This research was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada, the Canada Research Chairs Program, and Simon Fraser University. This work made use of 4D LABS shared facilities supported by the Canada Foundation for Innovation (CFI), British Columbia Knowledge Development Fund (BCKDF) and Simon Fraser University.

NaYF 4 / Ybの3+ / ER 3+アップコンバーティングナノ粒子（UCNP）の1合成<ol><li>以下のように装置を設定します。 <ol><li>定期的な撹拌プレート上で250ミリリットル加熱マントルを置き、熱電対の上にマントを差し込みます。 </li><li>適切なクランプで加熱マントル上に磁気撹拌棒を備えた250mlの丸底フラスコを置きます。 </li><li>丸底フラスコの左首に空気アダプタを取り付け、プラスチック管とのシュレンクラインにこの空気アダプタを接続してください。 </li><li>丸底フラスコの右首にガラスアダプタを取り付け、ガラスアダプタ上に温度計アダプターを固定します。温度計アダプタを介してフラスコに温度プローブを挿入し、熱電対にこれを接続します。 </li><li>丸底フラスコの中央の首に蒸留ヘッドを取り付けます。蒸留ヘッドの上にストッパーを配置します。真空に続いて、凝縮器に頭を接続distillatイオンアダプタと50 mlの丸底フラスコ。プラスチック管を通してバブラーに真空蒸留アダプターを接続します。 </li></ol></li><li>エルビウムの酢酸イットリウム、酢酸1.17グラム（3.9ミリモル）、イッテルビウム、酢酸の0.439グラムおよび0.0727グラム（0.1ミリモル）を計量し、丸底フラスコ反応に置きます。 </li><li>メスシリンダーを使用してフラスコにオレイン酸30 ml及びオクタデセンの75ミリリットルを追加します。 </li><li>何のオレイン酸およびオクタデセンを反応フラスコの側面に貼り付けられていないことを確認するために、5mlのメタノールを使用して丸底フラスコ反応の側面を洗い流します。 </li><li>ダブルマニホールドシュレンクラインに反応フラスコを接続し、窒素ラインに接続された反応フラスコを維持するために、対応するバルブを回します。 </li><li> 、熱電対の電源を入れ、80℃に温度を設定し、徐々にこの温度にシステムを加熱します。 80℃で、すべての出発物質が溶解した後、加熱マントルを除去し、反応を可能に30℃に冷却します。 </li><li>温度が30℃に達したとき、蒸留ヘッドを脱いで左首の中から首に空気アダプタを切り替えるとストッパーで左首を閉鎖。ゆっくりと真空ラインに窒素ラインからシュレンクライン上でバルブを回して反応フラスコに真空をご紹介します。低沸点成分の全ては、この時点での反応から引き出されます。 </li><li>溶液をバブリングを停止したときに、5℃/分の速度で115℃まで温度を上げ。 </li><li>温度が115°Cに達すると、加熱マントルを除去し、50℃まで反応を冷却、その後、15分間この温度を保ちます。その後、すぐに中央の首と左ヘッドへの空気アダプタに蒸留ヘッドを再び取り付けることにより、元のフォームに設定切り替えます。 </li><li>水酸化ナトリウム0.74グラム（12.5ミリモル）を秤量し、冷却プロセス中にNH 4 Fの0.50グラム（20.0ミリモル）、及びそれらを溶解します超音波処理によるメタノール50mlインチ</li><li>超音波処理の後、丸底フラスコ反応への溶液を注ぎ、メタノール5mlでフラスコの側面を洗い流します。 </li><li> 50℃で30分間攪拌したソリューションを残します。 </li><li>メタノールを蒸留するために75℃に温度を上げます。 </li><li>必要なときに蒸留の間に、収集フラスコを空にします。蒸留の終了後、できるだけ早く、窒素保護下で300℃まで反応を加熱します。 </li><li>温度が300°Cに達すると、1時間この温度を維持します。必要に応じて、温度を維持するためにアルミホイルでセットアップを覆います。その後、熱源を取り外し、反応物を室温まで冷却させます。 </li><li>それを室温に冷却した後、50 mlの3遠心分離チューブ（50 mlチューブに、各チューブあたりおよそ35 mlの溶液）、及びトップアップチューブに均等に溶液を分割し、無水エタノールを用いてスケール。遠心全てのT彼は15分間3400×gでチューブ。遠心分離した後、UCNPsは白い沈殿物として、チューブの側で観察されるはずです。 </li><li>上清を捨て、ヘキサン（各チューブあたりヘキサン7.5 ml）にUCNPsペレットを再分散し、50ミリリットルの規模にエタノールでチューブをトップアップ。 15分間3400×gで再び遠心分離管。 </li><li>遠心分離が完了した後、上清を廃棄し、さらに使用するための CHCl 3 30mlに再分散固体UCNPs。 </li></ol>有機色素分子とアップコンバーティングナノ粒子を含む水分散性Nanoassemblies 2.組立<ol><li>磁気撹拌棒を備えたシンチレーションバイアルにの CHCl 3 3ml中のポリ（スチレン- ALT -無水マレイン酸）を25mg（0.0147ミリモル）（PSMA）を溶解します。この量は、複数の試験の後に最適化された量です。 </li><li>アップコンバート250μlの（47 mg / mlの）を追加するシンチにクロロホルムストック溶液をナノ粒子llationバイアル。 </li><li>バイアルに蓋をし、磁気撹拌プレート上に置き、そして2時間室温で溶液を攪拌。 </li><li>ポリエーテルアミン2070 160mgの（0.0773ミリモル）を計量し、し、CHCl 3 1ml中にそれを溶解させます。次に、ピペットを用いて、一度にシンチレーションバイアルにこの溶液を加えます。解決策は、PSMA上の無水物基と2070アミンポリエーテルの反応を示す淡黄色に変わります。 </li><li>室温で溶液を一晩攪拌し続けます。 </li><li> 1時間、得られた溶液を攪拌し、その後、有機色素分子の適切な量を測定一度にシンチレーションバイアル内に分注します。 <ol><li>サンプルTPP-NP（nanoassemblyポリマーシェル、テトラフェニルポルフィリンとアップコンバートナノ粒子を含む）については、直接シンチレーションバイアルにテトラフェニルポルフィリン1mgを追加します。 nanoassemblyポリマーシェル、ジアリールエテン分子とアップコンバートのナノ粒子を含む試料DAE-UCNP（についてs）は、それぞれジアリールエテン分子の量は、2×10 -7モルです。反応溶液中に2ジアリールエテン分子を追加します。 2ジアリ​​ールエテン分子のためのボリュームがある：DAE-1O（1.8ミリモル）、111μLおよびDAE-2O（1.6ミリモル）、125μlの。 </li></ol></li><li>乳白色の懸濁液が形成されるまで、バイアルを超音波処理後、シンチレーションバイアルに、0.001M NaOH水溶液（11≈のpH）の3ミリリットルを追加し、ロータリーエバポレーターを用いて減圧下での CHCl 3溶媒を除去します。 </li><li>ロータリーエバポレーターでバックバイアルを置き、懸濁液は透明な溶液になったまで慎重に残りの CHCl 3 を削除します。 </li><li>その後、25分間20,600×gで解決策を遠心、2 1.5ミリリットルの円錐遠心チューブにシンチレーションバイアルからの溶液を移します。 </li><li>上清を捨て、その後、2つのチューブ（チューブあたり1.5ミリリットル）に、脱イオンH 2 Oの3ミリリットルの合計を追加し、ペレットを再分散するためにチューブを超音波処理脱イオンH 2 O中</li><li> 25分間20,600×gで再び2つのチューブを遠心。 </li><li>上清を捨て、その後、2つのチューブ（チューブあたり1.5ミリリットル）に、脱イオンH 2 Oの3ミリリットルの合計を追加します。脱イオンH 2 O中にペレットを再分散するためにチューブを超音波処理</li><li>更なる試験のための最終的なサンプルを得るために、0.2μmのシリンジフィルターを通して水のナノ粒子分散サンプルをフィルタリングします。 </li></ol>

<ol>
	<li>Fery-Forgues, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fluorescent+organic+nanocrystals+and+non-doped+nanoparticles+for+biological+applications.">Fluorescent organic nanocrystals and non-doped nanoparticles for biological applications.</a> Nanoscale. 5 (18), 8428-8442 (2013).</li><li>Vollrath, A., Schubert, S., Schubert, U. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fluorescence+imaging+of+cancer+tissue+based+on+metal-free+polymeric+nanoparticles.">Fluorescence imaging of cancer tissue based on metal-free polymeric nanoparticles.</a> J. Mater. Chem. B. 1, 1994-2007 (2013).</li><li>Cheng, X., Lowe, S. B., Reecec, P. J., Gooding, J. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Colloidal+silicon+quantum+dots:+from+preparation+to+the+modification+of+self-assembled+monolayers+(SAMs)+for+bio-applications.">Colloidal silicon quantum dots: from preparation to the modification of self-assembled monolayers (SAMs) for bio-applications.</a> Chem. Soc. Rev. 43, 2680-2700 (2014).</li><li>Luo, P. G., 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=Carbon-based+quantum+dots+for+fluorescence+imaging+of+cells+and+tissues.">Carbon-based quantum dots for fluorescence imaging of cells and tissues.</a> RSC Adv. 4, 10791-10807 (2014).</li><li>Wang, Y., Hu, R., Lin, G., Roy, I., Yong, K. -. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Functionalized+Quantum+Dots+for+Biosensing+and+Bioimaging+and+Concerns+on+Toxicity.">Functionalized Quantum Dots for Biosensing and Bioimaging and Concerns on Toxicity.</a> ACS Appl. Mater. Interfaces. 5 (8), 2786-2799 (2013).</li><li>Kairdolf, B. 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=Semiconductor+Quantum+Dots+for+Bioimaging+and+Biodiagnostic+Applications.">Semiconductor Quantum Dots for Bioimaging and Biodiagnostic Applications.</a> Annu. Rev. Anal. Chem. 6 (1), 143-162 (2013).</li><li>Huang, B., Bates, M., Zhuang, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Super-Resolution+Fluorescence+Microscopy.">Super-Resolution Fluorescence Microscopy.</a> Annu. Rev. Biochem. 78, 993-1016 (2009).</li><li>F&#246;lling, J., 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=Photochromic+Rhodamines+Provide+Nanoscopy+with+Optical+Sectioning.">Photochromic Rhodamines Provide Nanoscopy with Optical Sectioning.</a> Angew. Chem. Int. Ed. 46 (33), 6266-6270 (2007).</li><li>F&#246;lling, J., 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=Fluorescence+Nanoscopy+with+Optical+Sectioning+by+Two-Photon+Induced+Molecular+Switching+using+Continuous-Wave+Lasers.">Fluorescence Nanoscopy with Optical Sectioning by Two-Photon Induced Molecular Switching using Continuous-Wave Lasers.</a> Chem. Phys. Chem. 9 (2), 321-326 (2008).</li><li>Bossi, M., 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=Multicolor+Far-Field+Fluorescence+Nanoscopy+through+Isolated+Detection+of+Distinct+Molecular+Species.">Multicolor Far-Field Fluorescence Nanoscopy through Isolated Detection of Distinct Molecular Species.</a> Nano Lett. 8 (8), 2463-2468 (2008).</li><li>Berns, M. W., Krasieva, T., Sun, C. &. #. 8. 2. 1. 1. ;. H., Dvornikov, A., Rentzepis, P. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+polarity+dependent+fluorescence+"switch"+in+live+cells.">A polarity dependent fluorescence "switch" in live cells.</a> Photochem. Photobiol. B: Biol. 75, 51-56 (2004).</li><li>Zou, Y., 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=Amphiphilic+Diarylethene+as+a+Photoswitchable+Probe+for+Imaging+Living+Cells.">Amphiphilic Diarylethene as a Photoswitchable Probe for Imaging Living Cells.</a> J. Am. Chem. Soc. 130 (47), 15750-1 (2008).</li><li>Westphal, V., 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=Video-Rate+Far-Field+Optical+Nanoscopy+Dissects+Synaptic+Vesicle+Movement.">Video-Rate Far-Field Optical Nanoscopy Dissects Synaptic Vesicle Movement.</a> Science. 320, 246-249 (2008).</li><li>Zhuang, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fluorescent+Switches+Based+on+Photochromic+Compounds.">Fluorescent Switches Based on Photochromic Compounds.</a> Nat Photonics. 3, 365-367 (2009).</li><li>Cusido, J., Deniz, E., Raymo, F. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fluorescent+Switches+Based+on+Photochromic+Compounds.">Fluorescent Switches Based on Photochromic Compounds.</a> Eur. J. Org. Chem. 13, 2031-2045 (2009).</li><li>Raymo, F. M., Tomasulo, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electron+and+energy+transfer+modulation+with+photochromic+switches.">Electron and energy transfer modulation with photochromic switches.</a> Chem. Soc. Rev. 34, 327-336 (2005).</li><li>Feringa, B. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Molecular Switches. , (2010).</li><li>Tian, H., Yang, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+progresses+on+diarylethene+based+photochromic+switches.">Recent progresses on diarylethene based photochromic switches.</a> Chem. Soc. Rev. 33, 85-97 (2004).</li><li>Ubaghs, L., Sud, D., Branda, N. R., Perepichka, I. D., Perepichka, D., Branda, N. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Handbook in Thiophene-Based Materials: Applications in Organic Electronics and Photonics. 2, (2009).</li><li>Norsten, T. B., Branda, N. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photoregulation+of+Fluorescence+in+a+Porphyrinic+Dithienylethene+Photochrome.">Photoregulation of Fluorescence in a Porphyrinic Dithienylethene Photochrome.</a> J. Am. Chem. Soc. 123 (8), 1784-1785 (2001).</li><li>Giordano, L., Jovin, T. M., Irie, M., Jares-Erijman, E. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Diheteroarylethenes+as+Thermally+Stable+Photoswitchable+Acceptors+in+Photochromic+Fluorescence+Resonance+Energy+Transfer+(pcFRET).">Diheteroarylethenes as Thermally Stable Photoswitchable Acceptors in Photochromic Fluorescence Resonance Energy Transfer (pcFRET).</a> J. Am. Chem. Soc. 124 (25), 7481-7489 (2002).</li><li>F&#246;lling, J., 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=Synthesis+and+Characterization+of+Photoswitchable+Fluorescent+Silica+Nanoparticles.">Synthesis and Characterization of Photoswitchable Fluorescent Silica Nanoparticles.</a> Small. 4 (1), 134-142 (2008).</li><li>Jeong, J., 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=Photoreversible+cellular+imaging+using+photochrome-conjugated+fullerene+silica+nanoparticles.">Photoreversible cellular imaging using photochrome-conjugated fullerene silica nanoparticles.</a> Chem. Commun. 47, 10668-10670 (2011).</li><li>Gai, S., Li, C., Yang, P., Lin, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+progress+in+rare+earth+micro/nanocrystals:+soft+chemical+synthesis,+luminescent+properties,+and+biomedical+applications.">Recent progress in rare earth micro/nanocrystals: soft chemical synthesis, luminescent properties, and biomedical applications.</a> Chem. Rev. 114 (4), 2343-2389 (2014).</li><li>Carling, C. -. J., Boyer, J. -. C., Branda, N. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Multimodal+fluorescence+modulation+using+molecular+photoswitches+and+upconverting+nanoparticles.">Multimodal fluorescence modulation using molecular photoswitches and upconverting nanoparticles.</a> Org. Biomol. Chem. 10, 6159-6168 (2012).</li><li>Wu, T., Boyer, J. -. C., Barker, M., Wilson, D., Branda, N. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+"Plug-and-Play"+Method+to+Prepare+Water-Soluble+Photoresponsive+Encapsulated+Upconverting+Nanoparticles+Containing+Hydrophobic+Molecular+Switches.">A "Plug-and-Play" Method to Prepare Water-Soluble Photoresponsive Encapsulated Upconverting Nanoparticles Containing Hydrophobic Molecular Switches.</a> Chem. Mater. 25 (12), (2013).</li><li>Wu, T., Kaur, S., Branda, N. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Energy+transfer+between+amphiphilic+porphyrin+polymer+shells+and+upconverting+nanoparticle+cores+in+water-dispersible+nano-assemblies.">Energy transfer between amphiphilic porphyrin polymer shells and upconverting nanoparticle cores in water-dispersible nano-assemblies.</a> Org. Biol. Chem. 13, 2317-2322 (2015).</li><li>Irie, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photochromism:+Memories+and+Switches+Introduction.">Photochromism: Memories and Switches Introduction.</a> Chem. Rev. 100 (5), 1683-1684 (2000).</li></ol>

The authors have nothing to disclose.

このプロトコルに従って合成されたナノ粒子は、約22.5 nmの中心20から25ナノメートルのサイズ分布を有する。26,27それらはα-NaYF 4ホスト格子構造を有する球状粒子として分類することができます。このプロトコルで2つの重要なステップがあります。 UCNP合成では、粒子サイズの狭い分布を確実にするために、可能な限り正確な加熱温度および時間を維持することが重要です。?...

今日バイオイメージング剤の新しいタイプを開発する緊急の必要性が依然として存在します。多くの新規蛍光プローブが十分に文書化されている。1-6ただし 、画像の解像度の大幅な改善が課題である。7つの実用的な方法は、直接「光」の発光状態と「暗い」急冷状態との間の蛍光プローブを変調することです。 8-12この特定の方法は、誘導放出の枯渇（STED）顕微鏡13及び確率的光学再構築顕微鏡（STORM）などの技術を開発するために適用されている。14 蛍光を調節するための別のアプローチは、蛍光プローブと一緒に夫婦光応答性発色団である。15,16は、異性体の一方のみが、効率的なエネルギー移動アクセプターとして機能することができる2つの異性体間光応答発色団の切り替え、目からの蛍光の消光の制御を可能にしますフェルスター共鳴エネルギー移動（FRET）、および他の機構を介して電子プローブ。結果は、発光状態と異なる波長の光に光応答性発色団の暴露によって交互に行うことができる急冷状態の作成です。 光応答ジアリールエテン発色団は、可逆的に無色の開環異性体およびUVおよび可視光の照射により着色された閉環体との間で切り替えることができます。17〜19の熱2つの異性体の安定性と閉環体メイクの調整可能な吸収スペクトルジアリールエテン非常に良好な候補を制御FRETアクセプターとして。20-23ランタニドドープNaYF 4アップコンバージョンナノ粒子は、バイオイメージングのために有用である。24これらのナノ粒子は、近赤外光を吸収し、可視スペクトルのいくつかの領域の光を放出します。光応答ジアリールエテン発色団とナノ粒子を組み合わせることで蛍光変調の例としては、事前にされていますviously我々のグループによって報告された。25-27しかしながら 、各実施例に記載されたシステムは、より多様なシステムの開発を複雑にナノ粒子の表面にジアリールエテンを取り付けるために追加の合成修飾を必要としました。 本明細書において、我々は、自己組織化戦略を使用して水分散性有機色素分子と光応答アップコンバートナノ粒子を調製するための単純な「プラグ・アンド・プレイ」方式を示します。ポリマーの選択。 2070アミンポリ（スチレン- ALT -無水マレイン酸）とポリエーテルは、疎水性および親水性環境の両方を提供します。ポリマーの親水性領域は、水溶解性を維持するために重要であるのに対し、ポリマーヘルプの疎水性セクションでは、一緒に通常は水に不溶性の有機分子とアップコンバートナノ粒子を保持します。私たちは、第1の熱核法でアップコンバートナノ粒子の合成を実証します。そこで、ホを証明します有機分子とアップコンバートナノ粒子wのポリマーシェルの疎水性領域内にカプセル化されており、単純に便利なワークアップ手順に続いてアップコンバートナノ粒子、ポリマーと異なる有機色素分子の溶液を、共同攪拌して水性媒体中で安定したまま。また、外光照射を使用してアセンブリの蛍光発光を変調する方法を示します。私たちは、水分散性nanoassembliesが拡大していきますするには、この「プラグアンドプレイ」メソッドを使用しての範囲を期待しています。

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>yttrium acetate</td>
			<td>sigma</td>
			<td>326046</td>
			<td>Yttrium(III) acetate hydrate</td>
		</tr>
		<tr>
			<td>ytterbium acetate</td>
			<td>sigma</td>
			<td>544973</td>
			<td>&#160;Ytterbium(III) acetate hydrate&#160;</td>
		</tr>
		<tr>
			<td>erbium acetate</td>
			<td>sigma</td>
			<td>325570</td>
			<td>Erbium(III) acetate hydrate</td>
		</tr>
		<tr>
			<td>oleic acid</td>
			<td>sigma</td>
			<td>75096</td>
			<td>analytical standard</td>
		</tr>
		<tr>
			<td>octadecene</td>
			<td>sigma</td>
			<td>O806&#160;</td>
			<td>Technical grade&#160;</td>
		</tr>
		<tr>
			<td>NaOH</td>
			<td></td>
			<td>S5881&#160;</td>
			<td>reagent grade</td>
		</tr>
		<tr>
			<td>NH4F</td>
			<td></td>
			<td>216011</td>
			<td>ACS reagent</td>
		</tr>
		<tr>
			<td>poly(styrene-alt-maleic anhydride)</td>
			<td>sigma</td>
			<td>4422699</td>
			<td>Average Mn= 1700</td>
		</tr>
		<tr>
			<td>JeffAmine 2070</td>
			<td>Huntsman</td>
			<td>M-2070</td>
			<td></td>
		</tr>
		<tr>
			<td>Varian Carry 300</td>
			<td>Agilent</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>JDSU NIR laser</td>
			<td>JSDU</td>
			<td>L4-9897510-100M</td>
			<td>980 nm diode laser</td>
		</tr>
	</tbody>
</table>

a 'plug and play' method to create water-dispersible nanoassemblies containing an amphiphilic polymer, organic dyes and upconverting nanoparticles

In this protocol, we first describe a procedure to synthesize lanthanide doped upconverting nanoparticles (UCNPs). We then demonstrate how to generate amphiphilic polymers in situ, and describe a protocol to encapsulate the prepared UCNPs and different organic dye molecules (porphyrins and diarylethenes) using polymer shells to form stable water-dispersible nanoassemblies. The nanoassembly samples containing both the UCNPs and the diarylethene organic dyes have interesting photochemical and photophysical properties. Upon 365 nm UV irradiation, the diarylethene group undergoes a visual color change. When the samples are irradiated with visible light of another specific wavelength, the color fades and the samples return to the initial colorless state. The samples also emit visible light from the UCNPs upon irradiation with 980 nm near-infrared light. The emission intensity of the samples can be tuned through alternate irradiation with UV and visible light. Modulation of fluorescence can be performed for many cycles without observable degradation of the samples. This versatile encapsulation procedure allows for the transfer of hydrophobic molecules and nanoparticles from an organic solvent to an aqueous medium. The polymer helps to maintain a lipid-like microenvironment for the organic molecules to aid in preservation of their photochemical behavior in water. Thus this method is ideal to prepare water-dispersible photoresponsive systems. The use of near-infrared light to activate upconverting nanoparticles allows for lower energy light to be used to activate photoreactions instead of more harmful ultraviolet light.

吸収スペクトルおよび発光スペクトルは、サンプルDAE-UCNPのために収集しました。吸収スペクトルは、閉じたジアリールエテン発色団とアップコンバートナノ粒子間のスペクトルの重複を比較するために使用されています。サンプル（TPP-UCNP両方DAE-UCNP）の写真は、水性相中の両親媒性ポリマーシェル内に配置された有機色素分子およびアップコンバートナノ粒子の成功したカプセル化を実証?...

Watch this Scientific Journal Video about A 'Plug and Play' Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles at JoVE.com

A &#039;Plug and Play&#039; Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles

Organic dye molecules and oleic acid coated upconverting nanoparticles are not water-soluble. This protocol describes a &#8216;plug and play&#8217; method that enables the transfer of organic dye molecules and upconverting particles from their initial hydrophobic solvent to water.

「プラグアンドプレイ」両親媒性ポリマー、有機染料及びアップコンバーティングナノ粒子を含む水分散性Nanoassembliesを作成する方法を

In this protocol, we first describe a procedure to synthesize lanthanide doped upconverting nanoparticles (UCNPs). We then demonstrate how to generate ...

a-plug-play-method-to-create-water-dispersible-nanoassemblies

Research

JoVE Journal

Chemistry

A 'Plug and Play' Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles

9.8K ビュー.  Simon Fraser University. Organic dye molecules and oleic acid coated upconverting nanoparticles are not water-soluble. This protocol describes a ‘plug and play’ method that enables the transfer of organic dye molecules and upconverting particles from their initial hydrophobic solvent to water. 

ビデオ: A 'Plug and Play' Method to Create Water-dispersible Nanoassemblies Containing an Amphiphilic Polymer, Organic Dyes and Upconverting Nanoparticles

Analysis of Volatile and Oxidation Sensitive Compounds Using a Cold Inlet System and Electron Impact Mass Spectrometry

This video presents a protocol for the mass spectrometrical analysis of volatile and oxidation sensitive compounds using electron impact ionization. The analysis of volatile and oxidation sensitive compounds by mass spectrometry is not easily achieved, as all state-of-the-art mass spectrometric methods require at least one sample preparation step, e.g., dissolution and dilution of the analyte (electrospray ionization), co-crystallization of the analyte with a matrix compound (matrix-assisted laser desorption/ionization), or transfer of the prepared samples into the ionization source of the mass spectrometer, to be conducted under atmospheric conditions. Here, the use of a sample inlet system is described which enables the analysis of volatile metal organyls, silanes, and phosphanes using a sector field mass spectrometer equipped with an electron impact ionization source. All sample preparation steps and the sample introduction into the ion source of the mass spectrometer take place either under air-free conditions or under vacuum, enabling the analysis of compounds highly susceptible to oxidation. The presented technique is especially of interest for inorganic chemists, working with metal organyls, silanes, or phosphanes, which have to be handled using inert conditions, such as the Schlenk technique. The principle of operation is presented in this video.

This video presents a protocol for the mass spectrometrical analysis of volatile and oxidation sensitive compounds using electron impact ionization. The presented technique is especially of interest for inorganic chemists, working with metal organyls, silanes, or phosphanes which have to be handled using inert conditions, such as the Schlenk technique.

コー​​ルドインレットシステムおよび電子衝撃質量分析法を用いて揮発し、酸化に敏感な化合物の分析

This video presents a protocol for the mass spectrometrical analysis of volatile and oxidation sensitive compounds using electron impact ionization. The ...

化学

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

官能化有機金属構造体の合成とキャラクタリゼーション

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

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 ...

An ELISA Based Binding and Competition Method to Rapidly Determine Ligand-receptor Interactions

A comprehensive understanding of signaling pathways requires detailed knowledge regarding ligand-receptor interaction. This article describes two fast and reliable point-by-point protocols of enzyme-linked immunosorbent assays (ELISAs) for the investigation of ligand-receptor interactions: the direct ligand-receptor interaction assay (LRA) and the competition LRA. As a case study, the ELISA based analysis of the interaction between different lambda interferons (IFNLs) and the alpha subunit of their receptor (IL28RA) is presented: the direct LRA is used for the determination of dissociation constants (KD values) between receptor and IFN ligands, and the competition LRA for the determination of the inhibitory capacity of an oligopeptide, which was designed to compete with the IFNLs at their receptor binding site. Analytical steps to estimate KD and half maximal inhibitory concentration (IC50) values are described. Finally, the discussion highlights advantages and disadvantages of the presented method and how the results enable a better molecular understanding of ligand-receptor interactions.

The presented protocols describe two enzyme-linked immunosorbent assay (ELISA) based techniques for the rapid investigation of ligand-receptor interactions: The first assay allows the determination of dissociation constant between ligand and receptor. The second assay enables a rapid screening of blocking peptides for ligand-receptor interactions.

ELISAベースの結合と競争法は急速にリガンド - 受容体相互作用を決定するために、

A comprehensive understanding of signaling pathways requires detailed knowledge regarding ligand-receptor interaction. This article describes two fast and ...

The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified with furfurylamine to graft furan groups to the rubber backbone. These pendant furan groups are then cross-linked with a bis-maleimide via a Diels-Alder coupling reaction. Both reactions can be performed under a broad range of experimental conditions and can easily be applied on a large scale. The material properties of the resulting Diels-Alder cross-linked rubbers are similar to a peroxide-cured ethylene/propylene/diene rubber (EPDM) reference. The cross-links break at elevated temperatures (&#62; 150 &#176;C) via the retro-Diels-Alder reaction and can be reformed by thermal annealing at lower temperatures (50-70 &#176;C). Reversibility of the system was proven with infrared spectroscopy, solubility tests and mechanical properties. Recyclability of the material was also shown in a practical way, i.e., by cutting a cross-linked sample into small parts and compression molding them into new samples displaying comparable mechanical properties, which is not possible for conventionally cross-linked rubbers.

A simple two-step approach involving rubber modification and cross-linking yields fully reworkable, elastic rubber products.

サーモ可逆架橋ゴム経由アルダー化学の合成と性質

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ...

An Optimized Protocol for the Efficient Radiolabeling of Gold Nanoparticles by Using a 125I-labeled Azide Prosthetic Group

Here, we demonstrate a detailed protocol for the radiosynthesis of a 125I-labeled azide prosthetic group and its application to the efficient radiolabeling of DBCO-group-functionalized gold nanoparticles using a copper-free click reaction. Radioiodination of the stannylated precursor (2) was carried out by using [125I]NaI and chloramine T as an oxidant at room temperature for 15 min. After HPLC purification of the crude product, the purified 125I-labeled azide (1) was obtained with high radiochemical yield (75 &plusmn; 10%, n = 8) and excellent radiochemical purity (&gt;99%). For the synthesis of radiolabeled 13-nm-sized gold nanoparticles, the DBCO-functionalized gold nanoparticles (3) were prepared by using a thiolated polyethylene glycol polymer. A copper-free click reaction between 1 and 3 gave the 125I-labeled gold nanoparticles (4) with more than 95% of radiochemical yield as determined by radio-thin-layer chromatography (radio-TLC). These results clearly indicate that the present radiolabeling method using a strain-promoted copper-free click reaction will be useful for the efficient and convenient radiolabeling of DBCO-group-containing nanomaterials.

An Optimized Protocol for the Efficient Radiolabeling of Gold Nanoparticles by Using a 125I-labeled Azide Prosthetic Group

A detailed procedure for the synthesis of a 125I-labeled azide and the radiolabeling of dibenzocyclooctyne (DBCO)-group-conjugated, 13-nm-sized gold nanoparticles using a copper-free click reaction is described.

使用した金ナノ粒子の効率的な放射性標識のために最適化されたプロトコル<sup&gt; 125</sup&gt; I標識アジド補綴グループ

Here, we demonstrate a detailed protocol for the radiosynthesis of a 125I-labeled azide prosthetic group and its application to the efficient ...

Grafting Multiwalled Carbon Nanotubes with Polystyrene to Enable Self-Assembly and Anisotropic Patchiness

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a free-radical polymerization strategy to enable the modulation of the nanotube surface properties and produce supramolecular self-assembly of the nanostructures. First, a selective hydroxylation of the pristine nanotubes through a biphasic catalytically mediated oxidation reaction creates superficially distributed reactive sites at the sidewalls. The latter reactive sites are subsequently modified with methacrylic moieties using a silylated methacrylic precursor to create polymerizable sites. Those polymerizable groups can address further polymerization of styrene to produce a hybrid nanomaterial containing PS chains grafted to the nanotube sidewalls. The polymer-graft content, amount of silylated methacrylic moieties introduced and hydroxylation modification of the nanotubes are identified and quantified by Thermogravimetric Analysis (TGA). The presence of reactive functional groups hydroxyl and silylated methacrylate are confirmed by Fourier Transform Infrared Spectroscopy (FT-IR). Polystyrene-grafted carbon nanotube solutions in tetrahydrofuran (THF) provide wall-to-wall collinearly self-assembled nanotubes when cast samples are analyzed by transmission electron microscopy (TEM). Those self-assemblies are not obtained when suitable blanks are similarly cast from analogous solutions containing non-grafted counterparts. Therefore, this method enables the modification of the nanotube anisotropic patchiness at the sidewalls which results into spontaneous auto-organization at the nanoscale.

A procedure for the synthesis of polystyrene-grafted multiwalled carbon nanotubes using successive chemical modification steps to selectively introduce the polymer chains to the sidewalls and their self-assembly via anisotropic patchiness is presented.

ポリスチレン自己組織を有効にして異方的不均一性と多層カーボンナノ チューブを移植

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a ...

Time-resolved Photophysical Characterization of Triplet-harvesting Organic Compounds at an Oxygen-free Environment Using an iCCD Camera

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables the acquisition of photoluminescence spectra covering the time regime from nanoseconds up to 0.1 s. This enables us to follow the changes in the intensity (decay) and emission of the spectra over time. Using this method, it is possible to study diverse photophysical phenomena, such as the emission of phosphorescence, and the contributions of prompt and delayed fluorescence in molecules showing thermally activated delayed fluorescence (TADF). Remarkably, all spectra and decays are obtained in a single experiment. This can be done for solids (thin film, powder, crystal) and liquid samples, where the only limitations are the spectral sensitivity of the camera and the excitation wavelength (532 nm, 355 nm, 337 nm, and 266 nm). This technique is, thus, very important when investigating the excited state dynamics in organic emitters for their application in organic light-emitting diodes and other areas where triplet harvesting is of paramount importance. Since triplet states are strongly quenched by oxygen, emitters with efficient TADF luminescence, or those showing room temperature phosphorescence (RTP), must be correctly prepared in order to remove any dissolved oxygen from solutions and films. Otherwise, no long-lived emission will be observed. The method of degassing solid samples as presented in this work is basic and simple, but the degassing of liquid samples creates additional difficulties and is particularly interesting. A method of minimizing solvent loss and changing the sample concentration, while still enabling to remove oxygen in a very efficient and a repeatable manner, is presented in this work.

Here, we present a method of the spectroscopic characterization of organic molecules by means of time-resolved photoluminescence spectroscopy on the nanosecond-to-millisecond timescale in oxygen-free conditions. Methods to efficiently remove oxygen from the samples and, thus, limit luminescence quenching are also described.

時間分解光物性評価のトリプレット収穫有機化合物無酸素環境使用、iCCD カメラ

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables ...

Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule on the vibrational level of energy. Raman and IR spectroelectrochemistry can be used for advanced characterization of the structural changes in the organic electroactive compounds. Here, the step-by-step analysis by means of Raman and IR spectroelectrochemistry is shown. Raman and IR spectroelectrochemical techniques provide complementary information about structural changes occurring during an electrochemical process, i.e. allows for the investigation of redox processes and their products. The examples of IR and Raman spectroelectrochemical analysis are presented, in which the products of the redox reactions, both in solution and solid state, are identified.

A protocol of step-by-step Raman and IR spectroelectrochemical analysis is presented.

ラマン散乱とツールとしての IR 分光電気化学法共役有機化合物を分析するには

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule ...

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, allowing for the synthesis of isotactic poly(&#945;-hydroxy acids) with expected molecular weights (&#62;140 kDa) and narrow molecular weight distributions (Mw/Mn &#60; 1.1). This ring-opening polymerization is mediated by Ni and Zn complexes in the presence of an alcohol initiator and a photoredox Ir catalyst, irradiated by a blue LED (400 - 500 nm). The polymerization is performed at a low temperature (-15 &#176;C) to avoid undesired side reactions. The complete monomer consumption can be achieved within 4 - 8 hours, providing a polymer close to the expected molecular weight with narrow molecular weight distribution. The resulted number-average molecular weight shows a linear correlation with the degree of polymerization up to 1000. The homodecoupling 1H NMR study confirms that the obtained polymer is isotactic without epimerization. This polymerization reported herein offers a strategy for achieving rapid, controlled O-carboxyanhydrides polymerization to prepare stereoregular poly(&#945;-hydroxy acids) and its copolymers bearing various functional side-chain groups.

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

A protocol for the controlled photoredox ring-opening polymerization of O-carboxyanhydrides mediated by Ni/Zn complexes is presented.

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

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, ...