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>
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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 border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>4-Cyano-4-(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 Mn 300, contains 100&#160;ppm MEHQ as inhibitor, 300&#160;ppm BHT as inhibitor</td>
		</tr>
		<tr>
			<td>2,2&#8242;-Azobis(2-methylpropionitrile) (AIBN)</td>
			<td>Sigma-Aldrich</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Ru(bpy)3Cl2.6H2O</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 (40-60oC)</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 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>2L 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>&#955; = 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 mm)</td>
			<td>Beckton Dickson</td>
			<td>302017</td>
			<td>For deoxygenating reactions</td>
		</tr>
		<tr>
			<td>Needle (0.8 mm x 120 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

Facile and Efficient Preparation of Tri-component Fluorescent Glycopolymers via RAFT-controlled Polymerization

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and efficient synthesis of well-controlled fluorescent statistical glycopolymers using reversible addition-fragmentation chain-transfer (RAFT)-based polymerization is demonstrated. The synthesis starts with the preparation of &#946;-galactose-containing glycomonomer 2-lactobionamidoethyl methacrylamide obtained by reaction of lactobionolactone and N-(2-aminoethyl) methacrylamide (AEMA). 2-Gluconamidoethyl methacrylamide (GAEMA) is used as a structural analog lacking a terminal &#946;-galactoside. The following RAFT-mediated copolymerization reaction involves three different monomers: N-(2-hydroxyethyl) acrylamide as spacer, AEMA as target for further fluorescence labeling, and the glycomonomers. Tolerant of aqueous systems, the RAFT agent used in the reaction is (4-cyanopentanoic acid)-4-dithiobenzoate. Low dispersities (&#8804;1.32), predictable copolymer compositions, and high reproducibility of the polymerizations were observed among the products. Fluorescent polymers are obtained by modifying the glycopolymers with carboxyfluorescein succinimidyl ester targeting the primary amine functional groups on AEMA. Lectin-binding specificities of the resulting glycopolymers are verified by testing with corresponding agarose beads coated with specific glycoepitope recognizing lectins. Because of the ease of the synthesis, the tight control of the product compositions and the good reproducibility of the reaction, this protocol can be translated towards preparation of other RAFT-based glycopolymers with specific structures and compositions, as desired.

An efficient, three-step synthesis of RAFT-based fluorescent glycopolymers, consisting of glycomonomer preparation, copolymerization, and post-modification, is demonstrated. This protocol can be used to prepare RAFT-based statistical glycopolymers with desired structures.

通过RAFT控制聚合轻便和高效制备三组分荧光Glycopolymers

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and ...

科研

化学

Facile Preparation of Internally Self-assembled Lipid Particles Stabilized by Carbon Nanotubes

We present a facile method to prepare nanostructured lipid particles stabilized by carbon nanotubes (CNTs). Single-walled (pristine) and multi-walled (functionalized) CNTs are used as stabilizers to produce Pickering type oil-in-water (O/W) emulsions. Lipids namely, Dimodan U and Phytantriol are used as emulsifiers, which in excess water self-assemble into the bicontinuous cubic Pn3m phase. This highly viscous phase is fragmented into smaller particles using a probe ultrasonicator in presence of conventional surfactant stabilizers or CNTs as done here. Initially, the CNTs (powder form) are dispersed in water followed by further ultrasonication with the molten lipid to form the final emulsion. During this process the CNTs get coated with lipid molecules, which in turn are presumed to surround the lipid droplets to form a particulate emulsion that is stable for months. The average size of CNT-stabilized nanostructured lipid particles is in the submicron range, which compares well with the particles stabilized using conventional surfactants. Small angle X-ray scattering data confirms the retention of the original Pn3m cubic phase in the CNT-stabilized lipid dispersions as compared to the pure lipid phase (bulk state). Blue shift and lowering of the intensities in characteristic G and G&#39; bands of CNTs observed in Raman spectroscopy characterize the interaction between CNT surface and lipid molecules. These results suggest that the interactions between the CNTs and lipids are responsible for their mutual stabilization in aqueous solutions. As the concentrations of CNTs employed for stabilization are very low and lipid molecules are able to functionalize the CNTs, the toxicity of CNTs is expected to be insignificant while their biocompatibility is greatly enhanced. Hence the present approach finds a great potential in various biomedical applications, for instance, for developing hybrid nanocarrier systems for the delivery of multiple functional molecules as in combination therapy or polytherapy.

We report on a smart application of carbon nanotubes for kinetic stabilization of lipid particles that contain self-assembled nanostructures in their cores. The preparation of lipid particles requires rather low concentrations of carbon nanotubes permitting their use in biomedical applications such as drug delivery.

内部自组装脂质颗粒的简易制备碳纳米管稳定

We present a facile method to prepare nanostructured lipid particles stabilized by carbon nanotubes (CNTs). Single-walled (pristine) and multi-walled ...

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 ...

Facile Preparation of 4-Substituted Quinazoline Derivatives

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted 2-aminobenzophenones and thiourea in the presence of dimethyl sulfoxide (DMSO). This is a unique complementary reaction system in which thiourea undergoes thermal decomposition to form carbodiimide and hydrogen sulfide, where the former reacts with 2-aminobenzophenone to form 4-phenylquinazolin-2(1H)-imine intermediate, whilst hydrogen sulfide reacts with DMSO to give methanethiol or other sulfur-containing molecule which then functions as a complementary reducing agent to reduce 4-phenylquinazolin-2(1H)-imine intermediate into 4-phenyl-1,2-dihydroquinazolin-2-amine. Subsequently, the elimination of ammonia from 4-phenyl-1,2-dihydroquinazolin-2-amine affords substituted quinazoline derivative. This reaction usually gives quinazoline derivative as a single product arising from 2-aminobenzophenone as monitored by GC/MS analysis, along with small amount of sulfur-containing molecules such as dimethyl disulfide, dimethyl trisulfide, etc. The reaction usually completes in 4-6 hr at 160 &#186;C in small scale but may last over 24 hr when carried out in large scale. The reaction product can be easily purified by means of washing off DMSO with water followed by column chromatography or thin layer chromatography.

A protocol for facile preparation of 4-substituted quinazoline derivatives from 2-aminobenzophenones, thiourea and dimethyl sulfoxide is presented.

的4-取代喹唑啉衍生物简便制备

Reported in this paper is a very simple method for direct preparation of 4-substituted quinazoline derivatives from a reaction between substituted ...

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

科大-1作为香兰素的合成的非均相催化剂

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by &#960;-&#960; Stacking Interactions

In this study, an amphiphilic copolymer that includes a core-forming block with phenyl groups was synthesized by living anionic polymerization of phenyl glycidyl ether (PheGE) on methoxy-polyethylene glycol (mPEG-b-PPheGE). Characterization of the copolymer revealed a narrow molecular distribution (PDI &#60; 1.03) and confirmed the degree of polymerization of mPEG122-b-(PheGE)15. The critical micelle concentration of the copolymer was evaluated using an established fluorescence method with the aggregation behavior evaluated by dynamic light scattering and transmission electronic microscopy. The potential of the copolymer for use in drug delivery applications was evaluated in a preliminary manner including in vitro biocompatibility, loading and release of the hydrophobic anti-cancer drug doxorubicin (DOX). A stable micelle formulation of DOX was prepared with drug loading levels up to 14% (wt%), drug loading efficiencies &#62; 60% (w/w) and sustained release of drug over 4 days under physiologically relevant conditions (acidic and neutral pH, presence of albumin). The high drug loading level and sustained release is attributed to stabilizing &#960;-&#960; interactions between DOX and the core-forming block of the micelles.

The key steps of living anionic polymerization of phenyl glycidyl ether (PheGE) on methoxy-polyethylene glycol (mPEG-b-PPheGE) are described. The resulting block copolymer micelles (BCMs) were loaded with doxorubicin 14% (wt%) and sustained release of drug over 4 days under physiologically relevant conditions was obtained.

一个两亲性共聚物的阴离子聚合通过π-π堆积作用稳定嵌段共聚物胶束的制备

In this study, an amphiphilic copolymer that includes a core-forming block with phenyl groups was synthesized by living anionic polymerization of phenyl ...

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Direct cross-coupling between two alkenes via vinylic C-H bond activation represents an efficient strategy for the synthesis of butadienes with high atomic and step economy. However, this functionality-directed cross-coupling reaction has not been developed, as there are still limited directing groups in practical use. In particular, a stoichiometric amount of oxidant is usually required, producing a large amount of waste. Due to our interest in novel 1,3-butadiene synthesis, we describe the ruthenium-catalyzed olefination of electron-deficient alkenes using allyl acetate and without external oxidant. The reaction of 2-phenyl acrylamide and allyl acetate was chosen as a model reaction, and the desired diene product was obtained in 80% isolated yield with good stereoselectivity (Z,E/Z,Z = 88:12) under optimal conditions: [Ru(p-cymene) Cl2]2 (3 mol %) and AgSbF6 (20 mol %) in DCE at 110 &#186;C for 16 h. With the optimized catalytic conditions in hand, representative &#945;- and/or &#946;-substituted acrylamides were investigated, and all reacted smoothly, regardless of aliphatic or aromatic groups. Also, differently N-substituted acrylamides have proven to be good substrates. Moreover, we examined the reactivity of different allyl derivatives, suggesting that the chelation of acetate oxygen to the metal is crucial for the catalytic process. Deuterium-labeled experiments were also conducted to investigate the reaction mechanism. Only Z-selective H/D exchanges on acrylamide were observed, indicating a reversible cyclometalation event. In addition, a kinetic isotope effect (KIE) of 3.2 was observed in the intermolecular isotopic study, suggesting that the olefinic C-H metalation step is probably involved in the rate-determining step.

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

The ruthenium-catalyzed olefination of electron-deficient alkenes with allyl acetate is described here. By using aminocarbonyl as a directing group, this external oxidant-free protocol has high efficiency and good stereo- and regioselectivity, opening a novel synthetic route to (Z,E)-butadiene skeletons.

（2<em&gt;ž</em&gt;，4<em&gt;电子</em&gt;） - 通过电子缺陷烯烃与烯丙基乙酸酯的烯化反应制备二烯酰胺

Direct cross-coupling between two alkenes via vinylic C-H bond activation represents an efficient strategy for the synthesis of butadienes with high ...

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, ...

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity in aqueous CO2 reduction. Different from traditional metal nanocrystals, the synthesis of metal single atoms involves a matrix material that can confine those single atoms and prevent them from aggregation. We report an electrospinning and thermal annealing method to prepare Ni single atoms dispersed and coordinated in a graphene shell, as active centers for CO2 reduction to CO. During the synthesis, N dopants play a critical role in generating graphene vacancies to trap Ni atoms. Aberration-corrected scanning transmission electron microscopy and three-dimensional atom probe tomography were employed to identify the single Ni atomic sites in graphene vacancies. Detailed setup of electrochemical CO2 reduction apparatus coupled with an on-line gas chromatography is also demonstrated. Compared to metallic Ni, Ni single atom catalyst exhibit dramatically improved CO2 reduction and suppressed H2 evolution side reaction.

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Here, we present a protocol for the synthesis and electrochemical testing of transition metal single atoms coordinated in graphene vacancies as active centers for selective carbon dioxide reduction to carbon monoxide in aqueous solutions.

电化学 CO2还原的过渡金属单原子催化剂的合成及性能表征

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

半导体回转金属硫框架结晶的硫醇构建块的合成

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...