This work was supported by the World Premier International Research Center (WPI) Initiative on Materials Nanoarchitectonics and a Grant-in-Aid for Challenging Exploratory Research (No. 26620139), both of which were provided from MEXT, Japan.

金属錯体モノマーの調製（2 CAS RN 1381776-70-0、3 CAS RN 1261168-42-6、4 CAS RN 1261168-43-7;図1） <ol><li> Ruの単量体2の調製 <ol><li>有機前駆体を結合（5 9 CAS RN 1381776-63-1; 図1）（380ミリグラム、0.48ミリモル）および[Ruの（Pシメン）のCl 2]二量体（224ミリグラム、0.37ミリモル）で攪拌棒を備えました100ミリリットルの一口丸底フラスコ。 </li><li>混合物にメタノール（MeOH中）（25ml）に追加フラスコの関節にコンデンサを接続し、温度制御した油浴中で3時間、65℃で懸濁液を撹拌します。 </li><li>反応混合物を室温に冷却し、吸引濾紙を通して懸濁液を濾過します。 </li><li>ろ液は、視覚的に無色になるまで徹底的にMeOHでフィルター上の残渣を洗浄し、減圧下で残留物を乾燥させます。 </li><li>残渣4を組み合わせる &#39; - （4-メチルフェニル）-2,2&#39;：6＆＃39;、単口丸底フラスコ100ml中に攪拌棒を備えた2 &quot; - ターピリジン（216ミリグラム、0.68ミリモル）。 </li><li>混合物をMeOH（22.5 mL）および水（2.5 ml）を追加し、フラスコの接合部にコンデンサを接続し、16時間70℃で懸濁液を撹拌します。 </li><li>反応混合物を室温に冷却し、懸濁液を濾過します。 </li><li>減圧下、フィルター上の残渣を乾燥し、ジメチルスルホキシド（DMSO）（3mL）中に溶解します。 </li><li>酢酸エチル（EtOAc）での過剰にゆっくりDMSO溶液を加えます。 </li><li> 、得られた懸濁液をフィルターをEtOAcでフィルター上の残留物を洗い、減圧下でそれを乾燥させます。 </li></ol></li><li> Ptのモノマー3の調製 <ol><li>で撹拌棒で（360ミリグラム、0.50ミリモル）およびPt（シクロオクタ-1,5-ジエン）のCl 2（195ミリグラム、0.52ミリモル）;有機前駆体を結合した （ 図1 6 4 CAS RN 1261168-39-1） 100ミリリットルの一口丸底フラスコ。&lt;/李&gt; <li>混合物をMeOH（15ml）に追加フラスコの関節にコンデンサを接続し、12時間65℃で懸濁液を撹拌します。 </li><li>反応混合物を室温に冷却し、懸濁液を濾過します。 </li><li> MeOHで徹底的にフィルター上の残渣を洗浄し、減圧下でそれを乾燥させます。 </li></ol></li><li> Rhのモノマー4の調製 <ol><li>単口丸底フラスコ100mlに攪拌棒を（360ミリグラム、0.50ミリモル）とのRhCl 3・3H 2 O（137ミリグラム、0.52ミリモル）;有機前駆体（ 図1〜6） を組み合わせます。 </li><li>混合物をMeOH（50ml）に追加フラスコの関節にコンデンサを接続し、N 2雰囲気下で12時間65℃で懸濁液を撹拌します。 </li><li>反応混合物を室温に冷却し、懸濁液を濾過します。 </li><li> MeOHで徹底的にフィルター上の残渣を洗浄し、減圧下でそれを乾燥させます。 </li></ol></li></oL&gt; 水溶性有機金属錯体アレイ1の調製<ol><li> TGシーバー樹脂からのFmoc脱保護 <ol><li>ガラスフィルターを備えた底部にドレインおよび双方向ストップコック（ 図2a）を有する10 2mlの口フラスコに攪拌棒と同様に、購入TGシーバー樹脂（135 mg）を組み合わせます。 3ウェイストップコックおよびガラス栓をフラスコの接合部に接続します。 </li><li>真空ラインを用いてN 2との内部雰囲気を交換した後、無水グレードのジクロロメタン（CH 2 Cl 2）（1ml）中（ 図2b）で樹脂を膨潤。 </li><li>このために、無水グレードのジメチルホルムアミド（DMF）（3ml）およびピペリジン（1 ml）を加え、室温で2.5時間混合物を撹拌します。 </li><li>ドレインを通して濾過することによって溶液を除去。無水グレードをMeOH（3ミリリットル、3分間の撹拌）および無水グレードを CH 2 Cl 2（3ミリリットル、3で樹脂を洗浄分間の撹拌）を交互に3回後、無水グレードCH 2 Cl 2で（3ミリリットル、3分間の撹拌）の4倍（ 図2c）。 </li><li> 2.1.4で得られたすべてのソリューションを組み合わせて、50ミリリットルの体積にアセトニトリル（CH 3 CN）でそれらを希釈します。 1センチ光路長石英キュベット中に得られた溶液のアリコート（1ml）に移し、CH 3 CN（2ml）でそれを希釈します。 </li><li>ピペリジンジベンゾフルベン付加物（299 nmで6234）10、以下に従ってプロトコル2.1.5を介して調製された溶液の分光学的に得られた吸光度（A）の吸光係数に基づいて、（マイクロモルf）の脱保護のFmoc部分のモル数を決定します式： F = 0.05×10 6×3×A / 6234 </li></ol></li><li> Ruのモノマー2の読み込み中 <ol><li>無水グレードのCH 2 Cl 2（2.5 ml）を、ルテニウムモノマー2を追加</strong&gt;（64.9ミリグラム、53.2モル）、2-（1H-ベンゾトリアゾール-1-イル）-1,1,3,3-テトラメチルウロニウムヘキサフルオロホスフェート（HBTU）（30.3ミリグラム、79.8モル）、無水グレードのDMSO（2.5 mlの）、の順にN、N-ジイソプロピルエチルアミン（iは 2ネットPR）（20μl）を、N 2雰囲気下で洗浄した樹脂に、室温（ 図2d）で12時間、混合物をかき混ぜます。 </li><li>ドレインを通して濾過することによって溶液を除去。無水グレードDMSO（3ミリリットル、5分間の撹拌）3回、無水グレードをMeOH（3ミリリットル、3分間の撹拌）および無水グレードを CH 2 Cl 2（3ミリリットル、3分間の撹拌）を交互に3回樹脂を洗浄、無水グレードを CH 2 Cl 2（3 mlで3分間攪拌）で3回。 </li><li>洗浄した樹脂と撹拌し、N 2雰囲気下でこの順に（0.10 mlであり、1.5ミリモル）の無水グレードのCH 2 Cl 2（5mL）に、無水安息香酸（0.28 gであり、1.5ミリモル）、及びN -methylimidazoleを追加室温で2時間混合物。 </li><li>ドレインを通して濾過することによって溶液を除去。無水グレードのCHと、次に（3ミリリットル、3分間の撹拌）を交互に3回とし、無水グレードのCH 2 Cl 2で樹脂（3ミリリットル、3分間の撹拌）および無水グレードのメタノールを洗う2 Cl 2の（3ミリリットル、3分攪拌）3回。 </li><li>ロードされたRuモノマー2のモル数を定量化するために2.1.3-2.1.6で説明したようにプロトコルを繰り返します。 </li></ol></li><li> Fmocとサイド残留物tert-ブチル（Buはt）の読み込み中は、（L） -グルタミン酸（Gluの）（;図1 7 CAS RN 71989-18-9）で保護しました <ol><li> （無水グレードの CH 2 Cl 2（4.5ミリリットル）、Gluの・H 2 O（39.4ミリグラム、88.8μmol）を、HBTU（50.5 mgを、133.2マイクロモル）、無水グレードDMSO（0.5ミリリットル）を追加し、 私は 2ネットをPrは洗浄した樹脂に、N 2雰囲気下で、この順に50μl）を、部屋TEで12時間混合物を攪拌mperature（ 図2E）。 注：Gluの量・H 2 OおよびHBTUは徐々に樹脂定数上の反応性-NH 2の機能への化学量論を維持するために2.7にステップ2.3から減少しています。 </li><li> 2.2.2-2.2.4に記載されているようにプロトコルを繰り返します。 </li><li> （フラスコから樹脂の小さな部分を取り、トリフルオロ酢酸（CF 3 CO 2 H）（2.5マイクロリットル）の混合物に入れ、トリエチルシラン（ET 3のSiH）（0.5μl）を、1,2-ジクロロエタン47μl）を。 0.5時間混合物を超音波処理し、質量分析4,7,8,9（ 図3a）のために得られた溶液を使用しています。 </li><li>ロードされたのGluのモル数を定量化するために2.1.3-2.1.6で説明したようにプロトコルを繰り返します。 </li></ol></li><li> Ptのモノマー3の読み込み中 <ol><li>無水グレードDMSO（4.5ミリリットル）、白金単量体（32.9 mgを、33.3マイクロモル）、HBTU（18.9ミリグラム、50.0マイクロモル）、無水グレードのCH 2を追加します。Cl 2（0.5ミリリットル）、および私のPr 2洗浄した樹脂に、N 2雰囲気下で、この順序の純（20μL）とは、室温（ 図2F）で12時間、混合物をかき混ぜます。 </li><li>白金ローディングモノマー3のモル数を定量化するために2.2.2-2.2.5で説明したようにプロトコルを繰り返します。 </li></ol></li><li> Gluの読み込み中 <ol><li> （無水グレードの CH 2 Cl 2（4.5ミリリットル）、Gluの・H 2 O（27.8ミリグラム、62.9μmol）を、HBTU（35.8ミリグラム、94.4マイクロモル）、無水グレードDMSO（0.5ミリリットル）を追加し、 私は 2ネットをPrは50洗浄した樹脂に、N 2雰囲気下で、この順番でμl）を、室温で12時間混合物を攪拌します。 </li><li> 2.3.2-2.3.4（ 図3b）に記載のプロトコルを繰り返します。 </li></ol></li><li> Rhのモノマー4の読み込み中 <ol><li>無水グレードのDMSO（4.5ミリリットル）、Rhのモノマー4（21.8 mgを、2を追加します。洗浄した樹脂に、N 2雰囲気下で、この順番で3.3マイクロモル）、HBTU（13.3ミリグラム、35.0マイクロモル）、無水グレードの CH 2 Cl 2（0.5ミリリットル）、および私のPr 2 NEtの（20μL）とは、混合物を攪拌室温（ 図2グラム ）で12時間。 </li><li> 2.2.2で説明したようにプロトコルを繰り返します。 </li><li> 2.6.1で説明したようにプロトコルを繰り返します。 </li><li>ロードされたRhのモノマー4のモル数を定量化するために2.2.2-2.2.5で説明したようにプロトコルを繰り返します。 </li></ol></li><li> Gluの読み込み中 <ol><li> （無水グレードの CH 2 Cl 2（4.5ミリリットル）、Gluの・H 2 O（20.4ミリグラム、46.0μmol）を、HBTU（26.2ミリグラム、69.0マイクロモル）、無水グレードDMSO（0.5ミリリットル）を追加し、 私は 2ネットをPrは50洗浄した樹脂に、N 2雰囲気下で、この順番でμl）を、室温で12時間混合物を攪拌します。 </li><li> 2.3.2-2.3.4に記載されているように（プロトコルを繰り返します図3c）。 </li></ol></li><li> 2-ローディング[2-（2-メトキシエトキシ）エトキシ]酢酸（TEG）、酸（8 CAS RN 16024-58-1;図1） <ol><li> （無水グレードを CH 2 Cl 2（3ミリリットル）、TEG酸（14μL、91.0μmol）を、HBTU（51.7 mgを、136.5マイクロモル）、無水グレードの CH 2 Cl 2（2 ml）を追加し、 私は 2ネットをPrは50洗浄した樹脂に、N 2雰囲気下で、この順番でμl）を、室温で12時間混合物を攪拌します。 </li><li>ドレインを通して濾過することによって溶液を除去。無水グレードのDMSO（3 mlで5分間撹拌）で2回、無水グレードメタノール（3 mlで3分間攪拌）および無水グレードのCH 2 Cl 2（3 mlで3分間攪拌）交互に3回樹脂を洗浄、無水グレードを CH 2 Cl 2（3 mlで3分間攪拌）で3回。 </li></ol></li><li> 固相合成の終わりに、樹脂からの切断 <ol><li>ウォッシュジエチルエーテル（4 mlを5分間撹拌）で3回、真空下で乾燥させ、無水グレードのCH 2 Cl 2（1 mlで5分間撹拌）でそれを膨潤した樹脂。 </li><li>懸濁液に、CF 3 CO 2 H（0.1 ml）を、のEt 3にSiH（20μl）を、1,2-ジクロロエタンクロロアセチルクロリド（1.9mL）の混合物を添加し、室温で12時間混合物を撹拌します。 </li><li>ドレインを通して濾過することによって溶液を除去し、CF 3 CO 2 H（0.1ミリリットル）の新しい混合物を追加し、エ3のSiH（20μl）を、1,2-ジクロロエタン（1.9ミリリットル）樹脂に加え、混合物を攪拌室温で1時間。 </li><li>手順を繰り返し2.9.3ソリューションが視覚的に無色になるまで（ 図2H）。 </li><li>プロトコル2.9.2-2.9.4を経て得られたように、すべてのソリューションを組み合わせて、質量分析4,7,8,9（ 図3d）によって得られた溶液の内容を分析します。 </li><li> evaporatioによって、溶液の揮発性種を除去n及びCF 3 CO 2 H（0.3 ml）を、のEt 3にSiH（40μl）を、1,2-ジクロロエタン（3.8 ml）を混合物に残渣を溶解します。 </li><li>室温で24時間混合物を撹拌し、質量分析によって得られた溶液の内容を解析4,7,8,9 1（ 図3E）の側残基でのTのBu基の完全な脱保護を確認します。 </li><li>蒸発によって、溶液の揮発性種を削除します。 </li></ol></li><li> 1の精製 <ol><li> CH 2 Cl 2中のプロトコル2.9を介して得られた固体残留物を超音波処理し、溶液をデカント。デカント液は、視覚的に無色になるまで、このプロセスを繰り返します。 </li><li>質量分析により得られた固体残留物の内容を分析4,7,8,9。 </li><li> 、超音波処理しながらメタノール（100μL/ 10 mg）を用いて残留物を洗うソリューションをデカントし、得られた複数の内容を分析質量分析4,7,8,9によってオリッ残基。 </li><li>超音波処理によってCH 3 CN（90μL）および水（10μL）の混合物中の残留物（1 mg）を溶解し、リン酸緩衝生理食塩水（800μL、10ミリモル、をpH = 7.4）で得られた溶液を組み合わせます。混合物を超音波処理し、24時間、37℃で静置します。 </li><li> 1,2-ジクロロエタン（500μl）を、CH 3 CN（20μL）、およびCF 3 CO 2 H（20μL）の混合物でデカント上清中の着色された種を抽出します。質量分析4,7,8,9（ 図3F）により抽出液を分析します。 </li><li>水相が視覚的に無色になるまで抽出を繰り返します。有機溶液を合わせ、蒸発によって揮発性物質を除去。 </li></ol></li></ol>

<ol>
	<li>Takanashi, K., 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=Heterometal+Assembly+in+Dendritic+Polyphenylazomethines.">Heterometal Assembly in Dendritic Polyphenylazomethines.</a> Bull. Chem. Soc. Jpn. 80, 1563-1572 (2007).</li><li>Packheiser, R., Ecorchard, P., R&#252;ffer, T., Lang, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Heteromultimetallic+Transition+Metal+Complexes+Based+on+Unsymmetrical+Platinum(II)+Bis-Acetylides.">Heteromultimetallic Transition Metal Complexes Based on Unsymmetrical Platinum(II) Bis-Acetylides.</a> Organometallics. 27, 3534-3536 (2008).</li><li>Sculfort, S., Braunstein, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Intramolecular+d10-d10+Interactions+in+Heterometallic+Clusters+of+the+Transition+Metals.">Intramolecular d10-d10 Interactions in Heterometallic Clusters of the Transition Metals.</a> Chem. Soc. Rev. 40, 2741-2760 (2011).</li><li>Vairaprakash, P., Ueki, H., Tashiro, K., Yaghi, O. M. <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+Metal-Organic+Complex+Arrays.">Synthesis of Metal-Organic Complex Arrays.</a> J. Am. Chem. Soc. 133, 759-761 (2011).</li><li>Jacoby, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis:+Method+Couples+Various+Metals+in+Predetermined+Sequences.">Synthesis: Method Couples Various Metals in Predetermined Sequences.</a> C&amp;EN. 89, (2011).</li><li>White, P., Eds D&#246;rner, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthetic+Notes.">Synthetic Notes.</a> Peptide Synthesis 2008/2009. , (2009).</li><li>Sajna, K. V., Fracaroli, A. M., Yaghi, O. M., Tashiro, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Modular+Synthesis+of+Metal-Organic+Complex+Arrays+Containing+Precisely+Designed+Metal+Sequences.">Modular Synthesis of Metal-Organic Complex Arrays Containing Precisely Designed Metal Sequences.</a> Inorg. Chem. 54, 1197-1199 (2015).</li><li>Sukul, P. K., 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+Water-Soluble+Metal-Organic+Complex+Array+as+a+Multinuclear+Heterometallic+Peptide+Amphiphile+That+Shows+Unconventional+Anion+Dependency+in+Its+Self-Assembly.">A Water-Soluble Metal-Organic Complex Array as a Multinuclear Heterometallic Peptide Amphiphile That Shows Unconventional Anion Dependency in Its Self-Assembly.</a> Chem. Commun. 52, 1579-1581 (2016).</li><li>Fracaroli, A. M., Tashiro, K., Yaghi, O. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Isomers+of+Metal-Organic+Complex+Arrays.">Isomers of Metal-Organic Complex Arrays.</a> Inorg. Chem. 51, 6437-6439 (2012).</li><li>Gude, M., Ryf, J., White, P. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+Accurate+Method+for+the+Quantitation+of+Fmoc-Derivatized+Solid+Phase+Supports.">An Accurate Method for the Quantitation of Fmoc-Derivatized Solid Phase Supports.</a> Letters in Peptide Science. 9, 203-206 (2002).</li><li>Merrifield, R. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solid+Phase+Peptide+Synthesis.+I.+The+Synthesis+of+a+Tetrapeptide.">Solid Phase Peptide Synthesis. I. The Synthesis of a Tetrapeptide.</a> J. Am. Chem. Soc. 85, 2149-2154 (1963).</li></ol>

The authors have nothing to disclose.

樹脂からの望ましくない化学物質の完全な除去は、単に簡単にこれらの化学物質を溶解できる溶剤で洗浄することにより、常に可能ではありません。効率的に樹脂を洗浄するためのキー技術は、それが膨張し、内部に残っている化学物質が押し出されるように繰り返し収縮させることです。それは（ 例えば、プロトコル2.1.4）で洗浄されるように私たちの手順で樹脂を交互にCH 2</su...

複雑な分子構造の制御された合成は、常に合成化学における大きな課題となっています。この観点から、設計可能な様式で多核異種複合体を合成するためにはまだため、一般的に使用されるリガンド - 金属化ベースのアプローチからの可能な構造の結果の数の無機化学の分野で挑戦に値する対象であります単量体の金属錯体の調製。多核異種複合体のいくつかの例は、これまで1,2,3報告されているが、それらの合成の試行錯誤又は困難な性質は、構造体の広い範囲に適用可能であり、簡単な方法の開発が必要です。 この問題に対処するための新たなアプローチとして、2011年に我々は、Fmoc保護アミノ酸部分を有する種々の単核金属錯体を順次マルチ与えるように結合されている合成方法の4,5を報告固相ポリペプチド合成6のプロトコルを使用して、ペプチド配列をメタリックポリペプチド合成の連続的な性質のために、複数の金属中心の特定の配列は、それらの金属錯体の単量体のカップリング反応の回数および順序を制御することにより、合理的に設計可能です。後で、このアプローチは、二つの短いアレイ7との間の共有結合で結合することによって、より大きな、様々な及び/又は分枝状のアレイ構造を作ることがさらにモジュール化しました。 代表的な例として、ここでは、そのようなmultimetallicペプチド配列の合成は、通常、最近報告WSMOCA（ 図1 1 8 CAS RN 1827663-18-2）を選択することによって操作された方法を紹介します。一つの特定の配列の合成は、このプロトコルに記載されているが、同じ手順は、異性体9を含む異なる配列の広範囲の合成に適用可能です。我々は、このプロトを期待しますcolが分子がこれまで一般的になっている生体高分子を調べまれ金属錯体系の種の例が含まれていないシーケンス制御化合物の科学、に参加するより多くの研究者を鼓舞します。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Dichloro(p&#8208;cymene)ruthenium(II), dimer</td>
			<td>Kanto Chemical</td>
			<td>11443-65</td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloro(1,5-cyclooctadiene)platinum(II)</td>
			<td>TCI</td>
			<td>D3592</td>
			<td></td>
		</tr>
		<tr>
			<td>Rhodium(III) chloride trihydrate</td>
			<td>Kanto Chemical</td>
			<td>36018-62</td>
			<td></td>
		</tr>
		<tr>
			<td>Phosphate buffered saline, tablet</td>
			<td>Sigma Aldrich</td>
			<td>P4417-50TAB&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>NovaSyn TG Sieber resin</td>
			<td>Novabiochem</td>
			<td>8.55013.0005</td>
			<td></td>
		</tr>
		<tr>
			<td>HBTU</td>
			<td>TCI</td>
			<td>B1657</td>
			<td></td>
		</tr>
		<tr>
			<td>Benzoic anhydride</td>
			<td>Kanto Chemical</td>
			<td>04116-30</td>
			<td></td>
		</tr>
		<tr>
			<td>Fmoc-Glu(OtBu)-OH&#12539;H2O</td>
			<td>Watanabe Chemical Industries</td>
			<td>K00428</td>
			<td></td>
		</tr>
		<tr>
			<td>Trifluoroacetic acid</td>
			<td>Kanto Chemical</td>
			<td>40578-30</td>
			<td></td>
		</tr>
		<tr>
			<td>Triethylsilane</td>
			<td>TCI</td>
			<td>T0662</td>
			<td></td>
		</tr>
		<tr>
			<td>2-[2-(2-Methoxyethoxy)ethoxy]acetic acid</td>
			<td>Sigma Aldrich</td>
			<td>407003</td>
			<td>Dried over 3&#197; sieves</td>
		</tr>
		<tr>
			<td>Dithranol</td>
			<td>Wako Pure Chemical Industries</td>
			<td>191502</td>
			<td></td>
		</tr>
		<tr>
			<td>N-methylimidazole</td>
			<td>TCI</td>
			<td>M0508</td>
			<td></td>
		</tr>
		<tr>
			<td>N&#8208;ethyldiisopropylamine</td>
			<td>Kanto Chemical</td>
			<td>14338-32</td>
			<td></td>
		</tr>
		<tr>
			<td>Piperidine</td>
			<td>Kanto Chemical</td>
			<td>32249-30</td>
			<td></td>
		</tr>
		<tr>
			<td>4&#39;-(4-methylphenyl)-2,2&#39;:6&#39;,2&#34;-terpyridine</td>
			<td>Sigma Aldrich</td>
			<td>496375</td>
			<td></td>
		</tr>
		<tr>
			<td>Dehydrated grade dimethylsulfoxide</td>
			<td>Kanto Chemical</td>
			<td>10380-05&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Dehydrated grade methanol</td>
			<td>Kanto Chemical</td>
			<td>25506-05&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Dehydrated grade N,N&#8208;Dimethylformamide</td>
			<td>Kanto Chemical</td>
			<td>11339-84</td>
			<td>Amine Free</td>
		</tr>
		<tr>
			<td>Dehydrated grade dichloromethane</td>
			<td>Kanto Chemical</td>
			<td>11338-84</td>
			<td></td>
		</tr>
		<tr>
			<td>MeOH</td>
			<td>Kanto Chemical</td>
			<td>25183-81&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Dimethylsulfoxide</td>
			<td>Kanto Chemical</td>
			<td>10378-70</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Kanto Chemical</td>
			<td>14029-81</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetonitrile</td>
			<td>Kanto Chemical</td>
			<td>01031-70&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>1,2-dichloroethane</td>
			<td>Kanto Chemical</td>
			<td>10149-00</td>
			<td></td>
		</tr>
		<tr>
			<td>Diethyl ether</td>
			<td>Kanto Chemical</td>
			<td>14134-00&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Kanto Chemical</td>
			<td>10158-81</td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis of a water-soluble metal&#8211;organic complex array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

図1は、最終的な目的化合物、前駆体、及び中間体の分子構造を示し、図2は、樹脂の画像を示し、 図3は、選択された手続きステップでのサンプルのMALDI-TOF質量スペクトルを示します 。 図2aからの画像を2時間 、それはプロトコルのセクション2での反応工程中に受ける樹脂の色や外観の変化?...

Watch this Scientific Journal Video about Synthesis of a Water-soluble MetalÃ¢â‚¬â€œOrganic Complex Array at JoVE.com

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

水溶性有機金属錯体アレイの合成

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

synthesis-of-a-water-soluble-metalorganic-complex-array

Research

JoVE Journal

Chemistry

9.8K ビュー.  National Institute for Materials Science. A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

ビデオ: Synthesis of a Water-soluble Metal–Organic Complex Array

Synthesis, Cellular Delivery and In vivo Application of Dendrimer-based pH Sensors

The development of fluorescent indicators represented a revolution for life sciences. Genetically encoded and synthetic fluorophores with sensing abilities allowed the visualization of biologically relevant species with high spatial and temporal resolution. Synthetic dyes are of particular interest thanks to their high tunability and the wide range of measureable analytes. However, these molecules suffer several limitations related to small molecule behavior (poor solubility, difficulties in targeting, often no ratiometric imaging allowed). In this work we introduce the development of dendrimer-based sensors and present a procedure for pH measurement in vitro, in living cells and in vivo. We choose dendrimers as ideal platform for our sensors for their many desirable properties (monodispersity, tunable properties, multivalency) that made them a widely used scaffold for several biomedical devices. The conjugation of fluorescent pH indicators to the dendrimer scaffold led to an enhancement of their sensing performances. In particular dendrimers exhibit reduced cell leakage, improved intracellular targeting and allow ratiometric measurements. These novel sensors were successfully employed to measure pH in living HeLa cells and in vivo in mouse brain.

Synthesis, Cellular Delivery and In vivo Application of Dendrimer-based pH Sensors

Fluorescence sensors are powerful tools in life science. Here we describe a methodology to synthesize and use dendrimer-based fluorescent sensors to measure pH in living cells and in vivo. The dendritic scaffold enhances the properties of conjugated fluorescent dyes leading to improved sensing properties.

合成、細胞の配送および<em&gt;インビボ</em&gt;デンドリマーベースのpHセンサの応用

The development of  fluorescent indicators represented a revolution for life sciences. Genetically  encoded and synthetic fluorophores with sensing ...

化学

Atomically Defined Templates for Epitaxial Growth of Complex Oxide Thin Films

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain such surfaces are described. The first approach is the preparation of single terminated perovskite SrTiO3 (001) and DyScO3 (110) substrates. Wet etching was used to selectively remove one of the two possible surface terminations, while an annealing step was used to increase the smoothness of the surface. The resulting single terminated surfaces allow for the heteroepitaxial growth of perovskite oxide thin films with high crystalline quality and well-defined interfaces between substrate and film. In the second approach, seed layers for epitaxial film growth on arbitrary substrates were created by Langmuir-Blodgett (LB) deposition of nanosheets. As model system Ca2Nb3O10- nanosheets were used, prepared by delamination of their layered parent compound HCa2Nb3O10. A key advantage of creating seed layers with nanosheets is that relatively expensive and size-limited single crystalline substrates can be replaced by virtually any substrate material.

Various procedures are outlined to prepare atomically defined templates for epitaxial growth of complex oxide thin films. Chemical treatments of single crystalline SrTiO3 (001) and DyScO3 (110) substrates were performed to obtain atomically smooth, single terminated surfaces. Ca2 Nb3 O10- nanosheets were used to create atomically defined templates on arbitrary substrates.

複合酸化物薄膜のエピタキシャル成長のために原子的に定義されたテンプレート

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain ...

Water in Oil Emulsions: A New System for Assembling Water-soluble Chlorophyll-binding Proteins with Hydrophobic Pigments

Chlorophylls (Chls) and bacteriochlorophylls (BChls) are the primary cofactors that carry out photosynthetic light harvesting and electron transport. Their functionality critically depends on their specific organization within large and elaborate multisubunit transmembrane protein complexes. In order to understand at the molecular level how these complexes facilitate solar energy conversion, it is essential to understand protein-pigment, and pigment-pigment interactions, and their effect on excited dynamics. One way of gaining such understanding is by constructing and studying complexes of Chls with simple water-soluble recombinant proteins. However, incorporating the lipophilic Chls and BChls into water-soluble proteins is difficult. Moreover, there is no general method, which could be used for assembly of water-soluble proteins with hydrophobic pigments. Here, we demonstrate a simple and high throughput system based on water-in-oil emulsions, which enables assembly of water-soluble proteins with hydrophobic Chls. The new method was validated by assembling recombinant versions of the water-soluble chlorophyll binding protein of Brassicaceae plants (WSCP) with Chl a. We demonstrate the successful assembly of Chl a using crude lysates of WSCP expressing E. coli cell, which may be used for developing a genetic screen system for novel water-soluble Chl-binding proteins, and for studies of Chl-protein interactions and assembly processes.

This manuscript describes a simple and high-throughput method for assembling water-soluble proteins with hydrophobic pigments that is based on water-in-oil emulsions. We demonstrate the effectiveness of the method in the assembly of native chlorophylls with four variants of recombinant water-soluble-chlorophyll binding proteins (WSCPs) of Brassica plants expressed in E. coli.

油中水型エマルジョン：疎水性顔料と水溶性クロロフィル結合タンパク質を組み立てるための新しいシステム

Chlorophylls (Chls) and bacteriochlorophylls (BChls) are the primary cofactors that carry out photosynthetic light harvesting and electron transport. ...

Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and engineers. Growth of such anisotropic nanocrystals through a simple chemical method is a challenging task. In this study, we fabricate discotic nanodisks of zirconium phosphate [Zr(HPO4)2&#183;H2O] as a model material using hydrothermal, reflux and microwave-assisted methods. Growth of crystals is controlled by duration time, temperature, and concentration of reacting species. The novelty of the adopted methods is that discotic crystals of size ranging from hundred nanometers to few micrometers can be obtained while keeping the polydispersity well within control. The layered discotic crystals are converted to monolayers by exfoliation with tetra-(n)-butyl ammonium hydroxide [(C4H9)4NOH, TBAOH]. Exfoliated disks show isotropic and nematic liquid crystal phases. Size and polydispersity of disk suspensions is highly important in deciding their phase behavior.

A two dimensional model material of discotic zirconium phosphate was developed. The inorganic crystal with lamellar structure was synthesized by hydrothermal, reflux, and microwave-assisted methods. On exfoliation with organic molecules, layered crystals can be converted to monolayers, and nematic liquid crystal phase was formed at sufficient concentration of monolayers.

コロイド液の結晶を得ることが合成とディスコティックリン酸ジルコニウムの剥離

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

A Direct, Early Stage Guanidinylation Protocol for the Synthesis of Complex Aminoguanidine-containing Natural Products

The guanidine functional group, displayed most prominently in the amino acid arginine, one of the fundamental building blocks of life, is an important structural element found in many complex natural products and pharmaceuticals. Owing to the continual discovery of new guanidine-containing natural products and designed small molecules, rapid and efficient guanidinylation methods are of keen interest to synthetic and medicinal organic chemists. Because the nucleophilicity and basicity of guanidines can affect subsequent chemical transformations, traditional, indirect guanidinylation is typically pursued. Indirect methods commonly employ multiple protection steps involving a latent amine precursor, such as an azide, phthalimide, or carbamate. By circumventing these circuitous methods and employing a direct guanidinylation reaction early in the synthetic sequence, it was possible to forge the linear terminal guanidine containing backbone of clavatadine A to realize a short and streamlined synthesis of this potent factor XIa inhibitor. In practice, guanidine hydrochloride is elaborated with a carefully constructed protecting array that is optimized to survive the synthetic steps to come. In the preparation of clavatadine A, direct guanidinylation of a commercially available diamine eliminated two unnecessary steps from its synthesis. Coupled with the wide variety of known guanidine protecting groups, direct guanidinylation evinces a succinct and efficient practicality inherent to methods that find a home in a synthetic chemist&#39;s toolbox.

Here, we present a protocol for direct, early stage guanidinylation that enables rapid total synthesis of aminoguanidine-containing small organic molecules. An advanced synthetic intermediate used in the synthesis of a blood coagulation factor XIa inhibitor was prepared using this protocol.

複雑なアミノグアニジン含有天然物の合成のための直接、早期グアニジニルプロトコル

The guanidine functional group, displayed most prominently in the amino acid arginine, one of the fundamental building blocks of life, is an important ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

超分子コロイドの合成とキャラクタリゼーション

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

Chemo-enzymatic Synthesis of N-glycans for Array Development and HIV Antibody Profiling

We present a highly efficient way for the rapid preparation of a wide range of N-linked oligosaccharides (estimated to exceed 20,000 structures) that are commonly found on human glycoproteins. To achieve the desired structural diversity, the strategy began with the chemo-enzymatic synthesis of three kinds of oligosaccharyl fluoride modules, followed by their stepwise &#945;-selective glycosylations at the 3-O and 6-O positions of the mannose residue of the common core trisaccharide having a crucial &#946;-mannoside linkage. We further attached the N-glycans to the surface of an aluminum oxide-coated glass (ACG) slide to create a covalent mixed array for the analysis of hetero-ligand interaction with an HIV antibody. In particular, the binding behavior of a newly isolated HIV-1 broadly neutralizing antibody (bNAb), PG9, to the mixture of closely spaced Man5GlcNAc2 (Man5) and 2,6-di-sialylated bi-antennary complex type N-glycan (SCT) on an ACG array, opens a new avenue to guide the effective immunogen design for HIV vaccine development. In addition, our ACG array embodies a powerful tool to study other HIV antibodies for hetero-ligand binding behavior.

Chemo-enzymatic Synthesis of N-glycans for Array Development and HIV Antibody Profiling

A modular approach to the synthesis of N-glycans for attachment to an aluminum oxide-coated glass slide (ACG slide) as a glycan microarray has been developed and its use for the profiling of an HIV broadly neutralizing antibody has been demonstrated.

N型糖鎖アレイ開発および HIV 抗体のための化学酵素合成プロファイリング

We present a highly efficient way for the rapid preparation of a wide range of N-linked oligosaccharides (estimated to exceed 20,000 structures) that are ...

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst removal via host-guest interactions. The new NHC ligand possesses an adamantyl (guest) tethered linear ethylene glycol units for hydrophobic inclusion into the cavity of a &#946;-cyclodextrin (&#946;-CD) host compound. The new NHC ligand was applied to a Ru-based olefin metathesis catalyst. The Ru catalyst demonstrated excellent activity in representative ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROMP) reactions in aqueous media as well as organic solvent, CH2Cl2. After the reaction was complete, the lingering Ru residue was removed from the aqueous solution with the efficiency of more than 99% (53 ppm of Ru residue) by simple filtration utilizing a host-guest interaction between insoluble silica-grafted &#946;-CD (host) and the adamantyl moiety (guest) on the catalyst. The new Ru catalyst also demonstrated high removal efficiency via extraction when the reaction is run in organic solvent by partitioning the crude reaction mixture between layers of diethyl ether and water. In this way, the catalyst stays in aqueous layer only. In organic layer, the residual Ru amount was only 0.14 ppm in the RCM reactions of diallyl compounds.

A removable water-soluble N-heterocyclic carbene (NHC) ligand in aqueous media via host-guest interaction has been developed. We demonstrated representative olefin metathesis reactions in water as well as in dichloromethane. Via either host-guest interaction or extraction, the residual ruthenium (Ru) catalyst was as low as 0.14 ppm after the reaction.

水溶性ルテニウム オレフィン メタセシス触媒ホスト-ゲスト相互作用による水溶液からの異機種混在環境の除去

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst ...

Negative Additive Manufacturing of Complex Shaped Boron Carbides

Boron carbide (B4C) is one of the hardest materials in existence. However, this attractive property also limits its machineability into complex shapes for high wear, high hardness, and lightweight material applications such as armors. To overcome this challenge, negative additive manufacturing (AM) is employed to produce complex geometries of boron carbides at various length scales. Negative AM first involves gelcasting a suspension into a 3D-printed plastic mold. The mold is then dissolved away, leaving behind a green body as a negative copy. Resorcinol-formaldehyde (RF) is used as a novel gelling agent because unlike traditional hydrogels, there is little to no shrinkage, which allows for extremely complex molds to be used. Furthermore, this gelling agent can be pyrolyzed to leave behind ~50 wt% carbon, which is a highly effective sintering aid for B4C. Due to this highly homogenous distribution of in situ carbon within the B4C matrix, less than 2% porosity can be achieved after sintering. This protocol highlights in detail the methodology for creating near fully dense boron carbide parts with highly complex geometries.

A method called negative additive manufacturing is used to produce near fully dense complex shaped boron carbide parts of various length scales. This technique is possible via the formulation of a novel suspension involving resorcinol-formaldehyde as a unique gelling agent that leaves behind a homogenous carbon sintering aid after pyrolysis.

負の複雑な形をした炭化ホウ素の添加剤の製造

Boron carbide (B4C) is one of the hardest materials in existence. However, this attractive property also limits its machineability into complex shapes for ...

Molten-Salt Synthesis of Complex Metal Oxide Nanoparticles

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. Here, we introduce the molten-salt synthesis (MSS) method for making metal oxide nanomaterials. Advantages over other methods include its simplicity, greenness, reliability, scalability, and generalizability. Using pyrochlore lanthanum hafnium oxide (La2Hf2O7) as a representative, we describe the MSS protocol for the successful synthesis of complex metal oxide nanoparticles (NPs). Furthermore, this method has the unique ability to produce NPs with different material features by changing various synthesis parameters such as pH, temperature, duration, and post-annealing. By fine-tuning these parameters, we are able to synthesize highly uniform, non-agglomerated, and highly crystalline NPs. As a specific example, we vary the particle size of the La2Hf2O7&#160;NPs by changing the concentration of the ammonium hydroxide solution used in the MSS process, which allows us to further explore the effect of particle size on various properties. It is expected that the MSS method will become a more popular synthesis method for nanomaterials and more widely employed in the nanoscience and nanotechnology community in the upcoming years.

Here, we demonstrate a unique, relatively low-temperature, molten-salt synthesis method for preparing uniform complex metal oxide lanthanum hafnate nanoparticles.

複合金属酸化物ナノ粒子の溶融塩合成

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. ...