Name: synthesis and characterization of amphiphilic gold nanoparticles
Uploaded: 2019-07-02T13:00:00
Description: Watch this Scientific Journal Video about Synthesis and Characterization of Amphiphilic Gold Nanoparticles at JoVE.com

Z.P.G.和F.S.感谢瑞士国家科学基金会,特别是NCCR"分子系统工程"。Z.L.和F.S.感谢瑞士国家科学基金会第二部分赠款的支持。所有作者感谢曲昂富有成果的讨论和校对手稿。

1. 合成11种甲苯甲酸酯(MUS)
注: 此协议可在所需的任何规模下使用。这里描述了 10 g 的产品量表。
<ol><li>脱脱钠-10-硫磺酸钠
	<ol>
<li>添加 11-溴-1-未十进制 (25 mL, 111.975 mmol)、亚硫酸钠(28.75克、227.92毫摩尔)和溴化二铵(10mg)的混合物为200 mL甲醇(MeOH)和450 mL脱离子(DI)水(4:9 v/v MeOH:H2O比率),在1L圆底醇中.</li>
		<li>在102°C下将反应混合物回流48小时。这种反应对大气?...

<ol>
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该协议首先描述了MUS配体的合成,然后描述了两栖MUS:OT金纳米粒子的合成和表征。在纳米粒子合成过程中,以最小的盐含量合成MUS,使配体之间的化学计量比具有更好的可靠性,这是可重复合成MUS:OT纳米粒子的关键因素,具有目标疏水性内容 (图 8)。甲醇作为MUS和OT的常见溶剂,以及乙醇中颗粒的合成,可以可靠地合成MUS:OT金纳米粒子。这里介绍的表征方法构成获得足够纳米粒子信息?...

金纳米粒子的配体外壳可以设计成表现出几个不同的特性,可用于应对生物医学1、2、3、4的挑战。这种多功能性可以控制纳米粒子和生物分子5、6、7之间的分子间相互作用。疏水性和电荷起决定性作用,以及其他影响纳米粒子与生物分子5、8、9相互作用的表面参数。为了调整纳米粒子的表面特性,根据所寻求的特性,选择构成配体壳的硫酸盐分子提供了无数的可能性。例如,具有疏水性和亲水性(例如,带电)端群的配体分子混合物通常用于生成两栖纳米粒子10、11。
这种类型的纳米粒子的一个突出例子是由OT和MUS(下称MUS:OT纳米粒子)的混合物保护,这些混合物已被证明具有许多相关特性12,13,14。首先,配体壳的组成为66%MUS(下同66:34 MUS:OT),纳米粒子的胶体稳定性高,在脱离子水以及磷酸盐缓冲盐水(1x,4 mM磷酸盐,150 mM NaCl)中,其重量高达33%。此外,这些颗粒不会以相对较低的pH值沉淀:例如,在pH2.3和盐浓度为1M NaCl15时,这些纳米粒子在胶体上稳定数月。配体壳上两个分子之间的化学计量比很重要,因为它决定了具有高离子强度16的溶液中的胶体稳定性。
这些粒子已被证明通过能量无关的通路1,12穿过细胞膜而不对细胞膜进行波刺。这些粒子和脂质双层之间的自发融合是它们通过细胞膜17扩散的基础。这种相互作用背后的机制是尽量减少接触疏水性溶剂可访问的表面面积和水分子与脂质双层融合18。与全MUS纳米粒子(外壳上只有MUS配体的纳米粒子)相比,混合MUS:OT纳米粒子(例如,在66:34 MUS:OT成分下)的水文性较高,增加了芯直径的跨度,而该直径可以与脂质融合双层18。配体壳的不同自组装组织与66:34 MUS:OT纳米粒子与各种蛋白质(如白蛋白和泛性蛋白)的不同结合模式相关,而全MUS粒子19。最近,据报道,66:34 MUS:OT纳米粒子可用作广谱抗病毒剂,由于MUS配体多价静电结合和OT配体非局部联结联结到辣椒,可不可逆转地消灭病毒。蛋白质14.在所有这些情况下,已经发现疏水性含量以及纳米粒子的核心大小决定了这些生物-纳米相互作用是如何发生的。这些不同特性的MUS:OT纳米粒子已经促使许多计算机模拟研究,旨在澄清支持MUS:OT粒子和各种生物结构,如脂质双层20之间的相互作用的机制。
MUS:OT 保护的Au纳米粒子的制备带来了一些挑战。首先,带电配体(MUS)和疏水配体(OT)是不可混用的。因此,在整个合成过程中以及表征过程中,都需要考虑到纳米粒子和配体的溶解度。此外,MUS配体分子的纯度——特别是起始材料中无机盐的含量——影响纳米颗粒的质量、可重复性以及短期和长期胶体稳定性。
这里概述了由MUS和OT混合物保护的这种两栖金纳米粒子的详细合成和表征。报告用于合成带负电荷的MUS配体的协议,以确保不同纳米粒子合成物的纯度,从而保证其可重复性。然后,详细报道了基于常见的一相合成,然后彻底纯化这些纳米粒子的生成过程。各种必要的表征技术21,如TEM,UV-Vis,TGA和NMR,已经结合,以获得任何进一步的生物实验所需的所有参数。

<table>
	<tbody>
		<tr>
			<td>11-bromo-1-undecene</td>
			<td>Sigma Aldrich</td>
			<td>467642-25 ml</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium Sulfite</td>
			<td>Sigma Aldrich</td>
			<td>S0505-250 g</td>
			<td></td>
		</tr>
		<tr>
			<td>Benzyltriethyl-ammonium bromide</td>
			<td>Sigma Aldrich</td>
			<td>147125-25 g</td>
			<td></td>
		</tr>
		<tr>
			<td>Methanol</td>
			<td>VWR</td>
			<td>BDH1135-2.5 LP</td>
			<td></td>
		</tr>
		<tr>
			<td>DI water</td>
			<td>Millipore</td>
			<td>ZRXQ003WW</td>
			<td>Deionized water</td>
		</tr>
		<tr>
			<td>1 L round bottom flask</td>
			<td>DURAN</td>
			<td>24 170 56</td>
			<td></td>
		</tr>
		<tr>
			<td>Diethyl ether</td>
			<td>Sigma Aldrich</td>
			<td>1.00930 EMD Millipore</td>
			<td></td>
		</tr>
		<tr>
			<td>Stirring bar</td>
			<td>Sigma Aldrich</td>
			<td>Z329207,</td>
			<td></td>
		</tr>
		<tr>
			<td>Dow Corning High Vacuum Grease</td>
			<td>Sigma Aldrich</td>
			<td>Z273554 ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>Filtering flask</td>
			<td>DURAN</td>
			<td>20 201 63</td>
			<td></td>
		</tr>
		<tr>
			<td>Filtering Buchner Funnel</td>
			<td>FisherSci</td>
			<td>11707335</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethanol &#62;99.8%, ACS, Reagent</td>
			<td>VWR</td>
			<td>2081.321DP</td>
			<td></td>
		</tr>
		<tr>
			<td>Deuterium dioxide</td>
			<td>Sigma Aldrich</td>
			<td>151882 ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>Thioacetic acid 96%</td>
			<td>Sigma Aldrich</td>
			<td>T30805 ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>Carbon black</td>
			<td>Sigma Aldrich</td>
			<td>05105-1KG</td>
			<td></td>
		</tr>
		<tr>
			<td>Celite</td>
			<td>Sigma Aldrich</td>
			<td>D3877 SIGMA-ALDRICH</td>
			<td>Filtration medium</td>
		</tr>
		<tr>
			<td>Condenser</td>
			<td>Sigma Aldrich</td>
			<td>Z531154</td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrochloric acid, ACS reagent 37%</td>
			<td>Sigma Aldrich</td>
			<td>320331 SIGMA-ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium Hydroxide, BioXtra, pellets (anhydrous)</td>
			<td>Sigma Aldrich</td>
			<td>S8045 SIGMA-ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>Centrifuge tubes</td>
			<td>VWR</td>
			<td>525-0155P</td>
			<td></td>
		</tr>
		<tr>
			<td>250 mL round bottom flask</td>
			<td>DURAN</td>
			<td>24 170 37</td>
			<td></td>
		</tr>
		<tr>
			<td>500 mL round bottom flask</td>
			<td>DURAN</td>
			<td>24 170 46</td>
			<td></td>
		</tr>
		<tr>
			<td>Nitric acid, fACS reagent 70%</td>
			<td>Sigma Aldrich</td>
			<td>438073 SIGMA-ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>Gold(III) chloride trihydrate &#62;99.9% trace metal basis</td>
			<td>Sigma Aldrich</td>
			<td>520918 ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>1-octanethiol &#62;98.5%</td>
			<td>Sigma Aldrich</td>
			<td>471836 ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium Borohydride purum p.a.&#62;96%</td>
			<td>Sigma Aldrich</td>
			<td>71320 ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>Separatory funnel</td>
			<td>SIgma Aldrich</td>
			<td>Z330655 SIGMA</td>
			<td></td>
		</tr>
		<tr>
			<td>Funnel</td>
			<td>DURAN</td>
			<td>21 351 46</td>
			<td></td>
		</tr>
		<tr>
			<td>2V folded filtering papers</td>
			<td>Whatman</td>
			<td>1202-150</td>
			<td></td>
		</tr>
		<tr>
			<td>Amicon filters</td>
			<td>Merck</td>
			<td>UFC903024</td>
			<td></td>
		</tr>
		<tr>
			<td>Iodine, ACS reagent, &#62;99.8%, solid</td>
			<td>Sigma Aldrich</td>
			<td>207772 SIGMA-ALDRICH</td>
			<td></td>
		</tr>
		<tr>
			<td>5 mm NMR-Tubes, Type 5HP (high precision)</td>
			<td>Armar</td>
			<td>32210.503</td>
			<td>Length 178 mm</td>
		</tr>
		<tr>
			<td>Methanol-d4 99.8 atom%D</td>
			<td>Armar</td>
			<td>16400.2035</td>
			<td></td>
		</tr>
		<tr>
			<td>TGA crucible</td>
			<td>Thepro</td>
			<td>9095-9270.45</td>
			<td></td>
		</tr>
		<tr>
			<td>400 mesh carbon supported copper grid</td>
			<td>Electron Microscopy Science</td>
			<td>CF400-Cu</td>
			<td></td>
		</tr>
		<tr>
			<td>quartz cuvette</td>
			<td>Hellma Analytics</td>
			<td>100-1-40</td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis and characterization of amphiphilic gold nanoparticles

金纳米粒子覆盖着1-辛他醇(OT)和11-mercapto-1-undecane硫酸(MUS)的混合物,因为它们与细胞膜、脂质双层和病毒的相互作用得到了广泛的研究。亲水配体使这些颗粒在水溶液中胶体稳定,与疏水配体结合产生一种两栖粒子,可以装载疏水药物,与脂质膜融合,并抵抗非特异性蛋白质吸附。其中许多特性取决于纳米颗粒大小和配体壳的组成。因此,拥有可重复的合成方法和可靠的表征技术,以便确定纳米粒子特性和配体壳组合物至关重要。这里介绍了一个一相化学还原,然后彻底纯化以合成直径在5nm以下的纳米颗粒。纳米粒子表面两个配体之间的比率可以通过合成过程中使用的化学计量比进行调优。我们演示了各种常规技术,如透射电子显微镜 (TEM)、核磁共振 (NMR)、热重力分析 (TGA) 和紫外线可见 (UV-Vis) 光谱仪如何综合结合描述纳米粒子的物理化学参数。

合成MUS的反应步骤如图1所示。图2中所示,每个步骤的积的1个H NMR光谱。图3描述了二元MUS:OT两亲基金纳米粒子的合成工作流程。合成后,纳米粒子的制造包括用乙醇和DI水多次清洗颗粒。在纳米粒子的任何特征化之前,未结合的自由配体中纳米粒子的清洁度由D2 O中的1H NMR监测,如图4所示。 <...

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Synthesis and Characterization of Amphiphilic Gold Nanoparticles

两栖金纳米粒子可用于许多生物应用。提出了一种合成用配体二元混合物涂覆的金纳米粒子的协议,并给出了这些粒子的详细表征。

两栖金纳米粒子的合成与表征

Gold nanoparticles covered with a mixture of 1-octanethiol (OT) and 11-mercapto-1-undecane sulfonic acid (MUS) have been extensively studied because of ...

该协议解决了硫酸盐和两栖金纳米粒子的批量可重复性，我们的实验室用于细胞、病毒和蛋白质的实验。此技术解决了此类合成中常见的无机污染物。它还引入每一步后之间的制衡，以确保两栖金纳米粒子的可重复性。这种技术很费力，需要耐心。难度取决于规模，因此从小规模开始，熟悉每种仪器，然后进行扩展。首先，在1升圆形底瓶中加入11-Bromo-1-1-dede烯、硫酸钠和溴化苯乙烯二氧化氮200毫升甲醇和450毫升去离子水。在102摄氏度下回流反应混合物48小时，直到溶液变得无色。工作后，将分离的白色粉末悬浮在400毫升甲醇的圆形底部烧瓶中。使用滤瓶和硅酸盐过滤器过滤溶液，去除甲醇不溶性无机副产品。接下来，在500毫升甲醇中，在一升圆形底部烧瓶中溶解约30克未解-10-二硫磷酸钠。在溶液中加入2.6倍的硫乙酸，并在250瓦的紫外线灯前搅拌过夜。一旦反应完成，完全蒸发甲醇。在真空下干燥粉末，然后用二乙醚分散。过滤混合物，用二乙醚清洗固体产品，以去除任何多余的硫乙酸，直到二乙醚上清液中不再出现任何彩色物质。在高真空下干燥固体后，溶解在甲醇中，产生黄色至橙色溶液。接下来，在溶液中加入三克炭黑，并大力混合。然后，通过 Celite 过滤混合物，覆盖 2/3 的长笛滤纸。合成MUS，将大约400毫升的一摩尔盐酸和35克11-乙酰硫磺酸钠组合在一升圆形底瓶中。在102摄氏度下将混合物回流12小时，以切化硫酸盐组并获得硫醇。第二天，将产品转移到两升圆形底瓶中。为了保持溶液酸性，防止无机盐结晶，将200毫升的一个氢氧化钠和400毫升的去离子水加入烧瓶，使最终体积为1升。将透明溶液在四摄氏度下过夜，使产品结晶为细实固体，在潮湿时粘稠。第二天，将清澈的上清液清除。然后，将产品转移到50毫升离心管和离心机5分钟，4000倍g。离心后，将上清液放入另一个圆形底部烧瓶中。将白色颗粒转移到离心管中，并在高真空下干燥，获得约30%的甲醇可溶性MUS。重量177.2毫克金（III）氯化三水合物在一个小玻璃瓶。之后，在10毫升甲醇中溶解87毫克MUS，在20毫升玻璃瓶中溶解。在超声波浴中对溶液进行声波化，直到看不到固体材料，以确保完全溶解。在甲醇溶液中加入26微升1-Octanethiol，并鼓动其混合配体。在250毫升圆形底部烧瓶中加入500毫克的波罗氢钠和100毫升乙醇。大力搅拌，直到溶液清晰。将金盐溶解在100毫升乙醇中，放在500毫升的圆形底部烧瓶中，以800 RPM的速度搅拌，直到金盐完全溶解。接下来，将配体溶液添加到反应混合物中。等待 15 分钟，形成金硫酸盐复合物，这表示颜色从半透明黄色到浑浊黄色的变化。使用分离漏斗将先前准备好的波罗氢钠溶液滴入反应混合物中。调整水滴的间隔时间，以便添加波罗氢钠大约需要一个小时。一旦添加溴氢钠完成，取出添加漏斗，让反应混合物再搅拌一个小时。然后，使用放置在圆形底部烧瓶外端的磁铁拆下磁搅拌棒。将反应混合物储存在四摄氏度过夜，以沉淀纳米粒子。将上流乙醇除去后，将剩余的沉淀物转移到50毫升离心管，以4000倍g的离心机转3分钟。离心后，去掉上经剂。通过涡旋再次用乙醇分散纳米粒子。然后，再次将样品离心机。在真空下干燥纳米粒子以去除残留的乙醇。为了从自由亲水配体中清除纳米颗粒，将沉淀物溶解在15毫升的去维化水中，并将溶液转移到离心管中，过滤膜为30千达顿截止分子量。通过离心将纳米粒子溶液在 4000 倍 g 下浓缩 5 分钟。离心后，加入15毫升的去水，并离心机再次浓缩。要将纳米粒子变成可管理的粉末，请冷冻干燥剩余的水溶液。为了以配体比来描述纳米粒子，准备每毫升150毫克的甲醇-d4碘溶液。将溶液的600微升加入玻璃瓶中约5毫克的纳米颗粒中，蚀刻纳米颗粒。用石蜡膜包裹小瓶盖，并在超声波浴中声波化20分钟。然后，将溶液转移到 NMR 管中，通过 32 次扫描获得质子 NMR 频谱。MUS 合成如下所示。此处显示每个步骤的产品的质子 NMR 光谱。这里描述了二元MUS八烷基酚两栖金纳米粒子的合成工作流程。在表征之前，质子 NMR 监测了未绑定自由配体中纳米粒子的清洁度。纳米粒子的大小分布以TEM为特征，表明平均直径为2.4纳米，表面积约为18.08纳米，每个粒子体积为7.23纳米。通过获取UV-vis光谱测量局部表面等离子体和共振吸收。此处显示了具有代表性的质子 NMR 光谱，具有峰值分配和确定碘蚀纳米粒子配体比的配体比。纳米粒子的NNR光谱显示，MUS与辛烷thiol的比例为85比15。TGA对纳米粒子的表面覆盖进行了检查。根据 TGA 数据，配体密度估计为每纳米平方 4.8 配体。此处比较了各种合成产生的辛烷thiol的纳米对比。在这个程序中，要记住的最重要的事情是，一边是去除无机杂质，同时准备MUS配体，另一边是纳米粒子的工作。此过程可使用各种配体组合，但请确保始终单独描述每个批次。例如，这个程序可以回答的一个问题是，配体比在多大程度上与纳米粒子表面的测定度相对应。扩大配体的生产，证明纳米粒子的批量可重复性，使我们能够解决与生物学和医学有关的重要问题。例如，我们已经建立了这些纳米粒子的病毒特性。使用紫外线灯时请小心工作，处理液氮时始终佩戴防护手套。始终遵守化学品安全规则。

Research

JoVE Journal

Chemistry

Template Directed Synthesis of Plasmonic Gold Nanotubes with Tunable IR Absorbance

的模板导演电浆黄金纳米管的合成与可调谐红外吸收

A nearly parallel array of pores can be produced by anodizing aluminum foils in acidic environments1, 2. Applications of anodic aluminum oxide (AAO) ...

科研

化学

Nucleoside Triphosphates - From Synthesis to Biochemical Characterization

核苷三磷酸 - 从合成到生化特征

The  traditional strategy for the introduction of chemical functionalities is the  use of solid-phase synthesis by appending suitably modified ...

Synthesis and Characterization of Functionalized Metal-organic Frameworks

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Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Preparation and Characterization of SDF-1&#945;-Chitosan-Dextran Sulfate Nanoparticles

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SDF-1α - 壳聚糖硫酸葡聚糖纳米粒子的制备与表征

Chitosan (CS) and dextran sulfate (DS) are charged polysaccharides (glycans), which form polyelectrolyte complex-based nanoparticles when mixed under ...

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

合成和金插在介孔二氧化硅的墙壁催化性能

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties ...

Synthesis, Characterization, and Functionalization of Hybrid Au/CdS and Au/ZnS Core/Shell Nanoparticles

合成，表征和混合金/硫化镉和Au / ZnS核/壳纳米颗粒功能化

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large ...

A Simple Method for the Size Controlled Synthesis of Stable Oligomeric Clusters of Gold Nanoparticles under Ambient Conditions

根据环境条件的金纳米粒子的稳定低聚簇的大小控制合成的一种简便方法

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like ...

Synthesis and Characterization of Supramolecular Colloids

超分子胶体的合成与表征

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

Synthesis of Ligand-free CdS Nanoparticles within a Sulfur Copolymer Matrix

a硫磺共聚物基质内的免费配体硫化镉纳米粒子的合成

Aliphatic ligands are typically used during the synthesis of nanoparticles to help mediate their growth in addition to operating as high-temperature ...

Hydroquinone Based Synthesis of Gold Nanorods

金纳米棒基于对苯二酚合成

Gold nanorods are an important kind of nanoparticles characterized by peculiar plasmonic properties. Despite their widespread use in nanotechnology, the ...