この作品は、国家自然科学基金、中国の (21301104)、中央大学 (FRF-TP-16-019A3)、および、状態キー研究所の化学工学 (SKL-チェ-14A04) の基礎的研究資金によって支えられました。

1 合成のモノ-(2, 3-dimethylbutyl) ホスフィン酸 18 , 19 <ol><li>反応 <ol><li>重さ 31.80 g ナトリウム次亜リン酸水和物、16.00。g の酢酸、8.42 g 2, 3-ジメチル-1-ブテン、0.73 g ジ-tert-butylnperoxide (DTBP)、および 25.00 g テトラヒドロ フラン (THF) 100 mL テフロン ライニング ステンレス オートクレーブにオートクレーブに磁性攪拌器を入れ、それをシール</li>
		<li>は、磁気 stirringapparatus が属する垂直管炉オートクレーブを置きます。磁気攪拌装置を起動し、800 rpm に速度を設定します</li>。
		<li>は、オートクレーブに接続された温度コント ローラーの加熱プログラムを設定: 120 ° c 90 分間室温から加熱、8 h は、120 ° C で維持し、自然に部屋の温度に冷却します。加熱プログラムを起動します</li>。
	</ol></li> <li>治療後 <ol><li>250 mL 1 首丸底フラスコに製品を転送、50 ml の THF、テフロン ライニングを洗浄し、すべての製品が転送されることを確認する同じフラスコに追加します</li>。
		<li>THF と未反応のオレフィンをロータリーエバポレーターを使用して削除します</li>。
		<li>分離漏斗 250 mL にボッスクカを転送、80 mL のエチル エーテルと 30 mL の脱イオン水をフラスコをそれぞれ洗浄し、すべての製品が転送されることを確認する同じ分離漏斗にそれらを追加します</li>。
		上記の分離漏斗に <li>追加 50 mL 4 %naoh 水溶液は、精力的にそれを振るし、水相を分離します。3 回 20 mL 4 %naoh 溶液で有機相を抽出 (20 mL × 3) 水相 pH が 10 を超えていることを確認する</li>。
		<li>上記の手順で水溶液を組み合わせるし、500 mL の目標到達プロセスを分離することにそれらを転送します</li>。
		<li>10% H 2 の追加 90 mL 4 ソリューションしエチル エーテル 50 mL 積極的に振る; 有機相を分離、抽出 3 回 30 ml のエチル エーテルの水相 (30 mL × 3).</li>
		<li>1.2.6 の手順でエチル エーテルのソリューションを組み合わせて、別の 500 mL の目標到達プロセスを分離することにそれらを転送します</li>。
		<li>(100 mL × 4) 回 4 飽和塩化ナトリウム溶液 100 mL で洗い流して</li>。
		<li>は、4 g の無水 MgSO 4 水溶性水を削除するを追加します。固体を削除するフィルターし、クリーン 250 mL 1 首丸底フラスコの液体を収集します</li>。
		<li>エチル エーテルをロータリーエバポレーターを使用して粗製品の 17.92 g を取得するを削除します</li>。
	</ol></li></ol> 2。モノ-(2, 3-dimethylbutyl) ホスフィン酸の精製 <ol><li>アマンタジン溶液の調製 <ol><li>100 mL の脱イオン水 500 mL ビーカーに塩酸アマンタジンの 22.28 g を溶解します</li>。
		<li>飽和の NaOH 溶液と攪拌 5 分の追加 100 mL</li>
		<li>エチル エーテル 150 mL を追加し、2.1.2 のステップで生成される白色の沈殿物がなくなるまでかき混ぜる</li>。
		<li>500 mL を目標到達プロセスを分離ソリューションに転送、3 回のエチル エーテルとビーカーを洗う (50 mL × 3)、それらを組み合わせて、同じ漏斗と</li>。
		<li>水性相を分離し、(100 mL × 5) 回 5 飽和 NaCl 溶液と有機相を洗うです</li>。
		<li>は、4 g の無水 MgSO 4 水溶性水を削除するを追加します。アマンタジン エチル エーテル溶液を取得するフィルターします</li>。
	</ol></li> <li>アマンタジンの準備 &#8729; モノ-(2, 3-dimethylbutyl) ホスフィン酸塩 <ol><li>drop-wise 原油モノ-(2, 3-dimethylbutyl) ホスフィン酸製品をアマンタジン ソリューションに追加します。落下中にそれが適切にかき混ぜることができるようにエチル エーテル 150 mL を追加します</li>。
		<li>は、モノ-(2, 3-dimethylbutyl) ホスフィン酸この商品を含むすべての製品がアマンタジン ソリューションに転送されることを確実にエチル エーテル 50 mL で 1 つ首丸底フラスコを洗います。30 分間攪拌し、夜通し坐るようにします</li>。
		<li>減圧、および 200 mL のエチル エーテル フィルター ケーキを洗って下フィルター</li>。
	</ol></li> <li>モノ-(2, 3-dimethylbutyl) ホスフィン酸をリリース <ol><li>500 mL ビーカーにフィルター ケーキを転送、1 M HCl の 80 mL を追加し 5 分間かき混ぜる</li>
		<li>追加 70 mL 酢酸エチルと別の 5 分間攪拌</li>
		<li>ソリューションを分離漏斗 250 mL に転送し、水相を分離します</li>。
		<li>再び 40 mL の酢酸エチルで水相を抽出し、酢酸エチルのソリューションを組み合わせてです</li>。
		<li>30 ml 1 M HCl 2 回の (30 mL × 2) エチル酢酸溶液を洗浄し、飽和 3 NaCl (80 mL × 3)、時間の順番にします</li>。
		<li>は、4 g 無水 MgSO 4 水溶性水を削除するを追加します。フィルターし、250 mL の 1 首丸底フラスコの液体を収集します</li>。
		<li>回転蒸発器を用いて酢酸エチルを削除し、12.45 g の純粋なモノ-(2, 3-dimethylbutyl) ホスフィン酸 (収量: 82.9%).</li>
	</ol></li></ol> 3。合成 (2, 3-dimethylbutyl) (2,4,4 &#39;-trimethylpentyl) ホスフィン酸 <ol><li>反応 <ol><li>転送すべて純粋なモノ-(2, 3-dimethylbutyl) ホスフィン酸製品の 100 mL にテフロン ライニング ステンレス鋼オートクレーブ、4.95 g の酢酸、diisobutylene、DTBP の 0.30 g の 25.39 g を追加、マグネチックスターラーをオートクレーブに入れて、それをシール</li>
		<li>磁気攪拌装置が属する垂直管炉オートクレーブを置くし、磁気攪拌装置を開始します</li>。
		<li>設定温度コント ローラーの加熱プログラム: 135 ° c 90 分間室温から加熱、8 h 135 ° C で維持し、自然に部屋の温度に冷却します。加熱プログラムを起動します</li>。
		<li>反応系は部屋の温度に冷却するとき、DTBP の別の 0.30 g を追加し、加熱プログラムを再起動します</li>。
		<li>繰り返しステップ 3.1.4 一度</li>。
	</ol></li> <li>治療後 <ol><li>100 mL のエチル エーテル製品を希釈し、分離漏斗 250 mL に転送します</li>。
		<li>4 %30 mL で洗う NaOH 3 回 (30 mL × 3) その水相 pH が 10 を超えていることを確認します</li>。
		<li>10% H 2 の 70 mL を追加し、製品を酸性化する 4 ソリューションです</li>。
		<li>で洗って飽和 NaCl 溶液 (80 mL) 数回水相 pH pH 6-7 までです</li>。
		<li>は、4 g の無水 MgSO 4 水溶性水を削除するを追加します。固体を削除するフィルターし、クリーン 250 mL 1 首丸底フラスコの液体を収集します</li>。
		<li>エチル エーテルと未反応のオレフィンをロータリーエバポレーターを使用して粗製品の 15.10 g を取得するを削除します</li>。
	</ol></li></ol> 4。精製 (2, 3-dimethylbutyl) (2,4,4 &#39;-trimethylpentyl) ホスフィン酸 <ol><li>純粋な co-(2,3-dimethylbutyl) を取得 (2,4,4 &#39;-trimethylpentyl) ホスフィン酸複合体 <ol>40 mL に水酸化ナトリウムの溶解 2.30 g <li>脱イオン水。原油を含むフラスコに NaOH 溶液を追加 (2, 3-dimethylbutyl) (2,4,4 &#39;-trimethylpentyl) ホスフィン酸製品、5 分間精力的にそれを振る</li>
		<li>追加 0.5 M CoCl 2 ソリューション以上青い沈殿物が生成され、フラスコ内でソリューションですピンクまでを振りながら滴状 </li。> <li>フィルターと洗浄フィルター ケーキまで純水で青色の沈殿物は無色</li>。
		<li>250 mL のビーカーにフィルター ケーキを転送、アセトン 100 mL を加えて、防腐剤のフィルム シール、1 泊分の 4 ° C でそれを冷蔵します</li>。
		<li>バルクの中に閉じ込め、不純物をリリースする青い沈殿物廃タイ</li>。
		<li>フィルターと新鮮なアセトン 100 mL で洗います。常温でフィルター ケーキを乾燥し、分離漏斗 250 mL に転送します</li>。
	</ol></li> <li>再生成、(2, 3-dimethylbutyl) (2,4,4 &#39;-trimethylpentyl) ホスフィン酸 <ol><li>4、および青い沈殿するまで精力的に手ふれが消えるので 120 mL エチル エーテル、80 mL 10% H 2 を追加します</li>。
		<li>水相を分離、有機洗浄など 4 回 10% H 2 の 30 mL で順次相し、水相 pH pH 6-7 まで数回 (80 mL) NaCl 水溶液を飽和します</li>。
		<li>は、4 g の無水 MgSO 4 水溶性水を削除するを追加します。固体を除去・回収クリーン 250 mL 1 首丸底フラスコの液体フィルター</li>。
		<li>回転蒸発器を用いてエチル エーテルを削除し、純粋なプロダクトの 11.46 g (収量: 52.8%).</li>
	</ol>
	</li>
</ol>

<ol>
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プロトコルの中で最も重要なステップは、モノラル alkylphosphinic 酸合成 (図 1、) です。この反応より高い収穫より少ない dialkylphosphinic 酸副産物より良いです。NaH2PO2/olefin A のモル比を増加、歩留り向上し、dialkylphosphinic 酸副産物の生成を阻害します。ただし、大規模な改良近距離音響ホログラフィ2PO2用量またコストが増加し...

酸性有機リン抽出剤は希土類イオン1、2、(3,4) のような非非鉄金属、レアメタル (の抽出と分離の従来の湿式製錬分野で広く使用されてHf/Zr など5V6,7)、アクチノイド8等。近年、また二次資源リサイクルと高レベル廃液処理9の分野で注目を集めている彼ら。ジ-(2-エチルヘキシル) リン酸 (D2EHPA または P204) 2 ethylhexylphosphoric 酸モノ-2 - エチルヘキシル (EHEHPA、PC 88 a, または P507) とディ-(2, 4, 4'-trimethylpentyl)-dialkylphosphoric 酸の代表であるホスフィン酸 (Cyanex272)アルキルリン酸モノ-アルキル エステル、dialkylphosphinic 酸が最も一般的に使用される抽出剤がそれぞれです。次の順序での酸性度が低下: P204 &#62; P507 &#62; Cyanex 272。対応力を抽出、抽出能力とストリッピングの酸味がすべて P204 順 &#62; P507 &#62; Cyanex 272 と分離性能は逆の順序で。これらの 3 つの抽出剤はほとんどの場合に効果的です。ただし、そこにはまだいくつかの条件どこない非常に効率的な: 重希土類の分離、うち既存の主な問題は、選択度が低く P204、P507、ストリッピング酸味が高い低抽出能力と乳化傾向Cyanex 272 の抽出中にしたがって、新規抽出剤の開発は、近年大きな注目を集めています。
Dialkylphosphinic 酸抽出剤のクラスは、新しい抽出剤を開発する研究の最も重要な側面の一つと見なされます。最近の研究では、dialkylphosphinic 酸の抽出能力がアルキル置換基10,11の構造に大きく依存することを示した。それは Cyanex 27212のそれより低く P507 のそれよりも有意に高いから広い範囲をすることができます。ただし、新規 dialkylphosphinic 酸抽出剤の探査は商業オレフィン構造10,12,13,14,15に制限されて 16。グリニャール反応法による dialkylphosphinic 酸抽出剤を合成もできる、反応条件が厳格な12,17。
うち 2 つアルキルが異なる場合、NSDAPA は、新しい抽出剤の探査に扉を開きます。Dialkylphosphinic 酸の構造はより多様なそれとそのアルキル構造の両方を変更することによってその抽出・分離性能を微調整できます。NSDAPA の伝統的な合成法は、高度の毒性、厳しい反応条件および困難な浄化のような多くの欠点を持つリン源として PH3を使用しました。最近リン (図 1参照) をソースし、正常に合成 3 NSDAPAs18次亜リン酸ナトリウムを使用して NSDAPA を合成する方法を報告しました。この詳細なプロトコルが新しい実践、実験を繰り返し、NSDAPA 抽出剤の合成方法をマスターできます。私たちを取る (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) 例としてホスフィン酸。名およびオレフィン A、中間モノラル alkylphosphinic 酸、オレフィン B、および対応する NSDAPA の構造は表 1のとおりです。

<table><tbody><tr><td>2,3-dimethyl-1-butene</td><td>Adamas Reagent Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;12&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;99%&lt;/span&gt;</td></tr><tr><td>diisobutylene</td><td>Shanghai&amp;nbsp;Aladdin&amp;nbsp;Bio-Chem&amp;nbsp;Technology&amp;nbsp;Co.,&amp;nbsp;LTD</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;16&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity 97%&lt;/span&gt;</td></tr><tr><td>acetic acid</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;99.5%&lt;/span&gt;</td></tr><tr><td>di-&lt;span class=&quot;font9&quot;&gt;tert&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;-butylnperoxide&lt;/span&gt;</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;18&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;97.0%&lt;/span&gt;</td></tr><tr><td>tetrahydrofuran</td><td>Beijing Chemical Works</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O, purity A.R.&lt;/span&gt;</td></tr><tr><td>ethyl ether</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;10&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O, purity &amp;ge;99.7%&lt;/span&gt;</td></tr><tr><td>ethyl acetate</td><td>Xilong Chemical Co., Ltd.</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;8&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;99.5%&lt;/span&gt;</td></tr><tr><td>acetone</td><td>Beijing Chemical Works</td><td></td><td>Molecular formula: C&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;H&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;6&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;O, purity &amp;ge;99.5%&lt;/span&gt;</td></tr><tr><td>sodium hydroxide</td><td>Xilong Chemical Co., Ltd.</td><td></td><td>Molecular formula: NaOH, purity &amp;ge;96.0%</td></tr><tr><td>concentrated sulfuric acid</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: H&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;SO&lt;/span&gt;&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity 95-98%&lt;/span&gt;</td></tr><tr><td>hydrochloric acid</td><td>Beijing Chemical Works</td><td></td><td>Molecular formula: HCl, purity 36-38%</td></tr><tr><td>sodium chloride</td><td>Sinopharm Chemical Reagent Co., Ltd.</td><td></td><td>Molecular formula: NaCl, purity &amp;ge;99.5%</td></tr><tr><td>anhydrous magnesium sulfate</td><td>Tianjin Jinke Institute of Fine Chemical Industry</td><td></td><td>Molecular formula: MgSO&lt;span class=&quot;font8&quot;&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/span&gt;&lt;span class=&quot;font7&quot;&gt;, purity &amp;ge;99.0%&lt;/span&gt;</td></tr></tbody></table>

synthesis of high purity nonsymmetric dialkylphosphinic acid extractants

合成を提案する (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) ホスフィン酸高純度非対称 dialkylphosphinic 酸抽出剤の合成法を示すための例として。低毒性ナトリウム次亜リン酸は、(2, 3-ジメチル-1-ブテン) 中間 monoalkylphosphinic 酸を生成するオレフィンと反応するリン源として選ばれました。アマンタジンは dialkylphosphinic 酸副産物を削除する採用された monoalkylphosphinic 酸だけは dialkylphosphinic 酸できないためにアマンタジンと反応しながら、amantadine∙mono alkylphosphinic 酸塩を形成するアマンタジンと反応できるようその大きな立体障害。精製 monoalkylphosphinic 酸、オレフィン B (diisobutylene) 非対称 dialkylphosphinic 酸 (NSDAPA) を生成すると反応しました。シンプル ベース酸治療後で未反応の monoalkylphosphinic 酸を簡単に削除できるし、他の有機不純物は、コバルト塩の沈殿法による分けることができます。構造、(2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) ホスフィン酸は31P NMR、 1H NMR、MS、および FT-IR による確認電位差滴定法による純度と示唆された純度が 96% を超えることができます。

31P NMR スペクトルには、アマンタジンによる (図 1a ~ b) 前に、と浄化後のモノ-(2, 3-dimethylbutyl) ホスフィン酸に対して収集されました。31P NMR スペクトル、 1H NMR スペクトル、MS スペクトル、FT-IR スペクトルに対して収集された (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) ホスフィン酸 (図 3<strong c...

Watch this Scientific Journal Video about Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants at JoVE.com

Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants

高純度非対称 Dialkylphosphinic 酸抽出剤の合成

高純度非対称 dialkylphosphinic 酸抽出剤の合成のためのプロトコルが表示され、撮影 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) 例としてホスフィン酸。

We present the synthesis of (2,3-dimethylbutyl)(2,4,4&#39;-trimethylpentyl)phosphinic acid as an example to demonstrate a method for the synthesis of high ...

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Chemistry

Acid-base and Solubility Equilibria

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7.4K ビュー.  University of Science and Technology Beijing. 高純度非対称 dialkylphosphinic 酸抽出剤の合成のためのプロトコルが表示され、撮影 (2, 3-dimethylbutyl) (2, 4, 4'-trimethylpentyl) 例としてホスフィン酸。

ビデオ: Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants

Compact Quantum Dots for Single-molecule Imaging

Single-molecule imaging is an important tool for understanding the mechanisms of biomolecular function and for visualizing the spatial and temporal heterogeneity of molecular behaviors that underlie cellular biology 1-4. To image an individual molecule of interest, it is typically conjugated to a fluorescent tag (dye, protein, bead, or quantum dot) and observed with epifluorescence or total internal reflection fluorescence (TIRF) microscopy. While dyes and fluorescent proteins have been the mainstay of fluorescence imaging for decades, their fluorescence is unstable under high photon fluxes necessary to observe individual molecules, yielding only a few seconds of observation before complete loss of signal. Latex beads and dye-labeled beads provide improved signal stability but at the expense of drastically larger hydrodynamic size, which can deleteriously alter the diffusion and behavior of the molecule under study.
Quantum dots (QDs) offer a balance between these two problematic regimes. These nanoparticles are composed of semiconductor materials and can be engineered with a hydrodynamically compact size with exceptional resistance to photodegradation 5. Thus in recent years QDs have been instrumental in enabling long-term observation of complex macromolecular behavior on the single molecule level. However these particles have still been found to exhibit impaired diffusion in crowded molecular environments such as the cellular cytoplasm and the neuronal synaptic cleft, where their sizes are still too large 4,6,7.
Recently we have engineered the cores and surface coatings of QDs for minimized hydrodynamic size, while balancing offsets to colloidal stability, photostability, brightness, and nonspecific binding that have hindered the utility of compact QDs in the past 8,9. The goal of this article is to demonstrate the synthesis, modification, and characterization of these optimized nanocrystals, composed of an alloyed HgxCd1-xSe core coated with an insulating CdyZn1-yS shell, further coated with a multidentate polymer ligand modified with short polyethylene glycol (PEG) chains (Figure 1). Compared with conventional CdSe nanocrystals, HgxCd1-xSe alloys offer greater quantum yields of fluorescence, fluorescence at red and near-infrared wavelengths for enhanced signal-to-noise in cells, and excitation at non-cytotoxic visible wavelengths. Multidentate polymer coatings bind to the nanocrystal surface in a closed and flat conformation to minimize hydrodynamic size, and PEG neutralizes the surface charge to minimize nonspecific binding to cells and biomolecules. The end result is a brightly fluorescent nanocrystal with emission between 550-800 nm and a total hydrodynamic size near 12 nm. This is in the same size range as many soluble globular proteins in cells, and substantially smaller than conventional PEGylated QDs (25-35 nm).

We describe the preparation of colloidal quantum dots with minimized hydrodynamic size for single-molecule fluorescence imaging. Compared to conventional quantum dots, these nanoparticles are similar in size to globular proteins and are optimized for single-molecule brightness, stability against photodegradation, and resistance to nonspecific binding to proteins and cells.

1分子蛍光イメージングのためのコンパクトな量子ドット

Single-molecule imaging is an important tool for  understanding the mechanisms of biomolecular function and for visualizing the  spatial and temporal ...

工学

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

Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process.
The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications.

A procedure for the preparation of porous hybrid separation media composed of a macroporous polymer monolith internally coated by a high surface area microporous coordination polymer is presented.

リン酸化ペプチドの強化充実のためのマクロポーラスポリマーモノリスの高度に多孔性配位高分子コーティングの製造

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous ...

Extraction and Characterization of Surfactants from Atmospheric Aerosols

Surface-active compounds, or surfactants, present in atmospheric aerosols are expected to play important roles in the formation of liquid water clouds in the Earth&#39;s atmosphere, a central process in meteorology, hydrology, and for the climate system. But because specific extraction and characterization of these compounds have been lacking for decades, very little is known on their identity, properties, mode of action and origins, thus preventing the full understanding of cloud formation and its potential links with the Earth&#39;s ecosystems.
In this paper we present recently developed methods for 1) the targeted extraction of all the surfactants from atmospheric aerosol samples and for the determination of 2) their absolute concentrations in the aerosol phase and 3) their static surface tension curves in water, including their Critical Micelle Concentration (CMC). These methods have been validated with 9 references surfactants, including anionic, cationic and non-ionic ones. Examples of results are presented for surfactants found in fine aerosol particles (diameter &#60;1 &#956;m) collected at a coastal site in Croatia and suggestions for future improvements and other characterizations than those presented are discussed.

Methods are presented for the targeted extraction of surfactants present in atmospheric aerosols and the determination of their absolute concentrations and surface tension curves in water, including their Critical Micelle Concentration (CMC).

大気エアロゾルからの抽出および界面活性剤の特性評価

Surface-active compounds, or surfactants, present in atmospheric aerosols are expected to play important roles in the formation of liquid water clouds in ...

環境学

Facile Protocol for the Synthesis of Self-assembling Polyamine-based Peptide Amphiphiles (PPAs) and Related Biomaterials

Polyamine-based Peptide Amphiphiles (PPAs) are a new class of self-assembling amphiphilic biomaterials-related to the peptide amphiphiles (PAs). Traditional PAs possess charged amino acids as solubilizing groups (lysine, arginine), which are directly connected to a lipid segment or can contain a linker region made of neutral amino acids. Tuning the peptide sequence of PAs can yield diverse morphologies. Similarly, PPAs possess a hydrophobic segment and neutral amino acids, but also contain polyamine molecules as water solubilizing (hydrophilic) groups. As is the case with PAs, PPAs can also self-assemble into diverse morphologies, including small rods, twisted nano-ribbons, and fused nano-sheets, when dissolved in water. However, the presence of both primary and secondary amines on a single polyamine molecule poses a significant challenge when synthesizing PPAs. In this paper, we show a simple protocol, based on literature precedents, to achieve a facile synthesis of PPAs using solid phase peptide synthesis (SPPS). This protocol can be extended to the synthesis of PAs and other similar systems. We also illustrate the steps that are needed for cleavage from the resin, identification, and purification.

Facile Protocol for the Synthesis of Self-assembling Polyamine-based Peptide Amphiphiles PPAs and Related Biomaterials

The synthesis of polyamine-based peptide amphiphiles (PPAs) is a significant challenge due to the presence of multiple amine nitrogens, which requires judicious use of protecting groups to mask these reactive functionalities. In this paper, we describe a facile method for the preparation of these new class of self-assembling molecules.

自己組織化ペプチドのポリアミンによる両親媒性物質 (Ppa の) と関連生体材料の合成のための安易なプロトコル

Polyamine-based Peptide Amphiphiles (PPAs) are a new class of self-assembling amphiphilic biomaterials-related to the peptide amphiphiles (PAs). ...

Synthesis of Esters Via a Greener Steglich Esterification in Acetonitrile

The Steglich esterification is a widely-used reaction for the synthesis of esters from carboxylic acids and alcohols. While efficient and mild, the reaction is commonly performed using chlorinated or amide solvent systems, which are hazardous to human health and the environment. Our methodology utilizes acetonitrile as a greener and less hazardous solvent system. This protocol exhibits rates and yields that are comparable to traditional solvent systems and employs an extraction and wash sequence that eliminates the need for the purification of the ester product via column chromatography. This general method can be used to couple a variety of carboxylic acids with 1&#176; and 2&#176; aliphatic alcohols, benzylic and allylic alcohols, and phenols to obtain pure esters in high yields. The goal of the protocol detailed here is to provide a greener alternative to a common esterification reaction, which could serve useful for ester synthesis in both academic and industrial applications.

A modified Steglich esterification reaction was used to synthesize a small library of ester derivatives with primary and secondary alcohols. The methodology uses a non-halogenated and greener solvent, acetonitrile, and enables product isolation in high yields without the need for chromatographic purification.

アセトニ トリル中で環境に優しい転移エステルを介してエステルの合成

The Steglich esterification is a widely-used reaction for the synthesis of esters from carboxylic acids and alcohols. While efficient and mild, the ...

Preparation of Poly(pentafluorophenyl acrylate) Functionalized SiO2 Beads for Protein Purification

We demonstrate a simple method to prepare poly(pentafluorophenyl acrylate) (poly(PFPA)) grafted silica beads for antibody immobilization and subsequent immunoprecipitation (IP) application. The poly(PFPA) grafted surface is prepared via a simple two-step process. In the first step, 3-aminopropyltrimethoxysilane (APTMS) is deposited as a linker molecule onto the silica surface. In the second step, poly(PFPA) homopolymer, synthesized via the reversible addition and fragmentation chain transfer (RAFT) polymerization, is grafted to the linker molecule through the exchange reaction between the pentafluorophenyl (PFP) units on the polymer and the amine groups on APTMS. The deposition of APTMS and poly(PFPA) on the silica particles are confirmed by X-ray photoelectron spectroscopy (XPS), as well as monitored by the particle size change measured via dynamic light scattering (DLS). To improve the surface hydrophilicity of the beads, partial substitution of poly(PFPA) with amine-functionalized poly(ethylene glycol) (amino-PEG) is also performed. The PEG-substituted poly(PFPA) grafted silica beads are then immobilized with antibodies for IP application. For demonstration, an antibody against protein kinase RNA-activated (PKR) is employed, and IP efficiency is determined by Western blotting. The analysis results show that the antibody immobilized beads can indeed be used to enrich PKR while non-specific protein interactions are minimal.

Preparation of Polypentafluorophenyl acrylate Functionalized SiO2 Beads for Protein Purification

A protocol for the preparation of poly(pentafluorophenyl acrylate) (poly(PFPA)) grafted silica beads is presented. The poly(PFPA) functionalized surface is then immobilized with antibodies and used successfully for the protein separation through immunoprecipitation.

蛋白質の浄化のため Poly(pentafluorophenyl acrylate) 機能 SiO2ビーズの準備

We demonstrate a simple method to prepare poly(pentafluorophenyl acrylate) (poly(PFPA)) grafted silica beads for antibody immobilization and subsequent ...

Enzymatic Synthesis of Epoxidized Metabolites of Docosahexaenoic, Eicosapentaenoic, and Arachidonic Acids

The epoxidized metabolites of various polyunsaturated fatty acids (PUFAs), termed epoxy fatty acids, have a wide range of roles in human physiology. These metabolites are produced endogenously by the cytochrome P450 class of enzymes. Because of their diverse and potent biological effects, there is considerable interest in studying these metabolites. Determining the unique roles of these metabolites in the body is a difficult task, as the epoxy fatty acids must first be obtained in significant amounts and with high purity. Obtaining compounds from natural sources is often labor intensive, and soluble epoxide hydrolases (sEH) rapidly hydrolyze the metabolites. On the other hand, obtaining these metabolites via chemical reactions is very inefficient, due to the difficulty of obtaining pure regioisomers and enantiomers, low yields, and extensive (and expensive) purification. Here, we present an efficient enzymatic synthesis of 19(S),20(R)- and 16(S),17(R)-epoxydocosapentaenoic acids (EDPs) from DHA via epoxidation with BM3, a bacterial CYP450 enzyme isolated originally from Bacillus megaterium (that is readily expressed in Escherichia coli). Characterization and determination of purity is performed with nuclear magnetic resonance spectroscopy (NMR), high-performance liquid chromatography (HPLC), and mass spectrometry (MS). This procedure illustrates the benefits of enzymatic synthesis of PUFA epoxy metabolites, and is applicable to the epoxidation of other fatty acids, including arachidonic acid (AA) and eicosapentaenoic acid (EPA) to produce the analogous epoxyeicosatrienoic acids (EETs) and epoxyeicosatetraenoic acids (EEQs), respectively.

We present a method useful for large-scale enzymatic synthesis and purification of specific enantiomers and regioisomers of epoxides of arachidonic acid (AA), docosahexaenoic acid (DHA), and eicosapentaenoic acid (EPA) with the use of a bacterial cytochrome P450 enzyme (BM3).

ドコサヘキサエノイ酸、エイコサペンタエノイック、アラキドイン酸のエポキシ化代謝産物の酵素合成

The epoxidized metabolites of various polyunsaturated fatty acids (PUFAs), termed epoxy fatty acids, have a wide range of roles in human physiology. These ...

Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions

Aziridines, a class of reactive organic molecules containing a three-membered ring, are important synthons for the synthesis of a large variety of functionalized nitrogen-containing target compounds through the regiocontrolled ring-opening of C-substituted aziridines. Despite the tremendous progress in aziridine synthesis over the past decade, accessing contiguous bisaziridines efficiently remains difficult. Therefore, we were interested in synthesizing contiguous bisaziridines bearing an electronically diverse set of N-substituents beyond the single aziridine backbone for regioselective ring-opening reactions with diverse nucleophiles. In this study, chiral contiguous bisaziridines were prepared by organocatalytic asymmetric aziridination of chiral (E)-3-((S)-1-((R)-1-phenylethyl)aziridin-2-yl)acrylaldehyde with N-Ts-O-tosyl or N-Boc-O-tosyl hydroxylamine as the nitrogen source in the presence of (2S)-[diphenyl(trimethylsilyloxy)methyl]pyrrolidine as a chiral organocatalyst. Also demonstrated here are representative examples of regioselective ring-opening reactions of contiguous bisaziridines with a variety of nucleophiles such as sulfur, nitrogen, carbon, and oxygen, and the application of contiguous bisaziridines to the synthesis of multi-substituted chiral pyrrolidines by Pd-catalyzed hydrogenation.

Contiguous bisaziridines containing non-activated and activated aziridines were synthesized by asymmetric organocatalytic aziridinations and then subjected to chemoselective ring-opening reactions under acidic or basic conditions. The non-activated aziridine ring opens with less reactive nucleophiles under acidic conditions, whereas the activated aziridine ring opens with more reactive nucleophiles under basic conditions.

位置選択的開環反応のための連続ビサジリジンの調製

Aziridines, a class of reactive organic molecules containing a three-membered ring, are important synthons for the synthesis of a large variety of ...

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers

The growing consumption of synthetic polymers and the accumulation of polymer waste have led to a pressing need for new routes to sustainable materials. Achieving a closed-loop polymer economy via chemical recycling to monomer (CRM) is one such promising route. Our group recently reported a new CRM system based on polymers prepared by ring-opening metathesis polymerization (ROMP) of trans-cyclobutane fused cyclooctene (tCBCO) monomers. This system offers several key advantages, including the ease of polymerization at ambient temperatures, quantitative depolymerization to monomers under mild conditions, and a broad range of functionalities and thermomechanical properties. Here, we outline detailed protocols for the preparation of tCBCO-based monomers and their corresponding polymers, including the preparation of elastic polymer networks and compression molding of linear thermoplastic polymers. We also outline the preparation of high ring strain E-alkene tCBCO monomers and their living polymerization. Finally, the procedures for the depolymerization of linear polymers and polymer networks are also demonstrated.

Here, we describe protocols for the preparation of trans-cyclobutane fused cyclooctenes (tCBCO),&#160;their polymerization to prepare depolymerizable olefinic polymers, and the depolymerization of these polymers under mild conditions. Additionally, protocols for the preparation of depolymerizable networks and compression molding of rigid linear plastics based on this system are described.

縮合環シクロオクテンモノマーに基づく脱重合性オレフィン系ポリマー

The growing consumption of synthetic polymers and the accumulation of polymer waste have led to a pressing need for new routes to sustainable materials. ...

高純度非対称 Dialkylphosphinic 酸抽出剤の合成

要約

さらに動画を探す

この動画の章

1分子蛍光イメージングのためのコンパクトな量子ドット

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

リン酸化ペプチドの強化充実のためのマクロポーラスポリマーモノリスの高度に多孔性配位高分子コーティングの製造

大気エアロゾルからの抽出および界面活性剤の特性評価

自己組織化ペプチドのポリアミンによる両親媒性物質 (Ppa の) と関連生体材料の合成のための安易なプロトコル

アセトニトリル中で環境に優しい転移エステルを介してエステルの合成

蛋白質の浄化のため Poly(pentafluorophenyl acrylate) 機能 SiO₂ビーズの準備

ドコサヘキサエノイ酸、エイコサペンタエノイック、アラキドイン酸のエポキシ化代謝産物の酵素合成

位置選択的開環反応のための連続ビサジリジンの調製

縮合環シクロオクテンモノマーに基づく脱重合性オレフィン系ポリマー

高純度非対称 Dialkylphosphinic 酸抽出剤の合成

要約

さらに動画を探す

この動画の章

1分子蛍光イメージングのためのコンパクトな量子ドット

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

リン酸化ペプチドの強化充実のためのマクロポーラスポリマーモノリスの高度に多孔性配位高分子コーティングの製造

大気エアロゾルからの抽出および界面活性剤の特性評価

自己組織化ペプチドのポリアミンによる両親媒性物質 (Ppa の) と関連生体材料の合成のための安易なプロトコル

アセトニ トリル中で環境に優しい転移エステルを介してエステルの合成

蛋白質の浄化のため Poly(pentafluorophenyl acrylate) 機能 SiO2ビーズの準備

ドコサヘキサエノイ酸、エイコサペンタエノイック、アラキドイン酸のエポキシ化代謝産物の酵素合成

位置選択的開環反応のための連続ビサジリジンの調製

縮合環シクロオクテンモノマーに基づく脱重合性オレフィン系ポリマー

アセトニトリル中で環境に優しい転移エステルを介してエステルの合成

蛋白質の浄化のため Poly(pentafluorophenyl acrylate) 機能 SiO₂ビーズの準備