Hemispherical Synthesis of L-Lysine dendrimers for Clustering of Functional Groups and developing new Functions.

游离基卟啉和Zn(II)-卟啉以不同的方式组合成树突状聚赖氨酸（l -赖氨酸），如乱层、半层和双层。在610 nm处，8个Zn(II)-卟啉以双层方式有效猝灭（90%）至16或32个游离基卟啉。甲基紫素基团也被结合到树状大分子的表面，以建立一个新的电子传递系统。以不同的方式将Zn(II)-卟啉簇和甲基紫啉簇引入树突状聚l -赖氨酸中。（Zn8/MV16）K14和（Zn8/MV8）K14的合成参考了前人的报道。这两种树状大分子的荧光猝灭效率都是未结合的卟啉/甲基紫蛋白体系的6倍。在三乙醇胺存在下，在（Zn8/MV16）K14和（Zn8/MV8）K14中Zn(II)-卟啉的Soret波段连续照射下，紫色树状大分子溶液呈现亮蓝色，表明甲基紫根离子的生成。以6,10,16,20-四akis（4-氨基苯基）卟啉（TAP）为原料，设计合成了游离碱型和以Zn(II)-卟啉为中心的树突状聚l -赖氨酸s(Fbl/Zn8)K4和（Znl/Fb8）K4。树状大分子（Fbl/Zn8）K4)以DMF中（Fb1）K4和8个等效的Zn(II)-卟啉的混合物为参考进行荧光测量。Zn(II)-卟啉的Q波段在660 nm处激发后，Zn(II)-卟啉在610 nm处的发射明显猝灭。相反，游离基卟啉在660 nm和720 nm处的发射显著增加。最有趣的是程度。610 nm处的发射光谱下降幅度与660 nm处的发射光谱增加幅度基本相同。这一事实表明，能量转移是定量发生的。对（Zn1/Fb8）K4进行荧光测定，并与（Fb1/Zn8）K4进行比较。

Free -base porphyrins and Zn(II)-porphyrins were combined to a dendritic poly(L-lysine) in various fashions such as scramble, hemisphere, and double strata. Efficient quenching (90%) of emission at 610 nm was observed from 8 Zn(II)-porphyrins to 16 or 32 free base porphyrins in double strata fashion. Methyl viologen groups were also combined to the surface of the dendrimer to built a novel electron transfer system.Clusters of Zn(II)-porphyrins and methyl viologen were introduced to dendritic poly(L-lysine)s in different manners. The synthesis of (Zn8/MV16)K14 and (Zn8/MV8)K14 were carried out according to previous reports. Both of the dendrimers showed about six times more efficient fluorescence quenching in comparison with the unbound porphyrin/methyl viologen system. Furthermore, the purple colored dendrimer solution turned brilliant blue on continuous irradiation of the Soret band of Zn(II)-porphyrin in (Zn8/MV16)K14 and (Zn8/MV8)K14 in the presence of triethanolamine indicating the generation of methyl viologen radical ion.Free-base and Zn(II)-porphyrin centered dendritic poly(L-lysine)s (Fbl/Zn8)K4 and (Znl/Fb8)K4 were designed and synthesized using 6,10,16,20-tetrakis(4-amino-phenyl)porphyrin(TAP). The dendrimer (Fbl/Zn8)K4) was subjected to fluorescence measurements with reference to a mixture of (Fb1)K4 and eight equivalents of Zn(II)-porphyrin in DMF. Upon excitation at 660 nm for Q band of Zn(II)-porphyrin, the emission at 610 nm from Zn(II)-porphyrin was significantly quenched. Instead, emission from free-base porphyrin at 660 nm and 720 nm increased significantly. Most interestingly, extent.of decrease in the emission at 610 nm and the extent of increase in emission at 660 nm were almost same. This fact suggests that energy transfer occurred quantitatively. Fluorescence measurement for (Zn1/Fb8)K4 was also performed and compared with (Fb1/Zn8)K4.