Name: a simple method for the size controlled synthesis of stable oligomeric clusters of gold nanoparticles under ambient conditions
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TK确认来自斯洛文尼亚的研究机构的支持（ARRS，授予BI-US / 13-14-040和J3-6803）。 OS确认来自美国国立卫生研究院（NIH）资助RO1HL49277支持。

1.试剂的制备注意:化学品和解决方案时一定要小心。遵守适当的安全实践和戴手套，眼镜和白大褂在任何时候。要知道，相​​比于他们的对手散装纳米材料可能有额外的危害。 注意:所有的化学溶液被制成重模（克每摩尔公斤的溶剂），而不是摩尔（每升溶液克摩尔）。 <ol><li>氯化金制备<ol><li>溶解1g金（III）三水合物在100克氧化氢 ​​，得到25mM的氯金酸4。 </li></ol></li><li>硼砂的制备（钠2 B 4 O 7·10H 2 O） <ol><li>溶解3.81克硼砂为100克H 2 O操作给予0.1摩尔浓度硼砂（暖如有必要，以确保完整的解决方案）。 </li></ol></li><li>硫氰酸钠的制备<ol><li>溶解8.1克硫氰酸钠在100克的H 2 O操作给予1摩尔浓度硫氰酸钠。 </li></ol></li><li>碳酸钠的制备<ol><li>溶解5.3克无水碳酸钠在100g 氧化氢 ​​，得到0.5摩尔浓度的 Na 2 CO 3。 </li></ol></li><li>谷胱甘肽的制备<ol><li>溶解154毫克的还原型谷胱甘肽（GSH）每0.5摩尔浓度为1毫升的 Na 2 CO 3给出0.5摩尔浓度GSH。 </li></ol></li></ol> 2.黄金Oligoclusters的合成<ol><li>黄金Oligoclusters的延迟时间合成<ol><li>加入59.5毫升氧化氢 ​​含有搅拌棒的清洁125毫升惠顿玻璃瓶。使用任何平底干净的玻璃容器中，但要确保它是非常干净的。 </li><li>新增7毫升0.1N摩尔浓度的硼砂，带来解决方案，以一场轰轰烈烈的轰动。 </li><li>加入2.8毫升的〜25毫米氯金酸剧烈混合下，等待所需的延迟时间（除了氯金酸的开始延迟时间）。延迟时间将决定大小如表 1中所示的作为合成oligoclusters。 </li><li>希望以后的延迟时间，加入700μl1摩尔浓度的硫氰酸钠的下短时间剧烈搅拌（1200转，30秒）。 </li><li>移除搅拌棒和使反应进行完全O / N（在oligoclusters的粒度分布可进一步通过允许同时将反应进行到完成混合物不断搅拌O / N改善）。一旦反应已到完成所合成的粗oligoclusters是数周是稳定的。 </li></ol></li><li>附加Oligoclusters生长<ol><li>结合10mL在合成oligoclusters的向60ml HG的。合成的oligoclusters至HG的比率决定所得oligoclusters的大小，增加HG的相对量产生较大oligoclusters。 </li><li>加入900微升1摩尔浓度的硫氰酸钠的下短时间剧烈搅拌（1200转，30秒）。 </li><li>让反应去完成O / N（在oligoclusters的大小分布可以通过允许同时将反应进行到完成）混合物连续搅拌O / N得到进一步改善。 </li></ol></li></ol> 3. GSH衍生和Oligoclusters浓度<ol><li>添加70所合成原油oligoclusters（或oligoclusters从附加法）的毫升到70毫升30 kDa的截止离心过滤。 </li><li>旋在3000×g下15分钟。此浓缩的颗粒降低到〜250微升的体积。 </li><li>翻转装置上，并通过在500×g下3分钟纺丝设备恢复滞留。回收量应〜250微升。 </li><li>测量使用微量恢复的卷。 </li><li> 0.5质量摩尔浓度谷胱甘肽（或其他巯基）相等的体积加入1/9 个集中oligoclusters的恢复的卷（终浓度为50 mmolal GSH）。 </li><li>允许衍生反应在RT静置5-10分钟。衍生很快发生。过长的时间可能会溶解的颗粒。 </li><li>稀释衍生金融工具源化oligoclusters到50ml的Dulbecco磷酸盐缓冲盐水。 （其他缓冲器或H 2 O，可以选择作为该步骤中的稀释剂/洗涤缓冲液中。选择通常通过旨在下游应用决定。） </li><li>添加所有的稀释衍生oligoclusters 30 kDa的截止离心过滤的。 </li><li>旋转离心过滤器以3,000×g的15分钟。 </li><li>翻转装置上，并通过在500×g下3分钟纺丝设备恢复滞留。回收量应〜250微升。回收的浓缩颗粒是准备使用并且是稳定的，在4℃下个月。 </li></ol> 4.分析和Oligocluster合成验证<ol><li> Oligoclusters的凝胶电泳<ol><li>原油oligocluster准备电泳<ol><li>混合所合成oligocluster制剂2:1用含60％甘油负载缓冲液，〜0.15％溴酚蓝，和150 mmolal谷胱甘肽（0.5摩尔浓度的G库存SH溶解于0.5质量摩尔浓度的 Na 2 CO 3）。 </li><li>负载30微升到预制聚丙烯酰胺梯度凝胶（任何kDa的）中，用Tris-甘氨酸电泳缓冲液中运行（25毫摩尔Tris，192毫甘氨酸;没有使用SDS）中在恒定电压（200伏）26分钟。 </li></ol></li><li> GSH衍生Oligoclusters电泳<ol><li>稀释GSH-衍生oligocluster准备1:3与H 2 O（通常2微升GSH-oligoclusters与6微升H 2 O）。 </li><li>混合稀释谷胱甘肽衍生oligoclusters 2:1用含有60％甘油负载缓冲液，〜0.15％溴酚蓝，和150 mmolal碳酸氢钠。 </li><li>负载10微升到预制聚丙烯酰胺梯度凝胶（任何kDa的）中，用Tris-甘氨酸电泳缓冲液中运行（25毫摩尔Tris，192毫甘氨酸;没有使用SDS）中在恒定电压（200伏）26分钟。 </li></ol></li></ol></li><li>透射电子显微镜（TEM） <ol><li>准备Oligoclusters为TEM <ol><li>洗oligoclusters稀释20微升浓oligoclusters的用0.5ml的H 2 O和负载入到0.5ml的30 kDa的截止离心过滤。 </li><li>旋在14000 xg离心10分钟。 </li><li>用新鲜的0.5的H 2 O.毫升取出滤液和截留悬浮</li><li>重复洗涤两次，共3次洗涤。 </li><li> H中2 O稀释最终滞留500倍（oligoclusters准备在这一点网格）。 </li></ol></li><li>网格化Oligoclusters <ol><li>辉光放电碳包覆网格。 </li><li>存款0.6微升洗涤并稀释oligoclusters的到碳包覆辉光放电电网。 </li><li>允许电网风干10分钟。 </li><li>透射电镜在放大100000可视化oligoclusters。工作在80千伏这里显示的图像。 </li></ol></li></ol></li></ol>

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The authors have nothing to disclose.

此稿件为单分散黄金oligoclusters的台式合成（ 图3）详细的协议。该方法能够通过简单地改变加入氯金酸4的碱性溶液中，随后加入还原剂，硫氰酸钠之间的时间产生一个宽范围的尺寸的。加入氯金酸4的碱性缓冲水溶液的结果在氯金酸4的时间依赖性羟化羟基化金（Na +的[金（OH 4-X）氯X] - ）。在不到这羟化结果氯金酸是可用的，虽然羟化没有去完成，因为它是一个平衡的反应。成核和形成从头金单体可以仅由氯金酸4发起。羟基化的金仅能够添加到现有的金纳米颗粒，导致金oligoclusters的形成;我们的附加方法采用此16的优势。与延迟时间法形成Oligoclusters可以用作在其羟基化的金沉积，从而增加接种oligoclusters的大小种子。接种生长可通过改变羟基化金（HG）与合成的oligocluster（图1）的比率来控制。在两种方法中颗粒的尺寸可以很容易地选择合适的时间延迟（图2A，B）或通过选择起始种子权和加入羟基化金（HG）（图2C）的权利比来预测。为最有用的颗粒尺寸的预测呈现（表1）。谷胱甘肽衍生oligoclusters的增大尺寸可以通过电泳较大颗粒迁移少，出现来监测特别深，在后来的事实得到了金纳米颗粒的消光系数增加成比例地粒度。 氯金酸的羟基化是一个平衡反应，不会去完毕。 氯金酸的不完全的羟基化对附加反应影响最小的时候oligocluster种子的浓度仍然很高。当oligocluster种子的浓度很低，如使用长的延迟时间的种子和高HG时是这样的:种子比率，unhydroxylated 氯金酸的影响可以成为显著。在这些条件下氯金酸4能够以成核的新oligoclusters的合成，从而导致oligoclusters的异质群体。 由延迟时间或附加方法生产的合成的oligoclusters对于周稳定，只有显影金沉淀的微量。即使是后ING集中300倍的oligoclusters保持稳定，抵抗聚集。此处所描述的金oligoclusters还具有​​能够被集中没有事先衍生，从而使在较小体积中使用昂贵的衍生剂的额外的好处。与谷胱甘肽（GSH）被衍生化后，集群保持稳定长达一年。谷胱甘肽衍生还规定，使得当暴露于生理缓冲剂或动物血浆它们抵抗聚集强负电荷13，从而使它们适合于在体内实验。衍生可与多种含巯基的试剂来实现。 该oligoclusters对衍生的顺从与其它含巯基的分子17,18使面单层方便，易于修改，从而控制表面化学和oligoclusters的反应性。在此协议CA使用的其他化学品N为容易取代类似的化学品不损害合成。这包括与其他的碱性缓冲剂硼砂（如，碳酸盐）和硫氰酸钠的其他硫氰酸盐替代（例如，KSCN）。 该协议的主要属性是它的简单，它必须被强调。只有一个毫克体重秤和磁力搅拌器需要生产商业质量金oligoclusters其可用于先进的生物和材料的应用。广泛的适用性是由一系列的大小相比，可以生产和单分散性的帮助。此外，在内部生产成本低。 该oligoclusters是基膜和血液屏障通透性的研究特别有价值。它们可以通过不同的路由盐水易于给药和体内19-21跟踪。获得组织样本可以下随后检查电子显微镜16,22。除了 ​​透气性，生物分布提供了有价值的药理学的信息和不同大小的oligoclusters的混合物的管理提供有关粒子的身体内23-25 ​​相关尺寸分布的有价值的信息。最后，由于其独特的结构的它们不能表现局部表面等离子共振（LSPR）也许使得它们为荧光标记，这是不是在金纳米颗粒容易实现的理想候选，因为在荧光26的几乎完全猝灭的LSPR和荧光团的结果之间的干扰。

如在这两个生物医学应用和基础研究工具的使用金纳米颗粒就突飞猛进在过去的几十年。少数现代纳米材料已经被应用于许多不同的领域，发现它们在一切从太阳能电池板的光热癌症治疗中的用途;从电子生物传感器;从化学催化到药物递送系统1-7。在金纳米粒子在这些领域中的权益工具是由独特的性能金纳米粒子拥有包括特殊的结构，光学和电子性质8驱动。 有一个越来越多地使用金生物和化学测定纳米粒子9,10。尽管购买黄金纳米粒子的许多来源的可用性，他们来以相当的价格相比，在内部合成的成本的时候。市售纳米粒子的高成本使得内部合成德sirable。我们的程序包括由小2-3纳米的球形亚基金制成低聚纳米团簇的合成。具有所有的古典金纳米颗粒的优点，当涉及到渗透性或过滤速率测量，因为它们的模块化结构模拟物的蛋白质的结构低聚纳米簇是优选的选择。 目前，对在内部合成金纳米颗粒的最常见的方法包括氯化金（氯金酸4）水性条件11,12下的减少。与普通还原剂，如硼氢化钠（NaBH 4还原）或柠檬酸钠氯金酸4的还原，允许生产球形纳米颗粒13。通过这些方法合成金纳米粒子在它们有用的大小范围是有限的，因为他们成为盐的生物缓冲剂存在敏感，因为他们的核心直径增大。一种方法，先前已经描述对于纳米直径2-3从氯金酸4与硫氰酸钠还原的黄色纳米颗粒的碱性条件14,15下的合成。 在这里，我们描述了产生黄色纳米颗粒的葡萄状oligocluster而不需要额外的封端剂该方法的变形例。通过简单地改变加入氯金酸4的碱性溶液中，随后加入还原剂，硫氰酸钠的之间的时间，我们能够从〜3nm至〜25nm的变化所得到的金颗粒的尺寸。为了产生较大的颗粒，一个简单的附加过程可以用于通过加入羟基化金（HG）的生长这些oligoclusters在硫氰酸钠的存在下合成的oligoclusters。使用这两种方法，我们能够可靠地产生oligoclusters覆盖的范围从〜3nm至〜70纳米。事实上，这种方法可以让高品质的摹以及控制合成与标准的设备和试剂的数量有限的台式的条件下老oligoclusters潜在延伸金纳米颗粒作为研究工具的研究人员在化学合成很少或没有专业知识的优势。

<table><tbody><tr><td>125 ml Wheaton glass bottles</td><td>Fisher Scientific</td><td>SC-06-404F</td><td></td></tr><tr><td>Borax (Na&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;4&lt;/sub&gt;O&lt;sub&gt;7&lt;/sub&gt;&amp;middot;10H&lt;sub&gt;2&lt;/sub&gt;O)</td><td>Fisher Scientific</td><td>S25537</td><td></td></tr><tr><td>Gold(III) Chloride trihydrate</td><td>Sigma Aldrich</td><td>G4022</td><td></td></tr><tr><td>Sodium thiocyanate</td><td>Sigma Aldrich</td><td>251410</td><td></td></tr><tr><td>Sodium carbonate</td><td>Sigma Aldrich</td><td>S7795</td><td></td></tr><tr><td>Glutathione</td><td>Sigma Aldrich</td><td>G4251</td><td></td></tr><tr><td>Dulbecco&#039;s phosphate buffered saline (DPBS)</td><td>Corning</td><td>21-031-CV</td><td></td></tr><tr><td>Centricon Plus - 70</td><td>Millipore</td><td>UCF703008</td><td></td></tr><tr><td>Sodium bicarbonate</td><td>Sigma Aldrich</td><td>S6014</td><td></td></tr><tr><td>CF200-Cu Carbon film on 200 mesh copper grids&amp;nbsp;</td><td>Electron Microscopy Sciences</td><td>71150</td><td></td></tr><tr><td>10x Tris/Glycine buffer</td><td>Bio-Rad</td><td>161-0734</td><td></td></tr><tr><td>Any kD Mini-PROTEAN TGX Gel</td><td>Bio-Rad</td><td>456-9033</td><td></td></tr></tbody></table>

a simple method for the size controlled synthesis of stable oligomeric clusters of gold nanoparticles under ambient conditions

在碱性条件下还原稀水溶液氯金酸4硫氰酸钠（硫氰酸钠）产生2至3nm直径的纳米颗粒。窄粒度分布的这些黄色纳米颗粒的稳定葡萄状低聚簇通过两种方法在环境条件下合成。的延迟时间的方法，通过改变加入氯金酸4的碱性溶液中，随后加入还原剂，硫氰酸钠的之间的时间控制在oligoclusters亚基的数目。黄色oligoclusters产生范围在大小从〜3〜25纳米。这个尺寸范围可以通过利用羟基氯化金（Na +的[金（OH 4-X）氯X] - ）的附加 ​​方法进一步扩展到自动催化增加oligocluster纳米粒子的合成的亚基的数目，提供的3纳米的总范围至70纳米。粗oligocluster制剂显示窄粒度分布，不需要皮草疗法分馏对于大多数目的。形成的oligoclusters可以集中&gt; 300倍，无结块和粗反应混合物保持稳定，周没有进一步处理。因为这些寡聚集群可以衍生之前浓缩它们允许经济地使用昂贵的衍生剂。此外，我们提出两个模型由粒径的预测可以非常精确地进行。

金oligoclusters的合成通过凝胶电泳（图1）和透射电子显微镜（TEM）（图2）进行分析。 GSH包覆oligoclusters的尺寸可以通过电泳为较大颗粒迁移少和出现暗进行监测。此外，任何给定尺寸制剂的质量可以由带的电泳（即，对于给定的尺寸，具有较窄粒度分布的制剂将产生比相同尺寸的制剂更紧频带与更广泛的尺寸分布）后看到的广度来推断。 图2描述了时间延迟（延迟时间法）或HG的关系:种子（附加法）oligocluster大小。透射电镜计算的平均直径来确定延迟时间和韩庚:对延迟时间oligoclusters种子依赖性生长和附加的方法，分别为。概述了这两个过程的流程图（图3）满足部门首长以及提供预测的参数，以产生所需大小的oligoclusters一个表（表1）给出。 <img alt="图1" src="/files/ftp_upload/53388/53388fig1.jpg" /> 图1. 聚丙烯酰胺的延迟时间形成附加的方法。oligoclusters的梯度凝胶电泳中因延误时间产生Oligoclusters和附加方法进行梯度凝胶电泳分析。泳道2-4:由附加法形成oligoclusters:使氯金酸和碱加入硫氰酸钠5-8车道之间不同的延迟时间（45，135，和405秒）后形成oligoclusters。种子是由延迟时间的方法与405秒的延迟，由↓表示形成。被用于附加HG的数额不等。汞溶液（1毫米金）种子溶液（1毫米金）用于制备每个样品的比率是籼稻特德，作为4xHG，6xHG，12xHG和24xHG。 <a href="https://www-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/53388/53388fig1large.jpg" target="_blank">请点击此处下载此文件。</a> <img alt="图2" src="/files/ftp_upload/53388/53388fig2.jpg" /> 图 2. 延迟时间形成和附加方法金oligoclusters的直径。通过延迟时间准备和附加方法由TEM分析Oligoclusters。 A）和B）从参考文献16，版权所有2014年美国化学学会适应许可。 （A）的50纳米的代表性TEM照片×50从样品制备电网纳米领域使用的延迟时间法进行。在它们的制备（X轴）所使用的粒子（Y轴）与延迟时间的直径被表示，这两个轴是对数的。沉重的黑线（R 2 = 0.973）是经验3参数方程ð 延迟时间 = D 0 +一（1最佳拟合-电子-bt </SUP&gt;），其中D 的延迟时间是在纳米簇的平均直径，D 0是群集（〜3.5纳米）的最小直径; a是造成延长的延迟时间在芯尺寸的最大增加（〜20纳米） ， 和 b = 0.0021 秒 -1。加入提出了关于线性刻度的NaSCN（延迟时间法）前延迟时间不同后形成的oligoclusters的（B）的直径。 （C）不同量的HG上用405秒的延迟时间的延迟时间的方法形成预制金种子加（add-上法）后形成的oligoclusters的直径。如由重黑线，就可以很容易地看出，oligoclusters由附加法形成的直径是<img alt="公式4" src="/files/ftp_upload/53388/53388eq4.jpg" /> ，其中c HG和c 种子是在使HG的附加 ​​方法解决方案，并在作出oligoc使用氯金酸浓度<html>分别由延迟时间法，枝形吊灯。同样V HG和V 种子是相应的卷。 <a href="https://www-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/53388/53388fig2large.jpg" target="_blank">请点击此处下载此文件。</a> <img alt="图3" src="/files/ftp_upload/53388/53388fig3.jpg" /> 图3. 挂图图的延迟时间和制作不同大小的金oligoclusters附加的方法。流程图，概述了合成使用任一延迟时间或附加的方法不同大小的金oligoclusters的程序。氯金酸的碱溶液为蓝色。汞是红色的。金纳米粒子种子和oligoclusters是黑色的。 <a href="https://www-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/53388/53388fig3large.jpg" target="_blank">请点击此处下载此文件。</a> <table><tbody><tr>318px"&gt;延迟时间过程 </td><td colspan="6"> 附加程序 </td></tr><tr><td colspan="4"></td><td colspan="6"> 预测直径（纳米） </td></tr><tr><td> 延迟时间（秒） </td><td> 延迟时间（分钟） </td><td> 预测直径（纳米） </td><td> 测量直径±SD（NM） </td><td> 4×HG </td><td> 6×HG </td><td> 12×HG </td><td> 24×HG </td><td> 100×HG </td><td> 1000×HG </td></tr><tr><td> 1 </td><td> 0.02 </td><td> 3.5 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 2 </td><td> 0.03 </td><td> 3.6 </td><td> 3.1±1.3 </td><td> 6.1 </td><td> 6.9 </td><td> 8.4 </td><td> 10.5 </td><td> 16.7 </td><td> 36 </td></tr><tr><td> 3 </td><td> 0.05 </td><td> 3.6 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 4 </td><td> 0.07 </td><td> 3.7 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>五</td><td> 0.08 </td><td> 3.7 </td><td> 2.6±1.1 </td><td> 6.3 </td><td> 7.1 </td><td> 8.7 </td><td> 10.8 </td><td> 17.3 </td><td> 37 </td></tr><tr><td> 6 </td><td> 0.10 </td><td> 3.8 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 7 </td><td> 0.12 </td><td> 3.8 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 8 </td><td> 0.13 </td><td> 3.8 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 9 </td><td>0.15 </td><td> 3.9 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 10 </td><td> 0.17 </td><td> 3.9 </td><td></td><td> 6.7 </td><td> 7.5 </td><td> 9.2 </td><td> 11.4 </td><td> 18 </td><td> 39 </td></tr><tr><td> 11 </td><td> 0.18 </td><td> 4 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 12 </td><td> 0.20 </td><td> 4 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 13 </td><td> 0.22 </td><td> 4 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 14 </td><td> 0.23 </td><td> 4.1 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 15 </td><td> 0.25 </td><td> 4.1 </td><td> 3.3±1.5 </td><td> 70.0 </td><td> 7.9 </td><td> 9.7 </td><td> 12.0 </td><td> 19 </td><td> 41 </td></tr><tr><td> 20 </td><td> 0.33 </td><td> 4.3 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 25 </td><td> 0.42 </td><td> 4.5 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>三十</td><td> 0.50 </td><td> 4.7 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 35 </td><td> 0.58 </td><td> 4.9 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 40 </td><td> 0.67 </td><td> 5.1 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 45 </td><td> 0.75 </td><td> 5.3 </td><td> 6.4±2 </td><td> 9.1 </td><td> 10.1 </td><td> 12.5 </td><td>15.5 </td><td> 25 </td><td> 53 </td></tr><tr><td> 60 </td><td> 1.0 </td><td> 5.9 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 75 </td><td> 1.3 </td><td> 6.4 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 90 </td><td> 1.5 </td><td> 6.9 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 105 </td><td> 1.8 </td><td> 7.5 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 120 </td><td> 2.0 </td><td> 8 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 135 </td><td> 2.3 </td><td> 8.4 </td><td> 11±3 </td><td> 14.4 </td><td> 16.1 </td><td> 20 </td><td> 25 </td><td> 39 </td><td> 84 </td></tr><tr><td> 165 </td><td> 2.8 </td><td> 9.4 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 195 </td><td> 3.3 </td><td> 10 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 225 </td><td> 3.8 </td><td> 11 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 255 </td><td> 4.3 </td><td> 12 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 285 </td><td> 4.8 </td><td> 13 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 315 </td><td> 5.3 </td><td> 13 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 345 </td><td> 5.8 </td><td> 14 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 375 </td><td> 6.3 </td><td> 14 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 405 </td><td> 6.8 </td><td> 15 </td><td> 14±5 </td><td> 26 </td><td> 29 </td><td> 35 </td><td> 44 </td><td> 70 </td><td> 150 </td></tr><tr><td> 435 </td><td> 7.3 </td><td> 15 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 465 </td><td> 7.8 </td><td> 16 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 495 </td><td> 8.3 </td><td> 16 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 525 </td><td> 8.8 </td><td> 17 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 555 </td><td> 9.3 </td><td> 17 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 585 </td><td> 9.8 </td><td> 18 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 615 </td><td> 10 </td><td> 18 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 900 </td><td> 15 </td><td> 20 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 1200 </td><td> 20 </td><td> 22 </td><td> 20±11 </td><td> 37 </td><td> 42 </td><td> 51 </td><td> 64 </td><td> 102 </td><td> 219 </td></tr><tr><td> 1500 </td><td> 25 </td><td> 23 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 1800 </td><td>三十</td><td> 23 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 2100 </td><td> 35 </td><td> 23 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 2400 </td><td> 40 </td><td> 23 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 2700 </td><td> 45 </td><td> 23 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 3000 </td><td> 50 </td><td> 23 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 3300 </td><td> 55 </td><td> 23 </td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td> 3600 </td><td> 60 </td><td> 23 </td><td> 25±11 </td><td> 40 </td><td> 45 </td><td> 55 </td><td> 69 </td><td> 109 </td><td> 235 </td></tr></tbody></table> 表1. Oligocluster规模预测表。黄金oligoclusters的预测直径使用无论是延迟时间或附加方法形成。使用平均oligocluster 直径 D 延迟时间 = D 0 +一经验式计算为对延迟时间的方法的预测直径（1 -电子-bt），其中D是在纳米金oligoclusters的平均直径 D 0是的最小直径（3.5纳米）， 一个是在芯尺寸（20纳米）的最大增加，和b为 0.0021 秒 -1，如前面16所示。为附加方法预测直径的计算考虑到新的纳米颗粒不能从HG形成，而是沉积均匀地围绕预成形的球形种子，从而使它们大。没有其他的假设是必要的。它可以很容易地看出，第由附加法形成oligoclusters电子直径<img alt="公式6" src="/files/ftp_upload/53388/53388eq6.jpg" /> ，其中c HG和c 种子是在制造的HG的附加 ​​方法的溶液，并在由延迟时间法制作oligoclusters，分别使用氯金酸的浓度。同样V HG和V 种子是相应的卷。

Watch this Scientific Journal Video about A Simple Method for the Size Controlled Synthesis of Stable Oligomeric Clusters of Gold Nanoparticles under Ambient Conditions at JoVE.com

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

我们描述了通过的氯金酸（氯金酸4）用硫氰酸钠（硫氰酸钠）还原制备金纳米颗粒的高度稳定的寡聚簇的简单方法。所述oligoclusters具有窄的粒度分布，并且可以具有宽范围的尺寸和表面涂层来生产。

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 ...

a-simple-method-for-size-controlled-synthesis-stable-oligomeric

Universidad San Sebastian

Research

JoVE Journal

Chemistry

21.9K 次观看.  University of North Carolina at Chapel Hill. 我们描述了通过的氯金酸（氯金酸4）用硫氰酸钠（硫氰酸钠）还原制备金纳米颗粒的高度稳定的寡聚簇的简单方法。所述oligoclusters具有窄的粒度分布，并且可以具有宽范围的尺寸和表面涂层来生产。 

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

A Technique to Functionalize and Self-assemble Macroscopic Nanoparticle-ligand Monolayer Films onto Template-free Substrates

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface.&#160; The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates.&#160; The flow is mediated by a surface tension gradient3,4 and creates macroscopic, high-density, monolayer nanoparticle-ligand films.&#160; This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

A simple, robust and scalable technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates is described in this protocol.

一种技术，功能化和自组装纳米宏观 - 配体单层膜模板上无基材

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and ...

科研

化学

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+ (bpy = bipyridine), onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces.

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of novel materials. Coupled with analysis by in situ secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS), soft landing provides unprecedented insights into the interactions of well-defined species with surfaces.

在质谱选择离子软着陆准备好定义的表面原位二次离子质谱和红外光谱

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using ...

Synthesis of Immunotargeted Magneto-plasmonic Nanoclusters

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications including contrast enhancement in novel magnetomotive imaging modalities, simultaneous capture&#160;and detection of circulating tumor cells (CTCs),&#160;and multimodal molecular imaging combined with photothermal therapy of cancer cells. These applications have stimulated significant interest in development of protocols for synthesis of magneto-plasmonic nanoparticles with optical absorbance in the near-infrared (NIR) region and a strong magnetic moment. Here, we present a novel protocol for synthesis of such hybrid nanoparticles that is based on an oil-in-water microemulsion method. The unique feature of the protocol described herein is synthesis of magneto-plasmonic nanoparticles of various sizes from primary blocks which also have magneto-plasmonic characteristics. This approach yields nanoparticles with a high density of magnetic and plasmonic functionalities which are uniformly distributed throughout the nanoparticle volume. The hybrid nanoparticles can be easily functionalized by attaching antibodies through the Fc moiety leaving the Fab portion that is responsible for antigen binding available for targeting.

Here, we describe a protocol for synthesis of magneto-plasmonic nanoparticles with a strong magnetic moment and a strong near-infrared (NIR) absorbance. The protocol also includes antibody conjugation to the nanoparticles through the Fc moiety for various biomedical applications which require molecular specific targeting.

Immunotargeted的合成磁等离子团簇

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications ...

Synthesis, Assembly, and Characterization of Monolayer Protected Gold Nanoparticle Films for Protein Monolayer Electrochemistry

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently incorporated into film assemblies that serve as adsorption platforms for protein monolayer electrochemistry (PME). PME is utilized as the model system for studying electrochemical properties of redox proteins by confining them to an adsorption platform at a modified electrode, which also serves as a redox partner for electron transfer (ET) reactions. Studies have shown that gold nanoparticle film assemblies of this nature provide for a more homogeneous protein adsorption environment and promote ET without distance dependence compared to the more traditional systems modified with alkanethiol self-assembled monolayers (SAM).1-3 In this paper, MPCs functionalized with hexanethiolate ligands are synthesized using a modified Brust reaction4 and characterized with ultraviolet visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and proton (1H) nuclear magnetic resonance (NMR). MPC films are assembled on SAM modified gold electrode interfaces by using a "dip cycle" method of alternating MPC layers and dithiol linking molecules. Film growth at gold electrode is tracked electrochemically by measuring changes to the double layer charging current of the system. Analogous films assembled on silane modified glass slides allow for optical monitoring of film growth and cross-sectional TEM analysis provides an estimated film thickness. During film assembly, manipulation of the MPC ligand protection as well as the interparticle linkage mechanism allow for networked films, that are readily adaptable, to interface with redox protein having different adsorption mechanism. For example, Pseudomonas aeruginosa azurin (AZ) can be adsorbed hydrophobically to dithiol-linked films of hexanethiolate MPCs and cytochrome c (cyt c) can be immobilized electrostatically at a carboxylic acid modified MPC interfacial layer. In this report, we focus on the film protocol for the AZ system exclusively. Investigations involving the adsorption of proteins on MPC modified synthetic platforms could further the understanding of interactions between biomolecules and man-made materials, and consequently aid the development of biosensor schemes, ET modeling systems, and synthetic biocompatible materials.5-8

Alkanethiolate stabilized gold colloids known as monolayer protected clusters (MPCs) are synthesized, characterized, and assembled into thin films as an adsorption interface for protein monolayer electrochemistry of simple redox protein like Pseudomonas aeruginosa azurin (AZ) and cytochrome c (cyt c).

单层的合成，装配和表征蛋白质单分子膜的电化学保护的金纳米粒子薄膜

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently ...

生物工程

Gold Nanostar Synthesis with a Silver Seed Mediated Growth Method

The physical, chemical and optical properties of nano-scale colloids depend on their material composition, size and shape 1-5. There is a great interest in using nano-colloids for photo-thermal ablation, drug delivery and many other biomedical applications 6. Gold is particularly used because of its low toxicity 7-9. A property of metal nano-colloids is that they can have a strong surface plasmon resonance 10. The peak of the surface plasmon resonance mode depends on the structure and composition of the metal nano-colloids. Since the surface plasmon resonance mode is stimulated with light there is a need to have the peak absorbance in the near infrared where biological tissue transmissivity is maximal 11, 12.
We present a method to synthesize star shaped colloidal gold, also known as star shaped nanoparticles 13-15 or nanostars 16. This method is based on a solution containing silver seeds that are used as the nucleating agent for anisotropic growth of gold colloids 17-22. Scanning electron microscopy (SEM) analysis of the resulting gold colloid showed that 70 % of the nanostructures were nanostars. The other 30 % of the particles were amorphous clusters of decahedra and rhomboids. The absorbance peak of the nanostars was detected to be in the near infrared (840 nm). Thus, our method produces gold nanostars suitable for biomedical applications, particularly for photo-thermal ablation.

We synthesized star shaped gold nanostars using a silver seed mediated growth method. The diameter of the nanostars ranges from 200 to 300 nm and the number of tips vary from 7 to 10. The nanoparticles have a broad surface plasmon resonance mode centered in the near infrared.

黄金Nanostar合成银种子介导的生长方法

The physical, chemical and optical properties of nano-scale colloids depend on their material composition, size and shape 1-5. There is a great interest ...

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

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large extinction coefficients which can be tuned across the visible spectrum. Research into the plasmonic enhancement of optical transitions has become popular, due to the possibility of altering and in some cases improving photo-absorption or emission properties of nearby chromophores such as molecular dyes or quantum dots. The electric field of the plasmon can couple with the excitation dipole of a chromophore, perturbing the electronic states involved in the transition and leading to increased absorption and emission rates. These enhancements can also be negated at close distances by energy transfer mechanism, making the spatial arrangement of the two species critical. Ultimately, enhancement of light harvesting efficiency in plasmonic solar cells could lead to thinner and, therefore, lower cost devices. The development of hybrid core/shell particles could offer a solution to this issue. The addition of a dielectric spacer between a gold nanoparticles and a chromophore is the proposed method to control the exciton plasmon coupling strength and thereby balance losses with the plasmonic gains. A detailed procedure for the coating of gold nanoparticles with CdS and ZnS semiconductor shells is presented. The nanoparticles show high uniformity with size control in both the core gold particles and shell species allowing for a more accurate investigation into the plasmonic enhancement of external chromophores.

The synthesis of uniform gold nanoparticles coated with semiconductor shells of CdS or ZnS is performed. The semiconductor coating is conducted by first depositing a silver sulfide shell and exchanging the silver cations for zinc or cadmium cations.

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 ...

Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

Procedures utilizing millifluidic devices for chemical synthesis and time-resolved mechanistic studies are described by taking three examples. In the first, synthesis of ultra-small copper nanoclusters is described. The second example provides their utility for investigating time resolved kinetics of chemical reactions by analyzing gold nanoparticle formation using in situ X-ray absorption spectroscopy. The final example demonstrates continuous flow catalysis of reactions inside millifluidic channel coated with nanostructured catalyst.

Millifluidic devices are utilized for controlled synthesis of nanomaterials, time-resolved analysis of reaction mechanisms and continuous flow catalysis.

Millifluidics的化学合成和时间分辨机理研究

Procedures utilizing millifluidic devices for chemical synthesis and time-resolved mechanistic studies are described by taking three examples. In the ...

Synthesis and Characterization of Amphiphilic Gold Nanoparticles

Gold nanoparticles covered with a mixture of 1-octanethiol (OT) and 11-mercapto-1-undecane sulfonic acid (MUS) have been extensively studied because of their interactions with cell membranes, lipid bilayers, and viruses. The hydrophilic ligands make these particles colloidally stable in aqueous solutions and the combination with hydrophobic ligands creates an amphiphilic particle that can be loaded with hydrophobic drugs, fuse with the lipid membranes, and resist nonspecific protein adsorption. Many of these properties depend on nanoparticle size and the composition of the ligand shell. It is, therefore, crucial to have a reproducible synthetic method and reliable characterization techniques that allow the determination of nanoparticle properties and the ligand shell composition. Here, a one-phase chemical reduction, followed by a thorough purification to synthesize these nanoparticles with diameters below 5 nm, is presented. The ratio between the two ligands on the surface of the nanoparticle can be tuned through their stoichiometric ratio used during synthesis. We demonstrate how various routine techniques, such as transmission electron microscopy (TEM), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and ultraviolet-visible (UV-Vis) spectrometry, are combined to comprehensively characterize the physicochemical parameters of the nanoparticles.

Amphiphilic gold nanoparticles can be used in many biological applications. A protocol to synthesize gold nanoparticles coated by a binary mixture of ligands and a detailed characterization of these particles is presented.

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 ...

Large Area Substrate-Based Nanofabrication of Controllable and Customizable Gold Nanoparticles Via Capped Dewetting

Recent scientific advances in the utilization of metallic nanoparticle for enhanced energy conversion efficiency, improved optical device performance, and high-density data storage have demonstrated the potential benefit of their use in industrial applications. These applications require precise control over nanoparticle size, spacing, and sometimes shape. These requirements have resulted in the use of time and cost intensive processing steps to produce nanoparticles, thus making the transition to industrial application unrealistic. This protocol will resolve this issue by providing a scalable and affordable method for the large-area production of nanoparticle films with improved nanoparticle control compared to the current techniques. In this article, the process will be demonstrated with gold, but other metals can also be used.

This protocol details a novel nano-manufacturing technique that can be used to make controllable and customizable nanoparticle films over large areas based on the self-assembly of dewetting of capped metal films.

大面积地下纳米化的可控、可定制金纳米粒子通过包盖湿法

Recent scientific advances in the utilization of metallic nanoparticle for enhanced energy conversion efficiency, improved optical device performance, and ...

工程学

Gold Nanoparticle Synthesis

Gold nanoparticles (Au nanoparticles) that are ~12 nm in diameter were synthesized by rapidly injecting a solution of 150 mg (0.15 mmol) of tetrachloroauric acid in 3.0 g (3.7 mmol, 3.6 mL) of oleylamine (technical grade) and 3.0 mL of toluene into a boiling solution of 5.1 g (6.4 mmol, 8.7 mL) of oleylamine in 147 mL of toluene. While boiling and mixing the reaction solution for 2 hours, the color of the reaction mixture changed from clear, to light yellow, to light pink, and then slowly to dark red. The heat was then turned off, and the solution was allowed to gradually cool down to room temperature for 1 hour. The gold nanoparticles were then collected and separated from the solution using a centrifuge and washed three times; by vortexing and dispersing the gold nanoparticles in 10 mL portions of toluene, and then precipitating the gold nanoparticles by adding 40 mL portions of methanol and spinning them in a centrifuge. The solution was then decanted to remove any remaining byproducts and unreacted starting materials. Drying the gold nanoparticles in a vacuum environment produced a solid black pellet; which could be stored for long periods of time (up to one year) for later use, and then redissolved in organic solvents such as toluene.

A protocol for synthesizing ~12 nm diameter gold nanoparticles (Au nanoparticles) in an organic solvent is presented. The gold nanoparticles are capped with oleylamine ligands to prevent agglomeration. The gold nanoparticles are soluble in organic solvents such as toluene.