Examining the base stacking interaction in a dinucleotide context via reversible cyclobutane dimer analogue formation under UV irradiation.
Examining the base stacking interaction in a dinucleotide context via reversible cyclobutane dimer analogue formation under UV irradiation.
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通过紫外线照射下可逆的环丁烷二聚体类似物的形成来检查二核苷酸环境中的碱基堆积相互作用。
作者：
Liu,Degang;Li,Lei
取代的甲苯基被认为是胸腺嘧啶 (T) 残基的接近等排体。它们可以被 DNA 聚合酶识别，就像它们是胸腺嘧啶一样。尽管这些甲苯衍生物对自由基加成反应相对惰性，但我们最近的发现表明，二核苷酸类似物 TpTo (To = 2′-脱氧-1-(3-甲苯基)-β-D-呋喃核糖) 在紫外线照射下支持邻位光环加成反应，产生两个环丁烷嘧啶二聚体 (CPD) 类似物 2 和 3。我们的报告进一步表明，这些 CPD 物质的形成在 UVC 照射下是可逆的，类似于两个 T 之间形成的 CPD 物质的光化学性质。分析这些 CPD 类似物的稳定性表明，其中一种 (2) 比另一种 (3) 更稳定。负责 2 形成的 TpTo 构象异构体也比负责 3 形成的 TpTo 构象异构体更稳定，如根据构建的波德韦尔热力学循环计算的吉布斯自由能变化所示。这些不同的稳定性并不是由于不同的光化学性质造成的，正如由相应的光反应确定的量子产率所证明的那样。相反，它们归因于 TpTo 二核苷酸以及形成的 CPD 类似物中 T 和 To 环之间不同的堆积相互作用。还讨论了影响环堆积相互作用的因素。我们的概念验证方法表明，精心设计的波德韦尔循环与紫外线照射下可逆的 CPD 形成相结合，对于研究 DNA 碱基相互作用非常有用。
Substituted tolyl groups are considered as close isosteres of the thymine (T) residue. They can be recognized by DNA polymerases as if they were thymine. Although these toluene derivatives are relatively inert toward radical additions, our recent finding suggests that the dinucleotide analogue TpTo (To = 2′-deoxy-1-(3-tolyl)-β-D-ribofuranose) supports an ortho photocycloaddition reaction upon UV irradiation, producing two cyclobutane pyrimidine dimer (CPD) analogues 2 and 3. Our report here further shows that formation of these CPD species is reversible under UVC irradiation, resembling the photochemical property of the CPD species formed between two Ts. Analyzing the stability of these CPD analogues suggests that one (2) is more stable than the other (3). The TpTo conformer responsible for 2 formation is also more stable than that responsible for 3 formation, as indicated by the Gibbs free energy change calculated from the constructed Bordwell thermodynamic cycle. These different stabilities are not due to the varying photochemical properties, as proved by quantum yields determined from the corresponding photoreactions. Instead, they are ascribed to the different stacking interaction between the T and the To rings both in the TpTo dinucleotide as well as in the formed CPD analogues. Factors contributing to the ring stacking interactions are also discussed. Our proof-of-concept approach suggests that a carefully designed Bordwell cycle coupled with reversible CPD formations under UV irradiation can be very useful in studying DNA base interactions.
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影响因子：
15
作者：
Guckian, KM;Schweitzer, BA;Kool, ET
通讯作者：
Kool, ET
光环加成：通过能量和电子转移控制
影响因子：
62.1
作者：
F. Müller;J. Mattay
通讯作者：
J. Mattay
扩大胸腺嘧啶等排生物化学的视野：通过胸腺嘧啶和二核苷酸框架中的甲苯残基之间的光反应形成独特的环丁烷二聚体。
DOI：
10.1002/chem.201200816
发表时间：
2012
期刊：
Chemistry (Weinheim an der Bergstrasse, Germany)
影响因子：
--
作者：
Liu,Degang;Zhou,Yan;Pu,Jingzhi;Li,Lei
通讯作者：
Li,Lei
DOI：
10.1016/0047-2670(87)85038-4
发表时间：
1987
期刊：
Journal of Photochemistry
影响因子：
--
作者：
J. Mattay
通讯作者：
J. Mattay
影响因子：
16.6
作者：
Lin, Gengjie;Li, Lei
通讯作者：
Li, Lei