Asanuma Hiroyuki, Shirasuka Kenji, Takarada Tohru, Kashida Hiromu, Komiyama Makoto
Research Center for Advanced Science and Technology, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8904, Japan.
J Am Chem Soc. 2003 Feb 26;125(8):2217-23. doi: 10.1021/ja021153k.
Methyl Red H aggregate of predetermined size is successfully synthesized from the DNA conjugate involving multiple Methyl Red moieties in sequence. In the single stranded state, hypsochromicity monotonically increases with the number of incorporated dyes: the peak maximum of the conjugate involving six Methyl Reds appears at 415 nm, and the shift is as great as 69 nm (3435 cm(-)(1)) with respect to the monomeric transition. This large hypsochromicity accompanied by the narrowing of the band clearly demonstrates that H aggregate is formed in the single strand. H aggregation is further promoted at higher ionic strength. Upon addition of complementary DNA below the T(m), however, this H band disappears and a new peak appears at 448 nm, indicating that aggregated structure is changed by the duplex formation. This spectral change is completely reversible so that the H band at 415 nm appears again above T(m). Thus, aggregated structure can be reversibly controlled by the formation and dissociation of the DNA duplex.
通过依次包含多个甲基红部分的DNA共轭物成功合成了预定尺寸的甲基红H聚集体。在单链状态下,随着掺入染料数量的增加,紫移现象单调增加:包含六个甲基红的共轭物的最大峰值出现在415nm处,相对于单体跃迁,位移高达69nm(3435cm⁻¹)。这种伴随着谱带变窄的大紫移清楚地表明在单链中形成了H聚集体。在更高的离子强度下,H聚集进一步增强。然而,在低于解链温度(Tm)时加入互补DNA,这个H谱带消失,并且在448nm处出现一个新的峰值,表明聚集结构因双链体形成而改变。这种光谱变化是完全可逆的,因此在高于Tm时,415nm处的H谱带再次出现。因此,聚集结构可以通过DNA双链体的形成和解离来可逆地控制。