CB is thankful for his Future Fellowship from Australian Research Council (ARC-FT12010096) and UNSW Australia.

1.合成与POEGMA表征宏观CTA <ol><li>添加低聚（乙二醇）甲基醚甲基丙烯酸酯（OEGMA）（12克，4×10 -2摩尔），4-氰基-4-（phenylcarbonothioylthio）戊酸（CPADB）（0.224克，8×10 -4摩尔）， 2,2&#39;-偶氮二（2-甲基丙腈）（AIBN）（16.4毫克，0.1毫摩尔）和50毫升乙腈（MeCN中）到100毫升圆底烧瓶中。 </li><li>密封该烧瓶用适当大小的橡胶隔片和钢丝和从室温烧瓶冷却到&lt;4℃在冰 - 水浴中。 </li><li>通过用第二21g的针（1.3毫米×38毫米）作为通气口直接鼓泡入氮气通过21g的针（1.3毫米×120毫米），将反应混合物脱氧30分钟烧瓶中。 </li><li>在冰 - 水浴浸入淬火聚合和内容暴露于空气之前放置在油浴中的烧瓶中在70℃下5.5小时。 </li><li>通过在AC搅拌取出乙腈在〜40毫升四氢呋喃（THF）中的压缩空气和ontinuous流再溶解粗混合物。 </li><li>烧瓶滴加的内容添加到400毫升石油烈酒快速搅拌混合物（沸点40-60℃）和乙醚（70:30，体积/体积），继续搅拌直至上清液不再混浊。 注意:在冰浴冷却可被用来加速沉淀过程。 </li><li>倒出上清液并重新溶解在〜40毫升THF的聚合物残余物。 </li><li>重复该沉淀过程（步骤1.5-1.7）至少两次以上，以确保完全除去残余OEGMA单体。从纯化POEGMA宏观CTA首先通过搅拌下被压缩的空气和干燥的连续流在真空烘箱（20℃，10毫巴）4小时除去过量的溶剂。 </li><li>使用先前报道的方法确定由核磁共振的POEGMA宏-CTA（NMR）（Mn为，NMR）的数均分子量<s达&gt; 15。使用凝胶渗透色谱15（GPC）（二甲基乙酰胺作为流动相及用于校准的适当标准）计算聚合物分散度（D）。 注意:使用上述合成（步骤1.1-1.8）应该产生一个POEGMA宏观CTA采用M N，NMR = 9000和D &lt;1.15。如果合成POEGMA宏观CTA的分子量（和分散度）从这里提出的合成不同（7,000之间-克/摩尔1,000），形成蠕虫状胶束（如原位胶凝所示）仍然会出现使用在稍微改变反应时间尽管在（第2节）提出后续PISA方法。 </li></ol> 2. POEGMA-的制剂B -PBzMA使用纳米PISA <ol><li>制备的Ru（联吡啶）3 Cl 2中。6H 2 O的乙醇（EtOH中）的1毫克/毫升储液。存放在冰箱原液以减少溶剂蒸发。 </li><li>插入巴斯德吸管用脱脂棉小一叠第二吸管帮助紧紧包装。倾碱性氧化铝与棉塞移液器，得到大约5厘米的柱。由通过塔传递〜3毫升的BzMA的和收集deinhibited的BzMA洗脱液除去在商用的BzMA的单甲基醚氢醌抑制剂。 </li><li>添加POEGMA macroCTA中（〜9000克/摩尔; 76.9毫克，8.5×10 -6摩尔），deinhibited BzMA的（0.301克，1.71×10-3摩尔），吡啶钌3 CL 2 6H 2 O（128微克， 1.71×10 -7摩尔，1毫克/毫升的乙醇原液128微升），0.383毫升MeCN中和1.402毫升乙醇（1.913毫升总溶剂，80重量％，20体积/体积％的MeCN）至4毫升的玻璃小瓶。 </li><li>如步骤1.2-1.3所述执行脱氧过程。 </li><li>放在一个2000毫升玻璃烧杯中的瓶（ 图2）内衬蓝色LED带（λ 最大 = 460纳米，0.7毫瓦/厘米2），并在室温下用磁力搅拌照射。监测反应小瓶后定期20小时，当在小瓶倒置（ 图3）的高粘度溶液形成自由站立凝胶从反应器中取出。 注意:总时间，以产生自由站立凝胶应为约24小时使用这里提出的条件的蓝色光照射的。在灯光的照射反应堆小的差异（物理尺寸，强度等 ）可能需要稍微改变条件（特别是反应时间），实现了原位形成蠕虫状胶束。 </li><li>从反应器中取出后，通过将纳米颗粒的凝胶在空气中几分钟，直立存储封闭小瓶在黑暗猝灭聚合反应。 </li></ol>纳米形貌3.透射电子显微镜（TEM）影像<ol><li>将约40毫克粗nanopa的在4毫升的玻璃小瓶rticle凝胶（从第2节）。 </li><li>连续搅动使用涡旋混合器纳米粒子凝胶和加入4 7ml乙醇滴加历时至少5分钟。凝胶应成为溶剂加入过程中的自由流动的解决方案。 注意:如果该凝胶用EtOH稀释过快或不能充分搅拌，可能会发生纳米颗粒的一些沉淀。请参阅步骤3.3。 </li><li>通过玻璃棉过滤去除稀释的纳米粒子的宏观聚集。 </li><li>根据先前报道的方法进行稀释样品的TEM成像（醋酸铀染色）。15 </li></ol>

<ol>
	<li>Yu, Y., Eisenberg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Control+of+Morphology+through+Polymer&#8722;Solvent+Interactions+in+Crew-Cut+Aggregates+of+Amphiphilic+Block+Copolymers.">Control of Morphology through Polymer&#8722;Solvent Interactions in Crew-Cut Aggregates of Amphiphilic Block Copolymers.</a> J. Am. Chem. Soc. 119 (35), 8383-8384 (1997).</li><li>Zhang, L., Eisenberg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermodynamic+vs+Kinetic+Aspects+in+the+Formation+and+Morphological+Transitions+of+Crew-Cut+Aggregates+Produced+by+Self-Assembly+of+Polystyrene-b-poly(acrylic+acid)+Block+Copolymers+in+Dilute+Solution.">Thermodynamic vs Kinetic Aspects in the Formation and Morphological Transitions of Crew-Cut Aggregates Produced by Self-Assembly of Polystyrene-b-poly(acrylic acid) Block Copolymers in Dilute Solution.</a> Macromolecules. 32 (7), 2239-2249 (1999).</li><li>Zhang, L., Eisenberg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Multiple+Morphologies+of+'Crew-Cut'+Aggregates+of+Polystyrene-b-poly(acrylic+acid)+Block+Copolymers.">Multiple Morphologies of 'Crew-Cut' Aggregates of Polystyrene-b-poly(acrylic acid) Block Copolymers.</a> Science. 268 (5218), 1728-1731 (1995).</li><li>Yu, K., Zhang, L., Eisenberg, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Novel+Morphologies+of+&amp;#34;Crew-Cut&amp;#34;+Aggregates+of+Amphiphilic+Diblock+Copolymers+in+Dilute+Solution.">Novel Morphologies of &amp;#34;Crew-Cut&amp;#34; Aggregates of Amphiphilic Diblock Copolymers in Dilute Solution.</a> Langmuir. 12 (25), 5980-5984 (1996).</li><li>Blanazs, A., Ryan, A. J., Armes, S. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Predictive+Phase+Diagrams+for+RAFT+Aqueous+Dispersion+Polymerization:+Effect+of+Block+Copolymer+Composition,+Molecular+Weight,+and+Copolymer+Concentration.">Predictive Phase Diagrams for RAFT Aqueous Dispersion Polymerization: Effect of Block Copolymer Composition, Molecular Weight, and Copolymer Concentration.</a> Macromolecules. 45 (12), 5099-5107 (2012).</li><li>Ladmiral, V., Semsarilar, M., Canton, I., Armes, S. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polymerization-induced+self-assembly+of+galactose-functionalized+biocompatible+diblock+copolymers+for+intracellular+delivery.">Polymerization-induced self-assembly of galactose-functionalized biocompatible diblock copolymers for intracellular delivery.</a> J. Am. Chem. Soc. 135 (36), 13574-13581 (2013).</li><li>Sugihara, S., Blanazs, A., Armes, S. P., Ryan, A. J., Lewis, A. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Aqueous+Dispersion+Polymerization:+A+New+Paradigm+for+in+Situ+Block+Copolymer+Self-Assembly+in+Concentrated+Solution.">Aqueous Dispersion Polymerization: A New Paradigm for in Situ Block Copolymer Self-Assembly in Concentrated Solution.</a> J. Am. Chem. Soc. 133 (39), 15707-15713 (2011).</li><li>Wan, W. M., Hong, C. Y., Pan, C. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=One-pot+synthesis+of+nanomaterials+via+RAFT+polymerization+induced+self-assembly+and+morphology+transition.">One-pot synthesis of nanomaterials via RAFT polymerization induced self-assembly and morphology transition.</a> Chem. Comm. (39), 5883-5885 (2009).</li><li>Semsarilar, M., Jones, E. R., Blanazs, A., Armes, S. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficient+Synthesis+of+Sterically-Stabilized+Nano-Objects+via+RAFT+Dispersion+Polymerization+of+Benzyl+Methacrylate+in+Alcoholic+Media.">Efficient Synthesis of Sterically-Stabilized Nano-Objects via RAFT Dispersion Polymerization of Benzyl Methacrylate in Alcoholic Media.</a> Adv. Mater. 24 (25), 3378-3382 (2012).</li><li>Karagoz, B., 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=Polymerization-Induced+Self-Assembly+(PISA)+-+control+over+the+morphology+of+nanoparticles+for+drug+delivery+applications.">Polymerization-Induced Self-Assembly (PISA) - control over the morphology of nanoparticles for drug delivery applications.</a> Polym. Chem. 5 (2), 350-355 (2014).</li><li>Geng, 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=Shape+effects+of+filaments+versus+spherical+particles+in+flow+and+drug+delivery.">Shape effects of filaments versus spherical particles in flow and drug delivery.</a> Nat Nano. 2 (4), 249-255 (2007).</li><li>Blanazs, A., 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=Sterilizable+gels+from+thermoresponsive+block+copolymer+worms.">Sterilizable gels from thermoresponsive block copolymer worms.</a> J. Am. Chem. Soc. 134 (23), 9741-9748 (2012).</li><li>Pei, Y., Thurairajah, L., Sugita, O. R., Lowe, A. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=RAFT+Dispersion+Polymerization+in+Nonpolar+Media:+Polymerization+of+3-Phenylpropyl+Methacrylate+in+n-Tetradecane+with+Poly(stearyl+methacrylate)+Homopolymers+as+Macro+Chain+Transfer+Agents.">RAFT Dispersion Polymerization in Nonpolar Media: Polymerization of 3-Phenylpropyl Methacrylate in n-Tetradecane with Poly(stearyl methacrylate) Homopolymers as Macro Chain Transfer Agents.</a> Macromolecules. 48 (1), 236-244 (2015).</li><li>Fielding, L. A., Lane, J. A., Derry, M. J., Mykhaylyk, O. O., Armes, S. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermo-responsive+Diblock+Copolymer+Worm+Gels+in+Non-polar+Solvents.">Thermo-responsive Diblock Copolymer Worm Gels in Non-polar Solvents.</a> J. Am. Chem. Soc. 136 (15), 5790-5798 (2014).</li><li>Yeow, J., Xu, J., Boyer, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polymerization-Induced+Self-Assembly+Using+Visible+Light+Mediated+Photoinduced+Electron+Transfer-Reversible+Addition-Fragmentation+Chain+Transfer+Polymerization.">Polymerization-Induced Self-Assembly Using Visible Light Mediated Photoinduced Electron Transfer-Reversible Addition-Fragmentation Chain Transfer Polymerization.</a> ACS Macro Lett. 4 (9), 984-990 (2015).</li><li>Xu, J., Jung, K., Corrigan, N. A., Boyer, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Aqueous+photoinduced+living/controlled+polymerization:+tailoring+for+bioconjugation.">Aqueous photoinduced living/controlled polymerization: tailoring for bioconjugation.</a> Chem. Sci. 5 (9), 3568-3575 (2014).</li><li>Pei, 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=RAFT+dispersion+polymerization+of+3-phenylpropyl+methacrylate+with+poly[2-(dimethylamino)ethyl+methacrylate]+macro-CTAs+in+ethanol+and+associated+thermoreversible+polymorphism.">RAFT dispersion polymerization of 3-phenylpropyl methacrylate with poly[2-(dimethylamino)ethyl methacrylate] macro-CTAs in ethanol and associated thermoreversible polymorphism.</a> Soft Matter. 10 (31), 5787-5796 (2014).</li></ol>

The authors have nothing to disclose.

这种可视化协议表明仅仅通过观察凝胶状行为的发作，监测蠕虫状胶束的形成的能力。这种方法的效用在于以监测，相较于其他的方法在聚合过程中蠕虫形成的能力。可使用两种市售的单体（OEGMA和BzMA的）的两阶段的聚合，得到的自组装POEGMA- b -PBzMA两亲嵌段共聚物来执行此过程。 这里应注意的是，具有不同的反应器几何形状，光强度等 ，相对于与图2</stro...

非球形（和其他）纳米颗粒形态的合成历来使用开始具有良好定义的两亲二嵌段（或嵌段）共聚物的合成和纯化的多步自组装过程完成。其中最常见的自组装技术是由Eisenberg的在20世纪90年代普及并涉及两亲性嵌段共聚物在普通溶剂为两种聚合物嵌段，随后缓慢加入溶剂选择性为块1〜3之一的溶解。作为添加的选择性溶剂（通常为水）中，嵌段共聚物经受自组装以形成聚合物纳米颗粒。最终形态（或形态的混合物）的纳米粒子是由大量的因素，例如各聚合物嵌段，加水的速度与共用的溶剂的性质的相对长度来确定。然而，这种方法一般只允许生产nanopar的ticles在相对 ​​低的固体含量（小于1重量％），因此限制了它的实际的可扩展性4。此外，"中间"相，例如蠕虫状胶束可再现形成可以由于窄的范围的，以稳定这种非球形形态5所需的参数是困难的。 聚合诱导的自组装（PISA）的方法通过利用聚合过程本身来驱动的自组装的原位允许纳米颗粒合成在高得多的固体含量部分地解决了上述艾森伯格方法的缺点（通常为10-30重量％）6 -8。在一个典型的PISA方法中，活性聚合过程用于链延伸的溶剂可溶的大分子引发剂（或宏CTA）与单体是在反应介质中最初可溶，但形成不溶性聚合物。 PISA的方法已被用于通过系统性测试数前的合成蠕虫状胶束<html> perimental参数，并使用详细的相图作为合成"路线图"5,9。 尽管他们的具有挑战性的合成，存在蠕虫状纳米颗粒由于它们相对于它们的球形同行有趣的性质极大的兴趣。例如，我们已经证明，使用PISA方法合成的装载药物短期和长期的蠕虫状胶束具有体外细胞毒性显著更高相比球状胶束或囊泡10。他人在体内模型11中所示的纳米粒子的纵横比和血液循环时间之间的相关性。其他人已经表明蠕虫状纳米粒子的使用适当的PISA方法合成产生一个宏观凝胶由于纳米颗粒长丝的纳米级纠缠。这些凝胶表现出作为由于其热可逆溶胶-凝胶行为12灭菌凝胶的潜力。 内容】"&gt;该协议描述了在聚合过程中简单地观察该溶液的粘度允许原位监测蠕虫状胶束的形成的方法。相似的蠕虫状胶束凝胶的先前的研究已经表明，高于临界温度时，这些纳米颗粒经受可逆蜗杆球面过渡，因此形成在高温下自由流动的分散体。迄今为止，这些系统已经利用一个热敏感偶氮化合物以引发受控聚合13,14等凝胶化可能不容易在这些系统中观察到热聚合。从这些研究中，有人推测在较低温度下合成PISA衍生的纳米颗粒可允许原位这种凝胶行为观察。 最近我们报道了用一个浅显的室温光聚合技术来调解PISA过程中产生的纳米粒子不同形貌15。这里，可视化协议是由在聚合过程中观察溶液的粘度行为呈现为蠕虫状胶束的再生合成。该分散体聚合反应的进行很容易地利用市售的发光二极管（LED）（λ= 460纳米，0.7毫瓦/厘米2）。

<table><tbody><tr><td>4-Cyano-4-&lt;br /&gt;(phenylcarbonothioylthio)pentanoic acid (CPADB)</td><td>Sigma-Aldrich</td><td>722995-5G</td><td></td></tr><tr><td>Oligo(ethylene glycol) methyl ether methacrylate (OEGMA)</td><td>Sigma-Aldrich</td><td>447935-500ML</td><td>Average M&lt;sub&gt;n&lt;/sub&gt; 300, contains 100&amp;nbsp;ppm MEHQ as inhibitor, 300&amp;nbsp;ppm BHT as inhibitor</td></tr><tr><td>2,2&amp;prime;-Azobis(2-methylpropionitrile) (AIBN)</td><td>Sigma-Aldrich</td><td></td><td></td></tr><tr><td>Ru(bpy)&lt;sub&gt;3&lt;/sub&gt;Cl&lt;sub&gt;2&lt;/sub&gt;.6H&lt;sub&gt;2&lt;/sub&gt;O</td><td>Sigma-Aldrich</td><td>544981-1G</td><td></td></tr><tr><td>Benzyl methacrylate (BzMA)</td><td>Sigma-Aldrich</td><td>409448-1L</td><td>Contains monomethyl ether hydroquinone as inhibitor</td></tr><tr><td>Aluminium oxide (basic)</td><td>Chem-Supply Pty Ltd Australia</td><td>AL08371000</td><td></td></tr><tr><td>95% Ethanol (EtOH)</td><td>Sucrogen Bio Ethanol</td><td>80889</td><td></td></tr><tr><td>Acetonitrile (MeCN)</td><td>Chem-Supply Pty Ltd Australia</td><td>RP1005-G2.5L</td><td></td></tr><tr><td>Tetrahydrofuran (THF)</td><td>Chem-Supply Pty Ltd Australia</td><td>TA011-2.5L</td><td></td></tr><tr><td>Petroleum Spirits (40-60&amp;nbsp;&amp;#176;C)</td><td>Chem-Supply Pty Ltd Australia</td><td>PA044-2.5L</td><td></td></tr><tr><td>Diethyl Ether</td><td>Chem-Supply Pty Ltd Australia</td><td>EA0362.5L</td><td></td></tr><tr><td>Dimethylacetamide (DMAc)</td><td>VWR International Australia</td><td>ALFA22916.M1</td><td>For GPC analysis</td></tr><tr><td>Pasteur pipettes (230&amp;nbsp;mm)</td><td>Labtek</td><td>355.050.503</td><td></td></tr><tr><td>Glass beakers</td><td>Labtek</td><td>025.01.902 (2L)/ 2110654 (1L)</td><td>2&amp;nbsp;L beaker is for attaching LED strips to form the circular reactor</td></tr><tr><td>Commercial LED strip</td><td>EcoLab</td><td>n/a</td><td>&amp;lambda; = 460 nm, 4.8 W/m</td></tr><tr><td>4 ml Glass Vials</td><td>Labtek</td><td>APC502214B</td><td></td></tr><tr><td>0.9 ml Quartz Cuvette</td><td>Starna Scientific Ltd</td><td>21/Q/2</td><td></td></tr><tr><td>Needle (0.8 mm x 38&amp;nbsp;mm)</td><td>Beckton Dickson</td><td>302017</td><td>For deoxygenating reactions</td></tr><tr><td>Needle (0.8 mm x 120&amp;nbsp;mm)</td><td>B Braun Australia</td><td>4665643</td><td>For deoxygenating reactions</td></tr><tr><td>Sleeve stopper septa (rubber septum)</td><td>Sigma-Aldrich</td><td>z564680/z564702</td><td></td></tr><tr><td>Stirring hotplates</td><td>VWR International Australia/In Vitro Technologies</td><td>97018-488/RADRR91200</td><td></td></tr><tr><td>Vortex mixer</td><td>VWR International Australia</td><td>412-0098</td><td></td></tr><tr><td>Vacuum oven</td><td>In Vitro Technologies</td><td>MEMVO200</td><td></td></tr></tbody></table>

facile synthesis of worm-like micelles by visible light mediated dispersion polymerization using photoredox catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

在这项研究中，两步聚合协议用 ​​于使用PISA方法（ 图1）蠕虫状胶束的合成。在第一步骤中，进行OEGMA的聚合，得到一个POEGMA宏CTA其可以用作在随后的聚合步骤中的稳定剂。由于PBzMA的乙醇不溶性，最终导致纳米颗粒形成分散体的条件下将PET-RAFT聚合所得。在聚合过程中，最初透明反应混合物可以观察到成为按照分散聚合混浊，并最终转换到指示蠕虫状胶束?...

Watch this Scientific Journal Video about Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst at JoVE.com

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

使用Photoredox催化剂蠕虫状胶束的简便合成可见光介导的分散聚合

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

facile-synthesis-worm-like-micelles-visible-light-mediated-dispersion

Research

JoVE Journal

Chemistry

9.4K 次观看.  The University of New South Wales. This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

视频: Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

A Facile and Efficient Approach for the Production of Reversible Disulfide Cross-linked Micelles

Nanomedicine is an emerging form of therapy that harnesses the unique properties of particles that are nanometers in scale for biomedical application. Improving drug delivery to maximize therapeutic outcomes and to reduce drug-associated side effects are some of the cornerstones of present-day nanomedicine. Nanoparticles in particular have found a wide application in cancer treatment. Nanoparticles that offer a high degree of flexibility in design, application, and production based on the tumor microenvironment are projected to be more effective with rapid translation into clinical practice. The polymeric micellar nano-carrier is a popular choice for drug delivery applications.
In this article, we describe a simple and effective protocol for synthesizing drug-loaded, disulfide cross-linked micelles based on the self-assembly of a well-defined amphiphilic linear-dendritic copolymer (telodendrimer, TD). TD is composed of polyethylene glycol (PEG) as the hydrophilic segment and a thiolated cholic acid cluster as the core-forming hydrophobic moiety attached stepwise to an amine-terminated PEG using solution-based peptide chemistry. Chemotherapy drugs, such as paclitaxel (PTX), can be loaded using a standard solvent evaporation method. The O2-mediated oxidation was previously utilized to form intra-micellar disulfide cross-links from free thiol groups on the TDs. However, the reaction was slow and not feasible for large-scale production. Recently, an H2O2-mediated oxidation method was explored as a more feasible and efficient approach, and it was 96 times faster than the previously reported method. Using this approach, 50 g of PTX-loaded, disulfide cross-linked nanoparticles have been successfully produced with narrow particle size distribution and high drug loading efficiency. The stability of the resulting micelle solution is analyzed using disrupting conditions such as co-incubation with a detergent, sodium dodecyl sulfate, with or without a reducing agent. The drug-loaded, disulfide cross-linked micelles demonstrated less hemolytic activity when compared to their non-cross-linked counterparts.

To deliver cancer drugs to tumor sites with high specificity and reduced side effects, new methods based on nanoparticles are required. Here, we describe disulfide cross-linked micelles that can be easily prepared by hydrogen peroxide-mediated oxidation and are able to dissociate efficiently under a reducing tumor environment to release payloads.

可逆二硫键交联胶束生产的简便和有效途径

Nanomedicine is an emerging form of therapy that harnesses the unique properties of particles that are nanometers in scale for biomedical application. ...

科研

生物化学

A 'Plug and Play' Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles

In this protocol, we first describe a procedure to synthesize lanthanide doped upconverting nanoparticles (UCNPs). We then demonstrate how to generate amphiphilic polymers in situ, and describe a protocol to encapsulate the prepared UCNPs and different organic dye molecules (porphyrins and diarylethenes) using polymer shells to form stable water-dispersible nanoassemblies. The nanoassembly samples containing both the UCNPs and the diarylethene organic dyes have interesting photochemical and photophysical properties. Upon 365 nm UV irradiation, the diarylethene group undergoes a visual color change. When the samples are irradiated with visible light of another specific wavelength, the color fades and the samples return to the initial colorless state. The samples also emit visible light from the UCNPs upon irradiation with 980 nm near-infrared light. The emission intensity of the samples can be tuned through alternate irradiation with UV and visible light. Modulation of fluorescence can be performed for many cycles without observable degradation of the samples. This versatile encapsulation procedure allows for the transfer of hydrophobic molecules and nanoparticles from an organic solvent to an aqueous medium. The polymer helps to maintain a lipid-like microenvironment for the organic molecules to aid in preservation of their photochemical behavior in water. Thus this method is ideal to prepare water-dispersible photoresponsive systems. The use of near-infrared light to activate upconverting nanoparticles allows for lower energy light to be used to activate photoreactions instead of more harmful ultraviolet light.

Organic dye molecules and oleic acid coated upconverting nanoparticles are not water-soluble. This protocol describes a &#8216;plug and play&#8217; method that enables the transfer of organic dye molecules and upconverting particles from their initial hydrophobic solvent to water.

A&#39;即插即用&#39;的方法来创建水分散性Nanoassemblies包含两亲聚合物，有机染料和上变频纳米粒子

In this protocol, we first describe a procedure to synthesize lanthanide doped upconverting nanoparticles (UCNPs). We then demonstrate how to generate ...

化学

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism.

A method for the atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst is described.

使用苝作为可见光光催化功能化的乙烯基单体原子转移自由基聚合

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The ...

Fabrication of Polymer Microspheres for Optical Resonator and Laser Applications

This paper describes three methods of preparing fluorescent microspheres comprising &#960;-conjugated or non-conjugated polymers: vapor diffusion, interface precipitation, and mini-emulsion. In all methods, well-defined, micrometer-sized spheres are obtained from a self-assembling process in solution. The vapor diffusion method can result in spheres with the highest sphericity and surface smoothness, yet the types of the polymers able to form these spheres are limited. On the other hand, in the mini-emulsion method, microspheres can be made from various types of polymers, even from highly crystalline polymers with coplanar, &#960;-conjugated backbones. The photoluminescent (PL) properties from single isolated microspheres are unusual: the PL is confined inside the spheres, propagates at the circumference of the spheres via the total internal reflection at the polymer/air interface, and self-interferes to show sharp and periodic resonant PL lines. These resonating modes are so-called "whispering gallery modes" (WGMs). This work demonstrates how to measure WGM PL from single isolated spheres using the micro-photoluminescence (&#181;-PL) technique. In this technique, a focused laser beam irradiates a single microsphere, and the luminescence is detected by a spectrometer. A micromanipulation technique is then used to connect the microspheres one by one and to demonstrate the intersphere PL propagation and color conversion from coupled microspheres upon excitation at the perimeter of one sphere and detection of PL from the other microsphere. These techniques, &#181;-PL and micromanipulation, are useful for experiments on micro-optic application using polymer materials.

Protocols for the synthesis of microspheres from polymers, the manipulation of microspheres, and micro-photoluminescence measurements are presented.

用于光学谐振器和激光应用的聚合物微球的制造

This paper describes three methods of preparing fluorescent microspheres comprising &#960;-conjugated or non-conjugated polymers: vapor diffusion, ...

工程学

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, allowing for the synthesis of isotactic poly(&#945;-hydroxy acids) with expected molecular weights (&#62;140 kDa) and narrow molecular weight distributions (Mw/Mn &#60; 1.1). This ring-opening polymerization is mediated by Ni and Zn complexes in the presence of an alcohol initiator and a photoredox Ir catalyst, irradiated by a blue LED (400 - 500 nm). The polymerization is performed at a low temperature (-15 &#176;C) to avoid undesired side reactions. The complete monomer consumption can be achieved within 4 - 8 hours, providing a polymer close to the expected molecular weight with narrow molecular weight distribution. The resulted number-average molecular weight shows a linear correlation with the degree of polymerization up to 1000. The homodecoupling 1H NMR study confirms that the obtained polymer is isotactic without epimerization. This polymerization reported herein offers a strategy for achieving rapid, controlled O-carboxyanhydrides polymerization to prepare stereoregular poly(&#945;-hydroxy acids) and its copolymers bearing various functional side-chain groups.

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

A protocol for the controlled photoredox ring-opening polymerization of O-carboxyanhydrides mediated by Ni/Zn complexes is presented.

镍/锌配合物介导的O-Carboxyanhydrides 的控制 Photoredox 环开聚合

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, ...

Fabrication of Spherical and Worm-shaped Micellar Nanocrystals by Combining Electrospray, Self-assembly, and Solvent-based Structure Control

Micellar nanocrystals (micelles with encapsulated nanocrystals) have become an emerging major class of nanobiomaterials. We describe a method of fabricating micellar nanocrystals based on combining top-down electrospray, bottom-up self-assembly, and solvent-based structure control. This method involves first using electrospray to generate uniform ultrafine liquid droplets, each of which functions as a micro-reactor in which self-assembly reaction occurs forming micellar nanocrystals, with the structures (micelle shape and nanocrystal encapsulation) controlled by the organic solvent used. This method is largely continuous and produces high quality micellar nanocrystal products with an inexpensive structure control approach. By using a water-miscible organic solvent tetrahydrofuran (THF), worm-shaped micellar nanocrystals can be produced due to solvent-induced/facilitated micelle fusion. Compared with the common spherical micellar nanocrystals, worm-shaped micellar nanocrystals can offer minimized non-specific cellular uptake, thus enhancing biological targeting. By co-encapsulating multiple nanocrystals into each micelle, multifunctional or synergistic effects can be achieved. Current limitations of this fabrication method, which will be part of the future work, primarily include imperfect encapsulation in the micellar nanocrystal product and the incompletely continuous nature of the process.

The present work describes a method to fabricate micellar nanocrystals, an emerging major class of nanobiomaterials. This method combines top-down electrospray, bottom-up self-assembly, and solvent-based structure control. The fabrication method is largely continuous, can produce high quality products, and possesses an inexpensive means of structure control.

结合电喷雾、自组装和溶剂型结构控制制备球形和蜗杆状胶束纳米晶

Micellar nanocrystals (micelles with encapsulated nanocrystals) have become an emerging major class of nanobiomaterials. We describe a method of ...

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes and determine the corresponding photochemical mechanism. Then, we describe a protocol to perform ring-opening metathesis polymerization (ROMP) in solution and in miniemulsion using this NHC-photogenerating system. To photogenerate IMes, a system comprising 2-isopropylthioxanthone (ITX) as the sensitizer and 1,3-dimesitylimidazolium tetraphenylborate (IMesH+BPh4-) as the protected form of NHC is employed. IMesH+BPh4- can be obtained in a single step by anion exchange between 1,3-dimesitylimidazolium chloride and sodium tetraphenylborate. A real-time steady-state photolysis setup is described, which hints that the photochemical reaction proceeds in two consecutive steps: 1) ITX triplet is photo-reduced by the borate anion and 2) subsequent proton transfer takes place from the imidazolium cation to produce the expected NHC IMes. Two separate characterization protocols are implemented. Firstly, CS2 is added to the reaction media to evidence the photogeneration of NHC through formation of the IMes-CS2 adduct. Secondly, the amount of NHC released in situ is quantified using acid-base titration. The use of this NHC photo-generating system for the ROMP of norbornene is also discussed. In solution, a photopolymerization experiment is conducted by mixing ITX, IMesH+BPh4-, [RuCl2(p-cymene)]2 and norbornene in CH2Cl2, then irradiating the solution in a UV reactor. In a dispersed medium, a monomer miniemulsion is first formed then irradiated inside an annular reactor to produce a stable poly(norbornene) latex.

We describe a protocol to photogenerate N-heterocyclic carbenes (NHCs) by UV irradiation of a 2-isopropylthioxanthone/imidazolium tetraphenylborate salt system. Methods to characterize the photoreleased NHC and elucidate the photochemical mechanism are proposed. The protocols for ring-opening metathesis photopolymerization in solution and miniemulsion illustrate the potential of this 2-component NHC photogenerating system.

n-杂环卡本的光生成在光致环开环转移聚合中的应用

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes ...

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 ...

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. ...

使用Photoredox催化剂蠕虫状胶束的简便合成可见光介导的分散聚合

摘要

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此视频中的章节

可逆二硫键交联胶束生产的简便和有效途径

A'即插即用'的方法来创建水分散性Nanoassemblies包含两亲聚合物，有机染料和上变频纳米粒子

使用苝作为可见光光催化功能化的乙烯基单体原子转移自由基聚合

用于光学谐振器和激光应用的聚合物微球的制造

镍/锌配合物介导的O-Carboxyanhydrides 的控制 Photoredox 环开聚合

结合电喷雾、自组装和溶剂型结构控制制备球形和蜗杆状胶束纳米晶

n-杂环卡本的光生成在光致环开环转移聚合中的应用

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

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