Synthesis and photophysical properties of biaryl-substituted nucleos(t)ides. Polymerase synthesis of DNA probes bearing solvatochromic and pH-sensitive dual fluorescent and 19F NMR labels.
Synthesis and photophysical properties of biaryl-substituted nucleos(t)ides. Polymerase synthesis of DNA probes bearing solvatochromic and pH-sensitive dual fluorescent and 19F NMR labels.
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联芳基取代核苷的合成和光物理性质。
DOI：
10.1021/jo202321g
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
Michal Hocek
中科院分区：
文献类型：
--
作者：
Jan Riedl;R. Pohl;L. Rulíšek;Michal Hocek
设计了四种新的含氟联芳基荧光标记物，并通过联芳基硼酸酯的水溶液交叉偶联反应将其连接到核苷和核苷三磷酸（dNTPs）上。修饰的dNTPs是KOD XL聚合酶的良好底物，并被酶促掺入DNA探针中。系统地研究了联芳基修饰的核苷、dNTPs和DNA的电子物理性质。联芳基的不同取代模式用于在366-565 nm的宽范围内调谐发射最大值。使用计算化学的方法，发射最大值以令人满意的准确度再现，并且表明，对于所研究的探针观察到的大的溶剂化变色位移与基态（S（0））和激发态（S（1））的偶极矩的差异成比例，所述偶极矩的差异添加在已经为这些系统在真空中预测的较小位移之上。因此，我们提出了一组化合物，它们可以作为多用途碱基识别荧光团，通过发射最大值和荧光强度的变化来检测发夹、缺失和错配，并且也可以通过（19）F NMR光谱法方便地研究。此外，氨基苯并恶唑氟苯基标记的核苷酸和DNA也发挥pH敏感和溶剂化致变色的双重荧光，这可能意味着不同的应用。
The design of four new fluorinated biaryl fluorescent labels and their attachment to nucleosides and nucleoside triphosphates (dNTPs) by the aqueous cross-coupling reactions of biarylboronates is reported. The modified dNTPs were good substrates for KOD XL polymerase and were enzymatically incorporated into DNA probes. The photophysical properties of the biaryl-modified nucleosides, dNTPs, and DNA were studied systematically. The different substitution pattern of the biaryls was used for tuning of emission maxima in the broad range of 366-565 nm. Using methods of computational chemistry the emission maxima were reproduced with a satisfactory degree of accuracy, and it was shown that the large solvatochromic shifts observed for the studied probes are proportional to the differences in dipole moments of the ground (S(0)) and excited (S(1)) states that add on top of smaller shifts predicted already for these systems in vacuo. Thus, we present a set of compounds that may serve as multipurpose base-discriminating fluorophores for sensing of hairpins, deletions, and mismatches by the change of emission maxima and intensities of fluorescence and that can be also conviently studied by (19)F NMR spectroscopy. In addition, aminobenzoxazolyl-fluorophenyl-labeled nucleotides and DNA also exert dual pH-sensitive and solvatochromic fluorescence, which may imply diverse applications.
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影响因子：
15
作者：
Greco, NJ;Tor, Y
通讯作者：
Tor, Y
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16.6
作者：
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