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

1.合成とPOEGMAマクロCTAのキャラクタリゼーション<ol><li> 、オリゴ（エチレングリコール）メチルエーテルメタクリレート（OEGMA）〜（12 gで4×10 -2モル）、4-シアノ-4-（phenylcarbonothioylthio）ペンタン酸（CPADB）（0.224 gの8×10 -4モル）を添加2,2&#39;-アゾビス（2-メチルプロピオニトリル）（AIBN）を100mlの丸底フラスコに（16.4ミリグラム、0.1ミリモル）を、50mlのアセトニトリル（MeCN中）。 </li><li>適切なサイズのゴム隔壁と鋼線を用いてフラスコを密封し、氷水浴で&lt;4℃に室温からフラスコを冷却します。 </li><li>通気口としての第2の21のG針（0.8ミリメートルX 38ミリメートル）の演技で21 G針（0.8ミリメートルX 120ミリメートル）を介して、反応混合物中に直接窒素をバブリングすることにより30分間フラスコを脱酸素。 </li><li>氷水浴に浸漬することにより重合をクエンチし、空気にコンテンツを露出する前に5.5時間、70℃の油浴にフラスコを置きます。 </li><li>交流の下で攪拌することによってのMeCNを削除します圧縮空気と〜テトラヒドロフラン40ml（THF）に再溶解し、粗混合物をontinuousストリーム。 </li><li>急速に撹拌し、石油スピリットの混合物（沸点40〜60℃）とジエチルエーテルの400ミリリットルにフラスコ滴下の内容を追加します（70:30、v / v）を、上清がもはや曇っなるまで攪拌しないように続けています。 注：氷浴で冷却し、沈殿プロセスを加速するために使用することができます。 </li><li> 〜40mLのTHF中の上清および再溶解ポリマー残渣をデカント。 </li><li>沈殿処理を繰り返し、残留OEGMAモノマーの完全な除去を確実にするために、少なくとも2回以上（1.5〜1.7ステップ）。 4時間真空オーブン（20℃、10ミリバール）で、圧縮空気と乾燥の連続ストリームの下で最初に攪拌することにより、精製POEGMAマクロCTAから余分な溶媒を除去します。 </li><li>以前に報告された方法を用いて、核磁気共鳴（NMR）によってPOEGMAマクロCTAの数平均分子量（M N、NMR）を決定<s&gt; 15アップ。ポリマー分散度（D）を計算するゲル浸透クロマトグラフィー15（GPC）（移動相及び較正のための適切な基準としてジメチルアセトアミド）を使用。 注：上記の合成を使用したが（1.1から1.8ステップ）POEGMA MとマクロCTA nは、NMR = 9000、およびD &lt;1.15が得られるはずです。合成POEGMAマクロCTAの分子量（および分散）は、ここに提示合成異なる場合（7,000の間- 1,000グラム/モル）、蠕虫状ミセルの形成は、（ インサイツゲル化によって示されるように）はまだ使用して発生することができその後のPISAの方法論は、わずかに変更された反応時間ではある（セクション2）で発表しました。 </li></ol> PISAを使用して-PBzMAナノ粒子B POEGMA-の調製<ol><li> Ru（bpyで）3 Clで2。6H 2 Oのエタノール（EtOH）中の1mg / mlのストック溶液を準備します。溶媒の蒸発を最小限に抑えるために冷蔵庫にストック溶液を保管してください。 </li><li>綿ウールの小さな塊がきつく、それをパック助けるために第2のピペットを使用してパスツールピペットを差し込みます。約5cmの列を与えるために脱脂綿プラグ付きピペット内に塩基性酸化アルミニウムを注ぎます。カラムを通して〜BZMAの3ミリリットルを渡すとdeinhibited BZMAの溶離液を収集することにより、商業BZMAでモノメチルエーテルヒドロキノン阻害剤を除去します。 </li><li> POEGMAマクロCTA（〜9000グラム/モル; 76.9 mgであり、8.5×10 -6モル）を追加します。、（0.301グラム、1.71×10 -3モル）BZMAをdeinhibited、ルテニウム（BPY）3 Cl 2の6H 2 O（128μgの、 1.71×10 -7モル、4ミリリットルのガラスバイアルに1mg / mlのエタノールストック溶液の128μl）を、0.383ミリリットルのMeCNおよび1.402ミリリットルのEtOH（1.913ミリリットル全溶媒、80重量％、20（v / v）の％のMeCN） 。 </li><li>ステップ1.2から1.3に概説されているよう脱酸素手順を実行します。 </li><li> 2000ミリリットルのガラスビーカー内のバイアルを置きます（ 図2）は、青色LEDストリップが並んで（λ 最大 = 460nmで、0.7ミリワット/ cm 2）を磁気攪拌しながら、室温で照射します。日常的に20時間後に反応バイアルを監視し、バイアルは（ 図3）が反転したときに高粘度液が自立ゲルを形成する場合、反応器からそれを削除。 注意：ここで紹介する条件を用いて、青色光照射の約24時間でなければならない自立ゲルを得るための合計時間を。光照射用原子炉の小さな差（物理的な寸法、強度など ）は、蠕虫状ミセルのin situ形成を達成するためにわずかに変更された条件（具体的には、反応時間）を必要とするかもしれません。 </li><li>反応器から除去した後、数分間空気にナノ粒子ゲルを露出させ、暗所で直立密閉バイアルを格納することによって重合をクエンチしました。 </li></ol>ナノ粒子形態の3透過型電子顕微鏡（TEM）イメージング<ol><li>粗製のnanopaの約40ミリグラムを配置4ミリリットルのガラスバイアル中（セクション2から）rticleゲル。 </li><li>連続的にボルテックスミキサーを用いて、ナノ粒子ゲルを攪拌し、少なくとも5分間にわたってエタノール滴下を4mlを加えます。ゲルは、溶媒の添加の間、自由流動ソリューションとなるべきです。 注：ゲルがあまりにも急速にか十分に撹拌EtOHで希釈されている場合は、ナノ粒子のいくつかの沈殿が発生する可能性があります。ステップ3.3を参照してください。 </li><li>グラスウールを通して濾過することにより希釈されたナノ粒子からの任意の肉眼で見える凝集物を除去。 </li><li>以前に報告された手順に従って希釈されたサンプルの（酢酸ウラニル染色）のTEM撮影を行う。15 </li></ol>

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The authors have nothing to disclose.

この可視化プロトコルは、単にゲル様挙動の発生を観察することにより、ウォーム様ミセルの形成を監視する能力を示します。このアプローチの有用性は、他の方法と比較して、重合中にワームの形成をモニターする能力にあります。この手順は、自己組織化POEGMA- Bの -PBzMA両親媒性ジブロックコポリマーを得るために、2つの市販のモノマー（OEGMAとBZMA）の二段階重合法を用いて行う?...

非球形（および他の）ナノ粒子形態の合成は、伝統的に明確に定義された両親媒性ジブロック（またはマルチ）の共重合体の合成および精製始まる多段階の自己組織化手順を使用して達成されました。最も一般的な自己組織化技術の一つは、1990年代にアイゼンバーグによって普及し、ブロック1-3のいずれかの溶媒の選択をゆっくり加え、続いて、両方のポリマーブロックのための一般的な溶媒中の両親媒性ブロック共重合体の溶解に関与し。選択的な溶媒（通常は水）が添加されると、ブロック共重合体は、ポリマーナノ粒子を形成する自己集合を受けます。ナノ粒子の最終的な形態（または形態の混合物）は、各ポリマーブロック、水の添加速度と共通の溶媒の性質の相対的な長さなどの要因の多数によって決定されます。しかしながら、このアプローチは、一般的にのみnanoparの製造を可能にします比較的低い固形分含有量（1重量％未満）でticlesので、その実用的なスケーラビリティ4を制限します。また、このような蠕虫状ミセル等の「中間」相の再現可能な形成は、この非球形形態5を安定化するために必要なパラメータの狭い範囲のために困難であることができます。 重合によって誘導される自己集合（PISA）のアプローチは、部分的に非常に高い固形分含量（典型的には10〜30重量％）6でナノ粒子合成を可能にする、その場で自己組織化を駆動するために、重合プロセス自体を利用して、アイゼンバーグアプローチの欠点に対処します-8。典型的なPISAアプローチにおいて、リビング重合プロセスは、反応媒体中に最初は可溶性であるが、不溶性ポリマーを形成するモノマーと溶剤可溶性マクロ開始剤（またはマクロCTA）を拡張するチェーンに使用されます。 PISAアプローチは、系統的に元の数を試験することにより、ワームのようなミセルを合成するために使用されています<html> perimentalパラメータおよび合成「ロードマップ」5,9として詳細な相図を使用して。 その挑戦的な合成にもかかわらず、彼らの球状の対応に対するそれらの興味深い特性によるワームのようなナノ粒子に大きな関心が寄せられています。例えば、我々は、PISAのアプローチを用いて合成麻薬ロード短期および長期のワームのようなミセルは球状ミセルやベシクル10と比較して、 インビトロでの細胞毒性において有意に高かっ持っていることを実証しています。他のin vivoモデル11におけるナノ粒子のアスペクト比と血液循環時間との相関関係を示しています。他のものは、適切なPISA方法論を用いてウォーム状ナノ粒子の合成は、ナノ繊維のナノスケールの絡み合いに起因する巨視的ゲルが得られることを示しています。これらのゲルは、それらの熱可逆性ゾルゲル動作12により滅菌ゲルとしての可能性を実証しました。 &quot;ontent&gt;このプロトコルは、単純に、重合中に溶液粘度を観察することによって、ワームのようなミセルの形成のその場での監視を可能にする方法を説明している。同様のワームのようなミセルゲルの以前の研究では、その臨界温度以上、これらを実証しましたナノ粒子は、可逆ウォーム球転移を受けるので、高温で易流動性分散体を形成する。これまでに、これらのシステムは、制御された重合13,14を開始するために熱的に敏感なアゾ化合物を利用しているので、ゲル化が容易にこれらのシステムにおいて観察されないことが熱重合。これらの研究から中に、それはより低い温度でPISA派生したナノ粒子を合成すると、 その場で 、このゲル化挙動の観察を可能にすることができるという仮説が立てられました。 最近ではナノ粒子を得るためにPI​​SAのプロセスを媒介する容易な室温の光重合技術の使用を報告しました異なる形態15。ここでは、可視化プロトコルは、重合中に、溶液の粘度挙動を観察することにより、ワーム状ミセルの再現可能な合成のために提示されています。容易に商業的に入手可能な発光ダイオード（LED）（λ= 460nmで、0.7ミリワット/ cm 2で）を用いて分散重合が進行します。

<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.

本研究では、二段階重合プロトコルは、PISAのアプローチ（ 図1）を用いて、蠕虫状ミセルの合成に使用されます。第1のステップでは、OEGMAの重合が続く重合工程において安定化剤として使用することができるPOEGMAマクロCTAを得て行われます。最終的にナノ粒子の形成をもたらすエタノール中PBzMAの不溶性による分散条件下でPET-RAFT重合が進行?...

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.

Photoredox触媒を用いた可視光媒介分散重合によるワームのようなミセルの簡便な合成

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 ビュー.  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.

ビデオ: 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.

RAFT制御重合によるトライ成分蛍光グリコの容易かつ効率的な準備

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

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.

カーボンナノチューブにより安定化内部自己組織化脂質粒子の簡便な調製

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.

可視光応答型光触媒としてペリレンを使用した官能ビニルモノマーの原子移動ラジカル重合

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.

4-置換キナゾリン誘導体の簡便な準備

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.

HKUST-1バニリンの合成のための不均一触媒として、

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.

π-πスタッキング相互作用によって安定化されたブロック共重合体ミセルの調製のための両親媒性共重合体のアニオン重合

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; Z</em&gt;、4<em&gt; E</em&gt;） - 電子不足アルケンと酢酸アリルとの合成によるジエナミド

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.

OCarboxyanhydrides ニッケル/亜鉛錯体による媒介のユウロピウムの開環重合

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.

合成と電気化学的 CO2削減のため単一原子の遷移金属触媒の性能評価

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.

半導体 Gyroidal 金属硫黄フレームワークの結晶化に対するチオール ビルディング ブロックの合成

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