一步法合成具有叠氮功能的金纳米小颗粒：用于点击化学的多功能，水分散性试剂,Langmuir

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一步法合成具有叠氮功能的金纳米小颗粒：用于点击化学的多功能，水分散性试剂
Langmuir ( IF 3.7 ) Pub Date : 2017-05-18 00:00:00 , DOI: 10.1021/acs.langmuir.7b00632
Edward W. Elliott ₁ , Aurora L. Ginzburg ₁ , Zachary C. Kennedy ₁ , Zhenshuo Feng ₁ , James E. Hutchison ₁

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具有易于结合（例如通过点击化学）的官能团的纳米颗粒是制备定制的纳米杂交产物的重要前体。如果此类纳米颗粒对附聚稳定，则易于分散并且具有明确的表面化学性质和尺寸。作为可随时点击的试剂，它们可以存储到使用前，然后简单地分散并与适当的底物反应。金纳米颗粒（AuNPs）是用于此目的的极佳候选材料，并且已经开发了一些可点击的金纳米颗粒。但是，用于水性体系的AuNPs通常是通过困难的多步过程制备的，并且/或者在水中的分散性很差。在这里，我们报告了可点击，可水分散的AuNPs的一步合成。合成产生均匀的3。直径5 nm的核芯涂有定义明确的分子配体壳，使AuNPs稳定且可在水中分散。AuNP混合配体壳由羟基末端的基于乙二醇的配体（可促进在水中的分散）和少量叠氮基终止的配体组成，这些配体容易与炔烃发生点击反应。中流反应器的使用可对核尺寸和配体壳组成进行精细控制，并确保可重复的结果（例如，批次之间的核直径变化小于0.1 nm）。纯化的试剂已通过Cu催化的点击反应和应变促进的点击反应成功地偶联到了各种含炔的底物上。使用小角度X射线散射可以彻底表征颗粒的大小，形态，稳定性和表面成分，在点击反应之前和之后的¹ H NMR。母体纳米颗粒及其点击化学产品在存储过程中均稳定，并且在水中可分散一年以上，这表明它们在环境，生物和生物医学应用中具有潜力。

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Single-Step Synthesis of Small, Azide-Functionalized Gold Nanoparticles: Versatile, Water-Dispersible Reagents for Click Chemistry

Nanoparticles possessing functional groups that can be readily conjugated (e.g., through click chemistry) are important precursors for the preparation of customized nanohybrid products. Such nanoparticles, if they are stable against agglomeration, are easily dispersible and have well-defined surface chemistry and size. As click-ready reagents, they can be stored until their time of use and then simply dispersed and reacted with an appropriate substrate. Gold nanoparticles (AuNPs) are excellent candidates for this purpose, and some clickable gold nanoparticles have been developed; however, AuNPs for use in aqueous systems are often prepared through difficult multistep processes and/or can be poorly dispersible in water. Here we report a single-step synthesis of clickable, water-dispersible AuNPs. The synthesis yields uniform, 3.5 nm diameter cores coated with a well-defined molecular ligand shell that makes the AuNPs stable and dispersible in water. The AuNP mixed ligand shell consists of hydroxyl-terminated ethylene glycol-based ligands to promote dispersion in water and a small number of azide-terminated ligands that readily undergo click reactions with alkynes. The use of a mesofluidic reactor affords fine control over the core size and ligand shell composition and ensures reproducible results (e.g., less than 0.1 nm variation in core diameter between batches). The purified reagents were successfully coupled to a variety of alkyne-containing substrates using both Cu-catalyzed and strain-promoted click reactions. Particle size, morphology, stability, and surface composition were thoroughly characterized using small-angle X-ray scattering, transmission electron microscopy, X-ray photoelectron spectroscopy, UV–vis, and ¹H NMR before and after the click reactions. Both the parent nanoparticles and their click chemistry products are stable during storage and remained dispersible for over a year in water, suggesting their potential for environmental, biological, and biomedical applications.

更新日期：2017-06-02

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