Chiroptical detection of condensed nickel(II)-Z-DNA in the presence of the B-DNA via porphyrin exciton coupled circular dichroism.

Chiroptical detection of condensed nickel(II)-Z-DNA in the presence of the B-DNA via porphyrin exciton coupled circular dichroism.
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DOI:
10.1021/jp2047213
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发表时间:
2011-08-25
影响因子:
3.3
通讯作者:
Balaz, Milan
Balaz, Milan
中科院分区:
化学3区
文献类型:
--
作者:
Choi, Jung Kyu;Sargsyan, Gevorg;Shabbir-Hussain, Murtaza;Holmes, Andrea E.;Balaz, Milan

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在此,我们报道了一种在规范右手性B-DNA存在下浓缩左手性ZDNA的高度敏感和特异性的热学检测方法。用毫摩尔浓度的NiCl2诱导左旋胞嘧啶-鸟嘌呤寡核苷酸(AT ODN)在右旋腺嘌呤-胸腺嘧啶寡核苷酸(AT ODN)存在下选择性形成,并通过电子圆二色性证实。通过共振光散射、透射光谱和离心实验证实,镍(II)诱导的CG ODN的B-to-Z DNA跃迁伴随着Ni(II)-Z-DNA的同步缩聚。CG ODN的选择性冷凝使其能够通过离心从AT ODN中分离出来。添加Ni(II)后,未观察到AT ODN的结构变化。阴离子镍(II)中四(4-磺酰基)卟啉(NiTPPS)通过在卟啉Soret波段吸收区诱导强激子耦合圆二色性(ECCD)信号,在Z-DNA/B-DNA混合物中检测到左旋Z-DNA。双标志ECCD信号来源于非手性卟啉通过与浓缩的Z-DNA支架的分子间相互作用组装成螺旋阵列。未观察到Ni(II)-B-DNA-NiTPPS复合物的诱导CD信号。因此,在B-DNA存在的情况下,对Ni(II)诱导的浓缩Z-DNA的明确光谱识别是可能的。在95%的B-DNA (80 μmol)存在下,该方法的灵敏度低至5%的Z-DNA (4.4 μmol碱基对浓度)。因此,NiTPPS是一种通过CD信号放大应用于生物传感的高灵敏度探针。
Here, we report a highly sensitive and specific chiroptical detection method of condensed left-handed ZDNA in the presence of canonical right-handed B-DNA. The selective formation of a left-handed cytosine-guanine oligonucleotide (CG ODN) in the presence of a right-handed adenine-thymine oligonucleotide (AT ODN) was induced by millimolar concentrations of NiCl2 and confirmed by electronic circular dichroism. The nickel(II) induced B-to-Z DNA transition of the CG ODN was accompanied by the concurrent condensation of the Ni(II)-Z-DNA as confirmed by resonance light scattering, transmission spectroscopy, and centrifugation. The selective condensation of the CG ODN allowed its separation from the AT ODN using centrifugation. No structural changes were observed for the AT ODN upon addition of Ni(II). Anionic nickel(II) meso-tetra(4-sulfonatophenyl) porphyrin (NiTPPS) spectroscopically detected the left-handed Z-DNA in the Z-DNA/B-DNA mixture via a strong exciton coupled circular dichroism (ECCD) signal induced in the porphyrin Soret band absorption region. The bisignate ECCD signal originates from the assembly of achiral porphyrins into helical arrays by intermolecular interactions with the condensed Z-DNA scaffold. No induced CD signal was observed for the Ni(II)-B-DNA-NiTPPS complex. Hence, an unambiguous spectroscopic recognition of Ni(II) induced condensed Z-DNA in the presence of B-DNA is possible. The sensitivity of this chiroptical method was as low as 5% of the Z-DNA (4.4 μmol base pair concentration) in the presence of 95% of B-DNA (80 μmol). Thus, NiTPPS is a highly sensitive probe for applications in bio-sensing via the CD signal amplification.
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