我々 は確認してあります。

注意: は、実験用の上着、手袋と安全メガネを着用してご使用前に製品安全データシート (MSDS) をお読みください。すべての購入した材料は、さらに精製することがなく使用されています。
1. スチレン/PFO/水性 SDS ソリューションの混合物から成るエマルジョンの調製
<ol><li>5 mM の SDS 溶液を準備するには、高純度 H2o. の 10 mL の SDS の 14.5 mg を溶解します。 注: 高純度 H2O が使用されている (抵抗 (R) 18 MΩ cm、表面張力 (γ) = = 72.0 mN m-1 25 ° C で)。</li>
	<li>攪拌棒の 10 mL バイアルにスチレンの 1.5 g、PFO、0.6 g と SDS 溶液の 5 mM の 0.9 g を追加します。 注: スキャンでは共焦点レーザー蛍光顕微鏡観察、クマリン 102 の 2.6 mg、0.062 mg カルセインの混合物に追加します。</li>
	<li>室温下で 1,150 rpm で 60 分の混合物を攪拌し、80 ° C に温度を上げる</li>
	<li>1,150 rpm で 60 分や 80 ° C の混合物をかき混ぜる</li>
</ol>2. エマルジョンからなるのスチレン/PFO/水性 SDS ソリューションの混合物を用いた高分子微粒子の作製
<ol><li>攪拌棒の 10 mL バイアルにペルオキソ二硫酸カリウムの 3.9 mg、ピレンの 2 mg、スチレンの 1.5 g、PFO、0.6 g、SDS 溶液の 5 mM の 0.9 g を追加し、ゴムキャップでそれを封印します。</li>
	<li>バブルの窒素ガスによる 30 分の注射針を通して混合物を deoxygenate します。 注意: ゆっくりと泡の大きな量を生成する窒素ガスを流れ。</li>
	<li>乳剤を準備、1,150 rpm、室温で 60 分間混合物を攪拌し、80 ° C に温度を上げる</li>
	<li>1,150 rpm で 30 分や 80 ° C の混合物をかき混ぜる</li>
	<li>テスト チューブ (3 mL) の結果のソリューションで曇り部分 (1.8 mL) に転送し、重合反応を完全に終了する 30% エタノールを追加します。</li>
	<li>超音波 (電力: 130 W、周波数: 4.2 kHz) で得られたポリマー粒子を洗浄し、2300 x g で 10 分間遠心し、10 分。</li>
	<li>ポリマー粒子を得るためには、試験管から上澄みを削除します。</li>
	<li>試験管の結果の固体に 3 mL の水を追加します。超音波 (電力: 130 W、周波数: 4.2 kHz) 10 分と 2300 x g. で 10 分間遠心するテスト チューブから上澄みを削除します。</li>
	<li>洗濯手順 (手順 2.8) を繰り返して上澄みから泡は生成できません。中空高分子微粒子の固体を入手するために水を蒸発させます。</li>
</ol>3. 中空高分子微粒子を用いたマイクロ カプセルの調製
<ol><li>中空ポリスチレン粒子 (ステップ 2.9) の 1 mg を追加し、攪拌棒 10 mL バイアルに水 4 mL。</li>
	<li>超音波 (電力: 130 W、周波数: 4.2 kHz) 水の中空粒子を分散させるために 10 分。</li>
	<li>0.1 mL の水にトルエンの分散粒子を追加し、室温下で 100 rpm で 1 時間攪拌します。テスト チューブに液体を転送します。 注意: 1 分あたり回転が増えると、粒子の形態が変形します。</li>
	<li>2300 x で 10 分の液体を遠心分離機 g マイクロ カプセルを分離するためにそれを形成します。試験管から上澄みを削除します。</li>
</ol>

<ol><li>Okubo, M., Fujibayashi, T., Terada, A. <a target="_blank" href="https://link-springer-com.remotexs.ntu.edu.sg/article/10.1007/s00396-004-1210-4">Synthesis of micron-sized, monodisperse polymer particles of disc-like and polyhedral shapes by seeded dispersion polymerization.</a> Colloid Polym Sci. 283 (7), 793-798 (2005).</li>
<li>Fujibayashi, T., Okubo, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Preparation+and+Thermodynamic+Stability+of+Micron-Sized%2C+Monodisperse+Composite+Polymer+Particles+of+Disc-like+Shapes+by+Seeded+Dispersion+Polymerization%5BTitle%5D)+AND+%22Langmuir%22%5BJournal%5D)">Preparation and Thermodynamic Stability of Micron-Sized, Monodisperse Composite Polymer Particles of Disc-like Shapes by Seeded Dispersion Polymerization.</a> Langmuir. 23 (15), 7958-7962 (2007).</li>
<li>Okubo, M., Fujibayashi, T., Yamada, M., Minami, H. <a target="_blank" href="https://link-springer-com.remotexs.ntu.edu.sg/article/10.1007/s00396-004-1240-y">Micron-sized, monodisperse, snowman/confetti-shaped polymer particles by seeded dispersion polymerization.</a> Colloid Polym Sci. 283 (9), 1041-1045 (2005).</li>
<li>Xu, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Generation+of+Monodisperse+Particles+by+Using+Microfluidics%3A+Control+over+Size%2C+Shape%2C+and+Composition%5BTitle%5D)+AND+%22Angew+Chem+Int+Ed%22%5BJournal%5D)">Generation of Monodisperse Particles by Using Microfluidics: Control over Size, Shape, and Composition.</a> Angew Chem Int Ed. 44 (5), 724-728 (2005).</li>
<li>Serra, C. A., Chang, Z. <a target="_blank" href="http://onlinelibrary.wiley.com/doi/10.1002/ceat.200800219/abstract">Microfluidic-Assisted Synthesis of Polymer Particles.</a> Chem Eng Tech. 31 (8), 1099-1115 (2008).</li>
<li>Higuchi, T., Yabu, H., Shimomura, M. <a target="_blank" href="https://www-sciencedirect-com.remotexs.ntu.edu.sg/science/article/pii/S0927775705008101">Simple preparation of hemispherical polystyrene particles.</a> Colloids Surf A. 284, 250-253 (2006).</li>
<li>Sun, Z. Q., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Nonspherical+Colloidal+Crystals+Fabricated+by+the+Thermal+Pressing+of+Colloidal+Crystal+Chips%5BTitle%5D)+AND+%22Langmuir%22%5BJournal%5D)">Nonspherical Colloidal Crystals Fabricated by the Thermal Pressing of Colloidal Crystal Chips.</a> Langmuir. 21 (20), 8987-8991 (2005).</li>
<li>Deng, Y., et al. <a target="_blank" href="http://pubs.rsc.org/en/content/articlelanding/2008/jm/b714288a">A novel approach to the construction of 3-D ordered macrostructures with polyhedral particles.</a> J Mater Chem. 18 (4), 408-415 (2008).</li>
<li>Hyuk Im, S., Jeong, U., Xia, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Polymer+hollow+particles+with+controllable+holes+in+their+surfaces%5BTitle%5D)+AND+%22Nat+Mater%22%5BJournal%5D)">Polymer hollow particles with controllable holes in their surfaces.</a> Nat Mater. 4 (9), 671-675 (2005).</li>
<li>Saito, N., Kagari, Y., Okubo, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Effect+of+Colloidal+Stabilizer+on+the+Shape+of+Polystyrene%2FPoly%28methyl+methacrylate%29+Composite+Particles+Prepared+in+Aqueous+Medium+by+the+Solvent+Evaporation+Method%5BTitle%5D)+AND+%22Langmuir%22%5BJournal%5D)">Effect of Colloidal Stabilizer on the Shape of Polystyrene/Poly(methyl methacrylate) Composite Particles Prepared in Aqueous Medium by the Solvent Evaporation Method.</a> Langmuir. 22 (22), 9397-9402 (2006).</li>
<li>Cai, P. -j, Tang, Y. -j, Wang, Y. -t, Cao, Y. -j <a target="_blank" href="https://www-sciencedirect-com.remotexs.ntu.edu.sg/science/article/pii/S0254058410004694">Fabrication of polystyrene hollow spheres in W/O/W multiple emulsions.</a> Mater Chem Phys. 124 (1), 10-12 (2010).</li>
<li>Liang, S. -S., Chen, S. -L., Chen, S. -H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Diverse+macroporous+spheres+synthesized+by+multiple+emulsion+polymerization+for+protein+analyses%5BTitle%5D)+AND+%22Chem+Commun%22%5BJournal%5D)">Diverse macroporous spheres synthesized by multiple emulsion polymerization for protein analyses.</a> Chem Commun. 47 (29), 8385-8387 (2011).</li>
<li>Kondo, Y., Yoshino, N. <a target="_blank" href="https://www-sciencedirect-com.remotexs.ntu.edu.sg/science/article/pii/S1359029405000312">Hybrid fluorocarbon/hydrocarbon surfactants.</a> Curr Opin Colloid Interface Sci. 10 (3-4), 88-93 (2005).</li>
<li>Takahashi, Y., Kondo, Y., Schmidt, J., Talmon, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Self-Assembly+of+a+Fluorocarbon-Hydrocarbon+Hybrid+Surfactant%3A+Dependence+of+Morphology+on+Surfactant+Concentration+and+Time%5BTitle%5D)+AND+%22J+Phys+Chem+B%22%5BJournal%5D)">Self-Assembly of a Fluorocarbon-Hydrocarbon Hybrid Surfactant: Dependence of Morphology on Surfactant Concentration and Time.</a> J Phys Chem B. 114 (42), 13319-13325 (2010).</li>
<li>Takahashi, Y., Nasu, Y., Aramaki, K., Kondo, Y. <a target="_blank" href="https://www-sciencedirect-com.remotexs.ntu.edu.sg/science/article/pii/S0022113912003429">Unusual viscoelastic behavior of aqueous solutions of fluorocarbon-hydrocarbon hybrid surfactant and its morphological transformations.</a> J Fluor Chem. 145 (0), 141-147 (2013).</li>
<li>Yoshino, N., et al. <a target="_blank" href="http://pubs.acs.org/doi/abs/10.1021/la00002a016">Syntheses of Hybrid Anionic Surfactants Containing Fluorocarbon and Hydrocarbon Chains.</a> Langmuir. 11 (2), 466-469 (1995).</li>
<li>Zarzar, L. D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Dynamically+reconfigurable+complex+emulsions+via+tunable+interfacial+tensions%5BTitle%5D)+AND+%22Nature%22%5BJournal%5D)">Dynamically reconfigurable complex emulsions via tunable interfacial tensions.</a> Nature. 518 (7540), 520-524 (2015).</li>
</ol>

何を開示する必要があります。

10 wt % 水溶液の SDS 濃度の重量分率とスチレンと PFO の任意の重量分率上スチレン、PFO のヤヌス液滴を含むエマルジョンが得られました。ヤヌス液滴を含むエマルジョンの様々 な重量分画は、30 分間重合されている、中空のポリスチレン粒子はすべての成分を得られます。これらの結果を示すプロトコルがここでは単純なを示した。さらに、直径、穴のサイズ、穴中空ポリスチレン粒子量は、ここで説明したメソッドでは、重合時間によって制御できます。
私達は中空粒子の作製のための次のメカニズムを提案します。80 ° C の水溶液の SDS ソリューション、スチレン、および PFO の混合物を含む O/W エマルションに形成されたスチレンと PFO 成るヤヌス油滴PFO の液滴は、スチレン液滴の表面にあります。KPS、重合の創始者は水相に溶けるため、スチレン ・水性の SDS 溶液界面重合が促進されます。重合性グループを持たない PFO がその温度でエマルジョンに残ったに対し、スチレン三元系のエマルジョンでは 80 ° c、ポリスチレン重合しました。重合が終了した後は、ポリスチレン粒子の穴が PFO の除去によって結成されました。だから、表面に孔を有する中空カップ型ポリスチレン粒子は、スチレン、PFO、すべて重合時間の捏造いつでも重量分率だった。
90 分のラジカル重合により作製した中空のポリスチレン粒子にトルエンの少量を追加する中空のポリスチレン粒子の穴をシールをもたらします。この現象は、ヒョクら9によって報告と一致。イーサ方式は粒子の水性材料を含めることができます。
この記事では、スチレン、PFO、相互に混和性であるから成るヤヌス油滴を用いた中空高分子微粒子の作製方法を説明してきました。さまざまなアプリケーションで自分の潜在的な使用のため、非真球状ポリマー粒子の調製法はすでに検討されています。炭化水素油、フッ素油のヤヌス油滴を使用してこの戦略は、モノマーとドラッグデリバリー システムの様々 なタイプから非球状高分子微粒子の作製に適用されます。

真球状ポリマー微粒子は、各種産業分野で広く使用されている、それはよく知られているディンプル粒子、半球、ディスク、および楕円、シード重合1,2,で準備されていること3、特定のジオメトリの4、5マイクロリアクターを用いた非球形モノマー液滴の重合自己組織化高分子6、再沈と真球状ポリマーの変形を使用して外部の機械によって粒子は、7、8を強制します。真球状ポリマー粒子の溶媒9,10および複数のエマルジョンを使用して重合に腫れてから良溶媒の蒸発ミクロン サイズの中空ポリマー粒子を作製した特に、11,12。
この作品は、高分子微粒子の作製における炭化水素、フッ素オイルの相互の不混和現象の利用状況に着目します。ハイブリッド界面活性剤分子にフッ化炭素鎖と炭化水素鎖があります。以前は、我々 は従来の界面活性剤13,14,15で観察されるないハイブリッド界面活性剤の特徴を報告しています。互いに溶け合わない16炭化水素油、フッ素油、界面活性剤水溶液のソリューションを使用してエマルジョンも検討しました。ただし、エマルジョン17の研究は非常に少ないがあります。これらの研究は、炭化水素油とフッ素油界面活性剤水溶液のソリューションから成る油滴の形態を説明しています。
ここでは、炭化水素油、フッ素油、水性ナトリウム (SDS) ドデシル硫酸溶液から成るエマルションの油滴を用いたリビングラジカル重合法により中空高分子微粒子の作製の詳細なプロトコルを示す.非真球状ポリマー粒子の調製のための従来とは異なる新たな戦略を提案します。このメソッドことができます単に短時間で中空ポリマー粒子を製造します。さらに、中空ポリマー粒子を介してマイクロ カプセルの調製のプロトコルが表示されます。

<table><tbody><tr><td>&lt;strong&gt;Material&lt;/strong&gt;</td><td></td><td></td><td></td></tr><tr><td>Sodium dodecylsulfate, 95.0%</td><td>Wako Pure Chemical Industries, Ltd.</td><td>192-08672</td><td></td></tr><tr><td>Styrene, 99.0%</td><td>Tokyo Chemical Industry Co. Ltd.</td><td>S0095</td><td></td></tr><tr><td>Perfluorooctane, 99%</td><td>Fluorochem Ltd.</td><td>8706</td><td></td></tr><tr><td>Coumarin 102, 97.0%</td><td>Tokyo Chemical Industry Co. Ltd.</td><td>C2267</td><td></td></tr><tr><td>Calcein</td><td>Dojindo Molecular Technologies, Inc.</td><td>C001</td><td></td></tr><tr><td>Potassium peroxodisulfate, 98.0%</td><td>Kanto Chemical Co., Inc.</td><td>32375-30</td><td></td></tr><tr><td>Pyrene, 97.0%</td><td>Wako Pure Chemical Industries, Ltd.</td><td>167-05302</td><td></td></tr><tr><td>Ethanol, 99.5%</td><td>Kanto Chemical Co., Inc.</td><td>14033-00</td><td></td></tr><tr><td>Toluene, 99.5%</td><td>Kanto Chemical Co., Inc.</td><td>40180-00</td><td></td></tr><tr><td>&lt;strong&gt;Name&lt;/strong&gt;</td><td>&lt;strong&gt;Company&lt;/strong&gt;</td><td>&lt;strong&gt;Catalog Number&lt;/strong&gt;</td><td>&lt;strong&gt;Comments&lt;/strong&gt;</td></tr><tr><td>&lt;strong&gt;Equipment&lt;/strong&gt;</td><td></td><td></td><td></td></tr><tr><td>Scanning Electron Microscope</td><td>Hitachi High-Technologies Corporation</td><td>S-4800</td><td></td></tr><tr><td>Scanning Transmission Electron Microscope</td><td>Hitachi High-Technologies Corporation</td><td>S-4800</td><td></td></tr><tr><td>Ultrasonic cleaner</td><td>Branson Ultrasonics, Emerson Japan, Ltd.</td><td>Model 3510</td><td></td></tr><tr><td>Centrifuge</td><td>AS ONE Corporation</td><td>CN-1050</td><td></td></tr></tbody></table>

preparation of hollow polystyrene particles and microcapsules by radical polymerization of janus droplets consisting of hydrocarbon and fluorocarbon oils

この記事で我々 は中空粒子と炭化水素油 (スチレン) とフッ素オイルから成る油滴を用いたマイクロ カプセルの製造方法を示している (ペルフルオロ-n-オクタン、PFO) (ドデシル硫酸ナトリウム、界面活性剤水溶液のSDS) ソリューション。フッ素オイルが炭化水素油を混和性、2 つのオイルが分かれています。エマルジョンは 80 ° C のスチレン/PFO/SDS ソリューション水溶液を攪拌により作製しました。エマルジョンの種類と、エマルジョン液滴の形態は、光学顕微鏡と走査型共焦点レーザー蛍光顕微鏡で観察されます。互いに溶け合わないスチレンと PFO 成るヤヌス型形態と油滴が SDS 水溶液中で形成されることがわかった。スチレン/PFO/SDS 水溶液の 80 ° C の三元系混合物のラジカル重合によるポリスチレン粒子を作製します。ポリスチレンの形態を走査電子顕微鏡、走査透過電子顕微鏡観察により確認します。これらの観察は、表面の単一孔を有する中空粒子の調製を表示します。私たちの知る限りでは、このメソッドは、炭化水素、フッ素オイルの不混和現象を使用して新たな戦略です。中空の粒子は、マイクロ カプセルの調製にも適用できます。

形態とスチレン、PFO、および 5 mM SDS 溶液 (図 1) から成るエマルジョン液滴の組成を決定する光と走査共焦点レーザー蛍光顕微鏡観察を行った。走査電子顕微鏡 (SEM) と走査透過電子顕微鏡 (STEM) 観察は、マイクロ カプセル (図 2) と中空粒子の形成を示した。
DIC とスチレン/PFO/SDS 水溶液の混合から成るエマルジョンの共焦点レーザー蛍光顕微鏡画像ことを示す連続相水溶液 SDS カルセインに対応する緑の蛍光性を認めたので連続相、したがって、水中油型エマルションが形成される (図 1 aと1 b)。これらの画像は、油滴が相互に混和性であるスチレン、PFO で構成されることも示しています。DIC とクマリン 102 を含むエマルジョンの共焦点蛍光顕微鏡画像は、PFO の液滴の水とスチレン液滴間のインターフェイスであることを明らかにします。スチレン、PFO、および SDS ヤヌスを含む 5 mM 形エマルジョン水溶液の混合油滴、スチレン、PFO から成っています。
スチレン/PFO/5 mM SDS 溶液のエマルジョンのラジカル重合により作製した高分子微粒子の SEM および幹のイメージは地図表面に孔を有する中空非球形粒子の調製 (図 2 aと2 b). 生成速度、直径、および中空ポリスチレン粒子の穴の大きさ、SEM と幹を通じて 200 粒子を観察することによって評価されます。SEM 観察から推定した平均の直径は、1.3 μ m です。サイズは、動的光散乱の観測から推定したポリマー粒子の直径と一致。形成率は約 100% です。平均孔径と中空粒子の穴のボリュームは、それぞれ 0.8 ± 0.4 μ m と 0.9 ± 0.4 μ m3。したがって、0.8 μ m の孔を有する中空のポリスチレン粒子をエマルジョンでスチレンを含むヤヌス液滴のラジカル重合により作製しました。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56922/56922fig1.jpg"> 図 1。スチレン、PFO、および 5 mM SDS 溶液から成るエマルジョン液滴の形態。(a)の差動干渉の対照 (DIC) と水溶液の蛍光カルセインを含むエマルジョンの(b)共焦点レーザー蛍光顕微鏡画像。(c) DIC および(d)共焦点レーザー蛍光顕微鏡画像の油溶性蛍光クマリン 102 を含むエマルジョン。<a href="//cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56922/56922fig1large.jpg" target="_blank">この図の拡大版を表示するのにはここをクリックしてください</a>。
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56922/56922fig2.jpg"> 図 2。スチレン、PFO、および 5 mM SDS 溶液から成るエマルジョンを用いて作製したマイクロ カプセルと中空のポリスチレン粒子の形態。(a)中空ポリスチレン粒子の SEM および(b)の幹のイメージ。マイクロ カプセルの(c) SEM および(d)幹イメージ<a href="//cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56922/56922fig2large.jpg" target="_blank">この図の拡大版を表示するのにはここをクリックしてください</a>。

Watch this Scientific Journal Video about Preparation of Hollow Polystyrene Particles and Microcapsules by Radical Polymerization of Janus Droplets Consisting of Hydrocarbon and Fluorocarbon Oils at J

Preparation of Hollow Polystyrene Particles and Microcapsules by Radical Polymerization of Janus Droplets Consisting of Hydrocarbon and Fluorocarbon Oils

中空のポリスチレン粒子と炭化水素とフッ素オイルから成るヤヌス液滴のラジカル重合によるマイクロ カプセルの調製

中空高分子微粒子とスチレン、ペルフルオロ-nから成るエマルジョンを用いたリビングラジカル重合法によるマイクロ カプセルの作製のためのプロトコル-オクタンと水性 SDS (ドデシル硫酸ナトリウム) の解決策を提示します。

In this article, we have demonstrated a method for producing hollow particles and microcapsules using oil droplets consisting of hydrocarbon oil (styrene) ...

preparation-hollow-polystyrene-particles-microcapsules-radical

Nanyang Technological University

Research

JoVE Journal

Chemistry

9.9K ビュー.  Tokyo University of Science. 中空高分子微粒子とスチレン、ペルフルオロ-nから成るエマルジョンを用いたリビングラジカル重合法によるマイクロ カプセルの作製のためのプロトコル-オクタンと水性 SDS (ドデシル硫酸ナトリウム) の解決策を提示します。

ビデオ: Preparation of Hollow Polystyrene Particles and Microcapsules by Radical Polymerization of Janus Droplets Consisting of Hydrocarbon and Fluorocarbon Oils

Synthesis of Poly(N-isopropylacrylamide) Janus Microhydrogels for Anisotropic Thermo-responsiveness and Organophilic/Hydrophilic Loading Capability

Janus microparticles are compartmentalized particles with differing molecular structures and/or functionality on each of their two sides. Because of this unique property, Janus microparticles have been recognized as a new class of materials, thereby attracting a great deal of attention from various research fields. The versatility of these microparticles has been exemplified through their uses as building blocks for self-assembly, electrically responsive actuators, emulsifiers for painting and cosmetics, and carriers for drug delivery. This study introduces a detailed protocol that explicitly describes a synthetic method for designing novel Janus microhydrogels composed of a single base material, poly(N-isopropylacrylamide) (PNIPAAm). Janus microdroplets are firstly generated via a hydrodynamic focusing microfluidic device (HFMD) based on the separation of a supersaturated aqueous NIPAAm monomer solution and subsequently polymerized through exposure to UV irradiation. The resulting Janus microhydrogels were found to be entirely composed of the same base material, featured an easily identifiable compartmentalized morphology, and exhibited anisotropic thermo-responsiveness and organophilic/hydrophilic loading capability. We believe that the proposed method introduces a novel hydrogel platform with the potential for advanced synthesis of multi-functional Janus microhydrogels.

Synthesis of PolyN-isopropylacrylamide Janus Microhydrogels for Anisotropic Thermo-responsiveness and Organophilic/Hydrophilic Loading Capability

We present a protocol to synthesize Janus microhydrogels composed entirely of the same base material, poly(N-isopropylacrylamide) (PNIPAAm), with a clearly compartmentalized structure base on the phase separation of a supersaturated NIPAAm monomer solution. The synthesized Janus microhydrogels show unique properties such as anisotropic thermo-responsiveness and organophilic/hydrophilic loading capability.

ポリの合成（<em&gt; N</em&gt; -isopropylacrylamide）異方性熱応答性および有機性/親水性ローディング機能のためのヤヌスMicrohydrogels

Janus microparticles are compartmentalized particles with differing molecular structures and/or functionality on each of their two sides. Because of this ...

化学

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

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

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

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

ポリスチレンを使用しました<em&gt;ブロック</em&gt; - ポリ（アクリル酸）は、それらのホモポリマーおよび共重合用単量体として金属ナノ粒子をコーティングを採用

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

High-throughput Synthesis of Carbohydrates and Functionalization of Polyanhydride Nanoparticles

Transdisciplinary approaches involving areas such as material design, nanotechnology, chemistry, and immunology have to be utilized to rationally design efficacious vaccines carriers. Nanoparticle-based platforms can prolong the persistence of vaccine antigens, which could improve vaccine immunogenicity1. Several biodegradable polymers have been studied as vaccine delivery vehicles1; in particular, polyanhydride particles have demonstrated the ability to provide sustained release of stable protein antigens and to activate antigen presenting cells and modulate immune responses2-12.
The molecular design of these vaccine carriers needs to integrate the rational selection of polymer properties as well as the incorporation of appropriate targeting agents. High throughput automated fabrication of targeting ligands and functionalized particles is a powerful tool that will enhance the ability to study a wide range of properties and will lead to the design of reproducible vaccine delivery devices.
The addition of targeting ligands capable of being recognized by specific receptors on immune cells has been shown to modulate and tailor immune responses10,11,13 C-type lectin receptors (CLRs) are pattern recognition receptors (PRRs) that recognize carbohydrates present on the surface of pathogens. The stimulation of immune cells via CLRs allows for enhanced internalization of antigen and subsequent presentation for further T cell activation14,15. Therefore, carbohydrate molecules play an important role in the study of immune responses; however, the use of these biomolecules often suffers from the lack of availability of structurally well-defined and pure carbohydrates. An automation platform based on iterative solution-phase reactions can enable rapid and controlled synthesis of these synthetically challenging molecules using significantly lower building block quantities than traditional solid-phase methods16,17.
Herein we report a protocol for the automated solution-phase synthesis of oligosaccharides such as mannose-based targeting ligands with fluorous solid-phase extraction for intermediate purification. After development of automated methods to make the carbohydrate-based targeting agent, we describe methods for their attachment on the surface of polyanhydride nanoparticles employing an automated robotic set up operated by LabVIEW as previously described10. Surface functionalization with carbohydrates has shown efficacy in targeting CLRs10,11 and increasing the throughput of the fabrication method to unearth the complexities associated with a multi-parametric system will be of great value (Figure 1a).

In this article, a high throughput method is presented for the synthesis of oligosaccharides and their attachment to the surface of polyanhydride nanoparticles for further use in targeting specific receptors on antigen presenting cells.

無水物ナノ粒子のハイスループット糖鎖の合成と機能化

Transdisciplinary approaches involving areas such as material design, nanotechnology, chemistry, and immunology have to be utilized to rationally design ...

生物工学

High Throughput Single-cell and Multiple-cell Micro-encapsulation

Microfluidic encapsulation methods have been previously utilized to capture cells in picoliter-scale aqueous, monodisperse drops, providing confinement from a bulk fluid environment with applications in high throughput screening, cytometry, and mass spectrometry. We describe a method to not only encapsulate single cells, but to repeatedly capture a set number of cells (here we demonstrate one- and two-cell encapsulation) to study both isolation and the interactions between cells in groups of controlled sizes. By combining drop generation techniques with cell and particle ordering, we demonstrate controlled encapsulation of cell-sized particles for efficient, continuous encapsulation. Using an aqueous particle suspension and immiscible fluorocarbon oil, we generate aqueous drops in oil with a flow focusing nozzle. The aqueous flow rate is sufficiently high to create ordering of particles which reach the nozzle at integer multiple frequencies of the drop generation frequency, encapsulating a controlled number of cells in each drop. For representative results, 9.9 &mu;m polystyrene particles are used as cell surrogates. This study shows a single-particle encapsulation efficiency Pk=1 of 83.7% and a double-particle encapsulation efficiency Pk=2 of 79.5% as compared to their respective Poisson efficiencies of 39.3% and 33.3%, respectively. The effect of consistent cell and particle concentration is demonstrated to be of major importance for efficient encapsulation, and dripping to jetting transitions are also addressed. 
Introduction 
Continuous media aqueous cell suspensions share a common fluid environment which allows cells to interact in parallel and also homogenizes the effects of specific cells in measurements from the media. High-throughput encapsulation of cells into picoliter-scale drops confines the samples to protect drops from cross-contamination, enable a measure of cellular diversity within samples, prevent dilution of reagents and expressed biomarkers, and amplify signals from bioreactor products. Drops also provide the ability to re-merge drops into larger aqueous samples or with other drops for intercellular signaling studies.1,2 The reduction in dilution implies stronger detection signals for higher accuracy measurements as well as the ability to reduce potentially costly sample and reagent volumes.3 Encapsulation of cells in drops has been utilized to improve detection of protein expression,4 antibodies,5,6 enzymes,7 and metabolic activity8 for high throughput screening, and could be used to improve high throughput cytometry.9 Additional studies present applications in bio-electrospraying of cell containing drops for mass spectrometry10 and targeted surface cell coatings.11 Some applications, however, have been limited by the lack of ability to control the number of cells encapsulated in drops. Here we present a method of ordered encapsulation12 which increases the demonstrated encapsulation efficiencies for one and two cells and may be extrapolated for encapsulation of a larger number of cells.
To achieve monodisperse drop generation, microfluidic "flow focusing" enables the creation of controllable-size drops of one fluid (an aqueous cell mixture) within another (a continuous oil phase) by using a nozzle at which the streams converge.13 For a given nozzle geometry, the drop generation frequency f and drop size can be altered by adjusting oil and aqueous flow rates Qoil and Qaq. As the flow rates increase, the flows may transition from drop generation to unstable jetting of aqueous fluid from the nozzle.14 
When the aqueous solution contains suspended particles, particles become encapsulated and isolated from one another at the nozzle. For drop generation using a randomly distributed aqueous cell suspension, the average fraction of drops Dk containing k cells is dictated by Poisson statistics, where Dk = &lambda;k exp(-&lambda;)/(k!) and &lambda; is the average number of cells per drop. The fraction of cells which end up in the "correctly" encapsulated drops is calculated using Pk = (k x Dk)/&Sigma;(k' x Dk'). The subtle difference between the two metrics is that Dk relates to the utilization of aqueous fluid and the amount of drop sorting that must be completed following encapsulation, and Pk relates to the utilization of the cell sample. As an example, one could use a dilute cell suspension (low &lambda;) to encapsulate drops where most drops containing cells would contain just one cell. While the efficiency metric Pk would be high, the majority of drops would be empty (low Dk), thus requiring a sorting mechanism to remove empty drops, also reducing throughput.15
Combining drop generation with inertial ordering provides the ability to encapsulate drops with more predictable numbers of cells per drop and higher throughputs than random encapsulation. Inertial focusing was first discovered by Segre and Silberberg16 and refers to the tendency of finite-sized particles to migrate to lateral equilibrium positions in channel flow. Inertial ordering refers to the tendency of the particles and cells to passively organize into equally spaced, staggered, constant velocity trains. Both focusing and ordering require sufficiently high flow rates (high Reynolds number) and particle sizes (high Particle Reynolds number).17,18 Here, the Reynolds number Re =uDh/&nu; and particle Reynolds number Rep =Re(a/Dh)2, where u is a characteristic flow velocity, Dh [=2wh/(w+h)] is the hydraulic diameter, &nu; is the kinematic viscosity, a is the particle diameter, w is the channel width, and h is the channel height. Empirically, the length required to achieve fully ordered trains decreases as Re and Rep increase. Note that the high Re and Rep requirements (for this study on the order of 5 and 0.5, respectively) may conflict with the need to keep aqueous flow rates low to avoid jetting at the drop generation nozzle. Additionally, high flow rates lead to higher shear stresses on cells, which are not addressed in this protocol. The previous ordered encapsulation study demonstrated that over 90% of singly encapsulated HL60 cells under similar flow conditions to those in this study maintained cell membrane integrity.12 However, the effect of the magnitude and time scales of shear stresses will need to be carefully considered when extrapolating to different cell types and flow parameters. The overlapping of the cell ordering, drop generation, and cell viability aqueous flow rate constraints provides an ideal operational regime for controlled encapsulation of single and multiple cells.
Because very few studies address inter-particle train spacing,19,20 determining the spacing is most easily done empirically and will depend on channel geometry, flow rate, particle size, and particle concentration. Nonetheless, the equal lateral spacing between trains implies that cells arrive at predictable, consistent time intervals. When drop generation occurs at the same rate at which ordered cells arrive at the nozzle, the cells become encapsulated within the drop in a controlled manner. This technique has been utilized to encapsulate single cells with throughputs on the order of 15 kHz,12 a significant improvement over previous studies reporting encapsulation rates on the order of 60-160 Hz.4,15 In the controlled encapsulation work, over 80% of drops contained one and only one cell, a significant efficiency improvement over Poisson (random) statistics, which predicts less than 40% efficiency on average.12
In previous controlled encapsulation work,12 the average number of particles per drop &lambda; was tuned to provide single-cell encapsulation. We hypothesize that through tuning of flow rates, we can efficiently encapsulate any number of cells per drop when &lambda; is equal or close to the number of desired cells per drop. While single-cell encapsulation is valuable in determining individual cell responses from stimuli, multiple-cell encapsulation provides information relating to the interaction of controlled numbers and types of cells. Here we present a protocol, representative results using polystyrene microspheres, and discussion for controlled encapsulation of multiple cells using a passive inertial ordering channel and drop generation nozzle.

Combining monodisperse drop generation with inertial ordering of cells and particles, we describe a method to encapsulate a desired number of cells or particles in a single drop at kHz rates. We demonstrate efficiencies twice exceeding those of unordered encapsulation for single- and double-particle drops.

ハイスループットマイクロカプセル化シングルセルと複数セル

Microfluidic encapsulation methods have been previously utilized to capture cells in picoliter-scale aqueous, monodisperse drops, providing confinement ...

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.

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 ...

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 ...

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.

光共振器およびレーザ応用のためのポリマーマイクロスフェアの作製

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

工学

Microfluidic Preparation of Liquid Crystalline Elastomer Actuators

This paper focuses on the microfluidic process (and its parameters) to prepare actuating particles from liquid crystalline elastomers. The preparation usually consists in the formation of droplets containing low molar mass liquid crystals at elevated temperatures. Subsequently, these particle precursors are oriented in the flow field of the capillary and solidified by a crosslinking polymerization, which produces the final actuating particles. The optimization of the process is necessary to obtain the actuating particles and the proper variation of the process parameters (temperature and flow rate) and allows variations of size and shape (from oblate to strongly prolate morphologies) as well as the magnitude of actuation. In addition, it is possible to vary the type of actuation from elongation to contraction depending on the director profile induced to the droplets during the flow in the capillary, which again depends on the microfluidic process and its parameters. Furthermore, particles of more complex shapes, like core-shell structures or Janus particles, can be prepared by adjusting the setup. By the variation of the chemical structure and the mode of crosslinking (solidification) of the liquid crystalline elastomer, it is also possible to prepare actuating particles triggered by heat or UV-vis irradiation.

This article describes the microfluidic process and parameters to prepare actuating particles from liquid crystalline elastomers. This process allows the preparation of actuating particles and the variation of their size and shape (from oblate to strongly prolate, core-shell, and Janus morphologies) as well as the magnitude of actuation.

液晶エラストマーのアクチュエータのマイクロの準備

This paper focuses on the microfluidic process (and its parameters) to prepare actuating particles from liquid crystalline elastomers. The preparation ...

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.

生分解性ブロック共重合体の結晶化駆動自己組織化による単分散円筒ナノ粒子の合成

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

A Droplet-Based Microfluidic Approach and Microsphere-PCR Amplification for Single-Stranded DNA Amplicons

Droplet-based microfluidics enable the reliable production of homogeneous microspheres in the microfluidic channel, providing controlled size and morphology of the obtained microsphere. A microsphere copolymerized with an acrydite-DNA probe was successfully fabricated. Different methods such as asymmetric PCR, exonuclease digestion, and isolation on streptavidin-coated magnetic beads can be used to synthesize single-stranded DNA (ssDNA). However, these methods cannot efficiently use large amounts of highly purified ssDNA. Here, we describe a microsphere-PCR protocol detailing how ssDNA can be efficiently amplified and separated from dsDNA simply by pipetting from a PCR reaction tube. The amplification of ssDNA can be applied as potential reagents for the DNA microarray and DNA-SELEX (Systematic evolution of ligands by exponential enrichment) processes.

This work provides a method for the fabrication of droplet-based microfluidic platforms and the application of polyacrylamide microspheres for microsphere-PCR amplification. The microsphere-PCR method makes it possible to obtain single-stranded DNA amplicons without separating double-stranded DNA.

中空のポリスチレン粒子と炭化水素とフッ素オイルから成るヤヌス液滴のラジカル重合によるマイクロカプセルの調製

要約

さらに動画を探す

ポリの合成（

ポリスチレンを使用しました

無水物ナノ粒子のハイスループット糖鎖の合成と機能化

ハイスループットマイクロカプセル化シングルセルと複数セル

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

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

光共振器およびレーザ応用のためのポリマーマイクロスフェアの作製

液晶エラストマーのアクチュエータのマイクロの準備

生分解性ブロック共重合体の結晶化駆動自己組織化による単分散円筒ナノ粒子の合成

マイクロ液滴手法と一本鎖 DNA 産物の微粒子に PCR 増幅

中空のポリスチレン粒子と炭化水素とフッ素オイルから成るヤヌス液滴のラジカル重合によるマイクロ カプセルの調製

要約

さらに動画を探す

ポリの合成（

ポリスチレンを使用しました

無水物ナノ粒子のハイスループット糖鎖の合成と機能化

ハイスループットマイクロカプセル化シングルセルと複数セル

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

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

光共振器およびレーザ応用のためのポリマーマイクロスフェアの作製

液晶エラストマーのアクチュエータのマイクロの準備

生分解性ブロック共重合体の結晶化駆動自己組織化による単分散円筒ナノ粒子の合成

マイクロ液滴手法と一本鎖 DNA 産物の微粒子に PCR 増幅

中空のポリスチレン粒子と炭化水素とフッ素オイルから成るヤヌス液滴のラジカル重合によるマイクロカプセルの調製