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Dynamic Nature of Thiolate Monolayer in Au25(SR)18 Nanoclusters
ACS Nano ( IF 15.8 ) Pub Date : 2017-11-29 00:00:00 , DOI: 10.1021/acsnano.7b06999 Giovanni Salassa 1 , Annelies Sels 1 , Fabrizio Mancin 2 , Thomas Bürgi 1
ACS Nano ( IF 15.8 ) Pub Date : 2017-11-29 00:00:00 , DOI: 10.1021/acsnano.7b06999 Giovanni Salassa 1 , Annelies Sels 1 , Fabrizio Mancin 2 , Thomas Bürgi 1
Affiliation
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Thiolate monolayer, protecting a gold nanocluster, is responsible for its chemical behavior and interaction with the environment. Understanding the parameters that influence the stability and reactivity of the monolayer will enable its precise and controlled functionalization. Here we present a protocol for the investigation of the monolayer reactivity in Au25(SR)18 based on MALDI mass spectrometry and NMR spectroscopy. Thiol exchange reaction between cluster and thiol molecules has been investigated showing how this reaction is affected by several factors (stability of the thiols in solution, the affinity of the sulfur to the gold cluster, intermolecular interactions within the ligand layer, etc.). Furthermore, intercluster thiol exchange has been clarified to occur during collisions between particles without thiol release to the solution. In this reaction, the stability of the thiols in solution and the affinity of the sulfur to the gold for the two thiols do not affect the equilibrium position because for both thiols one S–Au bond is broken and one is formed within the cycle. Importantly, the rate of direct thiol exchange between clusters is comparable to that of the ligand exchange with free thiols. However, the thermodynamic driving force of the two reactions is different, since only the latter involves free thiol species.
中文翻译：
Au 25（SR）18纳米团簇中硫醇盐单层的动态性质
硫醇盐单层保护金纳米簇，是其化学行为及其与环境的相互作用的原因。了解影响单层稳定性和反应性的参数将使其精确且受控的功能化成为可能。在这里，我们介绍了一种基于MALDI质谱和NMR光谱研究Au 25（SR）18中单层反应性的协议。已经研究了簇与硫醇分子之间的硫醇交换反应，表明该反应如何受到几个因素的影响（溶液中硫醇的稳定性，硫与金簇的亲和力，配体层内的分子间相互作用等）。）。此外，已经证实簇间硫醇交换发生在粒子之间的碰撞期间，而硫醇没有释放到溶液中。在该反应中，溶液中硫醇的稳定性以及硫与金的亲和力对两种硫醇均不影响平衡位置，因为两种硫醇均会破坏一个S-Au键，并在循环中形成一个。重要的是，簇之间直接硫醇交换的速率可与游离硫醇进行配体交换的速率相比。然而，这两个反应的热力学驱动力是不同的，因为仅后者涉及游离的硫醇物质。
更新日期：2017-11-29
中文翻译：
Au 25（SR）18纳米团簇中硫醇盐单层的动态性质
硫醇盐单层保护金纳米簇，是其化学行为及其与环境的相互作用的原因。了解影响单层稳定性和反应性的参数将使其精确且受控的功能化成为可能。在这里，我们介绍了一种基于MALDI质谱和NMR光谱研究Au 25（SR）18中单层反应性的协议。已经研究了簇与硫醇分子之间的硫醇交换反应，表明该反应如何受到几个因素的影响（溶液中硫醇的稳定性，硫与金簇的亲和力，配体层内的分子间相互作用等）。）。此外，已经证实簇间硫醇交换发生在粒子之间的碰撞期间，而硫醇没有释放到溶液中。在该反应中，溶液中硫醇的稳定性以及硫与金的亲和力对两种硫醇均不影响平衡位置，因为两种硫醇均会破坏一个S-Au键，并在循环中形成一个。重要的是，簇之间直接硫醇交换的速率可与游离硫醇进行配体交换的速率相比。然而，这两个反应的热力学驱动力是不同的，因为仅后者涉及游离的硫醇物质。
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