在多任务深共熔溶剂中将DNA金属化的简便方法，可实现环保的C–C偶联反应和硝基苯还原,ACS Sustainable Chemistry & Engineering

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在多任务深共熔溶剂中将DNA金属化的简便方法，可实现环保的C–C偶联反应和硝基苯还原
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2019-07-25 00:00:00 , DOI: 10.1021/acssuschemeng.9b03224
Supratim Chakraborty ₁ , Manohara Halanur Mruthunjayappa ₁ , Kanakaraj Aruchamy ₁ , Nripat Singh ₂ , Kamalesh Prasad ₂ , Dharmalingam Kalpana ₃ , Debasis Ghosh ₁ , Nataraj Sanna Kotrappanavar _{1,

4} , Dibyendu Mondal ₁

Affiliation

金属化的DNA是一种令人兴奋的功能材料，对多功能应用具有广泛的用途。然而，常规的DNA金属化过程是耗时且多步骤的，并且最重要的是，在金属化过程中破坏了DNA的螺旋性。在本文中，已经证明了一种环保且快速的方法可以用Pd和Fe ₃ O ₄金属化鲑鱼糜DNA。在深共熔溶剂（DES； ChoCl–EG 1：2摩尔比）中使用，而不会干扰生物聚合物的结构完整性。DES除了在高温下保持DNA的稳定性外，还起着（i）DNA金属化的溶剂和（ii）在金属化过程中将Pd（II）还原为Pd（0）的还原剂的双重作用。显微镜研究证实了在金属化DNA（Pd–DNA–Fe ₃ O ₄）中逐步形成聚集的盘绕型形态。而Pd–DNA–Fe ₃ O ₄中Pd和Fe ₃ O ₄与DNA的相互作用是通过不同的分析工具进行的，这表明Pd与磷酸盐基团和Fe ₃ O ₄相互作用。与DNA的碱基对相互作用。圆二色光谱分析表明，在金属化过程之前和之后，DNA均保持B型。成功金属化后，Pd–DNA–Fe ₃ O ₄将其用作铃木偶联反应和硝基苯还原成苯胺的纳米生物催化剂。金属化的DNA对DES中可持续的Suzuki偶联反应显示出显着的催化活性和效率。在最佳条件下，记录了100％底物的转化率，而所需的C-C偶联产物的选择性为100％。利用DNA在DES中的高温稳定性，探索了金属化的DNA和DES的C–C偶联的可回收性（最多6个循环）潜力，而没有明显的催化活性损失，因此证明了该方法的绿色方面。当用作将硝基苯还原为苯胺的催化剂时，约90％的硝基苯转化率与66％的苯胺选择性达到了一致，这表明金属化DNA的整体组装是一种非常有效的体系，可以轻松地还原硝基苯。总体而言，本研究证明了DES中DNA金属化的一般过程以及金属化DNA作为催化剂在不同有机反应中的应用。

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Facile Process for Metallizing DNA in a Multitasking Deep Eutectic Solvent for Ecofriendly C–C Coupling Reaction and Nitrobenzene Reduction

Metallized DNA is an exciting functional material having widespread utility toward multifunctional applications. However, conventional DNA metallization processes are time-consuming and multistep and, most importantly, the helicity of DNA is destroyed during the metallization process. Herein, an ecofriendly and rapid approach has been demonstrated to metallize salmon milt DNA with Pd and Fe₃O₄ in deep eutectic solvent (DES; ChoCl–EG 1:2 mol ratio) without disturbing the structural integrity of the biopolymer. Besides maintaining the stability of DNA at high temperature, DES played the dual role of (i) a solvent for DNA metallization and (ii) a reducing agent for reduction of Pd(II) to Pd(0) during the metallization process. Microscopic studies confirmed the stepwise formation of aggregated coil type morphology in metallized DNA (Pd–DNA–Fe₃O₄). Whereas, the interactions between Pd and Fe₃O₄ with DNA in Pd–DNA–Fe₃O₄ were probed by different analytical tools, which suggested that Pd interacted with phosphate groups and Fe₃O₄ interacted with the base pairs of DNA. Circular dichroism spectroscopy analysis established that the B-form of DNA was maintained before and after the metallization process. After successful metallization, Pd–DNA–Fe₃O₄ was utilized as a nanobiocatalyst for Suzuki coupling reaction and reduction of nitrobenzene to aniline. The metallized DNA showed remarkable catalytic activity and efficiency for sustainable Suzuki coupling reaction in DES. Under optimized conditions, 100% conversion of the substrates was recorded with 100% selectivity of the desired C–C coupled product. Taking advantage of the high temperature stability of DNA in DES, the recyclability (up to 6 cycles) potential of both metallized DNA and DES toward C–C coupling was explored without significant loss in the catalytic activity, thus demonstrating the green aspects of the process. When utilized as a catalyst for the reduction of nitrobenzene to aniline, ∼90% conversion of nitrobenzene was achieved with 66% selectivity of aniline which suggested that the overall assembly of metallized DNA is a very efficient system to carry out facile nitrobenzene reduction. Overall, the present study demonstrates a general process for metallization of DNA in DES and the applications of the metallized DNA as a catalyst in different organic reactions.

更新日期：2019-07-25

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