著者は、機器設計における支援のために博士ウェスゴードン（ECBC）をお願いいたします。この作品は、プログラムCA08MSB317下エリックローウェンスタインとマイケル·ロバーツ（防衛脅威削減局）が資金提供2研究プログラムからの累積の結果を表しています。本明細書に引用された技術報告書がで得ることができる<a href="http://www.dtic.mil">http://www.dtic.mil</a> 。

所望の環境に1条件ペイント基質<ol><li>特定の温度および相対湿度（20℃、50％）に基板空調用環境室をプリセット。温度と含水量の両方が大幅に材料への吸収率に影響を与えることができるので、基板の状態が一貫して維持されていることを確認します。 </li><li> 0.32センチメートル厚いコート、全コーティング厚さの塗料の層（6 MIL-DTL-53039、溶媒分散性（SD）脂肪族ポリウレタンコーティングシステム）で20.25センチメートル2の表面積を有する5.08センチメートル半径ステンレス製のディスク（約100μmのプライマーとトップコート）。試験表面を有するステンレススチールトレイ上の（反復の所望の数を有する）基板が上向きに化学薬品にさらされる置く。 </li><li>ペトリ皿を有する基板をカバー。少なくとも60マイルのための環境室に試験基板を含むトレイを置きますnは理想的にO / N、可能ならば。 </li></ol>前処理付き基板の2。汚染<ol><li>そのような白衣、安全メガネ、手袋などのドン·個人用保護具。 </li><li>注意：低温貯蔵からの化学汚染物質を入手し、一次容器バイアルを室温に平衡化させる。このプロトコルで使用される化学物質は、化学薬品標準的な分析標準物質（CASARM、98.0％の純度）グレードのHDおよびCASARM（89.0％高純度）グレードVX（両液相）である。どちら核磁気共鳴またはガスクロマトグラフィー/質量分析分析から純度の情報を取得し、ファイルに保持します。 注：注意：化学兵器の処理にのみ適用される安全性、セキュリティ、および保証上の注意を使用して承認された施設で訓練を受けた担当者が行ってください。 </li><li>注意：ピペットチップで薬剤送達ツールを取り付け、薬剤の液滴（ 例えば 、1μl）を実現するためのツールを設定します。 Uncap汚染物質のバイアル、およびボンネット面にキャップを置き、上に向けたスレッド。ピペットをピックアップし、ゆっくりと汚染物質溶液中に先端を下げる。製造業者の指示に従って薬と薬剤送達ツールをロードします。静かにボンネットの作業面上にロードされたピペットを配置し、汚染物質のバイアルをおさらい。 </li><li>注意：試験基板を汚染する。 <ol><li>環境室から試験基板を含むトレーを取り外します。 </li><li>試験基板からペトリ皿を取り外し、ボンネット面に設定してください。デジタル汚染の前に各基板の外観を記録するために、各試験基板を撮影する。 </li><li>ロードされたピペットをピックアップし、最初のテスト基板上にエージェントの一滴（ 例えば 、1μl）を実現します。追加の基板を汚染しつつ蒸発を最小限に抑えるために、ポリスチレンのペトリ皿で​​汚染物質を覆う。基板ごとに繰り返します。ピペットチップ（Sをリロード必要に応じて2.3）TEP。 注：汚染物質の質量の配信を確認するために、クロマトグラフィーを介して分析用の基質の投与前と後のピペットの確認のサンプルを収集します。 </li><li>試験基板からペトリ皿を取り外し、ボンネット面に設定してください。デジタル初期の汚染物質の相互作用を記録するために、各試験基板を撮影。 </li><li>ペトリ皿で​​試験基板をカバー。 </li><li>バック環境室への基板のトレイを置きます。 </li></ol></li></ol> 3汚染物質の相互作用熟成期間<ol><li>サンプルの高齢化に先立ち、第4節で使用するために準備するためにステンレス製高真空実験室ベント。 </li><li>化学物質と環境の相互作用の動力学（ 例えば 、60分）に基づいて変化させることができる指定された期間環境室、お客様の年齢に汚染された基板を許可します。 </li><li> environmから基板を取り外しフードの作業面上のental室と場所。試験基板からペトリ皿を取り外し、デジタルポスト老化汚染物質の相互作用を記録するために各基板を撮影。 </li><li>試験サンプル（ 例えば 、複数の気密容器入り）をダブル含まれており、高真空チャンバーで作業フードに移す。 </li></ol> 4。高真空蒸着エミッション商工測定高真空チャンバは、ターボ分子ドラッグポンプ及びダイアフラムバッキングポンプ（ 図2）によってポンピングされる小容量容器である。四重極質量分析計に直接温度制御された基板ホルダーに対向し、高真空条件下で汚染された基質からリアルタイムのガスの発生を測定するために使用されるポートに取り付けられている。真空チャンバの仕様および材料に関する詳細は、参考4に含まれている。 <ol><li>チャンバが適切に通気されていることを確認します。 </li><li>注意：第3節で調製した試料を開梱し、試験基板からペトリ皿を取り外します。ステンレス製のピンセットを使用して、各温度制御された基板ホルダーに1試験基板を配置します。 </li><li>真空室を密封し、ポンプダウンシーケンスを開始します。チャンバは、基板が汚染されていた時に関連して指定されたエージングタイム（ 例えば 60分）で密封し、真空であるように、この手順を実行します。 </li><li>単位電荷値（m / zを ）当たりの特定の質量で識別時間（質量流束を直接測定）の関数として選択された質量フラグメントチャンネルを記録を開始します。汚染物質分圧が検出限界を下回るまで&lt;0.25 Hzでリアルタイムに：;：（m / zを = 109 HD のm / z = 114 VX）目的の分子からの一次質量断片に加えて、特定のバックグラウンドガス種を測定します（ - 8 Paの10）質量分析計の。 </li><li>の排出曲線を収集基板からの汚染物質の放出の持続時間。 </li><li>汚染物質の質量流量は、チャンバ圧のベースラインまで低下した後、質量分析計で放出曲線の記録を停止する。 </li><li>大気圧に高真空チャンバベント。 </li></ol>総残存汚染のために5。後処理評価<ol><li>高真空蒸気放出室（HVVEC）装置を開き、ステンレス製のピンセットを用いてチャンバから基板を取り外します。 </li><li>ガラス抽出ジャーに基板を配置し、瓶に溶媒抽出を20ml加える（ 例えば 、イソプロピルアルコール：VXをクロロホルム：HD）。瓶に蓋をし、瓶を3回旋回。 60分間抽出溶媒中の基質のままにしておきます。 </li><li>再び瓶を3回旋回した後、瓶を暴露する。きれいな、使い捨てガラスピペットを用いて、気体又は液体を介して分析のための分析バイアルに抽出溶媒の約1〜2 mlで転送するー7は、基板に保持された汚染物質の質量を測定した。 </li></ol> 6。データ解析とモデリング<ol><li>基板から質量流束に生の質量分析データ（測定されたイオン電流に由来する部分圧）を変換する。検出器に入射蒸気フラックスに検出されたガス種の分圧を変換するためのヘルツクヌーセン式の組み合わせを使用し、元の汚染事象から基板上の汚染領域を占めてスケーリング係数を含む。 </li><li>塗装を通じて汚染物質輸送のための飽和濃度と拡散定数値（キーマストランスポートパラメータ）を決定するために、逆の方法（ 例えば 、レーベンバーグ·マルカートアルゴリズム）を使用します。予測された蒸気流束（適用適切な境界条件（参照4から式4を参照）とのFickの第二法則に解析解）を実験的に決定蒸気フラックスを比較してください。 </li&gt; <li>汚染物質材料系のための濃度プロファイルを予測するためにマストランスポートパラメータを使用してください。 </li></ol>

<ol>
	<li>Willis, M. P., Mantooth, B. A., Lalain, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Novel+Methodology+for+the+Estimation+of+Chemical+Warfare+Agent+Mass+Transport+Dynamics,+Part+II:+Absorption.">Novel Methodology for the Estimation of Chemical Warfare Agent Mass Transport Dynamics, Part II: Absorption.</a> J. Phys. Chem. C. 116, 546-554 (2011).</li><li>Felder, R. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Estimation+of+Gas+Transport-Coefficients+from+Differential+Permeation,+Integral+Permeation,+and+Sorption+Rate+Data.">Estimation of Gas Transport-Coefficients from Differential Permeation, Integral Permeation, and Sorption Rate Data.</a> J. Membr. Sci. 3, 15-27 (1978).</li><li>Taviera, P., Mendes, A., Costa, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=On+the+Determination+of+Diffusivity+and+Sorption+Coefficients+Using+Different+Time-lag+Models.">On the Determination of Diffusivity and Sorption Coefficients Using Different Time-lag Models.</a> J. Membr. Sci. 221, 123-133 (2003).</li><li>Willis, M. P., Gordon, W. O., Lalain, T. A., Mantooth, B. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Characterization+of+Chemical+Agent+Transport+in+Paints.">Characterization of Chemical Agent Transport in Paints.</a> J. Hazard Mater. 260, 907-913 (2013).</li><li>Lalain, T., Mantooth, B., Shue, M., Pusey, S., Wylie, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> The Chemical Contaminant and Decontaminant Test Methodology Source Document. Second Edition. Report No. ECBC-TR-980. , (2011).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> MIL-DTL-53039B: Coating Aliphatic Polyurethane, Single Component, Chemical Agent Resistant. , (2005).</li><li>Shue, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Low-Level Analytical Methodology Updates to Support Decontaminant Performance Evaluations. Report No. ECBC-TR-883. , (2011).</li><li>Schwope, A. D., Klein, J. M., Sidman, K. R., Reid, R. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sorption-Desorption+Phenomena+of+Chemicals+from+Polymer+(Paint)+Films.">Sorption-Desorption Phenomena of Chemicals from Polymer (Paint) Films.</a> J. Hazard. Mater. 13, 353-367 (1986).</li><li>Li, F., Niu, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Control+of+Volatile+Organic+Compounds+Indoors+-+Development+of+an+Integrated+Mass-Transfer-Based+Model+and+Its+Application.">Control of Volatile Organic Compounds Indoors - Development of an Integrated Mass-Transfer-Based Model and Its Application.</a> Atmos. Environ. 41, 2344-2354 (2007).</li><li>Li, F., Niu, J., Zhang, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Physically-Based+Model+for+Prediction+of+VOCs+Emissions+from+Paint+Applied+to+an+Absorptive+Substrate.">A Physically-Based Model for Prediction of VOCs Emissions from Paint Applied to an Absorptive Substrate.</a> Build. Environ. 41, 1317-1325 (2006).</li><li>Li, F., Niu, J. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Simultaneous+Estimation+of+VOCs+Diffusion+and+Partition+Coefficients+in+Building+Materials+via+Inverse+Analysis.">Simultaneous Estimation of VOCs Diffusion and Partition Coefficients in Building Materials via Inverse Analysis.</a> Build. Environ. 40, 1366-1374 (2005).</li><li>Li, F., Niu, J. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+Inverse+Technique+to+Determine+Volatile+Organic+Compounds+Diffusion+and+Partition+Coefficients+in+Dry+Building+Material.">An Inverse Technique to Determine Volatile Organic Compounds Diffusion and Partition Coefficients in Dry Building Material.</a> Heat and Mass Transfer. 41, 834-842 (2005).</li><li>Li, F., Niu, J. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+Inverse+Approach+for+Estimating+the+Initial+Distribution+of+Volatile+Organic+Compounds+in+Dry+Building+Material.">An Inverse Approach for Estimating the Initial Distribution of Volatile Organic Compounds in Dry Building Material.</a> Atmos. Environ. 39, 1447-1455 (2005).</li><li>Vesely, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Diffusion+of+Liquids+in+Polymers.">Diffusion of Liquids in Polymers.</a> Int. Mater. Rev. 53, 299-315 (2008).</li><li>Goossens, E. L. J., van der Zanden, A. J. J., Wijen, H. L. M., van der Spoel, W. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Measurement+of+the+Diffusion+Coefficient+of+Water+in+Paints+and+Polymers+from+Their+Swelling+by+Using+an+Interferometric+Technique.">The Measurement of the Diffusion Coefficient of Water in Paints and Polymers from Their Swelling by Using an Interferometric Technique.</a> Prog. Org. Coat. 48, 112-117 (2003).</li><li>Arya, R. K., Vinjamur, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Measurement+of+Concentration+Profiles+Using+Confocal+Raman+Spectroscopy+in+Multicomponent+Polymeric+Coatings-Model+Validation.">Measurement of Concentration Profiles Using Confocal Raman Spectroscopy in Multicomponent Polymeric Coatings-Model Validation.</a> J. Appl. Polym. Sci. 128, 3906-3918 (2013).</li></ol>

著者らは、開示することは何もない。

塗料中のHDとVX用のマストランスポートパラメータは、蒸気排出データの数値逆解析によって決定した。算出されたパラメータと、それはその後、塗装中の汚染物質の分布の時間依存性濃度勾配マップを生成することが可能であった。逆解析結果はSD塗料におけるHDの溶解度がVXよりも高かったが、拡散率は低い約5倍であることが実証された。結果は、VX汚染プロファイルはSDペイントコーティ?...

化学兵器による材料の汚染に関連する質量輸送機構は、物理的状態遷移、モバイル種間の化学的相互作用、および材料のインターフェースを含む畳み込みさまざまなプロセスによって駆動される。効果的な除染技術、最適化された除染手順、および予測モデルを開発するには、それが戻っ環境への吸収を介した材料への汚染物質の輸送とその後の化学発光を含む、汚染処理が十分に理解されていることが重要です。したがって、環境条件の関数として汚染物質材料のペアのための表面下濃度プロファイルを評価できるようなアプローチが開発されることが必須である。連続スケールは、物理ベースモデルは、汚染された基材に吸収された薬剤の濃度分布を予測するために開発された。実験的に得られた物質移動パラメータは、tの予測を可能にする彼は汚染された材料ポスト除染からの発光を蒸気。材料中の濃度分布を予測する能力は、潜在的な蒸気の危険性の評価を容易にし、今度は、毒物学的ハザード1の正確な診断を可能にすることができる。このアプローチは、他のシナリオや条件ターン許可モデリングにおけるように拡散率と飽和濃度などの汚染物質の材料ペア特有の物質輸送パラメータの推定が可能になります。本研究では、化学兵器ビス（2 -クロロエチル）スルフィド（蒸留マスタード、ブリスター剤HD）およびO -エチルSで溶媒分散、ポリウレタン塗料コーティングの液相汚染を処理している- [2-（ジイソプロピルアミノ）エチル]チオエート（VX）、有機リン神経ガス。 開発した方法論はせずに、HDおよびVXなどの化学兵器を含む汚染された材料からのガス放出プロファイルを特徴づける他のアプローチ2,3を妨げる規制の多く。汚染された基板からの汚染物質の進化の時間分解質量分析測定は、オリジナルの浸透イベントから始まるの汚染のために吸収された濃度プロファイルを含む材料中の汚染物質のための物質輸送パラメータを計算するための逆解析による拡散輸送モデルを可能にする。環境条件の関数として材料中の汚染物質の濃度プロファイルの輪郭を描くための予測能力の設立により毒性学的危険性を評価し、最終的には効果的な除染のためのルートを開発する能力が来る。 本論文では、試料調製に関連した詳細が化学兵器剤の汚染物質との仕事だけでなく、汚染された物質からの実験データの収集とその後のモデリング4を含む、提示されている。実験ランをDESCように行った化学汚染物質や汚染除去、ソース文書5にribed、次のセクションで説明します。 図1に含まれるのサンプル調製および分析手順のフローチャート。

<table border="0" cellpadding="0" cellspacing="0" width="646">
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:203px;">Name of Material/Equipment</td>
			<td style="width:101px;">Company</td>
			<td style="width:97px;">Catalog Number</td>
			<td style="width:245px;">Comments/Description</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:203px;">Stainless Steel Tray</td>
			<td style="width:101px;">McMaster Carr</td>
			<td style="width:97px;">4189T1</td>
			<td style="width:245px;">13-5/8&#34; L x 9-3/4&#34; W, http://www.mcmaster.com/#stainless-steel-trays/=p8dcgp</td>
		</tr>
		<tr height="67">
			<td height="67" style="height:67px;width:203px;">MIL-DTL-53039 solvent-dispersible aliphatic polyurethane coating system</td>
			<td style="width:101px;"></td>
			<td style="width:97px;"></td>
			<td style="width:245px;">Substrates supplied by internal source</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:203px;">Environmental Chamber</td>
			<td style="width:101px;"></td>
			<td style="width:97px;"></td>
			<td style="width:245px;">Custom Design. Full details on vacuum chamber specifications and materials included in reference 4.</td>
		</tr>
		<tr height="33">
			<td height="33" style="height:33px;width:203px;">bis(2-chloroethyl) sulfide</td>
			<td style="width:101px;">CASARM</td>
			<td style="width:97px;"></td>
			<td style="width:245px;">TOXIC</td>
		</tr>
		<tr height="65">
			<td height="65" style="height:65px;width:203px;">O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate</td>
			<td style="width:101px;">CASARM</td>
			<td style="width:97px;"></td>
			<td style="width:245px;">TOXIC</td>
		</tr>
		<tr height="49">
			<td height="49" style="height:49px;width:203px;">Pipetter</td>
			<td style="width:101px;">Fisher Scientific</td>
			<td>22260201</td>
			<td style="width:245px;">Range of 1.0 &#181;L to 10 mL</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:203px;">Pipetter Tips</td>
			<td style="width:101px;">Fisher Scientific</td>
			<td style="width:97px;">13-683-709</td>
			<td style="width:245px;">0.1 mL Volume</td>
		</tr>
		<tr height="44">
			<td height="44" style="height:44px;width:203px;">Stainless Steel High Vacuum Experimental Chamber</td>
			<td style="width:101px;"></td>
			<td style="width:97px;"></td>
			<td style="width:245px;">Custom Design</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:203px;">Quadrupole Mass Spectrometer</td>
			<td style="width:101px;">ExTorr</td>
			<td style="width:97px;">RGA300</td>
			<td style="width:245px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:203px;">Stainless Steel Tweezers</td>
			<td style="width:101px;">McMaster Carr</td>
			<td style="width:97px;">5516A15</td>
			<td style="width:245px;">Any stainless steel tweezers are appropriate.</td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:203px;">Glass Extraction Jar</td>
			<td style="width:101px;">Scientific Specialties</td>
			<td style="width:97px;">170808</td>
			<td style="width:245px;">Jar fits a ~5 cm diameter substrate.&#160; Different glass jars with teflon lined lids are appropriate for different sized substrates.</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:203px;">Chloroform</td>
			<td style="width:101px;">Sigma-Aldrich</td>
			<td style="width:97px;">650498</td>
			<td style="width:245px;">HARMFUL.&#160; The extraction solvent for HD may change depending on the analytical method.</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:203px;">Isopropanol</td>
			<td style="width:101px;">Sigma-Aldrich</td>
			<td style="width:97px;">650447</td>
			<td style="width:245px;">HARMFUL.&#160; The extraction solvent for VX may change depending on the analytical method.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:203px;">Pasteur Pipette</td>
			<td style="width:101px;">VWR</td>
			<td style="width:97px;">14673-010</td>
			<td style="width:245px;">size= 5 3/4&#34;</td>
		</tr>
	</tbody>
</table>

an inverse analysis approach to the characterization of chemical transport in paints

材料内で発生する直接化学輸送や相互作用を特徴づける能力（ すなわち 、地下ダイナミクス）は、汚染物質の質量輸送と材料を除染するための能力を理解する上で重要な要素である。材料が汚染されている場合は、時間の経過とともに、材料のうち（そのような化学兵器剤の種のような）毒性の高い化学物質の輸送はと対話職員への経皮的浴びることができ、肌への蒸気曝露または転送をもたらすことができる材料。 、化学兵器の高い毒性のために、微量の化学量のリリースは、重大な関心事である。吸収された薬剤のマッピング地下濃度分布と輸送特性が露出の危険性がテストされていない条件で評価することができます。さらに、これらのツールは、最終的に改善された汚染除去または汚染除去手順を設計するために地下反応動力学を特徴付けるために使用することができる。 TOこの目標を達成するため、逆解析の質量輸送モデリングアプローチは、表面下濃度プロファイルの計算のための入力パラメータとして、汚染された塗装被膜からの蒸気放出の時間分解質量分光測定を利用して開発した。詳細は蒸留を含む生化学兵器の輸送特性を決定するために、物理ベース拡散モデルを用いて、汚染物質および材料の取扱い、放出された汚染物質の蒸気を測定するための質量分析の適用、及び逆解析の実施を含む、試料調製に設けられているマスタード（HD）および神経ガスVX。

VXとHD（の主質量フラグメントについての時間分解質量分析法に基づいて、SD-塗装基質から計算された質量VXのフラックスとHDの図3に、例の天板質量電荷比、m / zを = 114および109、それぞれ）。イオナイザ、質量分析器またはフィルタ、および電荷検出器：四重極質量分析計は、3つの主要なコンポーネントを有している。ガス種は、電子衝撃イオン化（熱フィラメン?...

Watch this Scientific Journal Video about An Inverse Analysis Approach to the Characterization of Chemical Transport in Paints at JoVE.com

An Inverse Analysis Approach to the Characterization of Chemical Transport in Paints

本論文では、さまざまな材料中の化学物質の物質輸送パラメータを定量化するための手順が提示されている。このプロセスは、高真空中でリアルタイムの、質量分析によって記録された放出プロファイルを蒸気に逆解析ベースの拡散モデルを用いることを含む。

塗料中の化学輸送のキャラに逆解析アプローチ

The ability to directly characterize chemical transport and interactions that occur within a material (i.e., subsurface dynamics) is a vital component in ...

an-inverse-analysis-approach-to-characterization-chemical-transport

Research

JoVE Journal

Chemistry

8.3K ビュー.  U.S. Army Edgewood Chemical Biological Center. 本論文では、さまざまな材料中の化学物質の物質輸送パラメータを定量化するための手順が提示されている。このプロセスは、高真空中でリアルタイムの、質量分析によって記録された放出プロファイルを蒸気に逆解析ベースの拡散モデルを用いることを含む。 

ビデオ: An Inverse Analysis Approach to the Characterization of Chemical Transport in Paints

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development

The involvement of free radicals in life sciences has constantly increased with time and has been connected to several physiological and pathological processes. This subject embraces diverse scientific areas, spanning from physical, biological and bioorganic chemistry to biology and medicine, with applications to the amelioration of quality of life, health and aging. Multidisciplinary skills are required for the full investigation of the many facets of radical processes in the biological environment and chemical knowledge plays a crucial role in unveiling basic processes and mechanisms. We developed a chemical biology approach able to connect free radical chemical reactivity with biological processes, providing information on the mechanistic pathways and products. The core of this approach is the design of biomimetic models to study biomolecule behavior (lipids, nucleic acids and proteins) in aqueous systems, obtaining insights of the reaction pathways as well as building up molecular libraries of the free radical reaction products. This context can be successfully used for biomarker discovery and examples are provided with two classes of compounds: mono-trans isomers of cholesteryl esters, which are synthesized and used as references for detection in human plasma, and purine 5',8-cyclo-2'-deoxyribonucleosides, prepared and used as reference in the protocol for detection of such lesions in DNA samples, after ionizing radiations or obtained from different health conditions.

Radical-based biomimetic chemistry has been applied to building-up libraries necessary for biomarker development.

ケミカルバイオロジーのフリーラジカル：化学的挙動からバイオマーカー探索·開発へ

The involvement of free radicals in life sciences has constantly increased with time and has been connected to several physiological and pathological ...

化学

Isolation and Chemical Characterization of Lipid A from Gram-negative Bacteria

Lipopolysaccharide (LPS) is the major cell surface molecule of gram-negative bacteria, deposited on the outer leaflet of the outer membrane bilayer. LPS can be subdivided into three domains: the distal O-polysaccharide, a core oligosaccharide, and the lipid A domain consisting of a lipid A molecular species and 3-deoxy-D-manno-oct-2-ulosonic acid residues (Kdo). The lipid A domain is the only component essential for bacterial cell survival. Following its synthesis, lipid A is chemically modified in response to environmental stresses such as pH or temperature, to promote resistance to antibiotic compounds, and to evade recognition by mediators of the host innate immune response. The following protocol details the small- and large-scale isolation of lipid A from gram-negative bacteria. Isolated material is then chemically characterized by thin layer chromatography (TLC) or mass-spectrometry (MS). In addition to matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) MS, we also describe tandem MS protocols for analyzing lipid A molecular species using electrospray ionization (ESI) coupled to collision induced dissociation (CID) and newly employed ultraviolet photodissociation (UVPD) methods. Our MS protocols allow for unequivocal determination of chemical structure, paramount to characterization of lipid A molecules that contain unique or novel chemical modifications. We also describe the radioisotopic labeling, and subsequent isolation, of lipid A from bacterial cells for analysis by TLC. Relative to MS-based protocols, TLC provides a more economical and rapid characterization method, but cannot be used to unambiguously assign lipid A chemical structures without the use of standards of known chemical structure. Over the last two decades isolation and characterization of lipid A has led to numerous exciting discoveries that have improved our understanding of the physiology of gram-negative bacteria, mechanisms of antibiotic resistance, the human innate immune response, and have provided many new targets in the development of antibacterial compounds.

Isolation and characterization of the lipid A domain of lipopolysaccharide (LPS) from gram-negative bacteria provides insight into cell surface based mechanisms of antibiotic resistance, bacterial survival and fitness, and how chemically diverse lipid A molecular species differentially modulate host innate immune responses.

グラム陰性菌からの単離とリピドAの化学特性評価

Lipopolysaccharide (LPS) is the major cell surface molecule of gram-negative bacteria, deposited on the outer leaflet of the outer membrane bilayer. LPS ...

Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in traditional materials, including low cost and mechanical flexibility. In a similar vein, it would be advantageous to expand the use of organics into high frequency electronics and spin-based electronics. This work presents a synthetic process for the growth of thin films of the room temperature organic ferrimagnet, vanadium tetracyanoethylene (V[TCNE]x, x~2) by low temperature chemical vapor deposition (CVD). The thin film is grown at &#60;60 &#176;C, and can accommodate a wide variety of substrates including, but not limited to, silicon, glass, Teflon and flexible substrates. The conformal deposition is conducive to pre-patterned and three-dimensional structures as well. Additionally this technique can yield films with thicknesses ranging from 30 nm to several microns. Recent progress in optimization of film growth creates a film whose qualities, such as higher Curie temperature (600 K), improved magnetic homogeneity, and narrow ferromagnetic resonance line-width (1.5 G) show promise for a variety of applications in spintronics and microwave electronics.

We present the synthesis of the organic-based ferrimagnet vanadium tetracyanoethylene (V[TCNE]x, x~2) via low temperature chemical vapor deposition (CVD). This optimized recipe yields an increase in Curie temperature from 400 K to over 600 K and a dramatic improvement in magnetic resonance properties.

有機マグネットの化学気相堆積、バナジウムテトラ

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in ...

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 ...

Glycan Node Analysis: A Bottom-up Approach to Glycomics

Synthesized in a non-template-driven process by enzymes called glycosyltransferases, glycans are key players in various significant intra- and extracellular events. Many pathological conditions, notably cancer, affect gene expression, which can in turn deregulate the relative abundance and activity levels of glycoside hydrolase and glycosyltransferase enzymes. Unique aberrant whole glycans resulting from deregulated glycosyltransferase(s) are often present in trace quantities within complex biofluids, making their detection difficult and sometimes stochastic. However, with proper sample preparation, one of the oldest forms of mass spectrometry (gas chromatography-mass spectrometry, GC-MS) can routinely detect the collection of branch-point and linkage-specific monosaccharides ("glycan nodes") present in complex biofluids. Complementary to traditional top-down glycomics techniques, the approach discussed herein involves the collection and condensation of each constituent glycan node in a sample into a single independent analytical signal, which provides detailed structural and quantitative information about changes to the glycome as a whole and reveals potentially deregulated glycosyltransferases. Improvements to the permethylation and subsequent liquid/liquid extraction stages provided herein enhance reproducibility and overall yield by facilitating minimal exposure of permethylated glycans to alkaline aqueous conditions. Modifications to the acetylation stage further increase the extent of reaction and overall yield. Despite their reproducibility, the overall yields of N-acetylhexosamine (HexNAc) partially permethylated alditol acetates (PMAAs) are shown to be inherently lower than their expected theoretical value relative to hexose PMAAs. Calculating the ratio of the area under the extracted ion chromatogram (XIC) for each individual hexose PMAA (or HexNAc PMAA) to the sum of such XIC areas for all hexoses (or HexNAcs) provides a new normalization method that facilitates relative quantification of individual glycan nodes in a sample. Although presently constrained in terms of its absolute limits of detection, this method expedites the analysis of clinical biofluids and shows considerable promise as a complementary approach to traditional top-down glycomics.

This article presents an enhanced form of a novel bottom-up glycomics technique designed to analyze the pooled compositional profile of glycans in unfractionated biofluids through the chemical breakdown of glycans into their constituent linkage-specific monosaccharides for detection by GC-MS. Potential applications include early detection of cancer and other glycan-affective disorders.

糖鎖ノード分析：グライコミクスへのボトムアップアプローチ

Synthesized in a non-template-driven process by enzymes called glycosyltransferases, glycans are key players in various significant intra- and ...

Microfluidic Pneumatic Cages: A Novel Approach for In-chip Crystal Trapping, Manipulation and Controlled Chemical Treatment

The precise localization and controlled chemical treatment of structures on a surface are significant challenges for common laboratory technologies. Herein, we introduce a microfluidic-based technology, employing a double-layer microfluidic device, which can trap and localize in situ and ex situ synthesized structures on microfluidic channel surfaces. Crucially, we show how such a device can be used to conduct controlled chemical reactions onto on-chip trapped structures and we demonstrate how the synthetic pathway of a crystalline molecular material and its positioning inside a microfluidic channel can be precisely modified with this technology. This approach provides new opportunities for the controlled assembly of structures on surface and for their subsequent treatment.

Herein, we describe the fabrication and operation of a double-layer microfluidic system made of polydimethylsiloxane (PDMS). We demonstrate the potential of this device for trapping, directing the coordination pathway of a crystalline molecular material and controlling chemical reactions onto on-chip trapped structures.

マイクロ流体空気圧ケージ：インチップクリスタルトラッピング、操作のための新しいアプローチと管理化学治療

The precise localization and controlled chemical treatment of structures on a surface are significant challenges for common laboratory technologies. ...

Original Experimental Approach for Assessing Transport Fuel Stability

The study of fuel oxidation stability is an important issue for the development of future fuels. Diesel and kerosene fuel systems have undergone several technological changes to fulfill environmental and economic requirements. These developments have resulted in increasingly severe operating conditions whose suitability for conventional and alternative fuels needs to be addressed. For example, fatty acid methyl esters (FAMEs) introduced as biodiesel are more prone to oxidation and may lead to deposit formation. Although several methods exist to evaluate fuel stability (induction period, peroxides, acids, and insolubles), no technique allows one to monitor the real-time oxidation mechanism and to measure the formation of oxidation intermediates that may lead to deposit formation. In this article, we developed an advanced oxidation procedure (AOP) based on two existing reactors. This procedure allows the simulation of different oxidation conditions and the monitoring of the oxidation progress by the means of macroscopic parameters, such as total acid number (TAN) and advanced analytical methods like gas chromatography coupled to mass spectrometry (GC-MS) and Fourier Transform Infrared - Attenuated Total Reflection (FTIR-ATR). We successfully applied AOP to gain an in-depth understanding of the oxidation kinetics of a model molecule (methyl oleate) and commercial diesel and biodiesel fuels. These developments represent a key strategy for fuel quality monitoring during logistics and on-board utilization.

Oxidation stability of transport fuels has become a concern for future fuel development. This work presents an original methodology developed by IFP Energies Nouvelles for assessing fuel stability using two different reactors. This methodology was successfully applied to gain an in-depth understanding of the oxidation kinetics and pathways of model molecules and commercial fuels.

交通燃料の安定性を評価するためのオリジナル実験的アプローチ

The study of fuel oxidation stability is an important issue for the development of future fuels. Diesel and kerosene fuel systems have undergone several ...

Using Capillary Electrophoresis to Quantify Organic Acids from Plant Tissue: A Test Case Examining Coffea arabica Seeds

Carboxylic acids are organic acids containing one or more terminal carboxyl (COOH) functional groups. Short chain carboxylic acids (SCCAs; carboxylic acids containing three to six carbons), such as malate and citrate, are critical to the proper functioning of many biological systems, where they function in cellular respiration and can serve as indicators of cell health. In foods, organic acid content can have significant impact on taste, with increased SCCA levels resulting in a sour or &#34;acid&#34; taste. Because of this, methods for the rapid analysis of organic acid levels are of particular interest to the food and beverage industries. Unfortunately, however, most methods used for SCCA quantification are dependent on time-consuming protocols requiring the derivatization of samples with hazardous reagents, followed by costly chromatographic and/or mass spectrometric analyses. This method details an alternate method for the detection and quantification of organic acids from plant material and food samples using free zonal capillary electrophoresis (CZE), sometimes simply referred to as capillary electrophoresis (CE). CZE provides a cost-effective method for measuring SCCAs with a low limit of detection (0.005 mg/ml). This article details the extraction and quantification of SCCAs from plant samples. While the method provided focuses on measurement of SCCAs from coffee beans, the method provided can be applied to multiple plant-based food materials.

Using Capillary Electrophoresis to Quantify Organic Acids from Plant Tissue: A Test Case Examining Coffea arabica Seeds

This article presents a method for the detection and quantification of organic acids from plant material using free zonal capillary electrophoresis. An example of the potential application of this method, determining the effects of a secondary fermentation on organic acid levels in coffee seeds, is provided.

植物組織からの有機酸を定量化するためにキャピラリー電気泳動を使用した：テストケースを調べます<em&gt;コーヒーノキアラビカ</em&gt;種子

Carboxylic acids are organic acids containing one or more terminal carboxyl (COOH) functional groups. Short chain carboxylic acids (SCCAs; carboxylic ...

Characterizing Electron Transport through Living Biofilms

Here we demonstrate the method of electrochemical gating used to characterize electrical conductivity of electrode-grown microbial biofilms under physiologically relevant conditions.1 These measurements are performed on living biofilms in aqueous medium using source and drain electrodes patterned on a glass surface in a specialized configuration referred to as an interdigitated electrode (IDA) array. A biofilm is grown that extends across the gap connecting the source and drain. Potentials are applied to the electrodes (ES and ED) generating a source-drain current (ISD) through the biofilm between the electrodes. The dependency of electrical conductivity on gate potential (the average of the source and drain potentials, EG = [ED + ES]/2) is determined by systematically changing the gate potential and measuring the resulting source-drain current. The dependency of conductivity on gate potential provides mechanistic information about the extracellular electron transport process underlying the electrical conductivity of the specific biofilm under investigation. The electrochemical gating measurement method described here is based directly on that used by M. S. Wrighton2,3 and colleagues and R. W. Murray4,5,6 and colleagues in the 1980&#39;s to investigate thin film conductive polymers.

A protocol for measuring electrical conductivity of living microbial biofilms under physiologically relevant conditions is presented.

生きているバイオ フィルムにおける電子輸送特性評価

Here we demonstrate the method of electrochemical gating used to characterize electrical conductivity of electrode-grown microbial biofilms under ...

Pretargeted Radioimmunotherapy Based on the Inverse Electron Demand Diels-Alder Reaction

While radioimmunotherapy (RIT) is a promising approach for the treatment of cancer, the long pharmacokinetic half-life of radiolabeled antibodies can result in high radiation doses to healthy tissues. Perhaps not surprisingly, several different strategies have been developed to circumvent this troubling limitation. One of the most promising of these approaches is pretargeted radioimmunotherapy (PRIT). PRIT is predicated on decoupling the radionuclide from the immunoglobulin, injecting them separately, and then allowing them to combine in vivo at the target tissue. This approach harnesses the exceptional tumor-targeting properties of antibodies while skirting their pharmacokinetic drawbacks, thereby lowering radiation doses to non-target tissues and facilitating the use of radionuclides with half-lives that are considered too short for use in traditional radioimmunoconjugates. Over the last five years, our laboratory and others have developed an approach to in vivo pretargeting based on the inverse electron-demand Diels-Alder (IEDDA) reaction between trans-cyclooctene (TCO) and tetrazine (Tz). This strategy has been successfully applied to pretargeted positron emission tomography (PET) and single-photon emission computed tomography (SPECT) imaging with a variety of antibody-antigen systems. In a pair of recent publications, we have demonstrated the efficacy of IEDDA-based PRIT in murine models of pancreatic ductal adenocarcinoma and colorectal carcinoma. In this protocol, we describe protocols for PRIT using a 177Lu-DOTA-labeled tetrazine radioligand ([177Lu]Lu-DOTA-PEG7-Tz) and a TCO-modified variant of the colorectal cancer targeting huA33 antibody (huA33-TCO). More specifically, we will describe the construction of huA33-TCO, the synthesis and radiolabeling of [177Lu]Lu-DOTA-PEG7-Tz, and the performance of in vivo biodistribution and longitudinal therapy studies in murine models of colorectal carcinoma.

This protocol describes the synthesis and characterization of a trans-cyclooctene (TCO)-modified antibody and a 177Lu-labeled tetrazine (Tz) radioligand for pretargeted radioimmunotherapy (PRIT). In addition, it details the use of these two constructs for in vivo biodistribution and longitudinal therapy studies in a murine model of colorectal cancer.

逆電子需要ディールス ・ アルダー反応に基づく pretargeted 放射免疫療法

While radioimmunotherapy (RIT) is a promising approach for the treatment of cancer, the long pharmacokinetic half-life of radiolabeled antibodies can ...