この作業は、共同プロジェクトのBOR4STORE（助成契約番号303428）およびインフラストラクチャのプログラムH2FC（助成契約番号FP7-284522）の下で、欧州燃料電池やHydruogen共同事業によってサポートされていました。

1.装置<ol><li>ガス供給、真空システム、センサー（温度、圧力）、および（浴中に浸漬することができます）サンプル環境：高圧ガス配管で接続された4つの主要コンポーネントで構成基本的な超臨界乾燥（SCD）装置を使用してください。建設は、高品質のステンレス鋼製バルブ、継手、および管であることを確認し、80〜300 Kの間の温度範囲内で少なくとも10 MPaのに圧力定格 注：概略図を図1に示されています。 </li><li>窒素SCD（NSCD）の治療のために、ガス供給は0-10 MPaの間の出口圧力制御のための圧力調整器を取り付けた研究純度（&gt; 99.999％）を窒素ガスであることを確認してください。装置に50 Lボトル（20 MPaで）を取り付け、使用する前に、純窒素で複数回、システムをパージします。 </li><li>真空システムは、0.1 Paの&lt;まで真空圧を達成することができるとして装置に接続されていることを確認微制御ニードルバルブ。好ましくは、オイルフリー粗引きポンプと直列に配置された分子ドラッグターボポンプを使用しています。 </li><li> 0.1〜7 Paの間の全測定可能な圧力範囲を達成するために、真空を測定するための低圧力センサと、高圧センサ：SCD処理時の圧力を正確に測定するための少なくとも2つの圧力センサを使用します。 </li><li>サンプルと熱的に接触しているセンサーと77から300 K（ 例えば 、Kタイプの熱電対）の間の正確な測定のために一次ガス投薬マニホールド内のセンサ：典型的なSCDの治療を行うのに必要な最小限の精度のために、少なくとも2つの温度センサを使用して。 </li><li>サンプルホルダーは、治療のために必要な試料の量を格納するための適切な内部容積を有しており、ステンレス鋼で構成されていることを確認してください。 注：バスと熱的に接触している長く円筒状のデザインを補助します。 </li><li>試料容器を閉じフィッティングがapproprであることを確認してください高い圧力と繰り返し使用iate（ 例えば 、Swagelok社VCR）。浴中に試料ホルダーを完全に浸漬するための配管の適切な長さ（浸漬管）を介して外部環境から隔離するためのバルブにサンプル容器の容量を接続します。 </li></ol><img alt="図1" src="/files/ftp_upload/52817/52817fig1.jpg" /> 。浴中の試料の浸漬後、周囲温度および（B）に（A）：図1超臨界窒素乾燥（NSCD）装置の典型的な実験室で使用するための単純化されたNSCD装置の概略図。この研究に記載された方法のためのガス供給は、窒素であるが、この一般的な装置は、CO 2のような温度及び圧力の実用的な範囲内にある臨界点を有する他のSCD流体に一般化です。コンポーネントは目との整合性のために標識されていますプロトコルは、本明細書に記載の電子。 <a href="https://www.jove.com/files/ftp_upload/52817/52817fig1highres.jpg" target="_blank">この図の拡大版を表示するには、こちらをクリックしてください。</a> 2.準備<ol><li>典型的には、アルゴングローブボックスのような不活性雰囲気中で、適当な条件下でロード試料0.2〜0.5グラム（湿式化学合成および標準乾燥方法以下の粉末状のγ-のMg（BH 4）2）試料ホルダーに、周囲温度で以下。フィルターガスケットで試料ホルダー（金具F2）を閉じて、バルブ（弁V4）を閉じます。装置に試料ホルダーを移し、（フィッティングF1）を取り付けます。 </li><li> V2を介して真空と避難する投薬マニホールドを開きます。オープンV3と避難。 V1を介して窒素で装置をパージし、V2を介して避難。オープンV4とシステム（&lt;0.1 ​​Pa）での最小圧力に到達するために、最大24時間、室温でサンプルを避難。 </li><li>サンプル槽を取り付けます（参照<stronG&gt;サンプルホルダーの周りに図2）。シザーリフト、または類似の機構上の位置に浴を上昇させることによって、これを実行します。 </li><li> 110 Kの（T Lを、ステップ3.1を参照してください）希望の未来液体の温度に加熱器を設定し、温度が平衡に達するまで装置を排気し続けます。 </li></ol><img alt="図2" src="/files/ftp_upload/52817/52817fig2.jpg" /> 図2.低温炉サンプルバース。NSCD処理中に試料ホルダーを収容するための適切なcryostatic温泉環境の概略図（左）と写真（右）、77から298 Kの間の試料温度の測定と制御を可能に<a href="https://www.jove.com/files/ftp_upload/52817/52817fig2highres.jpg" target="_blank">してください。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> 3.超臨界窒素暴露<ol&gt; <li> γ-MG（BH 4）2、（このプロトコルでデモの対象）のNSCD処理のためにこれは中程度の液体溶剤の密度に相当する110 Kの液体温度（T L）を選択します（〜0.6グラムミリリットル-1） ;他のNSCD処理プロセスにこのプロトコルの適用のために必要に応じて調整します（下の注を参照）。 </li><li> V2を閉じて真空にシステムをオフに閉じます。圧力が相図の液体領域に増加することができ、ゆっくりと開いV1を絞ります。 2 MPaであり、T Lでシステムを平衡化します。 </li><li> 4時間のために液体N 2でサンプルを浸します。 </li><li>ランプ≤2K分-1で150 Kにヒーターを設定します。 （このP maxは ≥10MPaであるべきである）圧力が装置の最大定格圧力よりも高いが増加しないように許可します。必要に応じて、慎重にV2を介して真空に過剰な圧力を排出。 P maxと150 Kでシステムを平衡化します</li><li> SUPのサンプルを浸し1時間ercritical N 2。 </li></ol><img alt="図3" src="/files/ftp_upload/52817/52817fig3.jpg" /> 図3.窒素の相図。流体密度は、（線形グレースケールに示されている）、窒素、の詳細な相図はREFPROP（状態の変更されたウェッブ·ベネディクト·ルービンの式）を用いて算出される。一定の密度の41様々な線が表示されています紫で。固相境界と沸騰遷移線が赤で示されています。青い線は、N 2を用いて、乾燥や抽出処理に関連する相図の領域の境界を示している。 <a href="https://www.jove.com/files/ftp_upload/52817/52817fig3highres.jpg" target="_blank">この図の拡大版を表示するには、こちらをクリックしてください。</a> 注：他の材料にこのプロトコルのアプリケーションでは、適切なNSCD治療SCHEMを確立対象種の効果的な溶媒和のために必要な条件を選択することによって、電子。 図3に示すN 2の相図を参照してください。液相の高い流体密度を達成するために（ 例えば、0.8〜1がg ml -1の）、中程度の液体密度のために80〜90 KのT Lを選択します（ 例えば、0.6〜0.8グラムミリリットル-1）、90から115 KのT Lの試行錯誤的なアプローチを選択する必要があるかもしれません。 4.超臨界窒素リリース<ol><li>慎重に、V2を絞る圧力はできるだけゆっくり減少することを可能にすることによって、真空にシステムをクラック。繰り返し12〜24時間のおおよその時間スパンで高真空（&lt;0.1 ​​Pa）での緩やかな減少を達成するために、必要に応じて、より高い真空率にシステムをクラック。 </li><li>試料を完全に排気するサンプル槽と全開V2を削除します。 RTおよび高真空（&lt;0.1 ​​Pa）とで平衡化。 </li><li> dと、RTで試料を脱気し、&lt;1〜24時間、0.1 Paのesired。 </li></ol> 5.後処理<ol><li>開閉弁V3とV4、及び装置（フィッティングF1）から試料ホルダーを取り外します。 </li><li>例えば、アルゴンを充填したグローブボックスとして、処理するための不活性環境に試料ホルダーを転送します。以下、周囲温度または、密閉容器内の試料（F2フィッティング）ホルダーとストアからサンプルを削除します。 </li></ol>

<ol>
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P., 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=Supercritical+N2+Processing+as+a+Route+to+the+Clean+Dehydrogenation+of+Porous+Mg(BH4)2.">Supercritical N2 Processing as a Route to the Clean Dehydrogenation of Porous Mg(BH4)2.</a> J. Am. Chem. Soc. 136 (23), 8181-8184 (2014).</li><li>Borgschulte, 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=Impurity+Gas+Analysis+of+the+Decomposition+of+Complex+Hydrides.">Impurity Gas Analysis of the Decomposition of Complex Hydrides.</a> J. Phys. Chem. C. 115, 17220-17226 (2011).</li><li>Filinchuk, 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=Porous+and+Dense+Magnesium+Borohydride+Frameworks:+Synthesis,+Stability,+and+Reversible+Absorption+of+Guest+Species.">Porous and Dense Magnesium Borohydride Frameworks: Synthesis, Stability, and Reversible Absorption of Guest Species.</a> Angew. Chem. Int. Ed. 50, 11162-11166 (2011).</li><li>Li, H. W., 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=Dehydriding+and+rehydriding+processes+of+well-crystallized+Mg(BH4)2+accompanying+with+formation+of+intermediate+compounds.">Dehydriding and rehydriding processes of well-crystallized Mg(BH4)2 accompanying with formation of intermediate compounds.</a> Acta Mater. 56 (6), 1342-1347 (2008).</li><li>Sch&#252;th, F., Bogdanovic, B., Felderhoff, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Light+metal+hydrides+and+complex+hydrides+for+hydrogen+storage.">Light metal hydrides and complex hydrides for hydrogen storage.</a> Chem. Comm. , 2249-2258 (2004).</li><li>Vitillo, J. G., Groppo, E., Bardaj&#237;, E. G., Baricco, M., Bordiga, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fast+carbon+dioxide+recycling+by+reaction+with+&#947;-Mg(BH4)2.">Fast carbon dioxide recycling by reaction with &#947;-Mg(BH4)2.</a> Phys. Chem. Chem. Phys. 16, 22482-22486 (2014).</li><li>Paskevicius, 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=In-Situ+X-ray+Diffraction+Study+of+&#947;-Mg(BH4)2+Decomposition.">In-Situ X-ray Diffraction Study of &#947;-Mg(BH4)2 Decomposition.</a> J. Phys. Chem. C. 116, 15321-15240 (2012).</li><li>Lemmon, E. W., Huber, M. L., McLinden, M. O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=NIST+standard+reference+database+23:+reference+fluid+thermodynamic+and+transport+properties.">NIST standard reference database 23: reference fluid thermodynamic and transport properties.</a> Standard Reference Data Program. , (2008).</li><li>Moquin, P. H. L., Temelli, F. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetic+modeling+of+hydrolysis+of+canola+oil+in+supercritical+media.">Kinetic modeling of hydrolysis of canola oil in supercritical media.</a> J. Supercrit. Fluid. 45, 94-101 (2008).</li><li>Myers, M. N., Giddings, J. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultra-High-Pressure+Gas+Chromatography+in+Micro+Columns+to+2000+Atmospheres.">Ultra-High-Pressure Gas Chromatography in Micro Columns to 2000 Atmospheres.</a> Sep. Sci. 1 (6), 761-776 (1966).</li><li>McLeary, E. E., Jansen, J. C., Kapteijn, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Zeolite+based+films,+membranes+and+membrane+reactors:+Progress+and+prospects.">Zeolite based films, membranes and membrane reactors: Progress and prospects.</a> Microporous Mesoporous Mater. 90, 198-220 (2006).</li><li>Richter, B., Ravnsb&#230;k, D. B., Tumanov, N., Filinchuk, Y., Jensen, T. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Manganese+borohydride;+synthesis+and+characterization.">Manganese borohydride; synthesis and characterization.</a> Dalton Trans. , (2015).</li><li>Liang, S., Tilotta, D. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Extraction+of+petroleum+hydrocarbons+from+soil+using+supercritical+argon.">Extraction of petroleum hydrocarbons from soil using supercritical argon.</a> Anal. Chem. 70 (3), 616-622 (1998).</li></ol>

著者らは、開示することは何もありません。

おそらく、その比較的低い臨界温度（126 K）に、N 2は、歴史的に効果的なSCD溶媒として見過ごされてきました。以前の報告では、3,17,42,43それは、それが（除いて、その相図のこの領域での低流体密度にわずかな溶媒和力を発揮する場合には、周囲温度またはより高い温度の処理のコンテキストでに示唆されています極めて高い圧力43）で。超臨界溶媒としてN 2...

超臨界流体抽出（SFE）と（SCD）の方法がよく、特に食品や石油産業における、だけでなく、化学合成、分析、および材料処理では、実用的なアプリケーションの広い範囲で確立されている乾燥。1-6乾燥の使用またはそれらの臨界点以上の条件で抽出媒体は、多くの場合、より速く、よりクリーンであり、より効率的な従来の（液体）技術よりも、高動作条件の僅かな調整により流体の溶媒和力に対して調整可能であるという追加の利点を有しています。3,7の簡単なSCD方式は、3つの基本的な手順で構成されています。最初のステップは、その高い密度が高い（そしておそらく選択的に対応し、その液体（または近超臨界液体）相に適切に選択されたSCD流体に対象不純物化合物を含む固体（あるいは液体）を出発原料を公開しています標的種に対して7）溶解力。 T彼は第二段階は、加熱流体とその溶解標的種を分離する可能性があり相境界を通過しないように密閉容器内に選択されたSCD流体の臨界点以上のシステムを圧縮されています。最後のステップはゆっくり相境界や道に沿って任意の有害な表面張力の影響に遭遇することなく、再度、脱出する標的種を含む液体溶液を可能にする、臨界温度以上の温度で真空にSCDの流体の圧力を低減します。 出発物質は、対象種が枯渇したままされ、必要に応じて繰り返し処理を施してもよいです。超臨界流体抽出の場合では、標的溶質種の所望の生成物であり、そしてさらなる使用のために溶液から回収される。他の場合には8,9、乾燥又は精製された出発物質は、所望の生成物であり、抽出された不純物を廃棄します。この後者のシナリオは、本明細書で言及しますSCDのアプローチとして、高表面積、例えば真空下での伝統的な熱処理方法は、多くの場合、毛穴をクリアで十分ではなく、有機金属構造体（MOF）、のような微孔性材料の前処理のための有効な戦略であることが発見されましたすべての不要なお客様、または孔の崩壊につながる。10二酸化炭素SCD（CSCD）処理の今のMOFためのルーチン合成後のプロセスであり、11は最大1000パーセント12の未処理の材料上に窒素がアクセス可能な表面積の増加につながるとこのような触媒活性のような他の改善、13その他の注目すべき超臨界流体の応用化学反応のために広く同調可能な媒体としては、14〜16超臨界流体クロマトグラフィー（SCFC）6,17,18とエアロゲルと先進複合材料の合成。19- 22 そののa）に近接：乾燥アプリケーションの場合、SCDの流体は2つの基準に基づいて選択されます標的種に対する条件周囲へ（便宜上およびエネルギーコストやプロセスの複雑さを低減するために）、およびb）その溶媒和力臨界点。二酸化炭素（CO 2）は、それが、非毒性、不燃性、および安価なあるため、多くの用途で便利なSCD液体であることが判明している、その近液に一般的な有機標的種の数に対して高い溶媒和力を発揮するように調整することができます。1-3,7-9他の一般的な超臨界溶媒（または共溶媒）（&lt;10 MPaのと273から323 Kの温度の圧力で）状態は、その周囲と超臨界状態の間の溶媒特性の著しい範囲に及ぶ（水、極性（プロトン性及び非プロトン性の）非極性、および周囲条件に比較的近い臨界点を有するからのスペクトルをカバーする23）、アセトン、エチレン、メタノール、エタノール、エタン、。 二酸化炭素は、これまでで使用される最も一般的なSCD流体です。確立CSCD方法において、反応性出発物質のCO 2は、非常に弱い反応性の臨界点近傍の温度であるため禁止要因ではありません。しかし、加熱下での（おそらく意図的に調整）不安定性に加えて、水またはCO 2の存在下で、彼らの強い反応に、いわゆる複合水素化物（ 例えば 、アラネートと水素化ホウ素）の取り扱いに存在する固有の課題のような物質の特定のクラス。24-26はまた、そこに高密度水素貯蔵化合物などの材料で大きな国際的関心がある27-30したがってまた、ナノ構造および/ ​​または多孔性の品種31-33。このような反応性、不安定な、およびナノ構造材料の効果的な精製の ​​ために、SCD法は、狭いキャビティ内への浸透のための適切な低分子直径を有し、またに対する高い溶媒和力を有する。34 A SCD流体を使用しなければならない有望な戦略でありますターゲットの不純物、WHIルを出発原料自体に向かって非反応残り。ここで、超臨界窒素（N 2）の使用は、抽出及び乾燥の用途のために特に有効な流体が提示されます。特定の超臨界窒素乾燥（NSCD）方法は、標的種はジボランとnブチル化合物（と似ているが、n個のブタン、具体的に識別できない）の両方を含むγ相マグネシウム、水素化ホウ素の精製の ​​ために説明します。以下のプロトコルは、簡単に他の超臨界窒素乾燥又は抽出プロセスに一般的な拡張のために変更することができます。

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>Compressed Nitrogen Gas</td>
			<td>Messer Schweiz AG</td>
			<td></td>
			<td>50 L bottle, purity &#62; 99.999%, &#60;3 ppmv H2O</td>
		</tr>
		<tr>
			<td>Liquid Nitrogen</td>
			<td>Pan Gas AG</td>
			<td></td>
			<td>Bulk storage, on site</td>
		</tr>
		<tr>
			<td>Custom Supercritical Drying Apparatus</td>
			<td>Empa</td>
			<td></td>
			<td>Swagelok (compression fitting and VCR) components</td>
		</tr>
		<tr>
			<td>Custom Cryogenic Furnace Bath</td>
			<td>Empa</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Custom Labview Interface</td>
			<td>Empa</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

supercritical nitrogen processing for the purification of reactive porous materials

Supercritical fluid extraction and drying methods are well established in numerous applications for the synthesis and processing of porous materials. Herein, nitrogen is presented as a novel supercritical drying fluid for specialized applications such as in the processing of reactive porous materials, where carbon dioxide and other fluids are not appropriate due to their higher chemical reactivity. Nitrogen exhibits similar physical properties in the near-critical region of its phase diagram as compared to carbon dioxide: a widely tunable density up to ~1 g ml-1, modest critical pressure (3.4 MPa), and small molecular diameter of ~3.6 &#197;. The key to achieving a high solvation power of nitrogen is to apply a processing temperature in the range of 80-150 K, where the density of nitrogen is an order of magnitude higher than at similar pressures near ambient temperature. The detailed solvation properties of nitrogen, and especially its selectivity, across a wide range of common target species of extraction still require further investigation. Herein we describe a protocol for the supercritical nitrogen processing of porous magnesium borohydride.

アルカリおよびアルカリ土類金属のホウ水素化物が分解して水素ガスの大きいコンテンツを配信する可能性のある水素貯蔵材料である。例えば、ジボランなど27,29の他の分解生成物はまた、時々脱着ガス中に検出されているが、その起源は先験的に明らかではありません;それは純粋な相分解の産物であることが可能であるが、また、化学合成からの残りの不純物の反応不純物または?...

Watch this Scientific Journal Video about Supercritical Nitrogen Processing for the Purification of Reactive Porous Materials at JoVE.com

Supercritical Nitrogen Processing for the Purification of Reactive Porous Materials

窒素は、その分子サイズが小さい、近超臨界液体領域で高密度、および化学的不活性に抽出または乾燥工程のための効果的な超臨界流体です。我々は、反応性、多孔性材料の精製処理のための超臨界窒素乾燥プロトコルを提示します。

反応性多孔質材料を精製するための超臨界窒素処理

Supercritical fluid extraction and drying methods are well established in numerous applications for the synthesis and processing of porous materials. ...

supercritical-nitrogen-processing-for-purification-reactive-porous

Research

JoVE Journal

Chemistry

14.6K ビュー.  Empa, Swiss Federal Laboratories for Materials Science and Technology. 窒素は、その分子サイズが小さい、近超臨界液体領域で高密度、および化学的不活性に抽出または乾燥工程のための効果的な超臨界流体です。我々は、反応性、多孔性材料の精製処理のための超臨界窒素乾燥プロトコルを提示します。 

ビデオ: Supercritical Nitrogen Processing for the Purification of Reactive Porous Materials

Folding and Characterization of a Bio-responsive Robot from DNA Origami

The DNA nanorobot is a hollow hexagonal nanometric device, designed to open in response to specific stimuli and present cargo sequestered inside. Both stimuli and cargo can be tailored according to specific needs. Here we describe the DNA nanorobot fabrication protocol, with the use of the DNA origami technique. The procedure initiates by mixing short single-strand DNA staples into a stock mixture which is then added to a long, circular, single-strand DNA scaffold in presence of a folding buffer. A standard thermo cycler is programmed to gradually lower the mixing reaction temperature to facilitate the staples-to-scaffold annealing, which is the guiding force behind the folding of the nanorobot. Once the 60 hr folding reaction is complete, excess staples are discarded using a centrifugal filter, followed by visualization via agarose-gel electrophoresis (AGE). Finally, successful fabrication of the nanorobot is verified by transmission electron microscopy (TEM), with the use of uranyl-formate as negative stain.

DNA origami is a powerful method for fabricating precise nanoscale objects by programming the self-assembly of DNA molecules. Here we describe a protocol for the folding of a bio-responsive robot from DNA origami, its purification and negative staining for transmission electron microscopic imaging (TEM).

DNA折り紙からバイオ応答ロボットの折りたたみとキャラクタリゼーション

The DNA nanorobot is a hollow hexagonal nanometric device, designed to open in response to specific stimuli and present cargo sequestered inside. Both ...

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 ...

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The composition of heavy crude oils and shale oils varies substantially depending on the origin of the mixture. In particular they contain an increased amount of nitrogen containing compounds compared to the conventionally used sweet crude oils. As nitrogen compounds have an influence on the operation of thermal processes occurring in coker units and steam crackers, and as some species are considered as environmentally hazardous, a detailed analysis of the reactions involving nitrogen containing compounds under pyrolysis conditions provides valuable information. Therefore a novel method has been developed and validated with a feedstock containing a high nitrogen content, i.e., a shale oil. First, the feed was characterized offline by comprehensive two-dimensional gas chromatography (GC &#215; GC) coupled with a nitrogen chemiluminescence detector (NCD). In a second step the on-line analysis method was developed and tested on a steam cracking pilot plant by feeding pyridine dissolved in heptane. The former being a representative compound for one of the most abundant classes of compounds present in shale oil. The composition of the reactor effluent was determined via an in-house developed automated sampling system followed by immediate injection of the sample on a GC &#215; GC coupled with a time-of-flight mass spectrometer (TOF-MS), flame ionization detector (FID) and NCD. A novel method for quantitative analysis of nitrogen containing compounds using NCD and 2-chloropyridine as an internal standard has been developed and demonstrated.

A method combining comprehensive two-dimensional gas chromatography with nitrogen chemiluminescence detection has been developed and applied to on-line analysis of nitrogen containing compounds in a complex hydrocarbon matrix.

オンライン複雑な炭化水素マトリックス中の窒素含有化合物の分析

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The ...

Insights into the Interactions of Amino Acids and Peptides with Inorganic Materials Using Single-Molecule Force Spectroscopy

The interactions between proteins or peptides and inorganic materials lead to several interesting processes. For example, combining proteins with minerals leads to the formation of composite materials with unique properties. In addition, the undesirable process of biofouling is initiated by the adsorption of biomolecules, mainly proteins, on surfaces. This organic layer is an adhesion layer for bacteria and allows them to interact with the surface. Understanding the fundamental forces that govern the interactions at the organic-inorganic interface is therefore important for many areas of research and could lead to the design of new materials for optical, mechanical and biomedical applications. This paper demonstrates a single-molecule force spectroscopy technique that utilizes an AFM to measure the adhesion force between either peptides or amino acids and well-defined inorganic surfaces. This technique involves a protocol for attaching the biomolecule to the AFM tip through a covalent flexible linker and single-molecule force spectroscopy measurements by atomic force microscope. In addition, an analysis of these measurements is included.

Here we present a protocol to measure the force of interactions between a well-defined inorganic surface and either peptides or amino acids by single-molecule force spectroscopy measurements using an atomic force microscope (AFM). The information obtained from the measurement is important to better understand the peptide-inorganic material interphase.

単一分子力分光法を用いて無機材料とアミノ酸とペプチドの相互作用への洞察

The interactions between proteins or peptides and inorganic materials lead to several interesting processes. For example, combining proteins with minerals ...

Facet-to-facet Linking of Shape-anisotropic Colloidal Cadmium Chalcogenide Nanostructures

Here, we describe a protocol that allows for shape-anisotropic cadmium chalcogenide nanocrystals (NCs), such as nanorods (NRs) and tetrapods (TPs), to be covalently and site-specifically linked via their end facets, resulting in polymer-like linear or branched chains. The linking procedure begins with a cation-exchange process in which the end facets of the cadmium chalcogenide NCs are first converted to silver chalcogenide. This is followed by the selective removal of ligands at their surface. This results in cadmium chalcogenide NCs with highly reactive silver chalcogenide end facets that spontaneously fuse upon contact with each other, thereby establishing an interparticle facet-to-facet attachment. Through the judicious choice of precursor concentrations, an extensive network of linked NCs can be produced. Structural characterization of the linked NCs is carried out via low- and high-resolution transmission electron microscopy (TEM), as well as energy-dispersive X-ray spectroscopy, which confirm the presence of silver chalcogenide domains between chains of cadmium chalcogenide NCs.

A protocol detailing how shape-anisotropic colloidal cadmium chalcogenide nanocrystals can be covalently linked via their end facets is presented here.

ファセットとファセットの形状異方性のコロイド カドミウム カルコゲナイド系ナノ構造のリンク

Here, we describe a protocol that allows for shape-anisotropic cadmium chalcogenide nanocrystals (NCs), such as nanorods (NRs) and tetrapods (TPs), to be ...

Fabrication and Testing of Catalytic Aerogels Prepared Via Rapid Supercritical Extraction

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three preparation methods are described: (a) the incorporation of metal salts into silica or alumina wet gels using an impregnation method; (b) the incorporation of metal salts into alumina wet gels using a co-precursor method; and (c) the addition of metal nanoparticles directly into a silica aerogel precursor mixture. The methods utilize a hydraulic hot press, which allows for rapid (&#60;6 h) supercritical extraction and results in aerogels of low density (0.10 g/mL) and high surface area (200-800 m2/g). While the work presented here focuses on the use of copper salts and copper nanoparticles, the approach can be implemented using other metal salts and nanoparticles. A protocol for testing the three-way catalytic ability of these aerogels for automotive pollution mitigation is also presented. This technique uses custom-built equipment, the Union Catalytic Testbed (UCAT), in which a simulated exhaust mixture is passed over an aerogel sample at a controlled temperature and flow rate. The system is capable of measuring the ability of the catalytic aerogels, under both oxidizing and reducing conditions, to convert CO, NO and unburned hydrocarbons (HCs) to less harmful species (CO2, H2O and N2). Example catalytic results are presented for the aerogels described.

Here we present protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms. Methods for preparing materials using copper salts and copper-containing nanoparticles are featured. Catalytic testing protocols demonstrate the effectiveness of these aerogels for three-way catalysis applications.

急速な超臨界抽出法によって作製した触媒のエアロゲルの作製と試験

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three ...

Deposition of Porous Sorbents on Fabric Supports

A microwave deposition technique for silanes, previously described for production of oleophobic fabrics, is adapted to provide a fabric support material that can be subsequently treated by dip coating. Dip coating with a sol preparation provides a supported porous layer on the fabric. In this case, the porous layer is a porphyrin functionalized sorbent system based on a powdered material that has been demonstrated previously for the capture and conversion of phosgene. A representative coating is applied to cotton fabric at a loading level of 10 mg/g. This coating has minimal impact on water vapor transport through the fabric (93% of the support fabric rate) while significantly reducing transport of 2-chloroethyl ethyl sulfide (CEES) through the material (7% of support fabric rate). The described approaches are suitable for use with other fabrics providing amine and hydroxyl groups for modification and can be used in combination with other sol preparations to produce varying functionality.

This report details a microwave-initiated approach for deposition of porphyrin functionalized porous organosilicate sorbents on a cotton fabric and demonstrates reduction in 2-chloroethyl ethyl sulfide (CEES) transport through the fabric resulting from this treatment.

ファブリックのサポートに多孔質吸着剤の成

A microwave deposition technique for silanes, previously described for production of oleophobic fabrics, is adapted to provide a fabric support material ...

Chemical Synthesis of Porous Barium Titanate Thin Film and Thermal Stabilization of Ferroelectric Phase by Porosity-Induced Strain

Barium titanate (BaTiO3, hereafter BT) is an established ferroelectric material first discovered in the 1940s and still widely used because of its well-balanced ferroelectricity, piezoelectricity, and dielectric constant. In addition, BT does not contain any toxic elements. Therefore, it is considered to be an eco-friendly material, which has attracted considerable interest as a replacement for lead zirconate titanate (PZT). However, bulk BT loses its ferroelectricity at approximately 130 &#176;C, thus, it cannot be used at high temperatures. Because of the growing demand for high-temperature ferroelectric materials, it is important to enhance the thermal stability of ferroelectricity in BT. In previous studies, strain originating from the lattice mismatch at hetero-interfaces has been used. However, the sample preparation in this approach requires complicated and expensive physical processes, which are undesirable for practical applications.
In this study, we propose a chemical synthesis of a porous material as an alternative means of introducing strain. We synthesized a porous BT thin film using a surfactant-assisted sol-gel method, in which self-assembled amphipathic surfactant micelles were used as an organic template. Through a series of studies, we clarified that the introduction of pores had a similar effect on distorting the BT crystal lattice, to that of a hetero-interface, leading to the enhancement and stabilization of ferroelectricity. Owing to its simplicity and cost effectiveness, this fabrication process has considerable advantages over conventional methods.

Here, we present a protocol for the synthesis of porous barium titanate (BaTiO3) thin film by a surfactant-assisted sol-gel method, in which self-assembled amphipathic surfactant micelles are used as an organic template.

化学合成チタン酸バリウム多孔質セラミックス薄膜の気孔率誘起歪による強誘電相の熱安定化

Barium titanate (BaTiO3, hereafter BT) is an established ferroelectric material first discovered in the 1940s and still widely used because of its ...

Synthesis and Bioconjugation of Thiol-Reactive Reagents for the Creation of Site-Selectively Modified Immunoconjugates

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. Yet maleimide-based conjugates display limited stability in vivo because the succinimidyl thioether linkage can undergo a retro-Michael reaction. This, of course, can lead to the release of the radioactive payload or its exchange with thiol-bearing biomolecules in circulation. Both of these processes can produce elevated activity concentrations in healthy organs as well as decreased activity concentrations in target tissues, resulting in reduced imaging contrast and lower therapeutic ratios. In 2018, we reported the creation of a modular, stable, and easily accessible phenyloxadiazolyl methyl sulfone reagent &#8212; dubbed &#8216;PODS&#8217; &#8212; as a platform for thiol-based bioconjugations. We have clearly demonstrated that PODS-based site-selective bioconjugations reproducibly and robustly create homogenous, well-defined, highly immunoreactive, and highly stable radioimmunoconjugates. Furthermore, preclinical experiments in murine models of colorectal cancer have shown that these site-selectively labeled radioimmunoconjugates exhibit far superior in vivo performance compared to radiolabeled antibodies synthesized via maleimide-based conjugations. In this protocol, we will describe the four-step synthesis of PODS, the creation of a bifunctional PODS-bearing variant of the ubiquitous chelator DOTA (PODS-DOTA), and the conjugation of PODS-DOTA to the HER2-targeting antibody trastuzumab.

In this protocol, we will describe the synthesis of PODS, a phenyoxadiazolyl methyl sulfone-based reagent for the site-selective attachment of cargos to the thiols of biomolecules, particularly antibodies. In addition, we will describe the synthesis and characterization of a PODS-bearing bifunctional chelator and its conjugation to a model antibody.

合成と化反応のサイト選択的に作成するためのチオール反応性の試薬の変更 Immunoconjugates

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. ...

Evaluation of Oxidative Stress in Biological Samples Using the Thiobarbituric Acid Reactive Substances Assay

Despite its limited analytical specificity and ruggedness, the thiobarbituric acid reactive substances (TBARS) assay has been widely used as a generic metric of lipid peroxidation in biological fluids. It is often considered a good indicator of the levels of oxidative stress within a biological sample, provided that the sample has been properly handled and stored. The assay involves the reaction of lipid peroxidation products, primarily malondialdehyde (MDA), with thiobarbituric acid (TBA), which leads to the formation of MDA-TBA2 adducts called TBARS. TBARS yields a red-pink color that can be measured spectrophotometrically at 532 nm. The TBARS assay is performed under acidic conditions (pH = 4) and at 95 &#176;C. Pure MDA is unstable, but these conditions allow the release of MDA from MDA bis(dimethyl acetal), which is used as the analytical standard in this method. The TBARS assay is a straightforward method that can be completed in about 2 h. Preparation of assay reagents are described in detail here. Budget-conscious researchers can use these reagents for multiple experiments at a low cost rather than buying an expensive TBARS assay kit that only permits construction of a single standard curve (and thus can only be used for one experiment). The applicability of this TBARS assay is shown in human serum, low density lipoproteins, and cell lysates. The assay is consistent and reproducible, and limits of detection of 1.1 &#956;M can be reached. Recommendations for the use and interpretation of the spectrophotometric TBARS assay are provided.

The goal of the thiobarbituric acid reactive substances assay is to assess oxidative stress in biological samples by measuring the production of lipid peroxidation products, primarily malondialdehyde, using visible wavelength spectrophotometry at 532 nm. The method described here can be applied to human serum, cell lysates, and low density lipoproteins.

チオバルビツール酸反応性物質アッセイを用いた生体試料における酸化ストレスの評価

Despite its limited analytical specificity and ruggedness, the thiobarbituric acid reactive substances (TBARS) assay has been widely used as a generic ...