この作品は、ヘルシンキ大学とジェーンとアートス・エルッコ財団によって支援されました。S.H.はエラスムス+EUのフェローシップに感謝します。

1. Ag-Pd/ZrO2 NPsの合成 
注: この手順では、Ag-Pd の Pd mol% は 1% に対応し、ZrO2 の Ag-Pd ローディングは 3 wt.% に対応しました。
<ol><li>ZrO2 パウダー1gを250 mLビーカーに入れます。</li>
	<li>AgNO 3(aq)(0.0059 mol/L)の50 mLと9.71 mLのK2PdCl4(aq)(0.00031 mol/L)溶液を室温で激しい磁気攪拌(500 rpm)下でビーカーに加えます。 </li>
	<li>10 mL のリジン (0.53 M) 水溶液を加えます。</li>
	<li>20分間、激しい攪拌(500rpm)下で混合物を保ちます。</li>
	<li>20分後、ピペットを使用して、1 mL/minの速度で、新たに調製したNaBH 4(aq)(0.035 M)溶液を滴下して懸濁液10mLに加えます。 プロセス全体を通して懸濁液を撹拌(500 rpm)下に保ちます。</li>
	<li>混合物を室温で30分間かき混ぜます。</li>
</ol>2. 触媒の分離と精製
<ol><li>懸濁液を遠心管に移し、10分間3,260 x gで遠心分離して混合物から固形分を分離する。</li>
	<li>慎重にピペットで液相を除去し、チューブに15 mL脱イオン水を加えます。<ol>
<li>固体の分散が得られるまで激しく振る。良好な分散が達成されない場合は、5分間超音波浴中にチューブを置きます。</li>
		<li>3,260 x g で分散液を10分間遠心する。</li>
	</ol>
</li>
	<li>洗浄手順(2.2~2.2.2.)を、脱イオン水を使用してさらに2回繰り返し、水の代わりにエタノールを使用します。</li>
	<li>エタノールを取り出し、オーブンで固体を60°Cで12時間乾燥させます。</li>
	<li>さまざまな顕微鏡、元素、分光技術によって調製されたAg-Pd/ZrO2 のNPを特徴付けます。</li>
</ol>3. Ag/ZrO2 NPsの合成 
注: この手順では、ZrO2 での Ag の荷重は 3 wt.% に対応しています。
<ol><li>ZrO2 パウダー1gを250 mLビーカーに入れます。</li>
	<li>AgNO 3(aq)(0.0059 mol/L)溶液を室温で激しい磁気攪拌(500 rpm)下でビーカーに50 mL添加します。</li>
	<li>10 mL のリジン (0.53 M) 水溶液を加えます。</li>
	<li>20分間、激しい攪拌(500rpm)下で混合物を保ちます。</li>
	<li>20分後、ピペットを使用して、1 mL/minの速度で、新たに調製したNaBH 4(aq)(0.035 M)溶液を滴下して懸濁液10mLに加えます。プロセス全体を通して懸濁液を撹拌(500 rpm)下に保ちます。</li>
	<li>混合物を室温で30分間かき混ぜます。</li>
</ol>4. 触媒の分離と精製
<ol><li>懸濁液を遠心管に移し、10分間3,260 x gで遠心分離して混合物から固形分を分離する。</li>
	<li>慎重にピペットで液相を除去し、チューブに15 mL脱イオン水を加えます。<ol>
<li>固体の分散が観察されるまで激しく振る。良好な分散が達成されない場合は、5分間超音波浴中にチューブを置きます。</li>
		<li>3,260 x g で分散液を10分間遠心する。</li>
	</ol>
</li>
	<li>洗浄手順(4.2~4.2.2.)を、脱イオン水を使用してさらに2回繰り返し、水の代わりにエタノールを使用します。</li>
	<li>エタノールを取り出し、オーブンで固体を60°Cで12時間乾燥させます。</li>
	<li>調製されたAg/ZrO2 のNPは、様々な顕微鏡、元素、分光技術によって特徴づけることができます。</li>
</ol>5. LSPR励起(光照明)下のニトロベンゼン還元に向けたプラスモニック触媒性能の検討
<ol><li>25 mL ラウンドボトムフラスコに30mgの触媒を磁気攪拌棒と一緒に入れる。</li>
	<li>ニトロベンゼン(0.03モル/L)の溶液をイソプロピルアルコール(IPA)に5 mL加えて反応器に加えます。</li>
	<li>次いで、11.22mgのKOH粉末(0.0002モル)を加える。</li>
	<li>1分間アルゴン流で懸濁液をバブリングして反応器をパージします。パージ後すぐにフラスコを密封します。</li>
	<li>温度制御された磁気撹拌機(500rpm)以上の70°Cで加熱したオイルバスに反応器を入れます。</li>
	<li>光源として425nmの波長を有する4つのLEDランプ、および0.5W/cm2の光強度を用いて管を照射する。ランプから反応フラスコまでの距離は7cmでなければなりません。</li>
	<li>活発な磁気撹拌(500rpm)下で70°Cで2.5時間反応を進める。</li>
	<li>次に、ライトを消し、反応器を開き、注射器と針を使用して1mLサンプルを採取します。0.45 μmフィルターを通してフィルター処理し、触媒微粒子を除去し、ガスクロマトグラフィーバイアルに入れ。</li>
</ol>LSPR励起(暗い状態)がない場合の反応
<ol><li>5に記載されているのと同じ手順に従うが、光照射を行わない。反応管をアルミホイルで包み、光の露出を防ぎます。</li>
</ol>ガスクロマトグラフィー(GC)分析製剤
<ol><li>約30 mmol/Lニトロベンゼン(NB)、アニリン30ミリモル/L(AN)、アゾベンゼン(AB)30ミリモル/Lを含むIPA溶液を調製します。</li>
	<li>適切な方法を使用して溶液のGC分析を実行します。カラム温度とガス流量のプログラムを変えることで、さまざまな方法でテストできます。選択した方法は、最小保持期間内の IPA、NB、AN、および AB に対応するピークを分離できる必要があります。</li>
	<li>この方法を選択したら、IPAで50mM、25mM、10mM、5 mM、2.5 mM NBの溶液セットを用意し、同じ濃度のIPAでANとABの別の溶液セットを調製します。</li>
	<li>準備されたソリューションの GC 分析を実行します。各クロマトグラムは2つのピークを提示する必要があります:高い1つはIPAに対応し、下の1つはNB、AN、またはABに対応します。各クロマトグラムについて、すべてのピークの保持時間とピーク領域をメモします。</li>
	<li>各サンプルの濃度対ピーク面積をプロットして、NB、AN、およびABのキャリブレーション曲線をトレースします。</li>
</ol>8. GC分析
<ol><li>手順 5 で収集したサンプルに対して GC 分析を実行します。と6.手順 7.2 で使用したのと同じ方法を使用します。と7.4.</li>
	<li>クロマトグラムごとに、保持時間とピーク面積をメモし、前にプロットしたキャリブレーションカーブを使用して、サンプル中のNB、AN、およびABの濃度を決定します。</li>
	<li>ニトロベンゼン変換、アニリンおよびアゾベンゼンの選択度を計算します。 <img alt="Equation 1" src="/files/ftp_upload/61712/61712eq1.jpg"> <img alt="Equation 2" src="/files/ftp_upload/61712/61712eq2.jpg"> <img alt="Equation 3" src="/files/ftp_upload/61712/61712eq3.jpg"> 最初 <img alt="Equation 4" src="/files/ftp_upload/61712/61712eq4.jpg"> のNB濃度(0.03 mol/L)、およびCNB、C AN、C ABは、それぞれ、GC分析による2.5時間反応後に、NB、AN、およびAB濃度に対応する。</li>
</ol>

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G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+Plasmon+Resonance+in+Bimetallic+Core-Shell+Nanoparticles.">Surface Plasmon Resonance in Bimetallic Core-Shell Nanoparticles.</a> Journal of Physical Chemistry C. 119 (29), 16836-16845 (2015).</li><li>Liu, Z., Huang, Y., Xiao, Q., Zhu, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+reduction+of+nitroaromatics+to+azoxy+compounds+on+supported+Ag-Cu+alloy+nanoparticles+through+visible+light+irradiation.">Selective reduction of nitroaromatics to azoxy compounds on supported Ag-Cu alloy nanoparticles through visible light irradiation.</a> Green Chemistry. 18 (3), 817-825 (2016).</li><li>Chaiseeda, K., Nishimura, S., Ebitani, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Gold+nanoparticles+supported+on+alumina+as+a+catalyst+for+surface+plasmon-enhanced+selective+reductions+of+nitrobenzene.">Gold nanoparticles supported on alumina as a catalyst for surface plasmon-enhanced selective reductions of nitrobenzene.</a> ACS Omega. 2 (10), 7066-7070 (2017).</li><li>Peiris, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal+nanoparticle+photocatalysts:+emerging+processes+for+green+organic+synthesis.">Metal nanoparticle photocatalysts: emerging processes for green organic synthesis.</a> Catalysis Science and Technology. 6 (2), 320-338 (2016).</li><li>Garc&#237;a-Garc&#237;a, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Silver-Based+Plasmonic+Catalysts+for+Carbon+Dioxide+Reduction.">Silver-Based Plasmonic Catalysts for Carbon Dioxide Reduction.</a> ACS Sustainable Chemistry and Engineering. 8 (4), 1879-1887 (2020).</li><li>Agrawal, A., Johns, R. W., Milliron, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Control+of+Localized+Surface+Plasmon+Resonances+in+Metal+Oxide+Nanocrystals.">Control of Localized Surface Plasmon Resonances in Metal Oxide Nanocrystals.</a> Annual Review of Materials Research. 47 (1), 1-31 (2017).</li><li>Lounis, S. D., Runnerstrom, E. L., Llord&#233;s, A., Milliron, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Defect+chemistry+and+Plasmon+physics+of+colloidal+metal+oxide+Nanocrystals.">Defect chemistry and Plasmon physics of colloidal metal oxide Nanocrystals.</a> Journal of Physical Chemistry Letters. 5 (9), 1564-1574 (2014).</li><li>Rej, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determining+Plasmonic+Hot+Electrons+and+Photothermal+Effects+during+H2+Evolution+with+TiN-Pt+Nanohybrids.">Determining Plasmonic Hot Electrons and Photothermal Effects during H2 Evolution with TiN-Pt Nanohybrids.</a> ACS Catalysis. 10 (9), 5261-5271 (2020).</li><li>Barragan, A. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photochemistry+of+Plasmonic+Titanium+Nitride+Nanocrystals.">Photochemistry of Plasmonic Titanium Nitride Nanocrystals.</a> The Journal of Physical Chemistry C. 123 (35), 21796-21804 (2019).</li></ol>

著者らは開示するものは何もない。

この方法で説明した知見は、Pdの固有の触媒活性(または他の触媒的な触媒的な金属ではない)が、バイメタル合金NPs35における可視光照射を介したLSPR励起によって有意に増強できることを示す。この場合、Ag(または別のプラズモニック金属)は、LSPR励起を介して可視光照射からエネルギーを収穫することができる。LSPR励起は、熱電荷キャリア(熱い電子と正孔)と局在?...

金属ナノ粒子(NPs)のいくつかの用途の中で、触媒は特別な注意を払うに値する。触媒は持続可能な未来において中心的な役割を果たし、エネルギー消費の減少、原材料の利用の改善、よりクリーンな反応条件1、2、3、4に貢献する。したがって、触媒の進歩は、化学プロセスの原子効率を高め、よりクリーンで経済的に実行可能で、より環境に優しいツールを提供することができます。銀(Ag)、金(Au)または銅(Cu)を包含する金属NPsは、これらのシステムが局在面プラズモン共鳴(LSPR)励起5、6、7、8を介してナノスケールで光と相互作用するユニークな方法から生じる可視範囲で興味深い光学特性を表示することができる。これらのNPでは、プラズモニックNPと呼ばれ、LSPRは、電子5、6、7、8の集合運動との(入ってくる電磁波からの)入射光子との共振相互作用を含む。この現象は、環境9、10、11の大きさ、形状、組成、および誘電率に依存する特性周波数で起こる。例えば、Ag、Au、およびCuの場合、これらの周波数は可視から近いIRまで、そのLSPR5、6、7、8、12、13を励起する太陽エネルギーの利用の可能性を開くことができる。
近年、プラスモニックNPsにおけるLSPR励起が、分子変換の速度を加速し、分子変換の選択性を制御するために寄与できることが実証されている5、14、15、16、17、18、19。これは、光からのエネルギーを使用して化学変換を加速、駆動、および/または制御するプラスモニック触媒と呼ばれるフィールドを生み出しました5,14,15,16,17,18,19.この文脈では、プラスモニックNPsにおけるLSPR励起が、LSPR励起熱担体と呼ばれるエネルギー熱電子および正孔の形成につながることが確立されている。これらのキャリアは、電子的または振動的活性化15、16を介して吸着された種と相互作用することができる。反応速度の増加に加えて、このプロセスは、従来の熱化学的に駆動されたプロセスを介してアクセスできない代替反応経路を提供することができ、反応選択性20、21、22、23、24、25を制御するための新しい道を開く。重要なことに、プラズモン崩壊はまた、熱放散につながる可能性があることは注目に値し、また、反応速度15、16の高速化に寄与することができるNPsの近傍の温度上昇につながる。
これらの興味深い特徴により、プラズモニック触媒は、様々な分子変換18に向けてうまく採用されている。それにもかかわらず、重要な課題は残っています。AgやAuなどのプラズモニックNPは、可視および近IR範囲で優れた光学特性を示しますが、その触媒特性は変換の範囲の点で制限されています。つまり、いくつかの変換に対して良好な触媒特性が表示されません。さらに、パラジウム(Pd)や白金(Pt)などの触媒に重要な金属は、可視または近照性の範囲でLSPR励起をサポートしていません。このギャップを埋めるために、プラスモニック金属と触媒金属を含むバイメタルNPは、効果的な戦略20、26、27、28、29を表します。これらのシステムでは、プラスモニック金属をアンテナとして用いて、光励起からLSPRを通してエネルギーを収穫し、触媒金属の分子変換を駆動、加速、制御するために使用することができます。したがって、この戦略は、我々は伝統的なプラズモニック金属NP 20、26、27、28、29を超えてプラズモニック触媒を拡張することができます。
本プロトコルは、プラスモニック触媒反応のためのプラスモニック触媒系として作用することができるZrO2(Ag-Pd/ZrO2)でサポートされるバイメタル銀パラジウム(Ag-Pd)合金NPのファシリティ合成を記述する。Ag-Pd/ZrO2 NPは、ZrO2支持に対応する金属前駆体を共含浸させることにより、次いで同時還元30を行った。このアプローチはZrO2サポートの表面に直接サイズ(直径)の約10 nmのバイメタルNPの形成につながった。このNPは、得られたAg-Pd NPsの光学特性を最大化しながら触媒金属の利用を最小限に抑えるためにPdの1モル%で構成された。ニトロベンゼンの還元のために、Ag-Pd/ZrO2 NPをプラスモニック触媒分解に適用するためのプロトコルが実証された。LSPR励起には425 nm LED照明を採用しました。ガスクロマトグラフィーは、暗色および光照射条件下での還元反応の変換および選択性をモニタリングするために行った。LSPR励起は、純粋に熱駆動条件に対するAg-Pd/ZrO2 NPにおける触媒性能および選択性の制御を強化しました。このプロトコルに記載されている方法は、ガスクロマトグラフィーと結合した単純な光触媒反応設定に基づいており、幅広い分子変換およびNPs組成物に適合させることができる。したがって、この方法は、光触媒活性の特性を、変換および反応選択性の観点から、異なるNPsの、無数の液相変換に対して可能にする。この記事は、新規参入者と現場の経験豊富な科学者の両方に重要なガイドラインと洞察を提供すると信じています。

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preparation of silver-palladium alloyed nanoparticles for plasmonic catalysis under visible-light illumination

局在した表面プラズモン共鳴(LSPR)は、さまざまな分子形変換の選択性を加速および制御することができます。これにより、これらの範囲でLSPR励起を支えるプラズモニックナノ粒子が触媒として採用される場合の反応を駆動し、制御するための持続可能な入力として、可視光または近IR光を使用する可能性が開かれます。残念ながら、パラジウム(Pd)などのいくつかの触媒金属には当てはまりません。この制限を克服する戦略の1つは、プラスモニック金属と触媒金属を含むバイメタルNPを採用することです。この場合、プラスモニック金属中のLSPR励起は、触媒成分によって駆動される加速および制御変換に寄与し得る。本明細書で報告される方法は、プラスモニック触媒系として作用するZrO2(Ag-Pd/ZrO2)で支持されるバイメタル銀パラジウム(Ag-Pd)NPsの合成に焦点を当てている。このNPは、ZrO2支持に対応する金属前駆体を共含浸させ、続いてZrO2支持体に直接バイメタルNPを形成する同時還元によって調製した。次に、Ag-Pd/ZrO2 NPを、LEDランプによる425nmの照明下でのニトロベンゼンの還元のためのプラスモニック触媒として使用した。ガスクロマトグラフィー(GC)を用いて、暗色および光照射条件下での還元反応の変換および選択性をモニタリングすることができ、非プラズモニックPdをプラスモニック金属Agで合金化した後のLSPR励起下での触媒性能の向上および制御を実証する。この技術は、幅広い分子変換およびNPs組成物に適応することができ、変換および選択性の点で異なるタイプの触媒反応のプラズモニック触媒活性の特性化に有用である。

図1Aは、純粋なZrO2酸化物(左)とAg-Pd/ZrO2のNPs(右)を含む固体試料のデジタル写真を示す。この色の色の変化は白色(ZrO2)から茶色(Ag-Pd/ZrO2)に変化し、ZrO2表面でのAg-Pd NPの堆積に関する最初の定性的証拠を提供する。図1Bは、Ag-Pd/ZrO2 NP(青色トレース)とZrO2(黒トレース)およびAg/ZrO2 NP(赤色の...

Watch this Scientific Journal Video about Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination at JoVE.com

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

ここで提示される銀パラジウム(Ag-Pd)合金ナノ粒子(NPs)の合成のためのプロトコルはZrO2(Ag-Pd/ZrO2)でサポートされています。可視光照射からエネルギーを収穫し、分子変換を加速・制御するシステムです。これは、Ag-Pd/ZrO2 NPによって触媒された光照射下でのニトロベンゼン還元によって示される。

可視光照明下におけるプラスモニック触媒のための銀パラジウム合金ナノ粒子の調製

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular ...

preparation-silver-palladium-alloyed-nanoparticles-for-plasmonic

Research

JoVE Journal

Chemistry

5.4K ビュー.  University of Helsinki. ここで提示される銀パラジウム(Ag-Pd)合金ナノ粒子(NPs)の合成のためのプロトコルはZrO2(Ag-Pd/ZrO2)でサポートされています。可視光照射からエネルギーを収穫し、分子変換を加速・制御するシステムです。これは、Ag-Pd/ZrO2 NPによって触媒された光照射下でのニトロベンゼン還元によって示される。

ビデオ: Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template&#39;s channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

This article describes the preparation of well-ordered nickel nanofoams via electroless metal deposition onto nanoporous templates obtained from self-assembled diblock copolymer based supramolecules.

ジブロック共重合体超分子からジャイロイドニッケルナノ構造

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, ...

化学

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan &#948; solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials&#39; morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by St&#246;ber&#39;s methods, which have smooth surfaces.

Silica nanoparticles were prepared using acid-catalysis of a siloxane precursor and microwave-assisted synthetic techniques resulting in the controlled growth of nanomaterials ranging from 30-250 nm in diameter. The growth dynamics can be controlled by varying the initial silicic acid concentration, time of the reaction, and temperature of reaction.

マイクロ波支援酸 - 触媒反応によりシリカナノ粒子の調製

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle ...

Synthesis of Immunotargeted Magneto-plasmonic Nanoclusters

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications including contrast enhancement in novel magnetomotive imaging modalities, simultaneous capture&#160;and detection of circulating tumor cells (CTCs),&#160;and multimodal molecular imaging combined with photothermal therapy of cancer cells. These applications have stimulated significant interest in development of protocols for synthesis of magneto-plasmonic nanoparticles with optical absorbance in the near-infrared (NIR) region and a strong magnetic moment. Here, we present a novel protocol for synthesis of such hybrid nanoparticles that is based on an oil-in-water microemulsion method. The unique feature of the protocol described herein is synthesis of magneto-plasmonic nanoparticles of various sizes from primary blocks which also have magneto-plasmonic characteristics. This approach yields nanoparticles with a high density of magnetic and plasmonic functionalities which are uniformly distributed throughout the nanoparticle volume. The hybrid nanoparticles can be easily functionalized by attaching antibodies through the Fc moiety leaving the Fab portion that is responsible for antigen binding available for targeting.

Here, we describe a protocol for synthesis of magneto-plasmonic nanoparticles with a strong magnetic moment and a strong near-infrared (NIR) absorbance. The protocol also includes antibody conjugation to the nanoparticles through the Fc moiety for various biomedical applications which require molecular specific targeting.

Immunotargeted磁気プラズモニックナノクラスターの合成

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications ...

Preparation and Characterization of SDF-1&#945;-Chitosan-Dextran Sulfate Nanoparticles

Chitosan (CS) and dextran sulfate (DS) are charged polysaccharides (glycans), which form polyelectrolyte complex-based nanoparticles when mixed under appropriate conditions. The glycan nanoparticles are useful carriers for protein factors, which facilitate the in vivo delivery of the proteins and sustain their retention in the targeted tissue. The glycan polyelectrolyte complexes are also ideal for protein delivery, as the incorporation is carried out in aqueous solution, which reduces the likelihood of inactivation of the proteins. Proteins with a heparin-binding site adhere to dextran sulfate readily, and are, in turn, stabilized by the binding. These particles are also less inflammatory and toxic when delivered in vivo. In the protocol described below, SDF-1&#945; (Stromal cell-derived factor-1&#945;), a stem cell homing factor, is first mixed and incubated with dextran sulfate. Chitosan is added to the mixture to form polyelectrolyte complexes, followed by zinc sulfate to stabilize the complexes with zinc bridges. The resultant SDF-1&#945;-DS-CS particles are measured for size (diameter) and surface charge (zeta potential). The amount of the incorporated SDF-1&#945; is determined, followed by measurements of its in vitro release rate and its chemotactic activity in a particle-bound form.

The objective of this protocol is to incorporate SDF-1&#945;, a stem cell homing factor, into dextran sulfate-chitosan nanoparticles. The resultant particles are measured for their size and zeta potential, as well as the content, activity, and in vitro release rate of SDF-1&#945; from the nanoparticles.

SDF-1α-キトサン硫酸デキストランナノ粒子の調製とキャラクタリゼーション

Chitosan (CS) and dextran sulfate (DS) are charged polysaccharides (glycans), which form polyelectrolyte complex-based nanoparticles when mixed under ...

A Simple Method for the Size Controlled Synthesis of Stable Oligomeric Clusters of Gold Nanoparticles under Ambient Conditions

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like oligomeric clusters of these yellow nanoparticles of narrow size distribution are synthesized under ambient conditions via two methods. The delay-time method controls the number of subunits in the oligoclusters by varying the time between the addition of HAuCl4 to alkaline solution and the subsequent addition of reducing agent, NaSCN. The yellow oligoclusters produced range in size from ~3 to ~25 nm. This size range can be further extended by an add-on method utilizing hydroxylated gold chloride (Na+[Au(OH4-x)Clx]-) to auto-catalytically increase the number of subunits in the as-synthesized oligocluster nanoparticles, providing a total range of 3 nm to 70 nm. The crude oligocluster preparations display narrow size distributions and do not require further fractionation for most purposes. The oligoclusters formed can be concentrated &#62;300 fold without aggregation and the crude reaction mixtures remain stable for weeks without further processing. Because these oligomeric clusters can be concentrated before derivatization they allow expensive derivatizing agents to be used economically. In addition, we present two models by which predictions of particle size can be made with great accuracy.

We describe a simple method for producing highly stable oligomeric clusters of gold nanoparticles via the reduction of chloroauric acid (HAuCl4) with sodium thiocyanate (NaSCN). The oligoclusters have a narrow size distribution and can be produced with a wide range of sizes and surface coats.

周囲条件下での金ナノ粒子の安定オリゴマークラスターのサイズ制御された合成のための簡単​​な方法

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like ...

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 ...

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 ...

A Protocol for the Production of Gliadin-cyanoacrylate Nanoparticles for Hydrophilic Coating

This article presents a protocol for the production of protein-based nanoparticles that changes the hydrophobic surface to hydrophilic by a simple spray coating. These nanoparticles are produced by the polymerization reaction of alkyl cyanoacrylate on the surface of cereal protein (gliadin) molecules. Alkyl cyanoacrylate is a monomer that instantly polymerizes at RT when it is applied to the surface of materials. Its polymerization reaction is initiated by the trace amounts of weakly basic or nucleophilic species on the surface, including moisture. Once polymerized, the polymerized alkyl cyanoacrylates show a strong affinity with the object materials because nitrile groups are in the backbone of poly (alkyl cyanoacrylate). Proteins also work as initiator for this polymerization because they contain amine groups that can initiate the polymerization of cyanoacrylate. If aggregated protein is used as an initiator, protein aggregate is surrounded by the hydrophobic poly(alkyl cyanoacrylate) chains after the polymerization reaction of alkyl cyanoacrylate. By controlling the experimental condition, particles in the nanometer range are produced. The produced nanoparticles readily adsorb to the surface of most materials including glass, metals, plastics, wood, leather, and fabrics. When the surface of a material is sprayed with the produced nanoparticle suspension and rinsed with water, the micellar structure of nanoparticle changes its conformation, and the hydrophilic proteins are exposed to the air. As a result, the nanoparticle-coated surface changes to hydrophilic.

This article presents a protocol for the production of protein-based nanoparticles that changes the hydrophobic surface to hydrophilic. The produced nanoparticle is an assembly of gliadin-cyanoacrylate diblock copolymers. Spray coating with the produced nanoparticle changes the surface of target material to a hydrophilic surface.

親水性コーティングのためのグリアジンシアノアクリレートナノ粒子の製造のためのプロトコル

This article presents a protocol for the production of protein-based nanoparticles that changes the hydrophobic surface to hydrophilic by a simple spray ...

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 ...

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared according to the methodology developed by surface organometallic chemistry (SOMC). In this framework, catalytic cycles can be determined by isolating crucial intermediates. All air-sensitive materials are handled under inert atmosphere (using gloveboxes or a Schlenk line) or high vacuum lines (HVLs, &#60;10-5 mbar). The preparation of SiO2-700 (silica dehydroxylated at 700 &#176;C) and subsequent applications (the grafting of complexes and catalytic runs) requires the use of HVLs and double-Schlenk techniques. Several well-known characterization methods are used, such as Fourier-transform infrared spectroscopy (FTIR), elemental microanalysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR), and state-of-the-art dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS). FTIR and elemental microanalysis permit scientists to establish the grafting and its stoichiometry. 1H and 13C SSNMR allows the structural determination of the hydrocarbon ligands coordination sphere. DNP SENS is an emerging powerful technique in solid characterization for the detection of poorly sensitive nuclei (15N, in our case). SiO2-700 is treated with about one equivalent of the metal precursor compared to the amount of surface silanol (0.30 mmol&#183;g-1) in pentane at room temperature. Then, volatiles are removed, and the powder samples are dried under dynamic high vacuum to afford the desired materials [(&#8801;Si-O-)Hf(&#951;2&#960;-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)]. After a thermal treatment under high vacuum, the grafted complex is converted into metal imido silica complex [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)]. [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] effectively promotes the metathesis of imines, using the combination of two imine substrates, N-(4-phenylbenzylidene)benzylamine, or N-(4-fluorobenzylidene)-4-fluoroaniline, with N-benzylidenetert-butylamine as substrates. A significantly lower conversion is observed with the blank runs; thus, the presence of the imido group in [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is correlated to the catalytic performance.

A new group IV metal catalyst for imine metathesis is prepared by grafting amine metal complex onto dehydroxylated silica. Surface metal fragments are characterized using FT-IR, elemental microanalysis, and solid-state NMR spectroscopy. Further dynamic nuclear polarization surface enhanced NMR spectroscopy experiments complement the determination of the coordination sphere.

表面有機金属化学の方法論を用いてシリカ支持触媒によるイミンメタセシス

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared ...