首页> 外文期刊>Journal of mass spectrometry: JMS >Studies of the intermolecular DNA triplexes of C+center dot GC and T center dot AT triplets by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry
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Studies of the intermolecular DNA triplexes of C+center dot GC and T center dot AT triplets by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry

机译:电喷雾电离傅里叶变换离子回旋共振质谱法研究C +中心点GC和T中心点AT三联体的分子间DNA三链体

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摘要

Formation and stabilities of four 14-mer intermolecular DNA triplexes, consisting of third strands with repeating sequence CTCT, CCTT, CTT, or TTT, were studied by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in the gas phase. The gas-phase stabilities of the triplexes were compared with their CD spectra and melting behaviors in solution, and parallel correlation between two phases were obtained. In the presence of 20 mm NH4+ (pH 5.5), the formation of the TTT triplex was not detected in both solution and the gas phase. Other triplexes showed the same order, CTCT > CCTT > CTT, of ion abundances in mass spectra and T-m values in solution. The more stable triplexes are those that contained higher percentage of C+center dot GC triplets and an alternating CT sequence. However, the CCTT with the same C+center dot GC triplets as the CTCT showed a higher stability than the latter during the gas-phase dissociation. Furthermore, a biphasic triplex-to-duplex-to-single transition was detected in the gas phase, while a monophasic triplex-to-single dissociation was observed in solution. The present results reveal that hydrogen bonds and electrostatic interactions dominate in the gas phase, while base stacking and hydrophobic interactions dominate in solution to stabilize the triplexes. Moreover, weak acidic conditions (pH 5-6) promote the formation of the parallel triplexes.
机译:通过电喷雾电离傅里叶变换离子回旋共振质谱(ESI-FTICR-MS)研究了四个14-mer分子间DNA三链体的形成和稳定性,它们由具有重复序列CTCT,CCTT,CTT或TTT的第三链组成。气相。将三元化合物的气相稳定性与其CD光谱和溶液中的熔融行为进行了比较,并获得了两相之间的平行相关性。在存在20 mm NH4 +(pH 5.5)的情况下,在溶液和气相中均未检测到TTT三链体的形成。其他三元组在质谱图中的离子丰度和溶液中的T-m值显示相同的顺序,即CTCT> CCTT> CTT。更稳定的三元组是包含更高百分比的C +中心点GC三联体和交替的CT序列的三元组。但是,在气相离解过程中,具有与CTCT相同的C +中心点GC三重态的CCTT显示出比后者更高的稳定性。此外,在气相中检测到双相三链体-双链-单向转变,而在溶液中观察到单相三链体-单向解离。目前的结果表明,氢键和静电相互作用在气相中占主导地位,而碱基堆积和疏水相互作用在溶液中占主导地位,以稳定三链体。此外,弱酸性条件(pH 5-6)会促进平行三链体的形成。

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