Mechanisms for DNA charge transport.
Mechanisms for DNA charge transport.
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DOI：
10.1021/cr900228f
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发表时间：
2010-03-10
期刊：
影响因子：
62.1
通讯作者：
Barton JK
中科院分区：
文献类型：
--
作者：
Genereux JC;Barton JK
自从我们第一次在DNA组件中发表关于远程电荷传输(CT)的挑衅性文章以来，DNA电荷传输(CT)化学在过去的15年里受到了科学研究人员的极大关注。1、2物理学家、化学家和生物学家的共同兴趣反映了DNA CT为信号传递提供灵敏途径的潜力，无论是在纳米级生物传感器的构建中，还是作为检测基因组损伤的酶工具。对dna CT化学的研究始于确定dna双螺旋--一种含有π堆叠的碱基对的溶液中的大分子组装--是否可能与π堆叠的固体具有相同的导电特性。物理学家们进行了复杂的实验来测量DNA样本的电导率，但将离散的DNA组件连接到设备中以测量电导率的方法各不相同，测定电导率的条件也不同。化学家利用各种空穴和电子供体构建了DNA组件，以测量溶液中的空穴和电子传输。在这里，DNA CT也被认为依赖于捐赠者和DNA碱基对堆栈之间的连接或耦合。重要的是，这些实验解决了关于DNA CT是否可能的争论。此外，这些研究表明，DNA CT，无论用于引发化学的氧化剂或还原剂，都可以发生在很长的分子距离上，但可以对碱基对堆栈中的扰动非常敏感。在这里，我们回顾了DNA电荷传输化学的一些关键特征，从一系列系统中举了例子，并在其机理含义的背景下考虑了这些特征。本审查的目的不是详尽无遗，而是说明性的。例如，我们描述的研究涉及使用悬挂式光氧化剂注入空穴在溶液中进行测量，使用共价修饰组件进行导电性研究，以及对DNA修饰电极进行电化学研究。我们不会详细讨论这些结构之间的差异，而是关注它们的相似性。正是这些不同系统之间的相似性使我们能够考虑不同的机制来描述DNA CT。因此，我们还回顾了已经提出的DNA CT的各种机制，并试图将这些机制建议与许多不同的DNA CT测量相协调。当然，研究人员之间的争论已经从“DNA CT可能吗？”到“它是如何工作的？”在这篇综述中，我们详细探讨了后一个问题。
DNA charge transport (CT) chemistry has received considerable attention by scientific researchers over the past 15 years since our first provocative publication on long-range CT in a DNA assembly. 1, 2 This interest, shared by physicists, chemists, and biologists, reflects the potential of DNA CT to provide a sensitive route for signaling, whether in the construction of nanoscale biosensors or as an enzymatic tool to detect damage in the genome. Research into DNA CT chemistry began as a quest to determine whether the DNA double helix, a macromolecular assembly in solution with π-stacked base pairs, might share conductive characteristics with π-stacked solids. Physicists carried out sophisticated experiments to measure the conductivity of DNA samples, but the means to connect discrete DNA assemblies into the devices to gauge conductivity varied, as did the conditions under which conductivities were determined. Chemists constructed DNA assemblies to measure hole and electron transport in solution using a variety of hole and electron donors. Here, too, DNA CT was seen to depend upon the connections, or coupling, between donors and the DNA base pair stack. Importantly, these experiments have resolved the debate over whether DNA CT is possible. Moreover, these studies have shown that DNA CT, irrespective of the oxidant or reductant used to initiate the chemistry, can occur over long molecular distances but can be exquisitely sensitive to perturbations in the base pair stack. Here we review some of the critical characteristics of DNA charge transport chemistry, taking examples from a range of systems, and consider these characteristics in the context of their mechanistic implications. This review is not intended to be exhaustive but instead to be illustrative. For instance, we describe studies involving measurements in solution using pendant photooxidants to inject holes, conductivity studies with covalently modified assemblies, and electrochemical studies on DNA-modified electrodes. We do not focus in detail on the differences among these constructs but instead on their similarities. It is the similarity among these various systems that allows us to consider different mechanisms to describe DNA CT. Thus, we review also the various mechanisms for DNA CT that have been put forth and attempt to reconcile these mechanistic proposals with the many disparate measurements of DNA CT. Certainly the debate among researchers has shifted from “Is DNA CT possible?” to “How does it work?”. In this review we explore this latter question in detail.
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