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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<li>Liu, Z., Huang, Y., Xiao, Q., Zhu, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Selective+reduction+of+nitroaromatics+to+azoxy+compounds+on+supported+Ag-Cu+alloy+nanoparticles+through+visible+light+irradiation%5BTitle%5D)+AND+%22Green+Chemistry%22%5BJournal%5D)">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/pubmed?term=((Gold+nanoparticles+supported+on+alumina+as+a+catalyst+for+surface+plasmon-enhanced+selective+reductions+of+nitrobenzene%5BTitle%5D)+AND+%22ACS+Omega%22%5BJournal%5D)">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/pubmed?term=((Metal+nanoparticle+photocatalysts%3A+emerging+processes+for+green+organic+synthesis%5BTitle%5D)+AND+%22Catalysis+Science+and+Technology%22%5BJournal%5D)">Metal nanoparticle photocatalysts: emerging processes for green organic synthesis.</a> Catalysis Science and Technology. 6 (2), 320-338 (2016).</li>
<li>García-García, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Silver-Based+Plasmonic+Catalysts+for+Carbon+Dioxide+Reduction%5BTitle%5D)+AND+%22ACS+Sustainable+Chemistry+and+Engineering%22%5BJournal%5D)">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/pubmed?term=((Control+of+Localized+Surface+Plasmon+Resonances+in+Metal+Oxide+Nanocrystals%5BTitle%5D)+AND+%22Annual+Review+of+Materials+Research%22%5BJournal%5D)">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., Llordés, A., Milliron, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Defect+chemistry+and+Plasmon+physics+of+colloidal+metal+oxide+Nanocrystals%5BTitle%5D)+AND+%22Journal+of+Physical+Chemistry+Letters%22%5BJournal%5D)">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/pubmed?term=((Determining+Plasmonic+Hot+Electrons+and+Photothermal+Effects+during+H2+Evolution+with+TiN-Pt+Nanohybrids%5BTitle%5D)+AND+%22ACS+Catalysis%22%5BJournal%5D)">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/pubmed?term=((Photochemistry+of+Plasmonic+Titanium+Nitride+Nanocrystals%5BTitle%5D)+AND+%22The+Journal+of+Physical+Chemistry+C%22%5BJournal%5D)">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。

<table><tbody><tr><td>2-Propanol (anhydrous, 99.5%)</td><td>Sigma-Aldrich</td><td>278475</td><td>CAS Number 67-63-0</td></tr><tr><td>Aniline (for synthesis)</td><td>Sigma-Aldrich</td><td>8.22256</td><td>CAS Number 62-53-3</td></tr><tr><td>Azobenzene (98%)</td><td>Sigma-Aldrich</td><td>424633</td><td>CAS Number 103-33-3</td></tr><tr><td>Ethanol</td><td>Honeywell</td><td>32221</td><td>CAS Number 64-17-5</td></tr><tr><td>Hydrochloric acid (37%)</td><td>VWR</td><td>PRLSMC310066</td><td>CAS Number 7647-01-0</td></tr><tr><td>L-Lysine (crystallized, &amp;ge;98.0% (NT))</td><td>Sigma-Aldrich</td><td>62840</td><td>CAS Number 56-87-1</td></tr><tr><td>Nitric acid (65%)</td><td>Merck</td><td>100456</td><td>CAS Number 7697-37-2</td></tr><tr><td>Nitrobenzene</td><td>Sigma-Aldrich</td><td>8.06770</td><td>CAS Number 98-95-3</td></tr><tr><td>Potassium hydroxide</td><td>Fisher</td><td>10448990</td><td>CAS Number 1310-58-3</td></tr><tr><td>Potassium tetrachloropalladate (II) (98%)</td><td>Sigma-Aldrich</td><td>205796</td><td>CAS Number 10025-98-6</td></tr><tr><td>Silver nitrate (ACS reagent, &amp;ge;99.0%)</td><td>Sigma-Aldrich</td><td>209139</td><td>CAS Number 7761-88-8</td></tr><tr><td>Sodium borohydride (fine granular for synthesis)</td><td>Sigma-Aldrich</td><td>8.06373</td><td>CAS Number 16940-66-2</td></tr><tr><td>Zirconium (IV) oxide (nanopowder, &amp;lt;100 nm particle size (TEM))</td><td>Sigma-Aldrich</td><td>544760</td><td>CAS Number 1314-23-4</td></tr></tbody></table>

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

Evaluating Plasmonic Transport in Current-carrying Silver Nanowires

Plasmonics is an emerging technology capable of simultaneously transporting a plasmonic signal and an electronic signal on the same information support1,2,3. In this context, metal nanowires are especially desirable for realizing dense routing networks4. A prerequisite to operate such shared nanowire-based platform relies on our ability to electrically contact individual metal nanowires and efficiently excite surface plasmon polaritons5 in this information support. In this article, we describe a protocol to bring electrical terminals to chemically-synthesized silver nanowires6 randomly distributed on a glass substrate7. The positions of the nanowire ends with respect to predefined landmarks are precisely located using standard optical transmission microscopy before encapsulation in an electron-sensitive resist. Trenches representing the electrode layout are subsequently designed by electron-beam lithography. Metal electrodes are then fabricated by thermally evaporating a Cr/Au layer followed by a chemical lift-off. The contacted silver nanowires are finally transferred to a leakage radiation microscope for surface plasmon excitation and characterization8,9. Surface plasmons are launched in the nanowires by focusing a near infrared laser beam on a diffraction-limited spot overlapping one nanowire extremity5,9. For sufficiently large nanowires, the surface plasmon mode leaks into the glass substrate9,10. This leakage radiation is readily detected, imaged, and analyzed in the different conjugate planes in leakage radiation microscopy9,11. The electrical terminals do not affect the plasmon propagation. However, a current-induced morphological deterioration of the nanowire drastically degrades the flow of surface plasmons. The combination of surface plasmon leakage radiation microscopy with a simultaneous analysis of the nanowire electrical transport characteristics reveals the intrinsic limitations of such plasmonic circuitry.

Silver nanowires can simultaneously transport electrons and optical information in the form of surface plasmons. A procedure is described here to realize such a shared circuitry and the limitations at propagating both information carriers are evaluated.

Plasmonics is an emerging technology capable of simultaneously transporting a plasmonic signal and an electronic signal on the same information ...

工学

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 ...

化学

Synthesis, Characterization, and Functionalization of Hybrid Au/CdS and Au/ZnS Core/Shell Nanoparticles

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large extinction coefficients which can be tuned across the visible spectrum. Research into the plasmonic enhancement of optical transitions has become popular, due to the possibility of altering and in some cases improving photo-absorption or emission properties of nearby chromophores such as molecular dyes or quantum dots. The electric field of the plasmon can couple with the excitation dipole of a chromophore, perturbing the electronic states involved in the transition and leading to increased absorption and emission rates. These enhancements can also be negated at close distances by energy transfer mechanism, making the spatial arrangement of the two species critical. Ultimately, enhancement of light harvesting efficiency in plasmonic solar cells could lead to thinner and, therefore, lower cost devices. The development of hybrid core/shell particles could offer a solution to this issue. The addition of a dielectric spacer between a gold nanoparticles and a chromophore is the proposed method to control the exciton plasmon coupling strength and thereby balance losses with the plasmonic gains. A detailed procedure for the coating of gold nanoparticles with CdS and ZnS semiconductor shells is presented. The nanoparticles show high uniformity with size control in both the core gold particles and shell species allowing for a more accurate investigation into the plasmonic enhancement of external chromophores.

The synthesis of uniform gold nanoparticles coated with semiconductor shells of CdS or ZnS is performed. The semiconductor coating is conducted by first depositing a silver sulfide shell and exchanging the silver cations for zinc or cadmium cations.

合成、キャラクタリゼーション、およびハイブリッドのAu / CdSのとAu / ZnSのコア/シェルナノ粒子の機能化

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large ...

Visible-light Induced Reduction of Graphene Oxide Using Plasmonic Nanoparticle

Present work demonstrates the simple, chemical free, fast, and energy efficient method to produce reduced graphene oxide (r-GO) solution at RT using visible light irradiation with plasmonic nanoparticles. The plasmonic nanoparticle is used to improve the reduction efficiency of GO. It only takes 30 min&#160;at RT by illuminating the solutions with Xe-lamp, the r-GO solutions can be obtained by completely removing gold nanoparticles through simple centrifugation step. The spherical gold nanoparticles (AuNPs) as compared to the other nanostructures is the most suitable plasmonic nanostructure for r-GO preparation. The reduced graphene oxide prepared using visible light and AuNPs was equally qualitative as chemically reduced graphene oxide, which was supported by various analytical techniques such as UV-Vis spectroscopy, Raman spectroscopy, powder XRD and XPS. The reduced graphene oxide prepared with visible light shows excellent quenching properties over the fluorescent molecules modified on ssDNA and excellent fluorescence recovery for target DNA detection. The r-GO prepared by recycled AuNPs is found to be of same quality with that of chemically reduced r-GO. The use of visible light with plasmonic nanoparticle demonstrates the good alternative method for r-GO synthesis.

A simple protocol for the preparation of reduced graphene oxide using visible light and plasmonic nanoparticle is described.

プラズモニックナノ粒子を用いてグラフェン酸化物の可視光誘起削減

Present work demonstrates the simple, chemical free, fast, and energy efficient method to produce reduced graphene oxide (r-GO) solution at RT using ...

Multifunctional Hybrid Fe2O3-Au Nanoparticles for Efficient Plasmonic Heating

One of the most widely used methods for manufacturing colloidal gold nanospherical particles involves the reduction of chloroauric acid (HAuCl4) to neutral gold Au(0) by reducing agents, such as sodium citrate or sodium borohydride. The extension of this method to decorate iron oxide or similar nanoparticles with gold nanoparticles to create multifunctional hybrid Fe2O3-Au nanoparticles is straightforward. This approach yields fairly good control over Au nanoparticle dimensions and loading onto Fe2O3. Additionally, the Au metal size, shape, and loading can easily be tuned by changing experimental parameters (e.g., reactant concentrations, reducing agents, surfactants, etc.). An advantage of this procedure is that the reaction can be done in air or water, and, in principle, is amenable to scaling up. The use of such optically tunable Fe2O3-Au nanoparticles for hyperthermia studies is an attractive option as it capitalizes on plasmonic heating of gold nanoparticles tuned to absorb light strongly in the VIS-NIR region. In addition to its plasmonic effects, nanoscale Au provides a unique surface for interesting chemistries and catalysis. The Fe2O3 material provides additional functionality due to its magnetic property. For example, an external magnetic field could be used to collect and recycle the hybrid Fe2O3-Au nanoparticles after a catalytic experiment, or alternatively, the magnetic Fe2O3 can be used for hyperthermia studies through magnetic heat induction. The photothermal experiment described in this report measures bulk temperature change and nanoparticle solution mass loss as functions of time using infrared thermocouples and a balance, respectively. The ease of sample preparation and the use of readily available equipment are distinct advantages of this technique. A caveat is that these photothermal measurements assess the bulk solution temperature and not the surface of the nanoparticle where the heat is transduced and the temperature is likely to be higher.

Multifunctional Hybrid Fe2O3-Au Nanoparticles for Efficient Plasmonic Heating

We describe the synthesis and properties of multifunctional Fe2O3-Au nanoparticles produced by a wet chemical approach and investigate their photothermal properties using laser irradiation. The composite Fe2O3-Au nanoparticles retain the properties of both materials, creating a multifunctional structure with excellent magnetic and plasmonic properties.

多機能ハイブリッドのFe<sub&gt; 2</sub&gt; O<sub&gt; 3</sub&gt; -Auナノ粒子の効率的なプラズモニック暖房

One of the most widely used methods for manufacturing colloidal gold nanospherical particles involves the reduction of chloroauric acid (HAuCl4) to ...

Colloidal Synthesis of Nanopatch Antennas for Applications in Plasmonics and Nanophotonics

We present a method for colloidal synthesis of silver nanocubes and the use of these in combination with a smooth gold film, to fabricate plasmonic nanoscale patch antennas. This includes a detailed procedure for the fabrication of thin films with a well-controlled thickness over macroscopic areas using layer-by-layer deposition of polyelectrolyte polymers, namely poly(allylamine) hydrochloride (PAH) and polystyrene sulfonate (PSS). These polyelectrolyte spacer layers serve as a dielectric gap in between silver nanocubes and a gold film. By controlling the size of the nanocubes or the gap thickness, the plasmon resonance can be tuned from about 500 nm to 700 nm. Next, we demonstrate how to incorporate organic sulfo-cyanine5 carboxylic acid (Cy5) dye molecules into the dielectric polymer gap region of the nanopatch antennas. Finally, we show greatly enhanced fluorescence of the Cy5 dyes by spectrally matching the plasmon resonance with the excitation energy and the Cy5 absorption peak. The method presented here enables the fabrication of plasmonic nanopatch antennas with well-controlled dimensions utilizing colloidal synthesis and a layer-by-layer dip-coating process with the potential for low cost and large-scale production. These nanopatch antennas hold great promise for practical applications, for example in sensing, ultrafast optoelectronic devices and for high-efficiency photodetectors.

A protocol for the colloidal synthesis of silver nanocubes and fabrication of plasmonic nanoscale patch antennas with sub-10 nm gaps is presented.

プラズモニクスとナノフォトニクスでのアプリケーションのためのNanopatchアンテナのコロイド合成

We present a method for colloidal synthesis of silver nanocubes and the use of these in combination with a smooth gold film, to fabricate plasmonic ...

In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films

Combinations of metal oxide semiconductors and gold nanoparticles (AuNPs) have been investigated as new types of materials. The in situ synthesis of AuNPs within the interlayer space of semiconducting layered titania nanosheet (TNS) films was investigated here. Two types of intermediate films (i.e., TNS films containing methyl viologen (TNS/MV2+) and 2-ammoniumethanethiol (TNS/2-AET+)) were prepared. The two intermediate films were soaked in an aqueous tetrachloroauric(III) acid (HAuCl4) solution, whereby considerable amounts of Au(III) species were accommodated within the interlayer spaces of the TNS films. The two types of obtained films were then soaked in an aqueous sodium tetrahydroborate (NaBH4) solution, whereupon the color of the films immediately changed from colorless to purple, suggesting the formation of AuNPs within the TNS interlayer. When only TNS/MV2+ was used as the intermediate film, the color of the film gradually changed from metallic purple to dusty purple within 30 min, suggesting that aggregation of AuNPs had occurred. In contrast, this color change was suppressed by using the TNS/2-AET+ intermediate film, and the AuNPs were stabilized for over 4 months, as evidenced by the characteristic extinction (absorption and scattering) band from the AuNPs.

In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films

Here, we present a protocol for the in situ synthesis of gold nanoparticles (AuNPs) within the interlayer space of layered titanate films without the aggregation of AuNPs. No spectral change was observed even after 4 months. The synthesized material has expected applications in catalysis, photo-catalysis, and the development of cost-effective plasmonic devices.

層状チタン酸透明フィルムの層間空間で凝集することなく金ナノ粒子のその場合成で

Combinations of metal oxide semiconductors and gold nanoparticles (AuNPs) have been investigated as new types of materials. The in situ synthesis of AuNPs ...

Fabrication of Periodic Gold Nanocup Arrays Using Colloidal Lithography

Within recent years, the field of plasmonics has exploded as researchers have demonstrated exciting applications related to chemical and optical sensing in combination with new nanofabrication techniques. A plasmon is a quantum of charge density oscillation that lends nanoscale metals such as gold and silver unique optical properties. In particular, gold and silver nanoparticles exhibit localized surface plasmon resonances-collective charge density oscillations on the surface of the nanoparticle-in the visible spectrum. Here, we focus on the fabrication of periodic arrays of anisotropic plasmonic nanostructures. These half-shell (or nanocup) structures can exhibit additional unique light-bending and polarization-dependent optical properties that simple isotropic nanostructures cannot. Researchers are interested in the fabrication of periodic arrays of nanocups for a wide variety of applications such as low-cost optical devices, surface-enhanced Raman scattering, and tamper indication. We present a scalable technique based on colloidal lithography in which it is possible to easily fabricate large periodic arrays of nanocups using spin-coating and self-assembled commercially available polymeric nanospheres. Electron microscopy and optical spectroscopy from the visible to near-infrared (near-IR) was performed to confirm successful nanocup fabrication. We conclude with a demonstration of the transfer of nanocups to a flexible, conformal adhesive film.

We demonstrate the fabrication of periodic gold nanocup arrays using colloidal lithographic techniques and discuss the importance of nanoplasmonic films.

コロイド リソグラフィーを用いた定期的な金 Nanocup アレイの試作

Within recent years, the field of plasmonics has exploded as researchers have demonstrated exciting applications related to chemical and optical sensing ...

A Continuous-flow Photocatalytic Reactor for the Precisely Controlled Deposition of Metallic Nanoparticles

In this work, a novel photocatalytic reactor for the pulsed and controlled excitation of the photocatalyst and the precise deposition of metallic nanoparticles is developed. Guidelines for the replication of the reactor and its operation are provided in detail. Three different composite systems (Pt/graphene, Pt/TiO2, and Au/TiO2) with monodisperse and uniformly distributed particles are produced by this reactor, and the photodeposition mechanism, as well as the synthesis optimization strategy, are discussed. The synthesis methods and their technical aspects are described comprehensively. The role of the ultraviolet (UV) dose (in each excitation pulse) on the photodeposition process is investigated and the optimum values for each composite system are provided.

For a continuous and scalable synthesis of noble-metal-based nanocomposites, a novel photocatalytic reactor is developed and its structure, operation principles, and product quality optimization strategies are described.

金属ナノ粒子の正確に制御された沈着量の連続的な流れの光触媒反応

In this work, a novel photocatalytic reactor for the pulsed and controlled excitation of the photocatalyst and the precise deposition of metallic ...

Photodeposition of Pd onto Colloidal Au Nanorods by Surface Plasmon Excitation

A protocol is described to photocatalytically guide Pd deposition onto Au nanorods (AuNR) using surface plasmon resonance (SPR). Excited plasmonic hot electrons upon SPR irradiation drive reductive deposition of Pd on colloidal AuNR in the presence of [PdCl4]2-. Plasmon-driven reduction of secondary metals potentiates covalent, sub-wavelength deposition at targeted locations coinciding with electric field &#8220;hot-spots&#8221; of the plasmonic substrate using an external field (e.g., laser). The process described herein details a solution-phase deposition of a catalytically-active noble metal (Pd) from a transition metal halide salt (H2PdCl4) onto aqueously-suspended, anisotropic plasmonic structures (AuNR). The solution-phase process is amenable to making other bimetallic architectures. Transmission UV-vis monitoring of the photochemical reaction, coupled with ex situ XPS and statistical TEM analysis, provide immediate experimental feedback to evaluate properties of the bimetallic structures as they evolve during the photocatalytic reaction. Resonant plasmon irradiation of AuNR in the presence of [PdCl4]2- creates a thin, covalently-bound Pd0 shell without any significant dampening effect on its plasmonic behavior in this representative experiment/batch. Overall, plasmonic photodeposition offers an alternative route for high-volume, economical synthesis of optoelectronic materials with sub-5 nm features (e.g., heterometallic photocatalysts or optoelectronic interconnects).

A protocol for anisotropic photodeposition of Pd onto aqueously-suspended Au nanorods via localized surface plasmon excitation is presented.

表面プラズモン励起によるコロイドAuナノロッドへのPdの光堆積

A protocol is described to photocatalytically guide Pd deposition onto Au nanorods (AuNR) using surface plasmon resonance (SPR). Excited plasmonic hot ...

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

要約

さらに動画を探す

Evaluating Plasmonic Transport in Current-carrying Silver Nanowires

Immunotargeted磁気プラズモニックナノクラスターの合成

合成、キャラクタリゼーション、およびハイブリッドのAu / CdSのとAu / ZnSのコア/シェルナノ粒子の機能化

プラズモニックナノ粒子を用いてグラフェン酸化物の可視光誘起削減

多機能ハイブリッドのFe

プラズモニクスとナノフォトニクスでのアプリケーションのためのNanopatchアンテナのコロイド合成

層状チタン酸透明フィルムの層間空間で凝集することなく金ナノ粒子のその場合成で

コロイドリソグラフィーを用いた定期的な金 Nanocup アレイの試作

金属ナノ粒子の正確に制御された沈着量の連続的な流れの光触媒反応

表面プラズモン励起によるコロイドAuナノロッドへのPdの光堆積

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

要約

さらに動画を探す

Evaluating Plasmonic Transport in Current-carrying Silver Nanowires

Immunotargeted磁気プラズモニックナノクラスターの合成

合成、キャラクタリゼーション、およびハイブリッドのAu / CdSのとAu / ZnSのコア/シェルナノ粒子の機能化

プラズモニックナノ粒子を用いてグラフェン酸化物の可視光誘起削減

多機能ハイブリッドのFe

プラズモニクスとナノフォトニクスでのアプリケーションのためのNanopatchアンテナのコロイド合成

層状チタン酸透明フィルムの層間空間で凝集することなく金ナノ粒子のその場合成で

コロイド リソグラフィーを用いた定期的な金 Nanocup アレイの試作

金属ナノ粒子の正確に制御された沈着量の連続的な流れの光触媒反応

表面プラズモン励起によるコロイドAuナノロッドへのPdの光堆積

コロイドリソグラフィーを用いた定期的な金 Nanocup アレイの試作