支持这项工作是由美国国家科学基金会职业奖第0954345号。

1。 CVD合成氮掺杂碳纳米管杯的（NCNCs） NCNCs合成采用化学气相沉积（CVD）技术在石英衬底使用液体前体（ 图1A）。 <ol><li>将一个3英尺长的一个Lindberg的/蓝色作为该反应室的管式炉中的石英管（2.5厘米）。将石英板（1“×12”）作为基片在管内产品的产品收集。密封的石英管中，用内置的气体和液体喷射连接/管，使用自制的不锈钢帽。 </li><li>使液体前体的溶液含有0.75％（重量）二茂铁，10％（重量）乙腈和89.25％（重量）二甲苯。的生长之前，绘制成的入口连接到石英管的气密注射器中的液体前体的约5ml。将注射器的注射器泵上。 </li><li>组装的CVD系统。将所有气体入口和出口。流量AR（845 SCCM）清除的CVD系统，并检查泄漏我们ING史努比液体泄漏检测器。吹扫20分钟后，打开H 2。的H 2的流量设置37.5 sccm的氩至127 sccm的。打开炉。炉的设定温度至800℃，并等待，直到它是稳定的，在800℃下</li><li>使用注射泵注入液体前体，在石英管内。喷射率设定在9毫升/小时6分钟，以填充注射管的死体积。然后掉头向下注射速率，以1毫升/小时的增长NCNCs的。增长90分钟后，关闭注射器泵和H 2气体流速，并关闭炉。保持氩气流动，维持惰性气氛中，直到将炉子冷却至室温。 </li><li>断开所有进气口和网点，并喷射系统。拆卸CVD系统和石英板。使用一个片面的刀片，以剥离膜从石英板NCNCs的。分散在乙醇中所采集的产品。呼吸保护是必要的，以防止INH通风柜外可能的碳材料，如果工作进行方向性。 </li></ol> 2。由混合物氧化合成NCNCs的酸<ol><li>将约10mg合成NCNCs到200ml圆底烧瓶中。向烧瓶中加入7.5毫升的浓HNO 3。简要超声水浴中更好的分散混合物。然后添加22.5毫升的浓H 2 SO 4慢慢。 （ 注意：强酸性混合物具有很强的腐蚀性，小心处理这些酸与安全保护）。超声反应混合物在室温水浴4小时。 </li><li>稀释的反应混合物与100毫升的水，同时在冰浴中冷却。通过聚四氟乙烯（PTFE）膜的孔径为220nm，使用水吸气过滤混合物。 </li><li>滤膜上的材料洗净，用200毫升0.01 M NaOH溶液，以消除任何酸性残留的副产品，18洗用200ml的0.01M HCl溶液，其次是实现大量水，直至滤液pH值呈中性。将得到的材料（氧化NCNCs）分散在水（20ml）中，通过超声处理。进一步的实验中，可以存储在室温下将所得的悬浮液。 </li></ol> 3。物理分离NCNCs的探头尖端超声<ol><li>的悬浮液转移到100毫升塑料杯中，在冰浴下在水中的氧化NCNCs。填充塑料杯容量为50毫升，用水。设置探针尖端超声波仪配备有1/4“直径的钛微尖在60％的最大量值（12瓦）。淹没微尖溶液的中心，然后处理12小时，用30秒开/关间隔。冰每30分钟，以防止过热。 </li><li>停止声波处理。过滤NCNC的220纳米孔径的PTFE过滤膜，以消除任何大颗粒的悬浮液通过。得到NCNC样品可存放在室温下为进一步的应用。 </lI&gt; <li> （可选）作为对比实验，分散在DMF另一个样本合成NCNCs的直接超声悬浮探针尖端超声12小时在相同的设置同上。 </li></ol> 4。由Kaiser测试胺官能团对NCNCs的定量分析<ol><li>准备试剂A：将1克苯酚和250μl的EtOH中，在2.5毫升吡啶中，加入50微升H 2 O至的0.01M hydrindantin的混合物。准备试剂B：茚三酮（50毫克）溶解在1毫升乙醇中。 </li><li>权衡NCNCs的样品（〜0.5毫克）微量天平和分散在1ml 3:2乙醇/水的小试管中。加入100μl试剂A和25微升样品悬浮液的试剂B。与parafilms密封试管，并加热该混合物，在100℃的油浴中10分钟。过滤样品通过注射器过滤器去除固体颗粒和收集滤液。 </li><li>费尔的可见光谱硝酸盐在同一进程中不添加NCNCs与空白样品的比色分析。记录的峰值集中在570 nm处的吸光度，并计算根据比尔 - 朗伯定律的胺负荷。 </li></ol> 5。官能NCNCs的与国民生产总值<ol><li>超声4ml的含有的分离NCNCs（0.01毫克/毫升）使用水浴超声波破碎仪5分钟，以实现均匀的分散体的水性悬浮液。 </li><li> 氯金酸水溶液（1毫克/毫升）的NCNC超声处理过程中的悬浮液加入1毫升。添加250μl的1％（重量）柠檬酸三钠水溶液中滴加。通过剧烈搅拌，将反应混合物在70℃下2小时的热板上。 </li><li>将反应混合物离心15分钟，在3400 rpm的转速下。收集沉淀物中的纳米金官能NCNCs，通过离心分离，并用水冲洗。分散在水（4ml）中的沉淀物。 </li></ol>

<ol>
	<li>Tasis, D., Tagmatarchis, N., Bianco, A., Prato, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chemistry+of+carbon+nanotubes.">Chemistry of carbon nanotubes.</a> Chem. Rev. 106 (3), 1105-1136 (2006).</li><li>Hilder, T. A., Hill, J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Modeling+the+loading+and+unloading+of+drugs+into+nanotubes.">Modeling the loading and unloading of drugs into nanotubes.</a> Small. 5 (3), 300-308 (2009).</li><li>Shvedova, A. A., Kisin, E. R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Unusual+inflammatory+and+fibrogenic+pulmonary+responses+to+single-walled+carbon+nanotubes+in+mice.">Unusual inflammatory and fibrogenic pulmonary responses to single-walled carbon nanotubes in mice.</a> American Journal of Physiology - Lung Cellular and Molecular Physiology. 289 (5), L698-L708 (2005).</li><li>Jia, G., Wang, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cytotoxicity+of+carbon+nanomaterials:+Single-wall+nanotube,+multi-wall+nanotube,+and+fullerene.">Cytotoxicity of carbon nanomaterials: Single-wall nanotube, multi-wall nanotube, and fullerene.</a> Environmental Science &amp; Technology. 39 (5), 1378-1383 (2005).</li><li>Carrero-S&#225;nchez, J. C., El&#237;as, A. L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Biocompatibility+and+toxicological+studies+of+carbon+nanotubes+doped+with+nitrogen.">Biocompatibility and toxicological studies of carbon nanotubes doped with nitrogen.</a> Nano Lett. 6 (8), 1609-1616 (2006).</li><li>Zhao, M. L., Li, D. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Differences+in+cytocompatibility+and+hemocompatibility+between+carbon+nanotubes+and+nitrogen-doped+carbon+nanotubes.">Differences in cytocompatibility and hemocompatibility between carbon nanotubes and nitrogen-doped carbon nanotubes.</a> Carbon. 49 (9), 3125-3133 (2011).</li><li>Allen, B. L., Kichambare, P. D., Star, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis,+characterization,+and+manipulation+of+nitrogen-doped+carbon+nanotube+cups.">Synthesis, characterization, and manipulation of nitrogen-doped carbon nanotube cups.</a> ACS Nano. 2 (9), 1914-1920 (2008).</li><li>Zhao, Y., Tang, Y., Chen, Y., Star, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Corking+carbon+nanotube+cups+with+gold+nanoparticles.">Corking carbon nanotube cups with gold nanoparticles.</a> ACS Nano. 6 (8), 6912-6921 (2012).</li><li>Stephan, O., Ajayan, P. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Doping+graphitic+and+carbon+nanotube+structures+with+boron+and+nitrogen.">Doping graphitic and carbon nanotube structures with boron and nitrogen.</a> Science. 266 (5191), 1683-1685 (1994).</li><li>Suenaga, K., Johansson, M. P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Carbon+nitride+nanotubulite+-+densely-packed+and+well-aligned+tubular+nanostructures.">Carbon nitride nanotubulite - densely-packed and well-aligned tubular nanostructures.</a> Chem. Phys. Lett. 300 (5-6), 695-700 (1999).</li><li>Chen, H., Yang, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synergism+of+C5N+six-membered+ring+and+vapor-liquid-solid+growth+of+CNx+nanotubes+with+pyridine+precursor.">Synergism of C5N six-membered ring and vapor-liquid-solid growth of CNx nanotubes with pyridine precursor.</a> J. Phys. Chem. B. 110 (33), 16422-16427 (2006).</li><li>Allen, B. L., Keddie, M. B., Star, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlling+the+volumetric+parameters+of+nitrogen-doped+carbon+nanotube+cups.">Controlling the volumetric parameters of nitrogen-doped carbon nanotube cups.</a> Nanoscale. 2 (7), 1105-1108 (2010).</li><li>Liu, J., Rinzler, A. G., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fullerene+pipes.">Fullerene pipes.</a> Science. 280 (5367), 1253-1256 (1998).</li><li>Zhao, Y., Allen, B. L., Star, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enzymatic+degradation+of+multiwalled+carbon+nanotubes.">Enzymatic degradation of multiwalled carbon nanotubes.</a> J. Phys. Chem. A. 115 (34), 9536-9544 (2011).</li><li>Wang, Y., Bai, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-yield+preparation+of+individual+nitrogen-containing+carbon+nanobells.">High-yield preparation of individual nitrogen-containing carbon nanobells.</a> Mater. Lett. 63 (2), 206-208 (2009).</li><li>Heller, D. A., Mayrhofer, R. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Concomitant+length+and+diameter+separation+of+single-walled+carbon+nanotubes.">Concomitant length and diameter separation of single-walled carbon nanotubes.</a> J. Am. Chem. Soc. 126 (44), 14567-14573 (2004).</li><li>Allen, B. L., Shade, C. M., Yingling, A. M., Petoud, S., Star, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Graphitic+nanocapsules.">Graphitic nanocapsules.</a> Adv. Mater. 21 (46), 4692-4695 (2009).</li><li>Wang, Z., Shirley, M. D., Meikle, S. T., Whitby, R. L. D., Mikhalovsky, S. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+surface+acidity+of+acid+oxidised+multi-walled+carbon+nanotubes+and+the+influence+of+in-situ+generated+fulvic+acids+on+their+stability+in+aqueous+dispersions.">The surface acidity of acid oxidised multi-walled carbon nanotubes and the influence of in-situ generated fulvic acids on their stability in aqueous dispersions.</a> Carbon. 47 (1), 73-79 (2009).</li><li>Liu, H., Zhang, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structural+and+morphological+control+of+aligned+nitrogen-doped+carbon+nanotubes.">Structural and morphological control of aligned nitrogen-doped carbon nanotubes.</a> Carbon. 48 (5), 1498-1507 (2010).</li><li>Mandumpal, J., Gemming, S., Seifert, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Curvature+effects+of+nitrogen+on+graphitic+sheets:+structures+and+energetics.">Curvature effects of nitrogen on graphitic sheets: structures and energetics.</a> Chem. Phys. Lett. 447 (1-3), 115-120 (2007).</li></ol>

作者宣称没有竞争经济利益。

我们的实验的主要目标是有效地产生氮掺杂碳纳米管的石墨纳米杯。但是，氮掺杂的CVD合成中并不能保证形成的叠层的杯形结构。根据该前体的化学成分和其他生长条件的不同，导致产物的形态可能有很大的差异，19氮源的浓度是影响结构的主要因素，因为中的氮原子的不相容性的的隔间结构的结果石墨晶格20，室的长度一般随着前体中的氮浓度减小。在较高浓度，横向分割层变?...

凭借其固有的内在的型腔和多功能的表面化学，中空的碳基纳米材料，如碳纳米管（CNTs），被认为是良好的纳米载体在药物传递中的应用。1,2但是，纯净的碳纳米管纤维结构，而无法 ​​进入空心内饰，并可能会导致严重的炎症反应，在生物系统中的细胞毒素的作用。3,4氮掺杂的碳纳米管，在另一方面，已被发现具有比未掺杂的多壁碳纳米管（MWCNTs）5,6更高的生物相容性，并可能有更好的药物交付性能。掺杂的氮原子成的碳纳米管的石墨晶格的查询结果在一个隔间的中空结构，可以分离出与典型长度在200纳米下取得个人氮掺杂碳纳米管杯（NCNCs）的类似叠杯。7,8与他们访问的内部和氮功能，允许进一步的化学官能化，这些单个的石墨杯是非常有利的药物输送应用。 在不同的合成方法，包括电弧放电和直流磁控溅射，化学气相沉积的氮掺杂的碳纳米管（CVD法）是最普遍的方法，因为一些优点，如更高的产量和更容易控制碳纳米管的生长条件。普遍采用的气-液-固（VLS）生长机制了解CVD生长过程中氮掺杂碳纳米管11通常有两种不同的方案使用金属催化剂在成长的种子。在“固定床”计划，首先定义大小的铁纳米粒子与五羰基铁的热分解合成，然后镀上石英片旋涂后续CVD生长在“浮动催化剂”计划，铁催化剂（通常12二茂铁）混合，并注入与碳和nitrogen前体，和设置在原位生成的铁催化纳米颗粒上沉积的碳和氮前体的二茂铁的热分解。固定床催化剂，同时提供了更好的尺寸控制在得到的NCNCs，产物的产率通常较低（&lt;1毫克），较浮动的催化剂相同的前体的量和生长时间的计划（&gt; 5毫克）。由于浮动催化剂计划也提供了相当均匀的粒度分布的NCNCs，本文采用CVD合成NCNCs。 CVD方法能提供合成NCNCs的具有纤维形态包括许多叠杯。虽然没有相邻杯之间的化学键合，保持有效的隔离的各个杯13的挑战，因为它们被牢固地插入到对方的腔和持有的多个非共价相互作用的无定形碳和外层。8 ATTE的分离的层叠的杯的MPTS包括化学方法和物理方法。强酸的混合物中的氧化处理，同时削减碳纳米管引入氧的功能，13,14，它也可以被应用成较短的部分切NCNCs是一个典型的程序。微波等离子体蚀刻程序，还示出的分离NCNCs。15相比，化学方法，物理分离更简单。我们以前的研究表明，可以通过简单的打磨与迫击炮和杵个人NCNCs的部分分离从他们的层叠结构。7此外，高强度的探针尖端超声，据报道，有效地切断单壁碳纳米管（碳纳米管） 16也显示有显着的影响分离NCNCs 8提供高强度的超声波探头尖端超声功率的NCNC的解决方案，基本上是“抖”叠杯和扰乱弱INTERA的持有杯ctions。虽然其他潜在的分离方法是低效或破坏性杯结构，探针尖端超声提供了一个高效，成本效益和较少破坏性的物理分离方法来获得个人的石墨杯。 首先在浓H 2 SO 4 HNO 3 /酸混合物分离与探针尖端超声处理前处理，所合成的原纤NCNCs。将得到的分离NCNCs是高亲水性的，并有效地分散在水中。之前我们已经确定了氮功能，如胺基上NCNCs和利用它们的化学反应的官能NCNCs。7,8,17的塞上NCNCs的商业纳米粒子，在这项工作中我们先前报道的方法相比，黄金纳米粒子（国民生产总值）有效地锚定到杯子的表面用柠檬酸钠还原氯金酸。由于轮辋NCNCs优惠氮的功能分布在开放，国民生产总值从黄金前体原位合成往往有更好的互动与开放式轮辋和形式国民生产总值的“软木塞”杯。这样的合成和官能化的方法导致一种新颖GNP的NCNC的的混合纳米材料的潜在应用价值的药物传递载体。

<table border="1">
 <tbody>
 <tr>
 <td>Reagent Name</td>
 <td>Company</td>
 <td>Catalogue Number</td>
 <td>Comment</td>
 </tr>
 <tr>
 <td></td>
 <td></td>
 <td>&nbsp;</td>
 <td>Reagents</td>
 </tr>
 <tr>
 <td>H2</td>
 <td>Valley National Gases</td>
 <td>Grade 5.0</td>
 <td></td>
 </tr>
 <tr>
 <td>Ar</td>
 <td>Valley National Gases</td>
 <td>Grade 5.0</td>
 <td></td>
 </tr>
 <tr>
 <td>Ferrocene</td>
 <td>Sigma-Aldrich</td>
 <td>F408-500G</td>
 <td></td>
 </tr>
 <tr>
 <td>Xylenes</td>
 <td>Fisher Scientific</td>
 <td>X5-500</td>
 <td></td>
 </tr>
 <tr>
 <td>Acetonitrile</td>
 <td>EMD</td>
 <td>AXO149-6</td>
 <td></td>
 </tr>
 <tr>
 <td>H2SO4</td>
 <td>Fisher Scientific</td>
 <td>A300-500</td>
 <td></td>
 </tr>
 <tr>
 <td>HNO3</td>
 <td>EMD</td>
 <td>NX0409-2</td>
 <td></td>
 </tr>
 <tr>
 <td>DMF</td>
 <td>Fisher Scientific</td>
 <td>D119-500</td>
 <td></td>
 </tr>
 <tr>
 <td>Ethanol</td>
 <td>Decon</td>
 <td>2716</td>
 <td></td>
 </tr>
 <tr>
 <td>Phenol</td>
 <td>Sigma-Aldrich</td>
 <td>P1037-100G</td>
 <td></td>
 </tr>
 <tr>
 <td>Pyridine</td>
 <td>EMD</td>
 <td>PX2020-6</td>
 <td></td>
 </tr>
 <tr>
 <td>Hydridantin</td>
 <td>Sigma-Aldrich</td>
 <td>H2003-10G</td>
 <td></td>
 </tr>
 <tr>
 <td>Ninhydrin </td>
 <td>Alfa Aesar</td>
 <td>43846</td>
 <td></td>
 </tr>
 <tr>
 <td>HAuCl4</td>
 <td>Sigma-Aldrich</td>
 <td>52918-1G</td>
 <td></td>
 </tr>
 <tr>
 <td>Sodium Citrate</td>
 <td>SAFC</td>
 <td>W302600</td>
 <td></td>
 </tr>
 <tr>
 <td></td>
 <td></td>
 <td>&nbsp;</td>
 <td>Equipment</td>
 </tr>
 <tr>
 <td>CVD Furnace</td>
 <td>Lindberg/Blue</td>
 <td>&nbsp;</td>
 <td></td>
 </tr>
 <tr>
 <td>TEM (low-resolution)</td>
 <td>FEI Morgagni</td>
 <td>&nbsp;</td>
 <td></td>
 </tr>
 <tr>
 <td>TEM (high-resolution)</td>
 <td>JOEL</td>
 <td>2100F</td>
 <td></td>
 </tr>
 <tr>
 <td>Probe-tip Sonicator</td>
 <td>Qsonica</td>
 <td>XL-2000</td>
 <td></td>
 </tr>
 <tr>
 <td>UV-Vis Spectrometer</td>
 <td>Perkin-Elmer</td>
 <td>Lambda 900</td>
 <td></td>
 </tr>
 <tr>
 <td>Zeta Potential Analyzer</td>
 <td>Brookheaven</td>
 <td>ZetaPlus</td>
 <td></td>
 </tr>
 <tr>
 <td>EDX spectroscopy</td>
 <td>Phillips</td>
 <td>XL30 FEG</td>
 <td></td>
 </tr>
 </tbody>
</table>

synthesis and functionalization of nitrogen-doped carbon nanotube cups with gold nanoparticles as cork stoppers

包括许多杯形的石墨称为车厢氮掺杂碳纳米管杯（NCNCs），氮掺杂碳纳米管。这些合成的化学气相沉积（CVD）法的石墨纳米杯层叠在头对尾的方式，仅通过非共价键相互作用。可以分离出单个NCNCs它们的层叠结构，通过一系列的化学和物理分离过程。首先，合成NCNCs的氧化强酸的混合物中引入含氧的缺陷，石墨壁。然后采用高强度超声探针尖端有效地分离成单个的石墨纳米杯堆叠NCNCs处理氧化NCNCs的。由于其丰富的氧气和氮气的表面功能，导致个别NCNCs极强的亲水性，并可以有效地功能化金纳米粒子（国民生产总值），优先适合在开场的杯软木塞。这些石墨纳米杯塞住的国民生产总值可能会发现广阔的应用前景的纳米容器和药物载体。

作为合成的NCNCs从CVD增长出现黑材料的地毯，石英衬底上。重约数mg NCNCs厚的薄膜，得到由剥离用刀片（ 图1B）。在不同的放大倍数（ 图1）的合成NCNCs的TEM图像显示的形态。在较低的放大倍率（ 图1C），所合成的NCNCs的显示长度通常为几微米，直径为20 - 30nm的原纤维结构。与未掺杂的碳纳米管的连续管状结构，在NCNC纤维隔间有许多的杯形部分。高分辨率的TEM?...

Watch this Scientific Journal Video about Synthesis and Functionalization of Nitrogen-doped Carbon Nanotube Cups with Gold Nanoparticles as Cork Stoppers at JoVE.com

Synthesis and Functionalization of Nitrogen-doped Carbon Nanotube Cups with Gold Nanoparticles as Cork Stoppers

我们讨论了个别石墨纳米杯的使用了一系列的技术，包括化学气相沉积，氧化和探针尖端的超声处理获得的合成。柠檬酸钠还原氯金酸<sub&gt; 4</sub&gt;石墨纳米杯，纳米金由于化学反应的杯子边缘有效地被塞住。

黄金纳米粒子作为软木塞氮掺杂碳纳米管杯的合成与功能构造

Nitrogen-doped carbon  nanotubes consist of many cup-shaped graphitic compartments termed as  nitrogen-doped carbon nanotube cups (NCNCs).  These ...

synthesis-functionalization-nitrogen-doped-carbon-nanotube-cups-with

Research

JoVE Journal

Engineering

22.7K 次观看.  University of Pittsburgh. 我们讨论了个别石墨纳米杯的使用了一系列的技术，包括化学气相沉积，氧化和探针尖端的超声处理获得的合成。柠檬酸钠还原氯金酸 4石墨纳米杯，纳米金由于化学反应的杯子边缘有效地被塞住。

视频: Synthesis and Functionalization of Nitrogen-doped Carbon Nanotube Cups with Gold Nanoparticles as Cork Stoppers

Fabrication, Densification, and Replica Molding of 3D Carbon Nanotube Microstructures

The introduction of new materials and processes to microfabrication has, in large part, enabled many important advances in microsystems, lab-on-a-chip devices, and their applications. In particular, capabilities for cost-effective fabrication of polymer microstructures were transformed by the advent of soft lithography and other micromolding techniques 1, 2, and this led a revolution in applications of microfabrication to biomedical engineering and biology. Nevertheless, it remains challenging to fabricate microstructures with well-defined nanoscale surface textures, and to fabricate arbitrary 3D shapes at the micro-scale. Robustness of master molds and maintenance of shape integrity is especially important to achieve high fidelity replication of complex structures and preserving their nanoscale surface texture. The combination of hierarchical textures, and heterogeneous shapes, is a profound challenge to existing microfabrication methods that largely rely upon top-down etching using fixed mask templates. On the other hand, the bottom-up synthesis of nanostructures such as nanotubes and nanowires can offer new capabilities to microfabrication, in particular by taking advantage of the collective self-organization of nanostructures, and local control of their growth behavior with respect to microfabricated patterns. 
Our goal is to introduce vertically aligned carbon nanotubes (CNTs), which we refer to as CNT "forests", as a new microfabrication material. We present details of a suite of related methods recently developed by our group: fabrication of CNT forest microstructures by thermal CVD from lithographically patterned catalyst thin films; self-directed elastocapillary densification of CNT microstructures; and replica molding of polymer microstructures using CNT composite master molds. In particular, our work shows that self-directed capillary densification ("capillary forming"), which is performed by condensation of a solvent onto the substrate with CNT microstructures, significantly increases the packing density of CNTs. This process enables directed transformation of vertical CNT microstructures into straight, inclined, and twisted shapes, which have robust mechanical properties exceeding those of typical microfabrication polymers. This in turn enables formation of nanocomposite CNT master molds by capillary-driven infiltration of polymers. The replica structures exhibit the anisotropic nanoscale texture of the aligned CNTs, and can have walls with sub-micron thickness and aspect ratios exceeding 50:1. Integration of CNT microstructures in fabrication offers further opportunity to exploit the electrical and thermal properties of CNTs, and diverse capabilities for chemical and biochemical functionalization 3.

We present methods for fabrication of patterned microstructures of vertically aligned carbon nanotubes (CNTs), and their use as master molds for production of polymer microstructures with organized nanoscale surface texture. The CNT forests are densified by condensation of solvent onto the substrate, which significantly increases their packing density and enables self-directed formation of 3D shapes.

制备，致密，副本三维碳纳米管微结构成型

The introduction of new materials and processes to microfabrication has, in large part, enabled many important advances in microsystems, lab-on-a-chip ...

科研

工程学

Dry Oxidation and Vacuum Annealing Treatments for Tuning the Wetting Properties of Carbon Nanotube Arrays

In this article, we describe a simple method to reversibly tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays. Here, CNT arrays are defined as densely packed multi-walled carbon nanotubes oriented perpendicular to the growth substrate as a result of a growth process by the standard thermal chemical vapor deposition (CVD) technique.1,2 These CNT arrays are then exposed to vacuum annealing treatment to make them more hydrophobic or to dry oxidation treatment to render them more hydrophilic. The hydrophobic CNT arrays can be turned hydrophilic by exposing them to dry oxidation treatment, while the hydrophilic CNT arrays can be turned hydrophobic by exposing them to vacuum annealing treatment. Using a combination of both treatments, CNT arrays can be repeatedly switched between hydrophilic and hydrophobic.2 Therefore, such combination show a very high potential in many industrial and consumer applications, including drug delivery system and high power density supercapacitors.3-5
The key to vary the wettability of CNT arrays is to control the surface concentration of oxygen adsorbates. Basically oxygen adsorbates can be introduced by exposing the CNT arrays to any oxidation treatment. Here we use dry oxidation treatments, such as oxygen plasma and UV/ozone, to functionalize the surface of CNT with oxygenated functional groups. These oxygenated functional groups allow hydrogen bond between the surface of CNT and water molecules to form, rendering the CNT hydrophilic. To turn them hydrophobic, adsorbed oxygen must be removed from the surface of CNT. Here we employ vacuum annealing treatment to induce oxygen desorption process. CNT arrays with extremely low surface concentration of oxygen adsorbates exhibit a superhydrophobic behavior.

This article describes a simple method to fabricate vertically aligned carbon nanotube arrays by CVD and to subsequently tune their wetting properties by exposing them to vacuum annealing or dry oxidation treatment.

干式氧化及真空退火处理调整的润湿性能的碳纳米管阵列

In this article, we describe a simple method to reversibly  tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays.  Here, CNT ...

Ambient Method for the Production of an Ionically Gated Carbon Nanotube Common Cathode in Tandem Organic Solar Cells

A method of fabricating organic photovoltaic (OPV) tandems that requires no vacuum processing is presented. These devices are comprised of two solution-processed polymeric cells connected in parallel by a transparent carbon nanotubes (CNT) interlayer. This structure includes improvements in fabrication techniques for tandem OPV devices. First the need for ambient-processed cathodes is considered. The CNT anode in the tandem device is tuned via ionic gating to become a common cathode. Ionic gating employs electric double layer charging to lower the work function of the CNT electrode. Secondly, the difficulty of sequentially stacking tandem layers by solution-processing is addressed. The devices are fabricated via solution and dry-lamination in ambient conditions with parallel processing steps. The method of fabricating the individual polymeric cells, the steps needed to laminate them together with a common CNT cathode, and then provide some representative results are described. These results demonstrate ionic gating of the CNT electrode to create a common cathode and addition of current and efficiency as a result of the lamination procedure.

A method of fabricating, in ambient conditions, organic photovoltaic tandem devices in a parallel configuration is presented. These devices feature an air-processed, semi-transparent, carbon nanotube common cathode.

对于一个以离子门控碳纳米管共阴极的串联有机太阳能电池的生产环境法

A method of fabricating organic photovoltaic (OPV) tandems that requires no vacuum processing is presented. These devices are comprised of two ...

Synthesis and Functionalization of 3D Nano-graphene Materials: Graphene Aerogels and Graphene Macro Assemblies

Efforts to assemble graphene into three-dimensional monolithic structures have been hampered by the high cost and poor processability of graphene. Additionally, most reported graphene assemblies are held together through physical interactions (e.g., van der Waals forces) rather than chemical bonds, which limit their mechanical strength and conductivity. This video method details recently developed strategies to fabricate mass-producible, graphene-based bulk materials derived from either polymer foams or single layer graphene oxide. These materials consist primarily of individual graphene sheets connected through covalently bound carbon linkers. They maintain the favorable properties of graphene such as high surface area and high electrical and thermal conductivity, combined with tunable pore morphology and exceptional mechanical strength and elasticity. This flexible synthetic method can be extended to the fabrication of polymer/carbon nanotube (CNT) and polymer/graphene oxide (GO) composite materials. Furthermore, additional post-synthetic functionalization with anthraquinone is described, which enables a dramatic increase in charge storage performance in supercapacitor applications.

This video method describes the synthesis of high surface area, monolithic 3D graphene-based materials derived from polymer precursors as well as single layer graphene oxide.

合成和3D纳米石墨烯材料的功能化：石墨烯气凝胶和石墨烯宏组件

Efforts to assemble graphene into three-dimensional monolithic structures have been hampered by the high cost and poor processability of graphene. ...

Fabrication of Low Temperature Carbon Nanotube Vertical Interconnects Compatible with Semiconductor Technology

We demonstrate a method for the low temperature growth (350 &#176;C) of vertically-aligned carbon nanotubes (CNT) bundles on electrically conductive thin-films. Due to the low growth temperature, the process allows integration with modern low-&#954; dielectrics and some flexible substrates. The process is compatible with standard semiconductor fabrication, and a method for the fabrication of electrical 4-point probe test structures for vertical interconnect test structures is presented. Using scanning electron microscopy the morphology of the CNT bundles is investigated, which demonstrates vertical alignment of the CNT and can be used to tune the CNT growth time. With Raman spectroscopy the crystallinity of the CNT is investigated. It was found that the CNT have many defects, due to the low growth temperature. The electrical current-voltage measurements of the test vertical interconnects displays a linear response, indicating good ohmic contact was achieved between the CNT bundle and the top and bottom metal electrodes. The obtained resistivities of the CNT bundle are among the average values in the literature, while a record-low CNT growth temperature was used.

A method for the growth of low temperature vertically-aligned carbon nanotubes, and the subsequent fabrication of vertical interconnect electrical test structures using semiconductor fabrication is presented.

低温碳纳米管垂直互连的制作兼容半导体技术

We demonstrate a method for the low temperature growth (350 &#176;C) of vertically-aligned carbon nanotubes (CNT) bundles on electrically conductive ...

Two-way Valorization of Blast Furnace Slag: Synthesis of Precipitated Calcium Carbonate and Zeolitic Heavy Metal Adsorbent

The aim of this work is to present a zero-waste process for storing CO2 in a stable and benign mineral form while producing zeolitic minerals with sufficient heavy metal adsorption capacity. To this end, blast furnace slag, a residue from iron-making, is utilized as the starting material. Calcium is selectively extracted from the slag by leaching with acetic acid (2 M CH3COOH) as the extraction agent. The filtered leachate is subsequently physico-chemically purified and then carbonated to form precipitated calcium carbonate (PCC) of high purity (&lt;2 wt% non-calcium impurities, according to ICP-MS analysis). Sodium hydroxide is added to neutralize the regenerated acetate. The morphological properties of the resulting calcitic PCC are tuned for its potential application as a filler in papermaking. In parallel, the residual solids from the extraction stage are subjected to hydrothermal conversion in a caustic solution (2 M NaOH) that leads to the predominant formation of a particular zeolitic mineral phase (detected by XRD), namely analcime (NaAlSi2O6&#8729;H2O). Based on its ability to adsorb Ni2+, as reported from batch adsorption experiments and ICP-OES analysis, this product can potentially be used in wastewater treatment or for environmental remediation applications.

A protocol for the parallel production of precipitated calcium carbonate and zeolitic material from blast furnace slag via mineral carbonation and alkaline hydrothermal conversion, respectively, is presented. The performance of the zeolitic material towards nickel adsorption is tested.

高炉矿渣的双向稳定物价：沉淀碳酸钙和沸石重金属吸附剂的合成

The aim of this work is to present a zero-waste process for storing CO2 in a stable and benign mineral form while producing zeolitic minerals with ...

Precision Milling of Carbon Nanotube Forests Using Low Pressure Scanning Electron Microscopy

A nanoscale fabrication technique appropriate for milling carbon nanotube (CNT) forests is described. The technique utilizes an environmental scanning electron microscope (ESEM) operating with a low pressure water vapor ambient. In this technique, a portion of the electron beam interacts with the water vapor in the vicinity of the CNT sample, dissociating the water molecules into hydroxyl radicals and other species by radiolysis. The remainder of the electron beam interacts with the CNT forest sample, making it susceptible to oxidation from the chemical products of radiolysis. This technique may be used to trim a selected region of an individual CNT, or it may be used to remove hundreds of cubic microns of material by adjusting ESEM parameters. The machining resolution is similar to the imaging resolution of the ESEM itself. The technique produces only small quantities of carbon residue along the boundaries of the cutting zone, with minimal effect on the native structural morphology of the CNT forest.

Low pressure scanning electron microscopy in a water vapor ambient is used to machine nanoscale to microscale features in carbon nanotube forests.

碳纳米管森林精密铣床使用低压扫描电子显微镜

A nanoscale fabrication technique appropriate for milling carbon nanotube (CNT) forests is described. The technique utilizes an environmental scanning ...

In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films

Combinations of metal oxide semiconductors and gold nanoparticles (AuNPs) have been investigated as new types of materials. The in situ synthesis of AuNPs within the interlayer space of semiconducting layered titania nanosheet (TNS) films was investigated here. Two types of intermediate films (i.e., TNS films containing methyl viologen (TNS/MV2+) and 2-ammoniumethanethiol (TNS/2-AET+)) were prepared. The two intermediate films were soaked in an aqueous tetrachloroauric(III) acid (HAuCl4) solution, whereby considerable amounts of Au(III) species were accommodated within the interlayer spaces of the TNS films. The two types of obtained films were then soaked in an aqueous sodium tetrahydroborate (NaBH4) solution, whereupon the color of the films immediately changed from colorless to purple, suggesting the formation of AuNPs within the TNS interlayer. When only TNS/MV2+ was used as the intermediate film, the color of the film gradually changed from metallic purple to dusty purple within 30 min, suggesting that aggregation of AuNPs had occurred. In contrast, this color change was suppressed by using the TNS/2-AET+ intermediate film, and the AuNPs were stabilized for over 4 months, as evidenced by the characteristic extinction (absorption and scattering) band from the AuNPs.

In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films

Here, we present a protocol for the in situ synthesis of gold nanoparticles (AuNPs) within the interlayer space of layered titanate films without the aggregation of AuNPs. No spectral change was observed even after 4 months. The synthesized material has expected applications in catalysis, photo-catalysis, and the development of cost-effective plasmonic devices.

在没有聚集的层状钛酸盐薄膜透明的层间金纳米粒子的原位合成

Combinations of metal oxide semiconductors and gold nanoparticles (AuNPs) have been investigated as new types of materials. The in situ synthesis of AuNPs ...

Controllable Nucleation of Cavitation from Plasmonic Gold Nanoparticles for Enhancing High Intensity Focused Ultrasound Applications

In this study, plasmonic gold nanoparticles were simultaneously exposed to pulsed near-infrared laser light and high intensity focused ultrasound (HIFU) for the controllable nucleation of cavitation in tissue-mimicking gel phantoms. This in vitro protocol was developed to demonstrate the feasibility of this approach, for both enhancement of imaging and therapeutic applications for cancer. The same apparatus can be used for both imaging and therapeutic applications by varying the exposure duration of the HIFU system. For short duration exposures (10 &#181;s), broadband acoustic emissions were generated through the controlled nucleation of inertial cavitation around the gold nanoparticles. These emissions provide direct localization of nanoparticles. For future applications, these particles may be functionalized with molecular-targeting antibodies (e.g. anti-HER2 for breast cancer) and can provide precise localization of cancerous regions, complementing routine diagnostic ultrasound imaging. For continuous wave (CW) exposures, the cavitation activity was used to increase the localized heating from the HIFU exposures resulting in larger thermal damage in the gel phantoms. The acoustic emissions generated from inertial cavitation activity during these CW exposures was monitored using a passive cavitation detection (PCD) system to provide feedback of cavitation activity. Increased localized heating was only achieved through the unique combination of nanoparticles, laser light and HIFU. Further validation of this technique in pre-clinical models of cancer is necessary.

This protocol demonstrates the controllable nucleation of cavitation in gel phantoms, through simultaneous exposure to both near-infrared pulsed laser light and high intensity focused ultrasound (HIFU). The cavitation activity can then be used for enhancing imaging and/or therapeutic uses of HIFU.

等离子金纳米粒子空化的可控核增强高强度聚焦超声应用

In this study, plasmonic gold nanoparticles were simultaneously exposed to pulsed near-infrared laser light and high intensity focused ultrasound (HIFU) ...

An Efficient Method for Selective Desalination of Radioactive Iodine Anions by Using Gold Nanoparticles-Embedded Membrane Filter

Here, we demonstrate a detail protocol for the preparation of nanomaterials-embedded composite membranes and its application to the efficient and ion-selective removal of radioactive iodines. By using citrate-stabilized gold nanoparticles (mean diameter: 13 nm) and cellulose acetate membranes, gold nanoparticle-embedded cellulose acetate membranes (Au-CAM) have easily been fabricated. The nano-adsorbents on Au-CAM were highly stable in the presence of high concentration of inorganic salts and organic molecules. The iodide ions in aqueous solutions could rapidly be captured by this engineered membrane. Through a filtration process using an Au-CAM containing filter unit, excellent removal efficiency (&gt;99%) as well as ion-selective desalination result was achieved in a short time. Moreover, Au-CAM provided good reusability without significant decrease of its performances. These results suggested that the present technology using the engineered hybrid membrane will be a promising process for the large-scale decontamination of radioactive iodine from liquid wastes.

An efficient method for the rapid and ion-selective desalination of radioactive iodine in several aqueous solutions is described by using gold nanoparticles-immobilized cellulose acetate membrane filters.