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一种可控制核心尺寸和单层功能的烷硫基稳定金纳米粒子的通用一步合成法。

A General One-Step Synthesis of Alkanethiyl-Stabilized Gold Nanoparticles with Control over Core Size and Monolayer Functionality.

作者信息

Borsley Stefan, Edwards William, Mati Ioulia K, Poss Guillaume, Diez-Castellnou Marta, Marro Nicolas, Kay Euan R

机构信息

EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, U.K.

出版信息

Chem Mater. 2023 Jul 17;35(15):6168-6177. doi: 10.1021/acs.chemmater.3c01506. eCollection 2023 Aug 8.

Abstract

In spite of widespread interest in the unique size-dependent properties and consequent applications of gold nanoparticles (AuNPs), synthetic protocols that reliably allow for independent tuning of surface chemistry and core size, the two critical determinants of AuNP properties, remain limited. Often, core size is inherently affected by the ligand structure in an unpredictable fashion. Functionalized ligands are commonly introduced using postsynthesis exchange procedures, which can be inefficient and operationally delicate. Here, we report a one-step protocol for preparing monolayer-stabilized AuNPs that is compatible with a wide range of ligand functional groups and also allows for the systematic control of core size. In a single-phase reaction using the mild reducing agent -butylamine borane, AuNPs that are compatible with solvents spanning a wide range of polarities from toluene to water can be produced without damaging reactive chemical functionalities within the small-molecule surface-stabilizing ligands. We demonstrate that the rate of reduction, which is easily controlled by adjusting the period over which the reducing agent is added, is a simple parameter that can be used irrespective of the ligand structure to adjust the core size of AuNPs without broadening the size distribution. Core sizes in the range of 2-10 nm can thus be generated. The upper size limit appears to be determined by the nature of each specific ligand/solvent pairing. This protocol produces high quality, functionally sophisticated nanoparticles in a single step. By combining the ability to vary size-related nanoparticle properties with the option to incorporate reactive functional groups at the nanoparticle-solvent interface, it is possible to generate chemically reactive colloidal building blocks from which more complex nanoparticle-based devices and materials may subsequently be constructed.

摘要

尽管人们对金纳米颗粒(AuNP)独特的尺寸依赖性性质及其相应应用有着广泛兴趣,但能够可靠地独立调节表面化学性质和核心尺寸(这两个决定AuNP性质的关键因素)的合成方案仍然有限。通常,核心尺寸会以不可预测的方式受到配体结构的内在影响。功能化配体通常通过合成后交换程序引入,这种方法可能效率低下且操作精细。在此,我们报告了一种制备单层稳定AuNP的一步法方案,该方案与多种配体官能团兼容,还能对核心尺寸进行系统控制。在使用温和还原剂叔丁胺硼烷的单相反应中,可以制备出与从甲苯到水等广泛极性的溶剂兼容的AuNP,而不会破坏小分子表面稳定配体中的活性化学官能团。我们证明,还原速率很容易通过调整添加还原剂的时间来控制,这是一个简单的参数,无论配体结构如何,都可用于调整AuNP的核心尺寸而不会拓宽尺寸分布。因此可以生成2 - 10纳米范围内的核心尺寸。尺寸上限似乎由每种特定配体/溶剂组合的性质决定。该方案一步就能制备出高质量、功能复杂的纳米颗粒。通过将改变与尺寸相关的纳米颗粒性质的能力与在纳米颗粒 - 溶剂界面引入反应性功能基团的选项相结合,有可能生成化学反应性胶体构建块,随后可据此构建更复杂的基于纳米颗粒的器件和材料。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f8d8/10413864/dbad605a42c4/cm3c01506_0002.jpg

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