ethanoretinal gave intense and negative beta-band compared with positive alpha-band.6.11-Methylretinal Analogs11-Methyl-, 13-demethyl-11-methyl-, and 9, 13-didemethyl- 11-methylretinals were synthesized. The conformation of all-trans 11-methylretinal were determined to be 10,12-di-S-cis. Photoisomerization of these analogs with aporetinochrome furnished corresponding 11-cis isomers in more than 90% regioselectivity.