The authors thank Dr. A. Tejeda-Cruz (X-ray; IIM-UNAM). R.Y. thanks CINVESTAV, Mexico for technical support. M.S.S acknowledges the financial support by Spanish Government, MINECO (MAT2012-31127). I.A.I thanks CONACyT (212318) and PAPIIT UNAM (IN100415), Mexico for financial support. E.G-Z. thanks CONACyT (156801 and 236879), Mexico for financial support. Thanks to U. Winnberg (ITAM and ITESM) for scientific discussions.

注意：この触媒の手順で使用される化学物質は、毒性および非発癌性が比較的低いです。このような安全眼鏡、手袋、白衣、完全長ズボンとクローズドつま先の靴のように、この実験手順を実行するとき、すべての適切な安全対策を使用してください。次の手順の一部は、標準的な空気のないハンドリング技術を必要とします。 触媒の1.アクティベーション（HKUST-1） <ol><li>触媒の結晶性のキャラクタリゼーション 注：HKUST-1は、市販の多孔性配位高分子（触媒）です。触媒の結晶性を確証するために、HKUST-1の試料は、粉末X線回折（PXRD）により特徴付けされる必要があります。 <ol><li>ブラッグブレンターノ幾何学におけるCu-Kα1放射線（λ= 1.5406Å）のための（160 W（40 kVで、40ミリアンペア）で動作する回折計で）HKUST-1の0.1グラムのサンプルのPXRDパターンを収集します。 0.02＆＃に5°〜60°（2θ）にPXRDパターンを記録します176;手順と時間44をカウント1秒。 </li></ol></li><li> HKUST-1の脱溶媒和<ol><li>触媒（HKUST-1）の0.05グラムを計量。 </li><li>スタンドに250ミリリットルの二口丸底フラスコをクランプし、丸底フラスコに磁気撹拌棒を挿入します。 </li><li>丸底フラスコに冷却器を取り付けます。 </li><li>完璧なシールを生成するために、フラスコとコンデンサーの関節の間にいくつかの真空グリースやテフロンテープを使用してください。 </li><li> （ホースのコックを介して ）真空ポンプに、上から、コンデンサーを接続します。 </li><li>ポンプによって生成された真空は約10 -2バールであることを確認します。 注：便宜上、この実験は、起動システムとして呼ぶことにする（真空ポンプに接続され、凝縮器に取り付けられた二口丸底フラスコ）を設定します。 </li><li> 250ミリリットルの二口丸底フラスコ内の触媒（0.05グラム）を配置します。 </li><li>の第二の首にゴム隔壁を挿入丸底フラスコと、それが適切に（フィット）を封止していることを確認してください。 </li><li>慎重に、砂浴に起動システムを配置します。 </li><li>真空ポンプを起動し、それが完全に開くまで慎重にコックを回します。ホットプレートを用いて、1時間100℃に活性化システムを加熱。 </li><li>丸底フラスコの底に均一に触媒を分散させるために、ホットプレートの最低速度で攪拌します。 </li><li>加熱の1時間後に熱（ホットプレート）をオフにして、（真空下で）室温まで冷却起動システムをしましょう​​。 </li><li>起動システムは、室温まで冷却した後、コックをオフにする（従って、活性化システムは、受動的真空下であろう）、ポンプをオフにします。 </li><li> 2口丸底フラスコに、隔壁を通して、窒素（N 2）で充填したバルーンを接続し、平衡圧力に達するのに数秒を待ちます。 注：触媒の活性化の後、uのそれを残しますまとまりのない金属部位（またはオープン金属部位）へのアクセスからの不活性雰囲気（N 2）NDER活性触媒を得るための鍵です。 </li><li>平衡圧力が達成されたN 2で充填したバルーンを削除します。 注：青緑色の色の変化を（そのまま受信HKUST-1）（起動時に）暗青色のが観察されます。 </li></ol></li></ol>不均一触媒を介したバニリンの2.合成<ol><li>有機溶媒の脱気<ol><li> 5分間N 2バブリングによるエタノールのドガ約70ミリリットル。 </li></ol></li><li>触媒反応の調製<ol><li> 2口丸底フラスコに脱気したエタノール10mlを加え、穏やかにホットプレート上でサスペンションをかき混ぜます。 </li><li>懸濁液にHの5ミリリットル2 O 2（H 2 O中30％）を追加します。 </li><li>懸濁液にアセトニトリルの0.25ミリリットルを追加します。 </li><li>フェルラ酸の0.50グラムを計量し、それを溶かしますビーカー内の脱ガスしたエタノール20ミリリットル。 </li><li>懸濁液に溶解したフェルラ酸を追加します。 </li><li>脱気したエタノール20mlでビーカーを洗浄し、サスペンションに追加します。 </li></ol></li><li>バニリンへのトランスフェルラ酸の酸化<ol><li>真空ポンプにコンデンサーを接続するホースを抜きます。 </li><li>コンデンサーを通過する水道水をオンにします。好ましくは、水ポンプを使用しています。 </li><li> 1時間100℃（還流）にサスペンションまで加熱します。 </li><li>熱や攪拌をオフにします。慎重に（凝縮器に取り付けられた）二口丸底フラスコを持ち上げて、常温に冷まします。 </li></ol></li><li>反応の後処理<ol><li>反応混合物を濾別し（ブフナー漏斗及びフラスコを使用して）、触媒（HKUST-1）を回収し、酢酸エチル200mlでそれを洗浄します。 注：濾過プロセスをスピードアップするために、すぐにCを回収し、洗浄する（吸引ビンに接続された）真空を使用atalyst。 </li><li>第1節のようにPXRDによる触媒のフレームワークの結晶性の保持を裏付けます。 </li><li> （ロータリーエバポレーターを用いて真空下）、合わせた有機相を濃縮し、100mlの酢酸エチルで再溶解します。 </li><li> NH 4 Clで（30ml）中の飽和溶液で有機相を（分液ロートを使用して）洗浄します。 </li><li>有機相を回収し、無水Na 2 SO 4（30グラム）でそれらをミックス。懸濁液を15分間放置してみましょう。 </li><li>サスペンションをオフに濾過し、ろ液を回収します。 </li><li>ロータリーエバポレーターで真空下（約20ミリリットルに）ろ液を濃縮します。 </li></ol></li><li>残留物の精製（バニリン） <ol><li>フラッシュカラムクロマトグラフィー44により残渣を精製します。固定相はシリカゲルであり、移動相は、酢酸エチル - ヘキサン（5:95）の混合溶媒です。 </li><li>シリカゲルでのクロマトグラフィーガラスカラム（1 cmの×30センチ）パック（1センチメートル×6センチ）。エチル - ヘキサン（5:95）の混合溶媒でカラムを飽和します。 </li><li>ガラスカラムの上部に慎重に集中ろ液を注ぎます。 </li><li>ゆっくりとガラスカラムに溶媒混合物を追加し、1200ミリリットルが収集されるまで、画分のすべてを収集します。 </li><li>乾燥するまでロータリーエバポレーターで有機画分（1200ミリリットル）を濃縮します。 </li><li>精製されたバニリンである最終的な固体粉末を回復します。 </li></ol></li></ol>

<ol>
	<li>Corma, A., Garc&#237;a, H., Llabr&#233;s i Xamena, F. X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Engineering+Metal+Organic+Frameworks+for+Heterogeneous+Catalysis.">Engineering Metal Organic Frameworks for Heterogeneous Catalysis.</a> Chem. Rev. 110 (8), 4606-4655 (2010).</li><li>Gascon, J., Corma, A., Kapteijn, F., Llabr&#233;s i Xamena, F. X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal+Organic+Framework+Catalysis:+Quo+vadis?.">Metal Organic Framework Catalysis: Quo vadis?.</a> ACS Catal. 4 (2), 361-378 (2014).</li><li>Ranocchiari, M., van Bokhoven, J. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalysis+by+metal-organic+frameworks:+fundamentals+and+opportunities.">Catalysis by metal-organic frameworks: fundamentals and opportunities.</a> Phys. Chem. Chem. Phys. 13, 6388-6392 (2011).</li><li>Dhakshinamoorthy, A., Alvaro, M., Garcia, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Commercial+metal-organic+frameworks+as+heterogeneous+catalysts.">Commercial metal-organic frameworks as heterogeneous catalysts.</a> Chem. Commu. 48 (92), 11275-11288 (2012).</li><li>Corma, A., Garc&#237;a, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lewis+Acids+as+Catalysts+in+Oxidation+Reactions:+From+Homogeneous+to+Heterogeneous+Systems.">Lewis Acids as Catalysts in Oxidation Reactions: From Homogeneous to Heterogeneous Systems.</a> Chem. Rev. 102 (10), 3837-3892 (2002).</li><li>Corma, A., Garc&#237;a, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lewis+Acids:+From+Conventional+Homogeneous+to+Green+Homogeneous+and+Heterogeneous+Catalysis.">Lewis Acids: From Conventional Homogeneous to Green Homogeneous and Heterogeneous Catalysis.</a> Chem. Rev. 103 (11), 4307-4366 (2003).</li><li>Chui, S. S. Y., Lo, S. M. F., Charmant, J. P. H., Orpen, A. G., Williams, I. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Chemically+Functionalizable+Nanoporous+Material+[Cu3(TMA)2(H2O)3]n.">A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n.</a> Science. 283 (5405), 1148-1150 (1999).</li><li>Farha, O. K., Shultz, A. M., Sarjeant, A. A., Nguyen, S. T., Hupp, J. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Active-Site-Accessible,+Porphyrinic+Metal&#8722;Organic+Framework+Materials.">Active-Site-Accessible, Porphyrinic Metal&#8722;Organic Framework Materials.</a> J. Am. Chem. Soc. 133 (15), 5652-5655 (2011).</li><li>Zhang, J. P., Horike, S., Kitagawa, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Flexible+Porous+Coordination+Polymer+Functionalized+by+Unsaturated+Metal+Clusters.">A Flexible Porous Coordination Polymer Functionalized by Unsaturated Metal Clusters.</a> Angew. Chem. Int. Ed. 46 (6), 889-892 (2007).</li><li>Wang, Z., Cohen, S. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Postsynthetic+modification+of+metal-organic+frameworks.">Postsynthetic modification of metal-organic frameworks.</a> Chem. Soc. Rev. 38 (5), 1315-1329 (2009).</li><li>Llabresi Xamena, F. X., Luz, J., Cirujano, F. G., Llabres i Xamena, F. X., Gascon, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chapter+7,+Strategies+for+Creating+Active+Sites+in+MOFs.">Chapter 7, Strategies for Creating Active Sites in MOFs.</a> Metal organic frameworks as heterogeneous catalysts. , (2013).</li><li>Cho, S. H., Ma, B., Nguyen, S. T., Hupp, J. T., Albrecht-Schmitt, T. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+metal-organic+framework+material+that+functions+as+an+enantioselective+catalyst+for+olefin+epoxidation.">A metal-organic framework material that functions as an enantioselective catalyst for olefin epoxidation.</a> Chem. Commun. (24), 2563-2565 (2006).</li><li>Xie, M. H., Yang, X. L., Wu, C. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+metalloporphyrin+functionalized+metal-organic+framework+for+selective+oxidization+of+styrene.">A metalloporphyrin functionalized metal-organic framework for selective oxidization of styrene.</a> Chem. Commun. 47 (19), 5521-5523 (2011).</li><li>Zhang, X., Llabr&#233;s i Xamena, F. X., Corma, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Gold(III)+-+metal+organic+framework+bridges+the+gap+between+homogeneous+and+heterogeneous+gold+catalysts.">Gold(III) - metal organic framework bridges the gap between homogeneous and heterogeneous gold catalysts.</a> J. Catal. 265 (2), 155-160 (2009).</li><li>Bohnsack, A. M., Ibarra, I. A., Bakhmutov, V. I., Lynch, V. M., Humphrey, S. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rational+Design+of+Porous+Coordination+Polymers+Based+on+Bis(phosphine)MCl2+Complexes+That+Exhibit+High-Temperature+H2+Sorption+and+Chemical.">Rational Design of Porous Coordination Polymers Based on Bis(phosphine)MCl2 Complexes That Exhibit High-Temperature H2 Sorption and Chemical.</a> J. Am. Chem. Soc. 135 (43), 16038-16041 (2013).</li><li>Ingleson, M. J., Perez-Barrio, J., Guilbaud, J. B., Khimyak, Y. Z., Rosseinsky, M. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Framework+functionalisation+triggers+metal+complex+binding.">Framework functionalisation triggers metal complex binding.</a> Chem. Commun. (23), 2680-2682 (2008).</li><li>Burrows, A. D., Frost, C. G., Mahon, M. F., Richardson, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Post-Synthetic+Modification+of+Tagged+Metal-Organic+Frameworks.">Post-Synthetic Modification of Tagged Metal-Organic Frameworks.</a> Angew. Chem. Int. Ed. 47 (44), 8482-8486 (2008).</li><li>Dinc&#259;, M., Long, J. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrogen+Storage+in+Microporous+Metal-Organic+Frameworks+with+Exposed+Metal+Sites.">Hydrogen Storage in Microporous Metal-Organic Frameworks with Exposed Metal Sites.</a> Angew. Chem. Int. Ed. 47 (36), 6766-6779 (2008).</li><li>Ibarra, I. 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=Structures+and+H2+Adsorption+Properties+of+Porous+Scandium+Metal-Organic+Frameworks.">Structures and H2 Adsorption Properties of Porous Scandium Metal-Organic Frameworks.</a> Chem. Eur. J. 16 (46), 13671-13679 (2010).</li><li>Gustafsson, 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=A+Family+of+Highly+Stable+Lanthanide+Metal&#8722;Organic+Frameworks:+Structural+Evolution+and+Catalytic+Activity.">A Family of Highly Stable Lanthanide Metal&#8722;Organic Frameworks: Structural Evolution and Catalytic Activity.</a> Chem. Mater. 22 (11), 3316-3322 (2010).</li><li>Mitchell, L., 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=Remarkable+Lewis+acid+catalytic+performance+of+the+scandium+trimesate+metal+organic+framework+MIL-100(Sc)+for+C-C+and+C=N+bond-forming+reactions.">Remarkable Lewis acid catalytic performance of the scandium trimesate metal organic framework MIL-100(Sc) for C-C and C=N bond-forming reactions.</a> Catal. Sci. Technol. 3 (3), 606-617 (2013).</li><li>Jeong, K. 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=Asymmetric+catalytic+reactions+by+NbO-type+chiral+metal-organic+frameworks.">Asymmetric catalytic reactions by NbO-type chiral metal-organic frameworks.</a> Chem. Sci. 2 (5), 877-882 (2011).</li><li>Henschel, A., Gedrich, K., Kraehnert, R., Kaskel, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalytic+properties+of+MIL-101.">Catalytic properties of MIL-101.</a> Chem. Commun. (35), 4192-4194 (2008).</li><li>Dhakshinamoorthy, 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=Iron(III)+metal-organic+frameworks+as+solid+Lewis+acids+for+the+isomerization+of+&#945;-pinene+oxide.">Iron(III) metal-organic frameworks as solid Lewis acids for the isomerization of &#945;-pinene oxide.</a> Catal. Sci. Techol. 2 (2), 324-330 (2012).</li><li>Kurfi&#345;tov&#225;, L., Seo, Y. K., Hwang, Y. K., Chang, J. S., &#268;ejka, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High+activity+of+iron+containing+metal-organic-framework+in+acylation+of+p-xylene+with+benzoyl+chloride.">High activity of iron containing metal-organic-framework in acylation of p-xylene with benzoyl chloride.</a> Catal. Today. 179 (1), 85-90 (2012).</li><li>Beier, M. 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=Aerobic+Epoxidation+of+Olefins+Catalyzed+by+the+Cobalt-Based+Metal-Organic+Framework+STA-12(Co).">Aerobic Epoxidation of Olefins Catalyzed by the Cobalt-Based Metal-Organic Framework STA-12(Co).</a> Chem. Eur. J. 18 (3), 887-898 (2012).</li><li>Ruano, D., D&#237;az-Garc&#237;a, M., Alfayate, A., S&#225;nchez-S&#225;nchez, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanocrystalline+M-MOF-74+as+Heterogeneous+Catalysts+in+the+Oxidation+of+Cyclohexene:+Correlation+of+the+Activity+and+Redox.">Nanocrystalline M-MOF-74 as Heterogeneous Catalysts in the Oxidation of Cyclohexene: Correlation of the Activity and Redox.</a> Chem. Cat. Chem. 7 (4), 674-681 (2015).</li><li>Prestipino, C., 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=Local+Structure+of+Framework+Cu(II)+in+HKUST-1+Metallorganic+Framework:Spectroscopic+Characterization+upon+Activation+and+Interaction+with+Adsorbates.">Local Structure of Framework Cu(II) in HKUST-1 Metallorganic Framework:Spectroscopic Characterization upon Activation and Interaction with Adsorbates.</a> Chem. Mater. 18 (5), 1337-1346 (2006).</li><li>Opanasenko, 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=Comparison+of+the+catalytic+activity+of+MOFs+and+zeolites+in+Knoevenagel+condensation.">Comparison of the catalytic activity of MOFs and zeolites in Knoevenagel condensation.</a> Catal. Sci. Technol. 3 (2), 500-507 (2013).</li><li>P&#233;rez-Mayoral, E., 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+of+quinolines+via+Friedl&#228;nder+reaction+catalyzed+by+CuBTC+metal-organic-framework.">Synthesis of quinolines via Friedl&#228;nder reaction catalyzed by CuBTC metal-organic-framework.</a> Dalton Trans. 41 (14), 4036-4044 (2012).</li><li>Schlichte, K., Kratzke, T., Kaskel, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Improved+synthesis,+thermal+stability+and+catalytic+properties+of+the+metal-organic+framework+compound+Cu3(BTC)2.">Improved synthesis, thermal stability and catalytic properties of the metal-organic framework compound Cu3(BTC)2.</a> Micropor. Mesopor. Mater. 73 (1-2), 81-88 (2004).</li><li>Addis, D., 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=Hydrosilylation+of+Ketones:+From+Metal-Organic+Frameworks+to+Simple+Base+Catalysts.">Hydrosilylation of Ketones: From Metal-Organic Frameworks to Simple Base Catalysts.</a> Chem. Asian J. 5 (11), 2341-2345 (2010).</li><li>Wu, 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=Kinetics+of+oxidation+of+hydroquinone+to+p-benzoquinone+catalyzed+by+microporous+metal-organic+frameworks+M3(BTC)2+[M+=+copper(II),+cobalt(II),+or+nickel(II);+BTC+=+benzene-1,3,5-tricarboxylate]+using+molecular+oxygen.">Kinetics of oxidation of hydroquinone to p-benzoquinone catalyzed by microporous metal-organic frameworks M3(BTC)2 [M = copper(II), cobalt(II), or nickel(II); BTC = benzene-1,3,5-tricarboxylate] using molecular oxygen.</a> Transition Met. Chem. 34 (3), 263-268 (2009).</li><li>Marx, S., Kleist, W., Baiker, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis,+structural+properties,+and+catalytic+behavior+of+Cu-BTC+and+mixed-linker+Cu-BTC-PyDC+in+the+oxidation+of+benzene+derivatives.">Synthesis, structural properties, and catalytic behavior of Cu-BTC and mixed-linker Cu-BTC-PyDC in the oxidation of benzene derivatives.</a> J. Catal. 281 (1), 76-87 (2011).</li><li>May, P., Cotton, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Molecules That Amaze Us. , 193 (2015).</li><li>Havkin-Frenkel, D., Belanger, F. C. <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 of Vanilla Science and Technology. , 3 (2011).</li><li>Zhao, 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=Preparation+of+ferulic+acid+from+corn+bran:+Its+improved+extraction+and+purification+by+membrane+separation.">Preparation of ferulic acid from corn bran: Its improved extraction and purification by membrane separation.</a> Food Bioprocess Technol. 92 (3), 309-313 (2014).</li><li>Gobley, T. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recherche+sur+le+principe+odorant+de+la+vanilla.">Recherche sur le principe odorant de la vanilla.</a> J. Pharm. Chem. 3, 401 (1858).</li><li>Tiemann, F., Haarmann, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Uber+das+coniferin+und+seine+Umwandlung+in+das+aromatisches+princip+der+vanilla.">Uber das coniferin und seine Umwandlung in das aromatisches princip der vanilla.</a> Ber. Dtsch. Chem. Ges. 7 (1), 608-623 (1858).</li><li>Dignum, M. J. W., Kerler, J., Verpoorte, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vanilla+production:+technological,+chemical,+and+biosynthetic+aspects.">Vanilla production: technological, chemical, and biosynthetic aspects.</a> Food. Rev. Int. 17 (2), 199-219 (2001).</li><li>Walton, N. J., Mayer, M. J., Narbad, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vanilin.">Vanilin.</a> Phytochemistry. 63 (5), 505-515 (2003).</li><li>Serra, S., Fuganti, C., Brenna, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Biocatalytic+preparation+of+natural+flavours+and+fragrances.">Biocatalytic preparation of natural flavours and fragrances.</a> Trends Biotechnol. 23 (4), 193-198 (2005).</li><li>Longo, M. A., Sanrom&#225;n, M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Production+of+Food+Aroma+Compounds:+Microbial+and+Enzymatic+Methodologies.">Production of Food Aroma Compounds: Microbial and Enzymatic Methodologies.</a> Food Technol. Biotechnol. 44 (3), 335-353 (2006).</li><li>Yepez, R., 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=Catalytic+activity+of+HKUST-1+in+the+oxidation+of+trans-ferulic+acid+to+vanillin.">Catalytic activity of HKUST-1 in the oxidation of trans-ferulic acid to vanillin.</a> New. J. Chem. 39 (7), 5112-5115 (2015).</li></ol>

The authors have nothing to disclose.

バニリンへのトランス -ferulic酸の触媒変換のための基本的なステップは、触媒（HKUST-1）の活性化でした。触媒は、（真空下で100℃で）、その場で活性化されていない場合、バニリンのトランス -ferulic酸の唯一の部分的変換は44を観察しました。換言すれば、金属部位を開くためのアクセス可能性は、触媒サイクル44のために重要であり、これは、多孔性配位高分子の中のCu（II）金属部位に配位した水を除去することによって達成することができます。 従って、この現象を調べるため三赤外線実験を行いました。最初の実験、HKUST-1（ 図1）の非活性化サンプルのFTIRスペクトルは3400センチメートル-1および3680センチメートル-1まとまりのない水（広い吸収帯）と協調水に対応するで特徴的な吸収バンドを示した（シャープ吸収バンド）、それぞれ。第二に、従来のオーブン（空気にさらさ）で活性化HKUST-1サンプルは、前の実験と比較して最小限の変更でFTIRスペクトルを示した：3400センチメートルでの吸収帯の強度の減少-1が、上の変化はありません3680センチメートル-1（ 図1）で鋭い吸収帯。この変更は、まとまりのない水の不完全な損失とCu（II）金属イオンへの配位水のメンテナンスを示唆しました。最後に、 その場で活性化された触媒のFTIRスペクトルは、吸収の強度に失われた二つの大きな変化（非活性化触媒に関して）、3400センチメートルでの吸収帯の強度を大幅に削減-1および完全性を示し3680センチメートルのバンド-1。触媒を真空（10 -2バール）下に100℃で活性化されたときにこのように、Cu（II）オープン金属部位への完全なアクセスを取得することが可能です。任意の水moleculの除去HKUST-1の細孔内部エス（非かつ協調的）。 触媒反応が終了すると（ 図2）44、触媒を濾過により容易に回収することができ、再利用します。もちろん、それは（10 -2バール、100℃で、真空下で）再活性化されなければなりません。触媒が回収されると、再活性化プロセスを容易にするために、約200 mlの酢酸エチルを用いてそれを洗浄することは必要とされています。その後、触媒を回収し、最終的に活性化システム（ 上記参照）中に移し、30分間（ブフナー漏斗上で）、室温で放置することができます。 反応のスケールアップは、この実験技術の現在の制限です。使用される触媒の最大量は44（フラッシュカラムクロマトグラフィーによるバニリンの単離後に得られた）は95％の変換収率をもたらし0.05 gでした。この触媒反応は、より高いquantitieで行われました触媒のS（結果的に、より多くのフェルラ酸と化学物質の残りの部分）と、変換収率が大幅にダウンして低下しました。 過酸化水素による活性化された不均一系触媒の組み合わせのみが、トランス -ferulic酸の酸化を触媒するために必要とされます。 （H 2 O 2なしHKUST-1と他ことなく、1）異種の触媒変換、ブランクテストを識別するために44行い ​​ました 。これらの反応が完了した後、同じ条件で、製品組成の分析は、バニリン44の存在を示しませんでした。 ここで提示触媒方法は、不均一系触媒（HKUST-1）は、それがその場で活性化されるとバニリンするトランス -ferulic酸の効果的な変換のために使用することができる方法を示しました。これは、再利用された後さらに、触媒の結晶化度の保持率は、PXRD 44によって確証しました。前の合成バニリンの方法論は、強力な酸化剤と毒性の溶媒41から43を使用しています。現在の方法論は完全にこのような危険を回避し、それはまた、不均一系触媒（HKUST-1）を再利用する機能を提供します。 最後に、我々は別のα、β不飽和カルボン酸の酸化のための触媒技術の適用性を調べています。

不均一系触媒1-4のような多孔性配位高分子（のPCP）の使用は比較的新しい研究分野です。 PCPが示す非常に興味深い特性、 例えば、多孔性の規則性、高表面積と金属のアクセスのために、彼らは不均一系触媒5-6のための新たな選択肢を提供することができます。触媒活性のPCPの生成は、多くの研究グループ7-10の主な焦点となっています。多孔性配位高分子は、金属イオン、有機リンカーで構成され、したがって、これらの材料の触媒活性は、これらの部品のいずれかによって提供されます。いくつかのPCPは、化学反応11を触媒することができる不飽和（アクティブ）な金属が含まれています。しかし、配位高分子内の不飽和金属部位（オープン金属部位）の生成は簡単な作業ではありません、それはに要約することができる合成挑戦表す：不安定なリガンド7-11の除去により空い協調の生成（i）を 、（ii）の有機金属配位子（あらかじめ合成）8,12-13を組み込むことにより、バイメタルのPCPの生成を、 （iii）の金属イオンのPCPの細孔内9,14-15または有機配位子10、16-17の合成後の変化。方法（i）は 、従って最も簡単であるので、最も頻繁に使用されます。典型的に、開いた金属部位の生成はH 2 18〜19の方へのPCPの親和性を高めるために使用されているだけでなく、活性の不均一触媒を20〜27を設計します。良好な触媒特性を達成するために、のPCPは、さらに開いた金属部位のアクセシビリティに、反応条件、熱安定性および化学的安定性が比較的高い触媒実験後の結晶化度の保持率を示す必要があります。 HKUST-1銅（Cu 3（BTC）2（H 2 O）3、BTC = 1,3,5-ベンゼントリカルボキシレート）7カルボキシレート配位子と水に配位されたCu（II）陽イオンで構成よく調べ多孔性配位高分子、。興味深いことに、これらの水分子は、（加熱により）除去することができ、これはハードルイス酸特性11を示す銅イオンの周りの正方形平面調整を提供します。 Bordigaと 共同研究者28は、これらの H 2 O分子の脱離は、結晶性（規則性の保持）と金属イオンの酸化状態（銅（II））の影響を受けなかった影響を及ぼさなかったことを示しました。触媒としてHKUST-1の使用は広範囲に芳香族分子34の過酸化水素による酸化（本研究のために非常に関連する）29-33を調査し、特にされています。 バニラは、化粧品、医薬品及び食品産業において最も広く使用されている香味剤の一つです。これは、蘭ヴァニラプラニフォリア、バニの硬化豆から抽出されますLLAのtahitiensisとバニラポンポン 。それはチョコレートフレーバー35-37が改善するので、マヤやアステカ文明（プレコロンビア人）は、最初の香味剤としてバニラの莫大な可能性を実現しました。バニラは、まず1858年38で分離された、それはバニリンの化学構造が最終的に決定されたことを1874年39までではなかったです。 （蘭ヴァニラプラニフォリア、バニラtahitiensisとバニラのポンポンから）バニリンの天然抽出は世界生産の1％のみを表しており、このプロセスは高価であり、40は非常に長いため、バニリンの残りの部分は、40合成されます。これらのプロセスは、強力な酸化剤および毒性の溶媒41〜43を使用するので、多くの生物工学的手法等リグニン、フェノールスチルベン、イソオイゲノール、オイゲノール、guaicolからバニリンの合成に用いることができるが、これらの方法は、環境に害を与えるという欠点を有します。ここで、我々はrを触媒としてHKUST-1を使用して、トランス -ferulic酸の酸化によってバニリンの製造のための合成戦略をEPORT。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>HKUST-1</td>
			<td>Sigma-Aldrich</td>
			<td>MFCD10567003</td>
			<td></td>
		</tr>
		<tr>
			<td>Ferulic Acid (trans-4-Hydroxy-3-methoxycinnamic acid)</td>
			<td>Sigma-Aldrich</td>
			<td>537-98-4</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethanol</td>
			<td>Sigma-Aldrich</td>
			<td>64-17-5</td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrogen peroxide solution</td>
			<td>Sigma-Aldrich</td>
			<td>&#160;7722-84-1</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetonitrile</td>
			<td>Sigma-Aldrich</td>
			<td>75-05-8</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Sigma-Aldrich</td>
			<td>141-78-6</td>
			<td></td>
		</tr>
		<tr>
			<td>Ammonium chloride</td>
			<td>Sigma-Aldrich</td>
			<td>12125-02-9</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium sulfate anhydrous</td>
			<td>Sigma-Aldrich</td>
			<td>7757-82-6</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Sigma-Aldrich</td>
			<td>141-78-6</td>
			<td></td>
		</tr>
		<tr>
			<td>n-Hexane</td>
			<td>Sigma-Aldrich</td>
			<td>110-54-3</td>
			<td></td>
		</tr>
		<tr>
			<td>Silica Gel</td>
			<td>Sigma-Aldrich</td>
			<td>112926-00-8</td>
			<td>&#160;Size 70/230</td>
		</tr>
		<tr>
			<td>250 mL two-neck round-bottom flask</td>
			<td>Sigma-Aldrich</td>
			<td>Z516872-1EA</td>
			<td>250 mL capacity</td>
		</tr>
		<tr>
			<td>Magnetic stirring bar</td>
			<td>Bel-Art products</td>
			<td>371100002</td>
			<td>Teflon, octagon</td>
		</tr>
		<tr>
			<td>Condenser</td>
			<td>Cole-Parmer</td>
			<td>JZ-34706-00</td>
			<td>200 mm Jacket length</td>
		</tr>
		<tr>
			<td>Vacuum pump (Approx. 10X-2 bar)</td>
			<td>Cole-Parmer</td>
			<td>JZ-78162-00</td>
			<td>Vacuum/Pressure Diaphragm Pump</td>
		</tr>
		<tr>
			<td>Stopcock</td>
			<td>Cole-Parmer</td>
			<td>EW-30600-00</td>
			<td>with a male luer slip</td>
		</tr>
		<tr>
			<td>Hose</td>
			<td>Cole-Parmer</td>
			<td>JZ-06602-04</td>
			<td>16.0 mm ID and 23.2 mm ED</td>
		</tr>
		<tr>
			<td>Rubber septums</td>
			<td>Cole-Parmer</td>
			<td>JZ-08918-34</td>
			<td>Silicone with PTFE coating</td>
		</tr>
		<tr>
			<td>Hot plate</td>
			<td>Cole-Parmer</td>
			<td>JZ-04660-15</td>
			<td>10.2 cm x 10.2 cm, 5 to 540 &#176;C</td>
		</tr>
		<tr>
			<td>Sand bath&#160;</td>
			<td>Cole-Parmer</td>
			<td>GH-01184-00</td>
			<td>Fluidized Sand Bath SBS-4, 50 to 600 &#176;C</td>
		</tr>
		<tr>
			<td>N2 gas</td>
			<td>INFRA</td>
			<td>Cod. 103</td>
			<td>Cylinder 9m &#179;</td>
		</tr>
		<tr>
			<td>Ballons (filled with N2 gas)</td>
			<td>Sigma-Aldrich</td>
			<td>Z154989-100EA</td>
			<td>Thick-wall, natural latex rubber</td>
		</tr>
		<tr>
			<td>Syringes with removable needles</td>
			<td>Sigma-Aldrich</td>
			<td>Z116912-100EA</td>
			<td>10 mL capacity</td>
		</tr>
		<tr>
			<td>Filter paper</td>
			<td>Cole-Parmer</td>
			<td>JZ-81050-24</td>
			<td>Grade No. 235 qualitative filter paper (90 mm diameter disc)</td>
		</tr>
		<tr>
			<td>Buchner funnel</td>
			<td>Cole-Parmer</td>
			<td>JZ-17815-04</td>
			<td>320 mL capacity which accept standard paper filter sizes&#160;</td>
		</tr>
		<tr>
			<td>Buchner flask</td>
			<td>Cole-Parmer</td>
			<td>JZ-34557-02</td>
			<td>250 mL capacity</td>
		</tr>
		<tr>
			<td>Rotary Evaporator</td>
			<td>Cole-Parmer</td>
			<td>JZ-28710-02</td>
			<td></td>
		</tr>
		<tr>
			<td>Beakers</td>
			<td>Cole-Parmer</td>
			<td>JZ-34502-(02,04,05)</td>
			<td>Pyrex Brand 1000 Griffin; 20, 50 and 100 mL</td>
		</tr>
		<tr>
			<td>Separation funnel&#160;</td>
			<td>Cole-Parmer</td>
			<td>JZ-34505-44</td>
			<td>Capacity for 125 mL with steam lenght of 60 mm</td>
		</tr>
		<tr>
			<td>Glass column for chromatography</td>
			<td>Cole-Parmer</td>
			<td>JZ-34695-42</td>
			<td>Column with fritted disk, 10.5 mm ID x 250 mm L</td>
		</tr>
		<tr>
			<td>PXRD diffractometer</td>
			<td>Bruker</td>
			<td></td>
			<td>AXS D8 Advance XRD</td>
		</tr>
		<tr>
			<td>FTIR spectrophotometer</td>
			<td>Thermo scientific</td>
			<td>FT-IR (JZ-83008-02); ATR (JZ-83008-26)</td>
			<td>Nicolet iS5 FT-IR Spectrometer, with KBr Windows and iD5 Diamond ATR</td>
		</tr>
	</tbody>
</table>

hkust-1 as a heterogeneous catalyst for the synthesis of vanillin

バニリン（4-hydoxy -3-メトキシベンズアルデヒド）は、バニラ豆の抽出物の主成分です。自然なバニラの香りは、バニリンに加えて、約200の異なる着臭剤化合物の混合物です。 （蘭ヴァニラプラニフォリア、バニラtahitiensisとバニラのポンポンから）バニリンの天然抽出は世界生産の1％のみを表しており、このプロセスは高価であり、非常に長いため、バニリンの生産の残りの部分が合成されます。多くの生物工学的ア ​​プローチは、これらのプロセスは、強力な酸化剤と有毒な溶媒を使用するので、環境に害を与えるという欠点を有する等リグニン、フェノールスチルベン、イソオイゲノール、オイゲノール、guaicolからバニリンの合成に使用することができます。このように、バニリンの生産に環境に優しい代替案は、現在調査中で、このように非常に望ましいものであると。多孔性配位高分子（のPCP）はREC高結晶性物質の新しいクラスでありますまったく別触媒反応のために使用されています。 HKUST-1銅（Cu 3（BTC）2（H 2 O）3、BTC = 1,3,5-ベンゼントリカルボキシレート）は、広く不均一触媒として研究されている、非常によく知られたPCPです。ここでは、触媒としてHKUST-1を使用して、トランス -ferulic酸の酸化によるバニリンの製造のための合成戦略を報告しています。

HKUST-1の3つの代表的なサンプルは、赤外分光法によって分析した：非活性化、（空気にさらさ）オーブン中で1時間100℃で活性化され、1 100℃で真空（10 -2バール）下で活性化時間。したがって、フーリエ変換赤外（FTIR）スペクトルは、単反射ダイヤモンドATRアクセサリー（ 図1）を有する分光計を用いて記録した変換します。すべてのスペクトルは、4000〜400センチで-1の範囲64スキャンを4センチ-1のスペクトル分解能で記録しました。 触媒としてHKUST-1を用いたトランス -ferulic酸の酸化から精製された生成物の組成を確認するために、1 H-NMRスペクトルは、25°C（ 図で11.74 Tの静磁場下でNMR分光計で行いました2）。そのために、5mgの試料をNMR試験管に導入し、重水素を入れる0.5mlのDクロロホルム（CDCl 3中）を加えました。 <img alt="図1" src="/files/ftp_upload/54054/54054fig1.jpg" /> 図1：25℃ での触媒（HKUST-1）のFTIRスペクトル非アクティブ化（緑線）、従来のオーブン（紫の線）で活性化し、真空（オレンジライン）で活性化。センター国立デラRECHERCHE科学研究（CNRS）と化学の王立協会の許可を得て、基準44から再生された。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54054/54054fig1large.jpg" target="_blank">この図の拡大版をご覧になるにはこちらをクリックしてください。</a> <img alt="図2" src="/files/ftp_upload/54054/54054fig2.jpg" /> 触媒（HKUST-1）を真空下で活性化したシリカゲル上でのカラムクロマトグラフィー精製後バニリンの1 H-NMRスペクトル（10 &lt;：図2SUP&gt; -5バー）および1時間100℃。

Watch this Scientific Journal Video about HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin at JoVE.com

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

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 ...

hkust-1-as-a-heterogeneous-catalyst-for-the-synthesis-of-vanillin

Nanyang Technological University

Research

JoVE Journal

Chemistry

10.1K ビュー.  Autonomous Metropolitan University-Azcapotzalco. 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. 

ビデオ: HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. Diiodomethyllithium is prepared by the deprotonation of diiodomethane with LiHMDS, in a THF/diethyl ether mixture, at -78 &#176;C in the dark. These conditions are essential for the stability of the LiCHI2 reagent generated. The subsequent dropwise addition of N-Ts aldimines to the preformed diiodomethyllithium solution affords an amino-diiodide intermediate, which is not isolated. Rapid warming of the reaction mixture to 0 &#176;C promotes cyclization to afford iodoaziridines with exclusive cis-diastereoselectivity. The addition and cyclization stages of the reaction are mediated in one reaction flask by careful temperature control.
Due to the sensitivity of the iodoaziridines to purification, assessment of suitable methods of purification is required. A protocol to assess the stability of sensitive compounds to stationary phases for column chromatography is described. This method is suitable to apply to new iodoaziridines, or other potentially sensitive novel compounds. Consequently this method may find application in range of synthetic projects. The procedure involves firstly the assessment of the reaction yield, prior to purification, by 1H NMR spectroscopy with comparison to an internal standard. Portions of impure product mixture are then exposed to slurries of various stationary phases appropriate for chromatography, in a solvent system suitable as the eluent in flash chromatography. After stirring for 30 min to mimic chromatography, followed by filtering, the samples are analyzed by 1H NMR spectroscopy. Calculated yields for each stationary phase are then compared to that initially obtained from the crude reaction mixture. The results obtained provide a quantitative assessment of the stability of the compound to the different stationary phases; hence the optimal can be selected. The choice of basic alumina, modified to activity IV, as a suitable stationary phase has allowed isolation of certain iodoaziridines in excellent yield and purity.

A protocol for the diastereoselective one-pot preparation of cis-N-Ts-iodoaziridines is described. The generation of diiodomethyllithium, addition to N-Ts aldimines and cyclization of the amino gem-diiodide intermediate to iodoaziridines is demonstrated. Also included is a protocol to rapidly and quantitatively assess the most appropriate stationary phase for purification by chromatography.

クロマトグラフィーのための最適な固定相の定量的な選択を伴う合成とIodoaziridinesの精製

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. ...

化学

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

ビスピリジン系リガンドの合成と二核抗癌剤として白金彼らの複合体形成のためのアミドカップリング反応

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

Synthesis of Cd-free InP/ZnS Quantum Dots Suitable for Biomedical Applications

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, quantum dots should be highly fluorescent and small/monodisperse in size. While commonly used cadmium-based quantum dots possess these qualities, they are potentially toxic due to the possible release of Cd2+ ions through nanoparticle degradation. Indium-based quantum dots, specifically InP/ZnS, have recently been explored as a viable alternative to cadmium-based quantum dots due to their relatively similar fluorescence characteristics and size. The synthesis presented here uses standard hot-injection techniques for effective nanoparticle growth; however, nanoparticle properties such as size, emission wavelength, and emission intensity can drastically change due to small changes in the reaction conditions. Therefore, reaction conditions such temperature, reaction duration, and precursor concentration should be maintained precisely to yield reproducible products. Because quantum dots are not inherently soluble in aqueous solutions, they must also undergo surface modification to impart solubility in water. In this protocol, an amphiphilic polymer is used to interact with both hydrophobic ligands on the quantum dot surface and bulk solvent water molecules. Here, a detailed protocol is provided for the synthesis of highly fluorescent InP/ZnS quantum dots that are suitable for use in biomedical applications.

In this protocol, the synthesis of Cd-free InP/ZnS quantum dots (QDs) is detailed. InP-based QDs are gaining popularity due to the toxicity of Cd2+ ions that may be released through nanoparticle degradation. After synthesis, QDs are solubilized in water using an amphiphilic polymer for use in biomedical applications.

バイオメディカル応用のための適切なカドミウムフリーのInP / ZnSの量子ドットの合成

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, ...

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of trifluoromethoxylated aromatic compounds remains a formidable challenge in organic synthesis. Conventional approaches often suffer from poor substrate scope, or require use of highly toxic, difficult-to-handle, and/or thermally labile reagents. Herein, we report a user-friendly protocol for the synthesis of methyl 4-acetamido-3-(trifluoromethoxy)benzoate using 1-trifluoromethyl-1,2-benziodoxol-3(1H)-one (Togni reagent II). Treating methyl 4-(N-hydroxyacetamido)benzoate (1a) with Togni reagent II in the presence of a catalytic amount of cesium carbonate (Cs2CO3) in chloroform at RT afforded methyl 4-(N-(trifluoromethoxy)acetamido)benzoate (2a). This intermediate was then converted to the final product methyl 4-acetamido-3-(trifluoromethoxy)benzoate (3a) in nitromethane at 120 &#176;C. This procedure is general and can be applied to the synthesis of a broad spectrum of ortho-trifluoromethoxylated aniline derivatives, which could serve as useful synthetic building blocks for the discovery and development of new pharmaceuticals, agrochemicals, and functional materials.

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

An operationally simple procedure for the synthesis of ortho-trifluoromethoxylated aniline derivatives via a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxyacetamide followed by thermally induced intramolecular OCF3-migration is reported.

の合成のためのプロトコル<em&gt;オルソ</em&gt; -trifluoromethoxylatedアニリン誘導体

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

タンパク質のバイオコンジュゲートの合成<em&gt;経由で</em&gt;システイン - マレイミドケミストリー

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

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 ...

NMR Spectroscopy as a Robust Tool for the Rapid Evaluation of the Lipid Profile of Fish Oil Supplements

The western diet is poor in n-3 fatty acids, therefore the consumption of fish oil supplements is recommended to increase the intake of these essential nutrients. The objective of this work is to demonstrate the qualitative and quantitative analysis of encapsulated fish oil supplements using high-resolution 1H and 13C NMR spectroscopy utilizing two different NMR instruments; a 500 MHz and an 850 MHz instrument. Both proton (1H) and carbon (13C) NMR spectra can be used for the quantitative determination of the major constituents of fish oil supplements. Quantification of the lipids in fish oil supplements is achieved through integration of the appropriate NMR signals in the relevant 1D spectra. Results obtained by 1H and 13C NMR are in good agreement with each other, despite the difference in resolution and sensitivity between the two nuclei and the two instruments. 1H NMR offers a more rapid analysis compared to 13C NMR, as the spectrum can be recorded in less than 1 min, in contrast to 13C NMR analysis, which lasts from 10 min to one hour. The 13C NMR spectrum, however, is much more informative. It can provide quantitative data for a greater number of individual fatty acids and can be used for determining the positional distribution of fatty acids on the glycerol backbone. Both nuclei can provide quantitative information in just one experiment without the need of purification or separation steps. The strength of the magnetic field mostly affects the 1H NMR spectra due to its lower resolution with respect to 13C NMR, however, even lower cost NMR instruments can be efficiently applied as a standard method by the food industry and quality control laboratories.

Here, high-resolution 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopy was used as a rapid and reliable tool for quantitative and qualitative analysis of encapsulated fish oil supplements.

魚油サプリメントの脂質プロファイルの迅速な評価のための強力なツールとしてNMR分光法

The western diet is poor in n-3 fatty acids, therefore the consumption of fish oil supplements is recommended to increase the intake of these essential ...

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). In the case of fast reversible electrochemical processes, current is predominantly affected by the rate of diffusion, which is the slowest and limiting stage. EIS is a powerful technique that allows separate analysis of stages of charge transfer that have different AC frequency response. The capability of the method was used to extract the value of charge transfer resistance, which characterizes the rate of charge exchange on the electrode-solution interface. The application of this technique is broad, from biochemistry up to organic electronics. In this work, we are presenting the method of analysis of organic compounds for optoelectronic applications.

Electrochemical impedance spectroscopy (EIS) of species that undergo reversible oxidation or reduction in solution was used for determination of rate constants of oxidation or reduction.

電気化学インピー ダンス分光電気化学定数推定法のためのツールとして

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity in aqueous CO2 reduction. Different from traditional metal nanocrystals, the synthesis of metal single atoms involves a matrix material that can confine those single atoms and prevent them from aggregation. We report an electrospinning and thermal annealing method to prepare Ni single atoms dispersed and coordinated in a graphene shell, as active centers for CO2 reduction to CO. During the synthesis, N dopants play a critical role in generating graphene vacancies to trap Ni atoms. Aberration-corrected scanning transmission electron microscopy and three-dimensional atom probe tomography were employed to identify the single Ni atomic sites in graphene vacancies. Detailed setup of electrochemical CO2 reduction apparatus coupled with an on-line gas chromatography is also demonstrated. Compared to metallic Ni, Ni single atom catalyst exhibit dramatically improved CO2 reduction and suppressed H2 evolution side reaction.

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Here, we present a protocol for the synthesis and electrochemical testing of transition metal single atoms coordinated in graphene vacancies as active centers for selective carbon dioxide reduction to carbon monoxide in aqueous solutions.

合成と電気化学的 CO2削減のため単一原子の遷移金属触媒の性能評価

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

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

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