作者承认提供的财政支持荷兰科学研究组织（NWO ECHO-STIP格兰特717.013.005，NWO VIDI格兰特723.014.006）。

1.核壳型二氧化硅颗粒的合成 注意:二氧化硅颗粒根据以下程序，这是基于STOBER方法24,25合成。 <ol><li> 荧光硅种子的合成 <ol><li>溶解荧光素异硫氰酸酯在5毫升乙醇中的105毫克（0.27毫摩尔）。 </li><li>加入100微升（3-氨基丙基）三乙氧基硅烷（APTES，0.43毫摩尔）到先前溶液中。 </li><li> 5分钟内超声处理溶液，并让它在室温下在氩气气氛下反应过夜，同时搅拌。染料 - 官能APTES复合使用，无需纯化。 </li><li>在一个1升圆底烧瓶中混合2.5毫升用25ml氨水（在水中25％）和250毫升乙醇的染料官能APTES的。 </li><li>上述反应混合物的弯液面下加入10 mL硅酸四乙酯（TEOS）的用玻璃吸管控制而的帮助e为磁搅拌器搅拌。 </li><li>同样地，5小时后，添加另外1.75 TEOS中并在氩气氛下过夜搅拌该混合物。 </li><li>倒入分散成几个45毫升管。 </li><li>离心管（350 XG，30分钟），除去上清液，并添加30毫升新鲜乙醇在每个管。再次超声处理3分钟的新的分散体，和离心机以除去上清液。重复这些步骤洗涤3次。 </li><li>保持在乙醇荧光种子在约13.6毫克/毫升的浓度，并在黑暗中（避免暴露于光）。 </li><li>制备非荧光种子按照相同的程序省略了除荧光染料。 注意:在此之后的步骤，获得在半径约100nm的种子。 </li></ol></li><li> 核壳型二氧化硅颗粒的合成 <ol><li>补的1L圆底烧瓶用51毫升乙醇，17个毫升去离子水，3.4氨毫升（在水中25％）和4-毫升种子分散体（54.4毫克荧光种子约）。 </li><li>填充塑料注射器用5ml的TEOS和10ml乙醇。 </li><li>补的第二塑料注射器1.34毫升氨（在水中25％），3.4毫升去离子水10.25毫升乙醇。 </li><li>两个注射器连接到圆底烧瓶用塑料管。 </li><li>装备用氩流量和磁力搅拌器的烧瓶中。氩入口具有被旁边的第二注射器，以避免从TEOS液滴氨气之间的接触，以防止二次成核的出口。 </li><li>在同一时间同时添加注射器的内容在使用蠕动泵同时搅拌该混合物1.7毫升/小时。确保获得自由下落的液滴，以避免滑翔墙壁，因此二次核上。 </li><li>停止加入后7小时以获得约300nm的核 - 壳粒子在半径。 </li><li>倒入烧瓶内容分成几个45毫升管中。 </li><li>离心管（350 XG，30分钟），除去上清液，并添加30毫升新鲜乙醇在每个管。再次超声处理3分钟的新的分散性，和离心机以除去上清液。重复这些步骤洗涤3次。 </li><li>保持核 - 壳粒子在乙醇中，在黑暗中（避免暴露于光）。 </li><li>准备按照相同的程序，但使用的非荧光种子非荧光二氧化硅颗粒。 </li></ol></li></ol> 2.二氧化硅胶体的功能化<ol><li> NVOC功能化胶体的合成 <ol><li>分散10毫克核壳型二氧化硅颗粒在1ml乙醇与12在50毫升圆底烧瓶硬脂醇的NVOC-C11-OH分子的毫克（0.03毫摩尔）和31毫克（0.11毫摩尔）（所得一起在20/80 NVOC-C11-OH /硬脂醇的摩尔比）。 </li><li>超声处理该混合物10分钟，以确保所有的分子被溶解和颗粒是很好dispeRSED。 </li><li>添加到该混合物磁力搅拌棒并用在室温下的氩源源不断蒸发乙醇。在继续之前，确保没有乙醇左，否则它会与粒子的硅烷醇基团反应。检查乙醇是否完全蒸发讲究烧瓶底部的温度。如果感觉冷，乙醇尚未完全蒸发。 </li><li>加热在连续搅拌下和在氩气下22源源不断烧瓶至180℃6小时。 </li><li>让烧瓶冷却到室温。 </li><li>添加3毫升三氯甲烷的到烧瓶中，并超声处理5分钟（或直到所有的固体成分已溶解或分散）。 </li><li>离心分散（2600 XG，4分钟），除去上清液，加入新鲜氯仿 。再次超声处理3分钟的新的分散性，和离心机以除去上清液。重复这些步骤洗6次。 </l我&gt; <li>干燥在70℃下在真空中粒子过夜，并将它们存储在一个干燥器中。 </li></ol></li><li> BTA-胶体的合成 <ol><li>分散10毫克在3ml 氯仿的NVOC-C11-OH /硬脂醇的20/80摩尔比官能化粒子。 </li><li>照射在UV烘箱（λ 最大 = 354纳米）的分散体1小时，以裂解NVOC基。确保该脱保护是在颗粒的表面上均匀通过用磁力搅拌器温和地搅拌该分散液的同时脱保护。这产生了胺官能化粒子（ 图1a）。 </li><li>溶解9毫克苯-1,3,5- tricarboxamide衍生物（BTA，0.01毫摩尔），8.7微升的N，N-二异丙基乙胺（DIPEA，0.05毫摩尔）和5.2毫克（苯并三唑-1-基氧基）三吡咯烷基六氟磷酸盐的（加入PyBOP，0.01毫摩尔）在1毫升氯仿中。 </li><li>该解决方案添加到胺官能p制品的分散性和在室温下和在氩气氛下搅拌过夜。 </li><li>离心分散（2600 XG，4分钟），除去上清液，加入3毫升新鲜氯仿的。再次超声处理3分钟的新的分散性，和离心机以除去上清液。重复这些步骤洗6次。 </li><li>干燥在70℃下该颗粒在真空中进行48小时，并把它们存储在一个干燥器中。 </li></ol></li></ol> 3.静态光散射测量（SLS） 注意:使用非荧光颗粒，由于荧光芯吸收波长相同的常规的光散射设备入射激光的光。 <ol><li>官能10毫克非荧光二氧化硅颗粒与硬脂醇只（无NVOC-C11-OH）以下在2.1节中描述的方法。 </li><li>制备500微升0.033毫克/毫升的非官能化粒子的分散液的水和一个的2毫克/毫升的环己烷硬脂涂覆醇颗粒的另一个。 </li><li>超声处理两分散体为至少20分钟，以确保颗粒被很好地分散。 </li><li>同时测量分散体的散射强度，将溶剂和从30° ​​至120°5°步骤基准溶剂。 </li><li>画出样品（Ⅰ 样品 ）的强度作为q的函数 （公式1）Q =4πñ 溶剂罪（θ/ 2）/λ0 与散射角θ，溶剂Ñ 溶剂的折射率和激光λ0的波长。 </li><li>利用软件将数据装配到下面的公式（ 例如 ，起源） （式2）I 采样 = CP（QR） 其中，C是由下式给出一个恒定和形式因数P（QR） （等式3）&lt;IMG ALT ="等式3"SRC ="/文件/ ftp_upload / 53934 / 53934eq3.jpg"/&gt; 其中球形胶体的平均半径为R。 </li><li>从适合每个分散提取R上 。 </li><li>计算瑞利比（Rθ），这是对于散射光的强度的绝对度量，根据以下等式，针对每个θ。 （公式4） <img alt="公式4" src="/files/ftp_upload/53934/53934eq4.jpg" /> 与样本的强度，溶剂和参考， 我 样 ， 我 溶剂 和I分别引用 ，溶剂的折射率和参考Ñ 溶剂和n 参考 ，相应地，与参考R 参考的瑞利比。在这里使用甲苯作为参考，使得n 水 = 1.332，N 甲苯 = 1.497，N = 环己烷 1.426; R 甲苯 = 2.74x10 -3米-1 26。 </li><li>计算自Rθ和等式5的胶体（ 正胶体 ）的平均折射率。 （式5） <img alt="公式5" src="/files/ftp_upload/53934/53934eq5.jpg" /> 与每体积N，用V 粒子发出的粒子v 颗粒的体积的颗粒数= 4/3πR3，并假设该结构系数S（q）的〜1，这是无相互作用颗粒的限制。 </li></ol> 4.定量活性中心每个粒子的数注意:在半径使用13纳米的小颗粒（具有较大的表面，以-volume比）。 <ol><li>功能化与/硬脂以下2.1节中描述的步骤酒精NVOC-C11-OH的20/80摩尔比小市售颗粒。 </li><li>分散20毫克小，官能化粒子在1ml CHCl 3中，照射在UV烘箱（λ 最大 = 354纳米）的分散体1小时，以裂解NVOC基。用磁力搅拌棒轻轻搅拌分散体，同时脱保护。以这种方式，胶体不沉降和它们的表面保持暴露于UV光，从而确保均匀的脱保护。 </li><li>降速所得胺官能颗粒（3400 xg离心，10分钟），去除上清。 </li><li>干燥的颗粒在70℃下2小时。 </li><li>溶解0.50毫克琥珀酰亚胺基3-（2-吡啶基）丙酸酯（SPDP，0.0016毫摩尔）在200微升二甲基甲酰胺（DMF）中的。 </li><li>的SPDP溶液添加到20毫克的干燥胺官能颗粒和涡流的系统30分钟。在这段时间内，对胶体所有可用伯胺已与SPDP反应。 </li><li>用1毫升DMF中的6次洗涤颗粒（或直到无游离的SPDP在上清液在λ= 375纳米的检测通过UV-Vis光谱）。在最后的洗涤步骤尝试去除尽可能多的上清液越好。 </li><li>在50μlDMF中溶解0.53毫克二硫苏糖醇（DTT，0.0034毫摩尔）。添加DTT溶液的颗粒和涡分散30分钟。在这段时间内的吡啶-2-硫酮基团被裂解。 </li><li>确定自由上清液中释放的吡啶-2-硫酮的在λ= 293纳米用微量紫外可见分光光度计的吸光度。 </li><li>构建一个校准曲线通过测定系列稀释的不同的已知量的SPDP的吸光度与过量的DTT，以确定在DMF吡啶-2-硫酮的消光系数ɛ（〜12.1x10 3 M -1 -1） 。 </li><li&gt;计算吡啶-2-硫酮，C P2T，它是从使用朗伯-比尔定律颗粒裂解的浓度: （公式6）ABS = C P2Tε升 用吡啶-2-硫酮çP2T的摩尔浓度，消光系数ɛ和路径长度l。 </li><li>计算每个颗粒的活性位点（胺）的数量用下面的方程 （式7） <img alt="公式7" src="/files/ftp_upload/53934/53934eq7.jpg" /> 与一种粒子M 粒子的质量 这是M 粒子 = 4 /3πR3ρ，用ρ= 1.295克/厘米3，颗粒M1 总 （20毫克）和总体积V 总 （50微升）的总加权质量。该公式假设所有可用胺与SPDP的反应和DTT减少附着在颗粒所有SPDP的分子。 </li></ol> 5.显示器胶体大会激光共聚焦显微镜注意:使用的核壳型二氧化硅颗粒（用荧光芯和非荧光壳）。 <ol><li>制备400μl的在环己烷BTA-官能化粒子的0.1％（重量）的分散体和超声处理的样品20分钟。 </li><li>照射在UV炉样品瓶（λ 最大 = 354纳米）切割掉BTA的邻硝基组。采取25微升等分试样在照射不同的时间，例如从0到30分钟，以监测聚类过程。 </li><li>放置在与间隔的帮助不同载玻片的不同等分试样，并用盖玻片封闭腔室（腔室尺寸为13mm直径×0.12毫米高度）。关闭室后，打开盖玻片倒置，让颗粒泥沙及adsorb到玻璃，这便于成像。 </li><li>每次照射时间为样品制备后尽快取每个样品的若干图片包含共焦显微镜。 </li></ol> 6.图像分析<ol><li> 用ImageJ的单峰的数目的量化 注:用于编写脚本在ImageJ的手册中介绍的所有命令: http://imagej.nih.gov/ij/docs/guide/user-guide.pdf <ol><li>平滑的共聚焦图像从边缘去除孤立像素并填写运行"平滑"功能小孔。 </li><li>鉴于只有芯是荧光，扩张明亮区域，直到属于同一群集的触摸和颗粒合并颗粒的边缘。为此，使用"扩张"过滤器。与约180纳米壳厚度的颗粒，并用0.02微米/像素的分辨率照片拍摄，两人扩张步骤是不够的。 </li><li>将图像转换进入运行"使二元"功能的二进制图像。 </li><li>通过运行工具"，"缩放设置..."，距离= 1称为= 0.02像素= 1单位=嗯""对于例如0.02微米/像素的分辨率拍摄的照片设置比例。 </li><li>应用阈值大小，从在焦粒子区分噪声和失焦颗粒。例如，用0.02微米/像素的分辨率拍摄的照片，所有区域小于0.2像素被排除。为此，使用"分析颗粒..."，"大小= 0.2-∞"命令。 </li><li>创建all.jpg图像，并与所有明亮区域的图像（集群和单峰）通过使用命令"，"结果"，在大小的文件全部.txt，_all.txt""和""JPEG"，"全" "。 </li><li>假设0.2和0.7像素之间，所有的明亮区域的大小和一个圆（圆=π4面积/周长2）0.7和1.0之间运行命令单线"分析颗粒..."，"圆= 0.7-1.0。" </li><li>创建singlets.jpg形象，与那些通过使用命令"，"结果"，_singlets.txt""和""JPEG"，"单峰"，"单线所有明亮区域的信息singlets.txt文件。 </li></ol></li><li> 处理用Matlab信息 <ol><li>阅读单.txt文件，并计算出每一个画面单（ 单线 ）的平均规模。 </li><li>使用一个单峰的平均大小来计算每个群集的粒子数（A 双峰 = 2A 单峰 ，一个三胞胎 = 3A 单峰 ...）和颗粒在与其它全部.txt文件的图像的总数。 </li><li>计算颗粒部分中的每个曝光时间为单峰:F 汗衫 =号码单峰/总颗粒</li><li>计算的双峰，三胞胎等分数:F 双峰 = 2 *双重数/总颗粒等 </li></ol></li></ol>

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B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Magnetic+assembly+of+colloidal+superstructures+with+multipole+symmetry.">Magnetic assembly of colloidal superstructures with multipole symmetry.</a> Nature. 457 (7232), 999-1002 (2009).</li><li>Vutukuri, H. 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=Colloidal+analogues+of+charged+and+uncharged+polymer+chains+with+tunable+stiffness.">Colloidal analogues of charged and uncharged polymer chains with tunable stiffness.</a> Angew. Chem. Int. Edit. 51 (45), 11249-11253 (2012).</li><li>De Greef, T. F. A., Meijer, E. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Materials+science:+Supramolecular+polymers.">Materials science: Supramolecular polymers.</a> Nature. 453 (7192), 171-173 (2008).</li><li>De Feijter, I., Albertazzi, L., Palmans, A. R. A., Voets, I. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Stimuli-responsive+colloidal+assembly+driven+by+surface-grafted+supramolecular+moieties.">Stimuli-responsive colloidal assembly driven by surface-grafted supramolecular moieties.</a> Langmuir. 31 (1), 57-64 (2015).</li><li>Celiz, A. D., Lee, T. C., Scherman, O. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polymer-mediated+dispersion+of+cold+nanoparticles:+using+supramolecular+moieties+on+the+periphery.">Polymer-mediated dispersion of cold nanoparticles: using supramolecular moieties on the periphery.</a> Adv. Mater. 21 (38-39), 3937-3940 (2009).</li><li>Cantekin, S., De Greef, T. F. A., Palmans, A. R. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Benzene-1,3,5-tricarboxamide:+A+versatile+ordering+moiety+for+supramolecular+chemistry.">Benzene-1,3,5-tricarboxamide: A versatile ordering moiety for supramolecular chemistry.</a> Chem. Soc. Rev. 41 (18), 6125-6137 (2012).</li><li>Mes, T., Van Der Weegen, R., Palmans, A. R. A., Meijer, E. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Single-chain+polymeric+nanoparticles+by+stepwise+folding.">Single-chain polymeric nanoparticles by stepwise folding.</a> Angew. Chem. Int. Edit. 50 (22), 5085-5089 (2011).</li><li>van Blaaderen, A., Vrij, 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+and+characterization+of+monodisperse+colloidal+organo-silica+spheres.">Synthesis and characterization of monodisperse colloidal organo-silica spheres.</a> J. Colloid Interf. Sci. 156 (1), 1-18 (1993).</li><li>Van Helden, A. K., Jansen, J. W., Vrij, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+and+characterization+of+spherical+monodisperse+silica+dispersions+in+nonaqueous+solvents.">Preparation and characterization of spherical monodisperse silica dispersions in nonaqueous solvents.</a> J. Colloid Interf. Sci. 81 (2), 354-368 (1981).</li><li>Israelachvili, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Intermolecular+and+Surface+Forces.">Intermolecular and Surface Forces.</a> Van der Waals forces between particles and surfaces. , 253-289 (2011).</li><li>van Blaaderen, A., Vrij, 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+and+characterization+of+colloidal+dispersions+of+fluorescent,+monodisperse+silica+spheres.">Synthesis and characterization of colloidal dispersions of fluorescent, monodisperse silica spheres.</a> Langmuir. 8 (12), 2921-2931 (1992).</li><li>Giesche, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+monodispersed+silica+powders+II.+Controlled+growth+reaction+and+continuous+production+process.">Synthesis of monodispersed silica powders II. Controlled growth reaction and continuous production process.</a> J. Eur. Ceram. Soc. 14 (3), 205-214 (1994).</li><li>Wu, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Correlations+between+the+Rayleigh+ratio+and+the+wavelength+for+toluene+and+benzene.">Correlations between the Rayleigh ratio and the wavelength for toluene and benzene.</a> Chem. Phys. 367 (1), 44-47 (2010).</li></ol>

当环己烷，具有1.426的折射率，被用作溶剂以分散BTA-胶体，范德华相互作用非常弱，由于胶体的折射率和溶剂几乎相同。注意，相比于在水中的裸二氧化硅胶体用于在环己烷中的SLS实验官能胶体的浓度要高得多。这是必要的，以获得足够强的散射，由于低对比度的折射率几乎匹配。立即检测出的环己烷样品中的痕量的水，尽管是间接地通过不可忽略的聚类由于毛细管力。因此，它是最重要的，以?...

介孔胶体材料发现在科学和技术的广泛应用，如用在原子和分子的物质1,2-基础研究的模型系统，因为光子材料3,4，作为药物递送系统5,6，用作涂料7和光刻表面图案形成8,9。由于疏液胶体，最终不可逆地聚集由于无所不在范德华相互作用亚稳材料，其操作成特定的靶结构是非常困难的。许多策略已经被开发，以控制胶体自组装包括使用添加剂以调整静电10,11或耗竭的相互作用12,13，或外部触发，如磁14或电动15字段。一个成熟的替代策略，以实现对结构的控制，这些系统的动力学和力学及其功能的机智^ h分子通过特定和定向力的相互作用。超分子化学提供小分子呈现位点特异性，定向性强但可逆的相互作用，其可以在强度由溶剂的极性，温度和光16进行调制的综合工具箱。因为它们的性能进行了散装和溶液中广泛的研究，这些分子是有吸引力的候选构造软材料进外来阶段以可预测的方式。尽管有这样的综合方法的潜在明确通过超分子化学编排胶体组装，这些学科很少接口裁缝介孔胶体材料17,18的属性。 超分子的胶体一个坚实的平台必须满足三个主要需求。首先，超分子结构部分的耦合应该温和条件下进行，以防止降解。其次，表面力在sepa​​rati组件不是直接接触大应该由栓系基序，这意味着未涂覆胶体应当几乎完全通过排除容积相互作用相互作用支配。因此，该胶体的物理 - 化学特性应适合于抑制在胶体体系，如范德华力或静电引力固有的其他相互作用。第三，表征应该允许大会的明确归属的超分子部分的存在。为了满足这些三个前提，超分子胶体健壮两步合成被开发（ 图1a）。在第一步骤中，疏水NVOC官能化的二氧化硅颗粒是在环己烷中分散的准备。该NVOC组能够容易地切割，从而产生胺官能化的颗粒。胺的反应性高可进行直接的后官能化，使用范围广的温和的反应条件所需的超分子结构部分。在此，我们公关通过用硬脂醇和苯-1,3,5- tricarboxamide（BTA）衍生物20的硅石珠粒官能epare超分子胶体。十八烷醇几个起着重要的作用:它使胶体亲有机并介绍这有助于降低胶体21,22之间的非特异性相互作用短程立体排斥。范德华力，因为胶体的折射率和溶剂23之间的紧密匹配的进一步降低。光及温敏短程吸引力表面力被保护双边贸易20的邻硝基掺入产生的。 邻硝基苄基部分是一个光可切割组块的相邻双边贸易间的氢键时在discotics酰胺掺入形成（ 图1b）。经紫外光光切割的BTA溶液中能够识别并具有相同的BTA分子相互作用通过3倍ħydrogen债券阵，与强烈依赖于温度17粘结强度。由于范德华吸引力是最小为环己烷硬脂涂覆的二氧化硅粒子以及轻型和温度无关，所观察到的刺激响应胶体组件必须BTA-介导的。 这种详细的视频演示了如何合成和表征超分子胶体以及如何通过共聚焦显微镜，研究在紫外线照射他们的自我组装。此外，简单图像分析协议从聚集胶体区分胶体汗衫及确定每簇报道胶体的量。的合成策略的多功能性允许容易地变化的粒径，表面覆盖率以及引入的结合部分，这对于一个大家族介孔高级材料的胶态积木的发展开辟了新的途径。

<table><tbody><tr><td>APTES</td><td>Sigma-Aldrich</td><td></td><td></td></tr><tr><td>FTIC</td><td>Sigma-Aldrich</td><td></td><td></td></tr><tr><td>TEOS</td><td>Sigma-Aldrich</td><td></td><td></td></tr><tr><td>LUDOX AS-40</td><td>Sigma-Aldrich</td><td></td><td>Silica particles of 13 nm in radius</td></tr><tr><td>MilliQ</td><td>---</td><td>---</td><td>18.2 M&amp;Omega;&amp;middot;cm at 25 &amp;deg;C</td></tr><tr><td>Ethanol</td><td>SolvaChrom</td><td></td><td>---</td></tr><tr><td>Ammonia (25% in water)</td><td>Sigma-Aldrich</td><td></td><td>---</td></tr><tr><td>Chloroform</td><td>SolvaChrom</td><td></td><td>---</td></tr><tr><td>Cyclohexane</td><td>Sigma-Aldrich</td><td></td><td>---</td></tr><tr><td>Dimethylformamide (DMF)</td><td>Sigma-Aldrich</td><td></td><td>---</td></tr><tr><td>Stearyl alcohol</td><td>Sigma-Aldrich</td><td></td><td>---</td></tr><tr><td>&lt;em&gt;N,N&lt;/em&gt;-Diisopropylethylamine (DIPEA)</td><td>Sigma-Aldrich</td><td></td><td>---</td></tr><tr><td>Benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP)</td><td>Sigma-Aldrich</td><td></td><td>---</td></tr><tr><td>Succinimidyl 3-(2-pyridyldithio)propionate (SPDP)</td><td>Sigma-Aldrich</td><td></td><td>---</td></tr><tr><td>Dithiothreitol (DTT)&amp;nbsp;</td><td>Sigma-Aldrich</td><td></td><td>---</td></tr><tr><td>NVOC-C11-OH</td><td>Synthesized</td><td>---</td><td>I. de Feijter, 2014 Responsive materials from adaptive supramolecular constructs, Doctoral thesis, Technical University of Eindhoven, The Netherlands</td></tr><tr><td>BTA</td><td>Synthesized</td><td>---</td><td>I. de Feijter, 2014 Responsive materials from adaptive supramolecular constructs, Doctoral thesis, Technical University of Eindhoven, The Netherlands</td></tr><tr><td>Centrifuge</td><td>Thermo Scientific</td><td></td><td>Heraeus Megafuge 1.0</td></tr><tr><td>Ultrasound bath</td><td>VWR</td><td></td><td>Ultrasonic cleaner</td></tr><tr><td>Peristaltic pumps</td><td>Harvard Apparatus</td><td></td><td>PHD Ultra Syringe Pump</td></tr><tr><td>UV-oven</td><td>Luzchem</td><td></td><td>LZC-a V UV reactor equipped with 8x8 UVA light bulbs (&amp;lambda;&lt;sub&gt;max&lt;/sub&gt;=354&amp;nbsp;nm)</td></tr><tr><td>Stirrer-heating plate</td><td>Heidolph</td><td></td><td>MR-Hei Standard&lt;br /&gt;&amp;nbsp;&lt;br /&gt;</td></tr><tr><td colspan="4">[header]</td></tr><tr><td>Light Scattering</td><td>ALV</td><td></td><td>CGS-3 MD-4 compact goniometer system, equipped with a Multiple Tau digital real time correlator (ALV-7004) and a solid-state laser (&amp;lambda;=532 nm, 40 mW)</td></tr><tr><td>UV-Vis spectrophotometer</td><td>Thermo Scientific</td><td></td><td>NanoDrop 1000 Spectrophotometer</td></tr><tr><td>Confocal microscope</td><td>Nikon</td><td></td><td>Ti Eclipse with an argon laser with &amp;lambda;&lt;sub&gt;excitation&lt;/sub&gt;=488&amp;nbsp;nm</td></tr><tr><td>Slide spacers</td><td>Sigma-Aldrich</td><td></td><td>Grace BioLabs Secure seal imaging spacer (1 well, diam. &amp;times; thickness 13 mm &amp;times; 0.12 mm)</td></tr><tr><td>Syringes</td><td>BD Plastipak</td><td></td><td>20 ml syringe</td></tr><tr><td>Plastic tubing</td><td>SCI</td><td>BB31695-PE/5</td><td>Ethylene oxide gas sterilizable micro medical tubing</td></tr><tr><td>Pulsating vortex mixer</td><td>VWR</td><td></td><td>Electrical: 120&amp;nbsp;V, 50/60&amp;nbsp;Hz, 150&amp;nbsp;W Speed Range: 500&amp;ndash;3,000 rpm</td></tr></tbody></table>

synthesis and characterization of supramolecular colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

鉴于用于合成在室温下和在温和的反应条件下的第二步骤中的超分子胶体（ 图1a），耦合BTA-衍生物（ 图1b）的两个步骤，其稳定性得到保证。 <img alt="图1" src="/files/ftp_upload/53934/53934fig1.jpg" /> 图1.超分子胶体的合成的方案。一 ）硬脂醇和NVOC保护烷基链与二氧化硅胶体的耦合，照射时随...

Watch this Scientific Journal Video about Synthesis and Characterization of Supramolecular Colloids at JoVE.com

Synthesis and Characterization of Supramolecular Colloids

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

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-and-characterization-of-supramolecular-colloids

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Chemistry

Anatomy and Physiology

Unit 1

Fundamentals of Chemistry

Solutions and Colloids

SCIENTISTS IN ACTION

9.7K 次观看.  Eindhoven University of Technology. A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

视频: Synthesis and Characterization of Supramolecular Colloids

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

For aqueous based supramolecular polymers, the simultaneous control over shape, size and stability is very difficult1. At the same time, the ability to do so is highly important in view of a number of applications in functional soft matter including electronics, biomedical engineering, and sensors. In the past, successful strategies to control the size and shape of supramolecular polymers typically focused on the use of templates2,3, end cappers4 or selective solvent techniques5. 
Here we disclose a strategy based on self-assembling discotic amphiphiles that leads to the control over stack length and shape of ordered, chiral columnar aggregates. By balancing electrostatic repulsive interactions on the hydrophilic rim and attractive non-covalent forces within the hydrophobic core of the polymerizing building block, we manage to create small and discrete spherical objects6,7. Increasing the salt concentration to screen the charges induces a sphere-to-rod transition. Intriguingly, this transition is expressed in an increase of cooperativity in the temperature-dependent self-assembly mechanism, and more stable aggregates are obtained. 
For our study we select a benzene-1,3,5-tricarboxamide (BTA) core connected to a hydrophilic metal chelate via a hydrophobic, fluorinated L-phenylalanine based spacer (Scheme 1). The metal chelate selected is a Gd(III)-DTPA complex that contains two overall remaining charges per complex and necessarily two counter ions. The one-dimensional growth of the aggregate is directed by &pi;-&pi; stacking and intermolecular hydrogen bonding. However, the electrostatic, repulsive forces that arise from the charges on the Gd(III)-DTPA complex start limiting the one-dimensional growth of the BTA-based discotic once a certain size is reached. At millimolar concentrations the formed aggregate has a spherical shape and a diameter of around 5 nm as inferred from 1H-NMR spectroscopy, small angle X-ray scattering, and cryogenic transmission electron microscopy (cryo-TEM). The strength of the electrostatic repulsive interactions between molecules can be reduced by increasing the salt concentration of the buffered solutions. This screening of the charges induces a transition from spherical aggregates into elongated rods with a length &gt; 25 nm. Cryo-TEM allows to visualise the changes in shape and size. In addition, CD spectroscopy permits to derive the mechanistic details of the self-assembly processes before and after the addition of salt. Importantly, the cooperativity -a key feature that dictates the physical properties of the produced supramolecular polymers- increases dramatically upon screening the electrostatic interactions. This increase in cooperativity results in a significant increase in the molecular weight of the formed supramolecular polymers in water.

The goal of this experiment is to determine and control the size, shape and stability of self-assembled discotic amphiphiles in water. For aqueous based supramolecular polymers such level of control is very difficult. We apply a strategy using both repulsive and attractive interactions. The experimental techniques applied to characterize this system are broadly applicable.

控制的大小，形状和稳定性超分子聚合物在水

For aqueous based supramolecular polymers, the simultaneous control over shape, size and stability is very difficult1. At the same time, the ability to do ...

科研

工程学

Confocal Imaging of Confined Quiescent and Flowing Colloid-polymer Mixtures

The behavior of confined colloidal suspensions with attractive interparticle interactions is critical to the rational design of materials for directed assembly1-3, drug delivery4, improved hydrocarbon recovery5-7, and flowable electrodes for energy storage8. Suspensions containing fluorescent colloids and non-adsorbing polymers are appealing model systems, as the ratio of the polymer radius of gyration to the particle radius&#160;and concentration of polymer control the range and strength of the interparticle attraction, respectively. By tuning the polymer properties and the volume fraction of the colloids, colloid fluids, fluids of clusters, gels, crystals, and glasses can be obtained9.&#160;Confocal microscopy, a variant of fluorescence microscopy, allows an optically transparent and fluorescent sample to be imaged with high spatial and temporal resolution in three dimensions. In this technique, a small pinhole or slit blocks the emitted fluorescent light from regions of the sample that are outside the focal volume of the microscope optical system. As a result, only a thin section of the sample in the focal plane is imaged. This technique is particularly well suited to probe the structure and dynamics in dense colloidal suspensions at the single-particle scale: the particles are large enough to be resolved using visible light and diffuse slowly enough to be captured at typical scan speeds of commercial confocal systems10. Improvements in scan speeds and analysis algorithms have also enabled quantitative confocal imaging of flowing suspensions11-16,37.&#160;In this paper, we demonstrate confocal microscopy experiments to probe the confined phase behavior and flow properties of colloid-polymer mixtures. We first prepare colloid-polymer mixtures that are density- and refractive-index matched. Next, we report a standard protocol for imaging quiescent dense colloid-polymer mixtures under varying confinement in thin wedge-shaped cells. Finally, we demonstrate a protocol for imaging colloid-polymer mixtures during microchannel flow.

Confocal microscopy is used to image quiescent and flowing colloid-polymer mixtures, which are studied as model systems for attractive suspensions. Image analysis algorithms are used to calculate structural and dynamic metrics for the colloidal particles that measure changes due to geometric confinement.

密闭静态和流动胶体聚合物混合物的共聚焦成像

The behavior of confined colloidal suspensions with attractive interparticle interactions is critical to the rational design of materials for directed ...

化学

Using Polystyrene-block-poly(acrylic acid)-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are encapsulated in polystyrene-block-poly(acrylic acid) (PSPAA) shells and then used as monomers for their self-assembly. Spherical PSPAA micelles upon acid treatment are known to assemble into cylindrical micelles. Exploiting this tendency, the core-shell nanoparticles are induced to aggregate, coalesce, and then transform into long chains. When more than one type of nanoparticles are used, random and block &#8220;copolymers&#8221; of nanoparticles can be obtained. Detailed procedures are reported for the PSPAA encapsulation of nanoparticles, homo- and co-polymerization of the core-shell nanoparticles, separation and purification of the resulting nanoparticle chains. Transformations of single-line chains into double- and triple-line chains are also presented. The synergy between the polymer shell and the embedded nanoparticles leads to an unusual chain-growth polymerization mode, giving long nanoparticle chains that are distinct from the products of the traditional step-growth aggregation process.

Using Polystyrene-block-polyacrylic acid-coated Metal Nanoparticles as Monomers for Their Homo- and Co-polymerization

We report protocols for &#8220;polymerizing&#8221; various types of polymer-encapsulated metal nanoparticles into long chains of &#8220;homo-&#8220; and &#8220;co-polymers&#8221;.

使用聚苯乙烯<em&gt;块</em&gt; - 聚（丙烯酸）涂层的金属纳米颗粒作为单体他们均聚物和共聚物聚合

We present a template-free method for &#8220;polymerizing&#8221; nanoparticles into long chains without side branches. A variety of nanoparticles are ...

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates

Functions of clusters in nano or sub-nano scale significantly depend on not only kinds of their components but also arrangements, or symmetry, of their components. Therefore, the arrangements in the clusters have been precisely characterized, especially for metal complexes. Contrary to this, characterizations of molecular arrangements in supramolecular clusters composed of organic molecules are limited to a few cases. This is because construction of the supramolecular clusters, especially obtaining a series of the supramolecular clusters, is difficult due to low stability of non-covalent bonds compare to covalent bonds. From this viewpoint, utilization of organic salts is one of the most useful strategies. A series of the supramolecules could be constructed by combinations of a specific organic molecule with various counter ions. Especially, primary ammonium carboxylates are suitable as typical examples of supramolecules because various kinds of carboxylic acids and primary amines are commercially available, and it is easy to change their combinations. Previously, it was demonstrated that primary ammonium triphenylacetates using various kinds of primary amines specifically construct supramolecular clusters, which are composed of four ammoniums and four triphenylacetates assembled by charge-assisted hydrogen bonds, in crystals obtained from non-polar solvents. This study demonstrates an application of the specific construction of the supramolecular clusters as a strategy to conduct systematical symmetric study for clarification of correlations between molecular arrangements in supramolecules and kinds and numbers of their components. In the same way with binary salts composed of triphenylacetates and one kind of primary ammoniums, ternary organic salts composed of triphenylacetates and two kinds of ammoniums construct the supramolecular clusters, affording a series of the supramolecular clusters with various kinds and numbers of the components.

This article describes construction of a series of hydrogen-bonding supramolecular clusters in crystals using primary ammonium triphenylacetates, which are recrystallized from non-polar solvents. This selective construction of the supramolecular clusters leads to effective systematical symmetric studies about a correlation between the supramolecular clusters and their components.

建筑和超分子集群与二元或三元铵Triphenylacetates一系列的体制性对称研究

Functions of clusters in nano or sub-nano scale significantly depend on not only kinds of their components but also arrangements, or symmetry, of their ...

Controlled Synthesis and Fluorescence Tracking of Highly Uniform Poly(N-isopropylacrylamide) Microgels

Stimuli-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels have various prospective practical applications and uses in fundamental research. In this work, we use single particle tracking of fluorescently labeled PNIPAM microgels as a showcase for tuning microgel size by a rapid non-stirred precipitation polymerization procedure. This approach is well suited for prototyping new reaction compositions and conditions or for applications that do not require large amounts of product. Microgel synthesis, particle size and structure determination by dynamic and static light scattering are detailed in the protocol. It is shown that the addition of functional comonomers can have a large influence on the particle nucleation and structure. Single particle tracking by wide-field fluorescence microscopy allows for an investigation of the diffusion of labeled tracer microgels in a concentrated matrix of non-labeled microgels, a system not easily investigated by other methods such as dynamic light scattering.

Controlled Synthesis and Fluorescence Tracking of Highly Uniform PolyN-isopropylacrylamide Microgels

Non-stirred precipitation polymerization provides a rapid, reproducible prototyping approach to the synthesis of stimuli-sensitive poly(N-isopropylacrylamide) microgels of narrow size distribution. In this protocol synthesis, light scattering characterization and single particle fluorescence tracking of these microgels in a wide-field microscopy setup are demonstrated.

可控合成和高度统一聚荧光追踪（<em&gt;ñ</em&gt; -isopropylacrylamide）微凝胶

Stimuli-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels have various prospective practical applications and uses in fundamental research. In this ...

Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers

The production of monodisperse cylindrical micelles is a significant challenge in polymer chemistry. Most cylindrical constructs formed from diblock copolymers are produced by one of three techniques: thin film rehydration, solvent switching or polymerization-induced self-assembly, and produce only flexible, polydisperse cylinders. Crystallization-driven self-assembly (CDSA) is a method which can produce cylinders with these properties, by stabilizing structures of a lower curvature due to the formation of a crystalline core. However, the living polymerization techniques by which most core-forming blocks are formed are not trivial processes and the CDSA process may yield unsatisfactory results if carried out incorrectly. Here, the synthesis of cylindrical nanoparticles from simple reagents is shown. The drying and purification of reagents prior to a ring-opening polymerization of &#949;-caprolactone catalyzed by diphenyl phosphate is described. This polymer is then chain extended by methyl methacrylate (MMA) followed by N,N-dimethyl acrylamide (DMA) using reversible addition&#8722;fragmentation chain-transfer (RAFT) polymerization, affording a triblock copolymer that can undergo CDSA in ethanol. The living CDSA process is outlined, the results of which yield cylindrical nanoparticles up to 500 nm in length and a length dispersity as low as 1.05. It is anticipated that these protocols will allow others to produce cylindrical nanostructures and elevate the field of CDSA in the future.

Crystallization-driven self-assembly (CDSA) displays the unique ability to fabricate cylindrical nanostructures of narrow length distributions. The organocatalyzed ring-opening polymerization of &#949;-caprolactone and subsequent chain extensions of methyl methacrylate and N,N-dimethyl acrylamide are demonstrated. A living CDSA protocol that produces monodisperse cylinders up to 500 nm in length is outlined.

通过结晶驱动生物降解块共聚物的自组装合成单分散圆柱状纳米粒子

The production of monodisperse cylindrical micelles is a significant challenge in polymer chemistry. Most cylindrical constructs formed from diblock ...

Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly

This protocol presents the use of Lewis acidic multi-role reagents to circumvent kinetic trapping observed during the self-assembly of information-encoded oligomeric strands mediated by paired dynamic covalent interactions in a manner mimicking the thermal cycling commonly employed for the self-assembly of complementary nucleic acid sequences. Primary amine monomers bearing aldehyde and amine pendant moieties are functionalized with orthogonal protecting groups for use as dynamic covalent reactant pairs. Using a modified automated peptide synthesizer, the primary amine monomers are encoded into oligo(peptoid) strands through solid-phase submonomer synthesis. Upon purification by high-performance liquid chromatography (HPLC) and characterization by electrospray ionization mass spectrometry (ESI-MS), sequence-specific oligomers are subjected to high-loading of a Lewis acidic rare-earth metal triflate which both deprotects the aldehyde moieties and affects the reactant pair equilibrium such that strands completely dissociate. Subsequently, a fraction of the Lewis acid is extracted, enabling annealing of complementary sequence-specific strands to form information-encoded molecular ladders characterized by matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS). The simple procedure outlined in this report circumvents kinetic traps commonly experienced in the field of dynamic covalent assembly and serves as a platform for the future design of robust, complex architectures.

A protocol is presented for the synthesis of information-encoded peptoid oligomers and for the sequence-directed self-assembly of these peptoids into molecular ladders using amines and aldehydes as dynamic covalent reactant pairs and Lewis acidic rare-earth metal triflates as multi-role reagents.

信息承载Peptoids及其序列定向动态共价自组装的合成

This protocol presents the use of Lewis acidic multi-role reagents to circumvent kinetic trapping observed during the self-assembly of information-encoded ...

聚合物接枝金属有机框架单层的自组装

Synthesis and Characterization of Self-Assembled Metal-Organic Framework Monolayers Using Polymer-Coated Particles

Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. Attempts to enhance the utility of MOFs have involved the preparation of various composites, including polymer-grafted MOFs. By directly grafting polymers to the external surface of MOFs, issues of incompatibility between polymers and MOFs can be overcome. Polymer brushes grafted from the surface of MOFs can serve to stabilize the MOF while enabling particle assembly into self-assembled metal-organic framework monolayers (SAMMs) via polymer-polymer interactions.
Control over the chemical composition and molecular weight of the grafted polymer can allow for tuning of the SAMM characteristics. In this work, instructions are provided on how to immobilize a chain transfer agent (CTA) onto the surface of the MOF UiO-66 (UiO = Universitetet i Oslo). The CTA&#160;serves as initiation sites for the growth of polymers. Once polymer chains are grown from the MOF surface, the formation of SAMMs is achieved through self-assembly at an air-water interface. The resulting SAMMs are characterized and shown to be freestanding by scanning electron microscopy imaging. The methods presented in this paper are expected to make the preparation of SAMMs more accessible to the research community and thereby expand their potential use as a&#160;MOF-polymer composite.

作者聚焦:探索自组装的 MOF-聚合物复合材料

A protocol for the synthesis and characterization of self-assembled metal-organic framework monolayers is provided using polymer-grafted, metal-organic framework (MOF) crystals. The procedure shows that polymer-grafted MOF particles can be self-assembled at an air-water interface resulting in well-formed, free-standing, monolayer structures as evidenced by scanning electron microscopy imaging.

使用聚合物包覆颗粒的自组装金属有机框架单层的合成和表征

Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. ...

超分子胶体的合成与表征

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控制的大小，形状和稳定性超分子聚合物在水

密闭静态和流动胶体聚合物混合物的共聚焦成像

使用聚苯乙烯

建筑和超分子集群与二元或三元铵Triphenylacetates一系列的体制性对称研究

可控合成和高度统一聚荧光追踪（

通过结晶驱动生物降解块共聚物的自组装合成单分散圆柱状纳米粒子

信息承载Peptoids及其序列定向动态共价自组装的合成

使用聚合物包覆颗粒的自组装金属有机框架单层的合成和表征

使用聚合物包覆颗粒的自组装金属有机框架单层的合成和表征

使用聚合物包覆颗粒的自组装金属有机框架单层的合成和表征