Nous reconnaissons l&#39;Institut militaire de Virginie (VMI) Département de chimie pour le soutien des expériences et de l&#39;instrumentation (LSC et JTH) électrochimiques. Le Bureau VMI du doyen de la Faculté soutenu frais de production associés aux publications JoVE. Nous reconnaissons l&#39;UNC EFRC: Centre pour carburants solaires, un centre de recherche Frontier énergie financé par le Département américain de l&#39;énergie, Bureau de la science, Bureau des sciences fondamentales de l&#39;énergie en vertu Prix Nombre DE-SC0001011, pour le soutien de la synthèse de composé et la caractérisation des matériaux (DPH ).

1. Synthétiser 1 Synthétiser une (PhTpy est 4&#39;-phényl-2,2 &#39;: 6&#39;, 2 &#39;&#39; - terpyridine; 5,5&#39;-dvbpy est le 5,5&#39;-divinyl-2,2&#39;-bipyridine; Figure 4) selon la la procédure décrite précédemment. 18 2. Préparer 1,3 mM Solution de monomère 1 dans une solution d&#39;électrolyte <ol><li> Préparer une solution d&#39;électrolyte 0,1 M d&#39;actions de tétra-n-butylammonium hexafluorophosphate, TBAPF 6, dans l&#39;acétonitrile, MeCN. <ol><li> Placez MeCN plus activé trois tamis moléculaires de A ou K 2 CO 3, pendant 24 heures pour éliminer H 2 O. accidentelle </li><li> Passer TBAPF 6 (0,969 g, 2,50 mmol) dans une flamme 25,00 ml séché fiole jaugée. </li><li> Filtrer le tamis moléculaire ou K 2 CO 3 particules du MeCN séché et amener le 25,00 ml fiole jaugée contenant TBAPF <sub&gt; 6 au volume. </li></ol></li><li> Placez 1 (0,0049 g, 5,2 x 10 -6 mole) dans et sec flacon 4 dram ou 10 ml ballon à fond rond et ajouter 4,00 ml de la solution mère de 0,1 M TBAPF 6 dans MeCN. </li><li> Transférer 3,5 à 4,0 ml de la solution électrolytique de couleur rouge-orange de 1 dans le compartiment central d&#39;une cellule à 3 compartiments, chaque compartiment séparés par une fritte de verre de porosité moyenne. </li><li> Remplir rapidement les compartiments externes de la cellule 3 compartiments à une hauteur égale que la solution centrale compartiment boursier, avec une partie du reste sec 0,1 M TBAPF 6 dans MeCN pour éviter les fuites dans les compartiments extérieurs. Remarque: Le temps est un facteur important parce que les solutions dans les différents compartiments vont lentement mélanger et changer de façon significative la concentration du compartiment principal si les hauteurs de solvants sont pas les mêmes. </li></ol> 3. Electropolymerize 1 sur un 3 mm Diamètre Verrey Carbon électrode ou 1,0 cm 2 FTO électrode <ol><li> Préparer cloisons pour les tubes de dégazage azote / argon et pour les électrodes. <ol><li> Couper une fente dans chacun des trois septa en caoutchouc et guider une mince polytétrafluoroéthylène, PTFE, tube à travers la fente. </li><li> Faites glisser l&#39;électrode de référence de 3 Ag / AgNO par l&#39;une des cloisons, placez le électrode de référence / PTFE / tube septum dans l&#39;un des compartiments extérieurs, et sceller le compartiment avec le septum. </li><li> Guide la contre-électrode fil de platine / gaze à travers un lieu de septum différente platine fil / tube de PTFE / septum dans l&#39;un des compartiments extérieurs, et sceller le compartiment avec le septum. Si la fente ne est pas suffisamment importante ou un fil suffisamment rigide pour éviter de plier le fil, utilisez une aiguille de grand calibre pour guider la contre-électrode en fil de platine à travers le septum. </li><li> Guide un fraîchement poli 3 mm électrode de carbone vitreux à travers le septum restant et le placer de telle sorte que l&#39;électrode est suspeDEMVSO dans la solution ou, pour une diapositive FTO, guider un fil relié à une pince crocodile à travers le septum, puis serrer la diapositive FTO avec la pince crocodile et assurez-vous que le côté conducteur de la lame est perpendiculaire à la contre-électrode en immersion . <ol><li> Avant d&#39;insérer l&#39;électrode en carbone vitreux: polonais du carbone vitreux en plaçant alumine (0,5 um) sur un tampon de polissage mouillée, puis, déplacer l&#39;électrode dans une figure-huit mouvement pendant 30 secondes tout en maintenant l&#39;électrode perpendiculairement à la plage - à polir tous les côtés de l&#39;électrode uniformément - et rincer toute alumine restante avec un H 2 O vaporisateur d&#39;eau suivi d&#39;un rinçage MeCN gicler bouteille. </li><li> Avant le serrage du coulisseau FTO: envelopper plusieurs couches de ruban en Kapton non-conducteur autour de la partie centrale d&#39;une lame de FTO 30 x 10 mm de sorte qu&#39;une partie 10 x 10 mm de la lame est exposée. </li><li> Recueillir un spectre de la diapositive FTO UV-Vis en plaçant / tenant la lame FTO dans une position dans la trajectoire du faisceau du spectromètre qui a été prédéterminé pour assurer l&#39;uniformité. </li></ol></li></ol></li><li> De-aérer les solutions dans la cellule électrochimique trois compartiments. <ol><li> Branchez une extrémité du tube Tygon à l&#39;azote / argon d&#39;alimentation et branchez l&#39;autre extrémité à un laveur de gaz contenant MeCN. </li><li> Coupez un autre morceau de tube Tygon, connectez une extrémité à l&#39;sortante MeCN lavé azote / argon, et connectez l&#39;autre extrémité à un répartiteur à 4 voies. </li><li> Raccorder les tubes de PTFE aux trois connexions restantes du 4 way splitter. </li><li> Immerger les tubes de PTFE dans les solutions dans chacun des compartiments et mettez le flux d&#39;azote / argon de telle sorte qu&#39;une bouillonnement rapide de la solution commence. </li><li> Continuer de dégazage de la solution pendant 5-10 minutes, puis retirez les tubes de PTFE juste au-dessus de la surface de la solution, laissant le flux d&#39;azote / argon sur afin de maintenir une pression positive de gaz inerte sur le système et empêcher solution convection provoquée par barbotage. </li></ol></li><li> Réaliser des expériences électrochimiques. <ol><li> Connecter les électrodes du potentiostat à électrodes appropriées dans la cellule à 3 compartiments. </li><li> Effectuez une voltamétrie cyclique, CV, expérience avec les paramètres suivants: potentiel de commutation = 0 V et -1,81 V; scanner / vitesse de balayage = 100 mV / s; nombre de cycles = 5. </li><li> Lorsque l&#39;expérience de CV est terminée, retirez le travail (carbone vitreux ou FTO) électrode de la solution de polymérisation et rincer délicatement la surface de l&#39;électrode avec MeCN d&#39;une pipette ou un vaporisateur pour enlever toute solution de monomère restant. </li></ol></li></ol> Détermination de couverture 4. Surface <ol><li> Placer l&#39;électrode de travail rincés dans une solution fraîchement préparée de 0,1 M TBAPF 6 / MeCN dans une cellule électrochimique contenant une contre-électrode et une électrode de référence (de préférence de la même électrode de référence utilisée pour le electropolymerization). </li><li> Effectuez une voltamétrie cyclique, CV, expérience avec les paramètres suivants: potentiel de commutation = 0 et 1,5 V; scanner / vitesse de balayage = 100 mV / s; nombre de cycles = 15. </li><li> Intégrer la charge sous les pics anodique et cathodique pour la électropolymère adsorbé Ru (III / II) En couple, en moyenne la charge sous la pics anodiques et cathodiques, et en utilisant l&#39;équation 1 déterminer la couverture de surface. </li><li> Pour le coulisseau FTO: lieu / FTO maintenir le coulisseau dans la position prédéterminée à l&#39;avant du porte-échantillon UV-Vis de telle sorte que le faisceau passe à travers le chemin film coloré. La diapositive FTO peut être humide ou sec, mais faire des comparaisons dans les mêmes conditions que les spectres vierge ont été recueillies sous. </li><li> Soustraire le spectre obtenu pour le spectre FTO qui a été recueilli pour cette diapositive spécifique avant électropolymérisation à partir du spectre de la pellicule-on-FTO afin de produire un spectre d&#39;absorption du film lui-même. </li></ol>

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Electroanal. Chem. Interfacial Electrochem. 115, 65-74 (1980).</li><li>Laviron, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=General+expression+of+the+linear+potential+sweep+voltammogram+in+the+case+of+diffusionless+electrochemical+systems.">General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems.</a> J. Electroanal. Chem. 101, 19-28 (1979).</li><li>Ratcliff, E. L., Jenkins, J. L., Nebesny, K., Armstrong, N. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrodeposited,+&#34;Textured&#34;+Poly(3-hexyl-thiophene)+(e-P3HT)+Films+for+Photovoltaic+Applications.">Electrodeposited, &#34;Textured&#34; Poly(3-hexyl-thiophene) (e-P3HT) Films for Photovoltaic Applications.</a> Chemistry of Materials. 20, 5796-5806 (2008).</li></ol>

No conflicts of interest declared.

Électropolymérisation propose une large gamme de variables contrôlables qui ne sont pas communs à d&#39;autres techniques. En plus des variables de réaction standard comme réactif (monomère) concentration, la température, solvant, etc., électropolymérisation peut en outre être contrôlé par les paramètres d&#39;expérimentation électrochimiques communes aux méthodes électrochimiques. CV taux de balayage, les potentiels de commutation, et le nombre de cycles affectent le dépôt de électropolym?...

L&#39;électropolymérisation est une technique de polymérisation qui utilise un potentiel appliquée pour initier la polymérisation des précurseurs monomères directement à la surface d&#39;une électrode et a été exploitée pour produire électroactif mince et / ou photochimique films polypyridyl actives sur les surfaces d&#39;électrodes et semi-conducteurs. 4.1 Électrocatalyse, 5-10 transfert d&#39;électrons, 11, 12 photochimie, 13-16 électrochromisme, 17 et 18 chimie de coordination ont été étudiés dans les films électropolymérisé. Cette technique a été développée à l&#39;Université de Caroline du Nord dans une collaboration Meyer-Murray pour l&#39;électropolymérisation de vinyle 3, 5, 7, 8, 11-15, 19, 20 et pyrrole 6, 9, 21-24 moi dérivatiséTal complexes sur une variété de substrats conducteurs. La figure 1 présente un certain nombre de ligands basés pyridyle commun qui, lorsqu&#39;elles sont coordonnées à des complexes de métaux, ont produit électropolymères. Dans électropolymérisation réductrice, électropolymérisation de composés vinyliques contenant un produit lors de la réduction de ligands pyridyle conjugués à des groupes vinyle, tandis que avec des ligands pyrrole fonctionnalisé, électropolymérisation est initiée par l&#39;oxydation des groupements pyrrole, ce qui entraîne l&#39;oxydation électropolymérisation (figure 2). L&#39;électropolymérisation technologie a été développée dans le but de fournir une méthode générale pour fixer directement pratiquement ne importe quel complexe de métal de transition à une électrode. La polyvalence de la méthode ouvre la porte à de nombreuses enquêtes de électropolymère électrodes modifiées. Contrairement à d&#39;autres stratégies de fixation, qui impliquent une liaison directe à l&#39;électrode, électropolymérisation offre la advantage de ne pas nécessiter surface de l&#39;électrode pré-modification. . Par conséquent, il peut être appliqué à ne importe quel nombre de substrats conducteurs, quelle que soit la composition de la surface ou de la morphologie 4, 10, 25, 26 Cette polyvalence est le résultat de la modification des propriétés physiques comme la longueur de la pousse polymère; les monomères sont solubles dans la solution électrolytique, mais que la polymérisation se produit et rigidifie la réticulation du film, la précipitation et l&#39;adsorption physique de la surface de l&#39;électrode se produit (figure 3). 27 Par rapport à l&#39;oxyde lié à une surface de carboxylate, qui sont instables sur les surfaces d&#39;oxyde dans l&#39;eau, ou des complexes de phosphonate en dérivé, qui sont instables à un pH élevé de, couramment utilisés dans la recherche sur les combustibles solaire, ces structures de film électrode-polymère d&#39;interface offrent l&#39;avantage supplémentaire de stabilité dans une variété de médias, y compris des solvants organiques et d&#39;eau sur une large gamme de pH (0-14).28-30 électropolymérisation peut aussi déposer des films avec de grandes plages de couvertures de surface apparente, de la sous-monocouche à des dizaines ou des centaines d&#39;équivalents monocouche, tandis que les structures carboxylate ou phosphonate dérivé complexes d&#39;interface sont limitées à des couvertures de surface monocouche. Bien que ne importe quel nombre de pyridyle et polypyridyl contenant des composés vinyliques ou pyrrole sont capables de polymérisation, [Ru II (PhTpy) (5,5&#39;-dvbpy) (MeCN)] (PF 6) 2, (1; PhTpy est 4&#39;-phényl -2,2 &#39;: 6&#39;, 2 &#39;&#39; - terpyridine; 5,5&#39;-dvbpy est 5,5&#39;-divinyl-2,2&#39;-bipyridine; Figure 4) sera utilisé en tant que complexe de modèle pour démontrer électropolymérisation réductrice sur le carbone vitreux et l&#39;oxyde d&#39;étain dopé au fluor, FTO, électrodes dans le présent rapport. 1 est un exemple d&#39;un précurseur de électropolymère moderne qui a des applications électrocatalytiques potentiels et, en raison de son métal-litransfert de charge gand, MLCT, spectre d&#39;absorption se trouvant dans la région visible du spectre lumineux, peut être étudiée avec des UV-Vis spectroscopie. 18, 30 Se il vous plaît noter que certains résultats présentés ici pour une ont déjà été publiés sous une forme légèrement modifiée. 18

<table border="0" cellpadding="0" cellspacing="0" width="652">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:384px;">Name of Reagent/ Equipment</td>
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			<td style="width:160px;">Catalog Number</td>
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			<td height="20" style="height:20px;">Tetrabutylammonium hexafluorophosphate for electrochemical analysis, &#8805;99.0%,&#160;</td>
			<td>Sigma-Aldrich</td>
			<td>86879-25G</td>
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			<td height="20" style="height:20px;width:384px;">Acetonitrile&#160;(Optima LC/MS), Fisher Chemical</td>
			<td>Fisher Scientific</td>
			<td>A955-4</td>
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			<td height="20" style="height:20px;">3 mm dia. Glassy Carbon Working Electrode</td>
			<td>CH Instruments</td>
			<td>CH104</td>
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		<tr height="20">
			<td height="20" style="height:20px;">Non-Aqueous Ag/Ag+ Reference Electrode w/ porous Teflon Tip</td>
			<td>CH Instruments</td>
			<td>CHI112</td>
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			<td height="20" style="height:20px;">Platinum&#160;gauze</td>
			<td>Alfa Aesar</td>
			<td>AA10282FF&#160;</td>
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			<td height="20" style="height:20px;">Electrode Polishing Kit</td>
			<td>CH Instruments</td>
			<td>CHI120</td>
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			<td height="20" style="height:20px;width:384px;">Cole-Parmer KAPTON TAPE&#160;1/2IN X 36 YD</td>
			<td>Fisher Scientific</td>
			<td>NC0099200</td>
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		<tr height="20">
			<td height="20" style="height:20px;width:384px;">Fisherbrand Polypropylene Tubing&#160;4-Way&#160;Connectors</td>
			<td>Fisher Scientific</td>
			<td>15-315-32B</td>
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		<tr height="20">
			<td height="20" style="height:20px;">500mL Bottle, Gas Washing, Tall Form, Coarse Frit</td>
			<td>Chemglass</td>
			<td>CG-1114-15</td>
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		<tr height="20">
			<td height="20" style="height:20px;">3 compartment H-Cell for electrochemistry</td>
			<td colspan="2">Custom made H-cell with 3 compartments</td>
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	</tbody>
</table>

reductive electropolymerization of a vinyl-containing poly-pyridyl complex on glassy carbon and fluorine-doped tin oxide electrodes

Modification de la surface de l&#39;électrode contrôlable est important dans un certain nombre de domaines, en particulier ceux avec des applications solaires sur les carburants. L&#39;électropolymérisation est une technique de modification de surface qui électrolytiques un film polymère à la surface d&#39;une électrode en utilisant un potentiel appliquée pour initier la polymérisation de substrats dans la couche de Helmholtz. Cette technique utile a été établie par une collaboration Murray-Meyer à l&#39;Université de Caroline du Nord à Chapel Hill dans les années 1980 et utilisée pour étudier de nombreux phénomènes physiques des films contenant des complexes inorganiques comme le substrat monomère. Ici, nous présentons une procédure d&#39;électrodes de revêtement inorganique avec un complexe en effectuant électropolymérisation réductrice du complexe poly-pyridyle contenant des groupes vinyle sur le carbone vitreux et le fluor oxyde d&#39;étain dopé électrodes revêtues. Recommandations sur les configurations de cellules électrochimiques et des procédures de dépannage sont inclus. Bien que non explicitly décrit ici, électropolymérisation oxydative de composés contenant du pyrrole suit des procédures similaires à base de vinyle électropolymérisation réductrice mais sont beaucoup moins sensibles à l&#39;oxygène et l&#39;eau.

Électropolymère croissance est plus facilement reconnue lorsque l&#39;on observe l&#39;évolution de l&#39;expérience CV prescrit (protocole de STEP du texte 3.3.2). La figure 5, un exemple d&#39;une croissance électropolymère (diamètre de 3 mm) 0,071 cm 2 vitreux de l&#39;électrode de carbone avec une. Le premier cycle de l&#39;expérience produit un voltamogramme ressemblant à peu près ce qui est prévu pour une solution de ruthénium de concentration similaire <st...

Watch this Scientific Journal Video about Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes at JoVE.com

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

A procedure for performing reductive electropolymerization of vinyl-containing compounds onto glassy carbon and fluorine doped tin-oxide coated electrodes is presented. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization.

L&#39;électropolymérisation réductrice d&#39;un complexe de poly-pyridyl-vinyle contenant de Glassy Carbon dopé au fluor et l&#39;oxyde d&#39;étain Electrodes

Controllable electrode surface modification is important in a number of fields, especially those with solar fuels applications. Electropolymerization is ...

reductive-electropolymerization-vinyl-containing-poly-pyridyl-complex

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JoVE Journal

Chemistry

11.7K vues.  Virginia Military Institute. A procedure for performing reductive electropolymerization of vinyl-containing compounds onto glassy carbon and fluorine doped tin-oxide coated electrodes is presented. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization. 

Vidéo: Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

Improved In-gel Reductive &#946;-Elimination for Comprehensive O-linked and Sulfo-glycomics by Mass Spectrometry

Separation of proteins by SDS-PAGE followed by in-gel proteolytic digestion of resolved protein bands has produced high-resolution proteomic analysis of biological samples. Similar approaches, that would allow in-depth analysis of the glycans carried by glycoproteins resolved by SDS-PAGE, require special considerations in order to maximize recovery and sensitivity when using mass spectrometry (MS) as the detection method. A major hurdle to be overcome in achieving high-quality data is the removal of gel-derived contaminants that interfere with MS analysis. The sample workflow presented here is robust, efficient, and eliminates the need for in-line HPLC clean-up prior to MS. Gel pieces containing target proteins are washed in acetonitrile, water, and ethyl acetate to remove contaminants, including polymeric acrylamide fragments. O-linked glycans are released from target proteins by in-gel reductive &#946;-elimination and recovered through robust, simple clean-up procedures. An advantage of this workflow is that it improves sensitivity for detecting and characterizing sulfated glycans. These procedures produce an efficient separation of sulfated permethylated glycans from non-sulfated (sialylated and neutral) permethylated glycans by a rapid phase-partition prior to MS analysis, and thereby enhance glycomic and sulfoglycomic analyses of glycoproteins resolved by SDS-PAGE.

Improved In-gel Reductive &amp;#946;-Elimination for Comprehensive O-linked and Sulfo-glycomics by Mass Spectrometry

In order to comprehensively explore the diversity of O-linked glycans, a new procedure for in-gel reductive &#946;-elimination, combined with permethylation and a rapid phase-partition method, is applied to the analysis of O-linked glycans directly released from glycoproteins resolved by SDS-PAGE and amenable to subsequent glycomic analysis by mass spectrometry.

Amélioration dans le gel sulfo-réductrices glycomique β-élimination complète pour O-liés et par spectrométrie de masse

Separation of proteins by SDS-PAGE followed by in-gel proteolytic digestion of resolved protein bands has produced high-resolution proteomic analysis of ...

Recherche

Chimie

Atomically Defined Templates for Epitaxial Growth of Complex Oxide Thin Films

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

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

Modèles atomique définies pour croissance épitaxiale d&#39;oxyde complexe couches minces

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

Transport of Surface-modified Carbon Nanotubes through a Soil Column

Carbon nanotubes (CNTs) are widely manufactured nanoparticles, which are being utilized in a number of consumer products, such as sporting goods, electronics and biomedical applications. Due to their accelerating production and use, CNTs constitute a potential environmental risk if they are released to soil and groundwater systems. It is therefore essential to improve the current understanding of environmental fate and transport of CNTs. The transport and retention of CNTs in both natural and artificial media have been reported in literature, but the findings widely vary and are thus not conclusive. There are a number of physical and chemical parameters responsible for variation in retention and transport. In this study, a complete procedure of selected multiwalled carbon nanotubes (MWCNTs) is presented starting from their surface modification to a complete set of laboratory column experiments at critical physical and chemical scenarios. Results indicate that the stability of the commercially available MWCNTs are critical with their attached surface functional group which can also influence the transport and retention of MWCNT through the surrounding medium.

Surface properties of a nanoparticle are important for their interaction with the surrounding medium. Therefore the surface modification of carbon nanotubes can be critical for their transport and retention through porous media. Here, lab scale column experiments are used to understand the possible transport and retention of these nanoparticles.

Le transport des nanotubes de carbone modifiés en surface par une colonne de sol

Carbon nanotubes (CNTs) are widely manufactured nanoparticles, which are being utilized in a number of consumer products, such as sporting goods, ...

Photochemical Oxidative Growth of Iridium Oxide Nanoparticles on CdSe@CdS Nanorods

We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide (CdSe@CdS) nanorod photocatalysts. Seeded rods are grown using a colloidal hot-injection method and then moved to an aqueous medium by ligand exchange. CdSe@CdS nanorods, an iridium precursor and other salts are mixed and illuminated. The deposition process is initiated by absorption of photons by the semiconductor particle, which results with formation of charge carriers that are used to promote redox reactions. To insure photochemical oxidative growth we used an electron scavenger. The photogenerated holes oxidize the iridium precursor, apparently in a mediated oxidative pathway. This results in the growth of high quality crystalline iridium oxide particles, ranging from 0.5 nm to about 3 nm, along the surface of the rod. Iridium oxide grown on CdSe@CdS heterostructures was studied by a variety of characterization methods, in order to evaluate its characteristics and quality. We explored means for control over particle size, crystallinity, deposition location on the CdS rod, and composition. Illumination time and excitation wavelength were found to be key parameters for such control. The influence of different growth conditions and the characterization of these heterostructures are described alongside a detailed description of their synthesis. Of significance is the fact that the addition of iridium oxide afforded the rods astounding photochemical stability under prolonged illumination in pure water (alleviating the requirement for hole scavengers).

A protocol for the photochemical oxidative growth of small crystalline iridium oxide nanoparticles on the surface of CdSe@CdS seeded rod nanoparticles is presented.

Photochimique oxydant croissance de l&#39;oxyde d&#39;iridium nanoparticules sur CdSe @ CdS nanorods

We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide ...

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.

Analyse en ligne de composés azotés dans les Matrices d&#39;hydrocarbures complexes

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 ...

Investigations on the Ga(III) Complex of EOB-DTPA and Its 68Ga Radiolabeled Analogue

We demonstrate a method for the isolation of EOB-DTPA (3,6,9-triaza-3,6,9-tris(carboxymethyl)-4-(ethoxybenzyl)-undecanedioic acid) from its Gd(III) complex and protocols for the preparation of its novel non-radioactive, i.e., natural Ga(III) as well as radioactive 68Ga complex. The ligand as well as the Ga(III) complex were characterized by nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry and elemental analysis. 68Ga was obtained by a standard elution method from a 68Ge/68Ga generator. Experiments to evaluate the 68Ga-labeling efficiency of EOB-DTPA at pH 3.8&#8211;4.0 were performed. Established analysis techniques radio TLC (thin layer chromatography) and radio HPLC (high performance liquid chromatography) were used to determine the radiochemical purity of the tracer. As a first investigation of the 68Ga tracers&#39; lipophilicity the n-octanol/water distribution coefficient of 68Ga species present in a pH 7.4 solution was determined by an extraction method. In vitro stability measurements of the tracer in various media at physiological pH were performed, revealing different rates of decomposition.

Investigations on the GaIII Complex of EOB-DTPA and Its 68Ga Radiolabeled Analogue

A procedure for the isolation of EOB-DTPA and subsequent complexation with natural Ga(III) and 68Ga is presented herein, as well as a thorough analysis of all compounds and investigations on labeling efficiency, in vitro stability and the n-octanol/water distribution coefficient of the radiolabeled complex.

Enquêtes sur le complexe Ga (III) de EOB-DTPA et son<sup&gt; 68</sup&gt; Ga radiomarqué analogique

We demonstrate a method for the isolation of EOB-DTPA (3,6,9-triaza-3,6,9-tris(carboxymethyl)-4-(ethoxybenzyl)-undecanedioic acid) from its Gd(III) ...

Grafting Multiwalled Carbon Nanotubes with Polystyrene to Enable Self-Assembly and Anisotropic Patchiness

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a free-radical polymerization strategy to enable the modulation of the nanotube surface properties and produce supramolecular self-assembly of the nanostructures. First, a selective hydroxylation of the pristine nanotubes through a biphasic catalytically mediated oxidation reaction creates superficially distributed reactive sites at the sidewalls. The latter reactive sites are subsequently modified with methacrylic moieties using a silylated methacrylic precursor to create polymerizable sites. Those polymerizable groups can address further polymerization of styrene to produce a hybrid nanomaterial containing PS chains grafted to the nanotube sidewalls. The polymer-graft content, amount of silylated methacrylic moieties introduced and hydroxylation modification of the nanotubes are identified and quantified by Thermogravimetric Analysis (TGA). The presence of reactive functional groups hydroxyl and silylated methacrylate are confirmed by Fourier Transform Infrared Spectroscopy (FT-IR). Polystyrene-grafted carbon nanotube solutions in tetrahydrofuran (THF) provide wall-to-wall collinearly self-assembled nanotubes when cast samples are analyzed by transmission electron microscopy (TEM). Those self-assemblies are not obtained when suitable blanks are similarly cast from analogous solutions containing non-grafted counterparts. Therefore, this method enables the modification of the nanotube anisotropic patchiness at the sidewalls which results into spontaneous auto-organization at the nanoscale.

A procedure for the synthesis of polystyrene-grafted multiwalled carbon nanotubes using successive chemical modification steps to selectively introduce the polymer chains to the sidewalls and their self-assembly via anisotropic patchiness is presented.

Greffage des Nanotubes de carbone multiparois avec polystyrène pour permettre à l’auto-assemblage et morcellement anisotrope

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a ...

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

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

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

Spectroscopie d’impédance électrochimique comme outil d’Estimation constante taux électrochimique

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

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven effective in gas adsorption, separations, and catalysis. MOFs are most commonly synthesized as bulk powder, requiring additional processes to adhere them to functional devices and fabrics that risk decreasing the powder porosity and adsorption capacity. Here, we demonstrate a method of first coating fabrics with metal oxide films using atomic layer deposition (ALD). This process creates conformal films of controllable thickness on each fiber, while providing a more reactive surface for MOF nucleation. By submerging the ALD coated fabric in solution during solvothermal MOF synthesis, the MOFs create a conformal, well-adhered coating on the fibers, resulting in a MOF-functionalized fabric, without additional adhesion materials that may block MOF pores and functional sites. Here we demonstrate two solvothermal synthesis methods. First, we form a MIL-96(Al) layer on polypropylene fibers using synthetic conditions that convert the metal oxide to MOF. Using initial inorganic films of varying thicknesses, diffusion of the organic linker into the inorganic allows us to control the extent of MOF loading on the fabric. Second, we perform a solvothermal synthesis of UiO-66-NH2 in which the MOF nucleates on the conformal metal oxide coating on polyamide-6 (PA-6) fibers, thereby producing a uniform and conformal thin film of MOF on the fabric. The resulting materials can be directly incorporated into filter devices or protective clothing and eliminate the maladroit qualities of loose powder.

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks are effective in gas storage and heterogeneous catalysis, but typical synthesis methods result in loose powders that are difficult to incorporate into smart materials. We demonstrate a method of first coating fabrics with ALD metal oxides, resulting in conformal films of MOF on the fabrics during solvothermal synthesis.

Solvothermal synthèse de MIL-96 et UiO-66-NH2 sur couches atomiques dépôt de revêtements d’oxyde métallique sur des nattes de fibre

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven ...

Negative Additive Manufacturing of Complex Shaped Boron Carbides

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

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

Fabrication Additive négative du complexe en forme de carbures de bore

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