A Cationic dye triplet as a unique "glue" that can connect fully matched termini of DNA duplexes
A Cationic dye triplet as a unique "glue" that can connect fully matched termini of DNA duplexes
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阳离子染料三联体作为独特的“胶水”，可以连接完全匹配的 DNA 双链体末端
DOI：
10.1002/chem.201003059
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发表时间：
2011
影响因子：
4.3
通讯作者：
H.
中科院分区：
文献类型：
--
作者：
Kashida;H.; Hayashi;T.; Fujii;T.; Asanuma;H.
在这项研究中，我们提出在5 '末端连接在D-苏醇（Z残基）上的三个连续的阳离子p-甲基二苯乙烯唑通过链间簇的形成充当连接DNA双链体的独特“胶水”。对甲基芪类化合物的链间聚集（ZZ三联体）导致350 nm处的谱带变窄和蓝移，这可以归因于对甲基芪类化合物的吸收。 然而，发现在8-mer天然核苷酸的5′末端包含ZZ三联体的单链DNA缀合物不会引起如此大的光谱变化，这意味着ZZ三联体的内在自组装性质很弱。有趣的是，当这种缀合物与互补的8聚体天然寡核苷酸杂交时，观察到显著的光谱变化，表明通过ZZ三联体的链间聚类的双链体的二聚化。冷喷雾电离质谱法也证明了双链体的二聚化。只有当一个ZZ三联体连接到5′端而不是3′端时，才观察到这种链间聚簇。此外，链间簇的稳定性通过增加DNA部分的核碱基的数目而增加，并且当错配碱基对被掺入或当Z残基旁边的碱基被缺失时，稳定性显著下降。当我们将ZZ三联体应用于使用两个互补的DNA缀合物形成纳米线时，每个缀合物在5′末端具有一个ZZ三联体作为突出端，我们通过非变性PAGE分析证明了纳米线的成功形成。由于具有三个核苷酸的天然粘性末端不充当“胶水”，因此具有独特胶水性质的ZZZ三联体是构建基于DNA的纳米结构的主要候选者。
In this study, we propose that three consecutive cationicp‐methylstilbazoles tethered onD‐threoninols (Zresidues) at 5′ termini act as a unique “glue” connecting DNA duplexes by their interstrand cluster formation. Interstrand clustering ofp‐methylstilbazoles (ZZZtriplets) induces narrowing and hypsochromic shift of bands at 350 nm, which can be assigned to the absorption ofp‐methylstilbazole. However, single‐stranded DNA conjugates involving aZZZtriplet at the 5′ terminus of 8‐mer native nucleotides is found not to induce such large spectral changes, which implies that the intrinsic self‐assembling property ofZZZtriplets is weak. Interestingly, when this conjugate is hybridized with a complementary 8‐mer native oligonucleotide, a remarkable spectral change is observed, indicating the dimerization of a duplex through the interstrand clustering ofZZZtriplets. Dimerization of the duplex is also evidenced by cold‐spray ionization mass spectrometry. This interstrand clustering is observed only when aZZZtriplet is tethered to a 5′ rather than 3′ terminus. Furthermore, the stability of the interstrand cluster increases by increasing the number of nucleobases of the DNA portion, and when mismatched base pairs are incorporated or when a base next to theZresidue is deleted, the stability substantially drops. When we apply theZZZtriplet to the formation of a nanowire using two complementary DNA conjugates, each of which has aZZZtriplet at the 5′ termini as overhang, we demonstrate the successful formation of a nanowire by native PAGE analysis. Since native sticky ends that have three nucleotides do not serve as “glue”,ZZZtriplets with their unique glue‐like properties are prime candidates for constructing DNA‐based nanoarchitectures.