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An Enolisable Barbiturate with Adjustable Hydrogen-Bonding Structure for UV/Vis Detection of Nucleic Acid Bases and Related Compounds

机译:可调节氢键结构的可释放巴比妥酸酯,用于紫外/可见光检测核酸碱基和相关化合物

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摘要

The use of hydrogen-bonding patterns in the same way as is known from DNA building blocks is a challenge for the construction of novel types of suitable chromophoric probes. This feature has been utilised for the construction of a novel type of UV/Vis probe for detection of supramolecular AAD or DAD sequences (A=hydrogen bond acceptor, D=hydrogen bond donor). Here we report on the structure of the enolisable chromophore 1-n-butyl-5-(4-nitrophenyl)barbituric acid (1), which has an adjustable hydrogenbonding pattern. The position of the keto-enol equilibrium of this dye is strongly influenced both by the solvent polarity and by the chemical environment. Furthermore, the recognition properties of the barbiturate were examined by the use of seven artificial receptors: the pyridine bases 2,6-diaminopyridine (DAP), 2,6-diacetamidopyridine (DAC) and 2,6-bis(trifluoroaceta-mido)pyridine (TFA), as well as the nucleic acid bases 9-ethyladenine (EtAd), 9-ethylguanine (EtGu), 1-n-butyleytosine (BuCy) and 1-n-butylthymine (BuTy). It was found that 1 can interact with these bases either through acid-base interaction or by hydrogen-bonding complexation. The balance between the interactions is dependent both on the basicity strength and on the presence of a suitable recognition sequence in the base. The induced formation of the enol form of I thus causes a significant UV/Vis shift as function of the nature of the base.
机译:以与从DNA构件中已知的相同的方式使用氢键结合模式对于构建新型类型的合适发色探针是一个挑战。此功能已用于构建新型UV / Vis探针,用于检测超分子AAD或DAD序列(A =氢键受体,D =氢键供体)。在这里,我们报告可固化的发色团1-n-丁基-5-(4-硝基苯基)巴比妥酸(1)的结构,该结构具有可调节的氢键模式。该染料的酮-烯醇平衡位置受溶剂极性和化学环境的影响很大。此外,通过使用七个人工受体来检查巴比妥酸酯的识别特性:吡啶碱基2,6-二氨基吡啶(DAP),2,6-二乙酰氨基吡啶(DAC)和2,6-双(三氟乙酰氨基)吡啶(TFA),以及核酸碱基9-乙基腺嘌呤(EtAd),9-乙基鸟嘌呤(EtGu),1-正丁基蛋氨酸(BuCy)和1-正丁基胸腺嘧啶(BuTy)。发现1可以通过酸碱相互作用或通过氢键络合而与这些碱相互作用。相互作用之间的平衡既取决于碱度强度,也取决于碱基中合适的识别序列的存在。因此,诱导的I型烯醇形式的形成导致显着的UV / Vis位移,这是碱性质的函数。

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