Riconosciamo il Virginia Military Institute (VMI) Dipartimento di Chimica per il supporto di esperimenti elettrochimici e strumentazione (LSC e JTH). L&#39;Ufficio VMI del Preside della Facoltà sostenuto canoni di produzione associati con le pubblicazioni JoVE. Riconosciamo l&#39;UNC EFRC: Centro per Combustibili solari, un Frontier Centro di ricerca energetica finanziata dal Dipartimento dell&#39;Energia degli Stati Uniti, Office of Science, Ufficio di Scienze di base dell&#39;energia sotto Award Numero DE-SC0001011, per il supporto della sintesi composto e caratterizzazione dei materiali (DPH ).

1. Sintetizzare 1 Synthesize 1 (PhTpy è 4&#39;-fenil-2,2 &#39;: 6&#39;, 2 &#39;&#39; - terpyridine; 5,5&#39;-dvbpy è 5,5&#39;-divinil-2,2&#39;-bipiridina, Figura 4) secondo la procedura descritta in precedenza. 18 2. Preparare 1,3 mm monomero Soluzione 1 in una soluzione elettrolitica <ol><li> Preparare una soluzione elettrolitica 0,1 m stock di tetracloruro n -butylammonium esafluorofosfato, TBAPF 6, in acetonitrile, MeCN. <ol><li> Mettere MeCN over attivato 3 setacci molecolari A o K 2 CO 3, per 24 ore per rimuovere accidentale H 2 O. </li><li> Posizionare TBAPF 6 (0,969 g, 2,50 mmol) in un 25,00 ml fiamma secca pallone tarato. </li><li> Filtrare il setaccio molecolare o K 2 CO 3 particolati dal MeCN essiccata e portare il pallone tarato 25.00 ml contenente TBAPF <sub&gt; 6 a volume. </li></ol></li><li> Mettere 1 (0,0049 g, 5,2 x 10 -6 mol) in e secco 4 dram fiala o un pallone a fondo tondo da 10 ml e aggiungere 4,00 ml della soluzione madre di 0,1 M TBAPF 6 in MeCN. </li><li> Trasferire 3,5-4,0 ml della soluzione elettrolitica di colore rosso-arancio di 1 nel vano centrale di una cella 3-vano, con ciascun compartimento separato da un mezzo fritta di vetro porosità. </li><li> Riempire rapidamente i compartimenti esterna della cella 3-vano ad un altezza pari come soluzione madre vano centrale, con alcuni dei restanti secca 0,1 M TBAPF 6 in MeCN per evitare perdite ai compartimenti esterni. Nota: Il tempo è un fattore importante in quanto le soluzioni nei diversi comparti lentamente mescolare e modificare significativamente la concentrazione del compartimento principale se le altezze solvente non sono gli stessi. </li></ol> 3. Electropolymerize 1 su 3 mm di diametro in vetroy Carbon elettrodi o 1,0 cm 2 FTO elettrodi <ol><li> Preparare setti per i tubi di degasaggio di azoto / argon e per gli elettrodi. <ol><li> Tagliare una fessura in ciascuno dei setti 3 gomma e guidare un sottile politetrafluoroetilene, PTFE, tubo attraverso la fessura. </li><li> Inserire l&#39;elettrodo 3 di riferimento Ag / AgNO attraverso uno dei setti, collocare l&#39;elettrodo di riferimento / PTFE tubo / setto in uno degli scomparti esterni, e sigillare il vano con il setto. </li><li> Guida il controelettrodo filo di platino / garza attraverso un luogo diverso setto platino filo / PTFE tubo / setto in uno degli scomparti esterni, e sigillare il vano con il setto. Se la fessura non è sufficientemente grande o filo sufficientemente rigida da evitare piegare il filo, utilizzare una vasta ago foro per guidare la contro-elettrodo filo di platino attraverso il setto. </li><li> Guida una appena lucidato 3 millimetri elettrodo di carbone vetroso il setto rimanente e posizionarlo in modo tale che l&#39;elettrodo è Sospnded nella soluzione o, per uno scivolo FTO, guidare un filo collegato ad un coccodrillo il setto, poi serrare la diapositiva FTO con il morsetto e assicurarsi che il lato conduttore della slitta è perpendicolare al controelettrodo quando sommerso . <ol><li> Prima di inserire l&#39;elettrodo di carbone vetroso: polacco carbonio vetroso mettendo allumina (0,5 micron) su un blocco di lucidatura bagnata, quindi, spostare l&#39;elettrodo in una figura-8 proposta di 30 secondi mentre si tiene l&#39;elettrodo perpendicolare al pad - per lucidare tutti i lati dell&#39;elettrodo uniformemente - e risciacquare qualsiasi allumina residuo con una H 2 O spruzzatore di acqua seguita da una spruzzetta risciacquo MeCN. </li><li> Prima di serraggio diapositiva FTO: avvolgere più strati di non-conduttivo nastro Kapton intorno alla parte centrale di una FTO slitta 30 x 10 mm in modo tale che una porzione 10 x 10 mm della slitta è esposto. </li><li> Raccogliere uno spettro UV-Vis della slitta FTO mettendo / tenendo il vetrino FTO in un positione nel percorso ottico dello spettrometro che è stato predeterminato per garantire la coerenza. </li></ol></li></ol></li><li> De-aerare le soluzioni della cella elettrochimica 3 scomparti. <ol><li> Collegare un&#39;estremità del tubo Tygon all&#39;azoto / fornitura argon e collegare l&#39;altra estremità a una rondella gas contenente MeCN. </li><li> Tagliare un pezzo di tubo Tygon, collegare un&#39;estremità alla outflowing MeCN lavata di azoto / argon, e collegare l&#39;altra estremità a un 4 vie splitter. </li><li> Collegare i tubi in PTFE per i 3 restanti collegamenti del 4 vie splitter. </li><li> Immergere i tubi di PTFE nelle soluzioni in ciascuno dei compartimenti e accendere il flusso di azoto / argon tale che una rapida gorgogliamento della soluzione inizia. </li><li> Continuare de-aerazione la soluzione per 5-10 minuti, quindi tirare i tubi PTFE appena sopra la superficie della soluzione, lasciando il flusso di azoto / argon sul per mantenere una pressione positiva di gas inerte nel sistema e per impedire che la soluzione convection causata dalla spumeggiante. </li></ol></li><li> Effettuare esperimenti elettrochimici. <ol><li> Collegare elettrodi dalla potenziostato agli elettrodi appropriati nella cella 3-vano. </li><li> Eseguire un voltammetria ciclica, CV, esperimento con i seguenti parametri: potenzialità di commutazione = 0 V e -1,81 V; scansione / velocità di scansione = 100 mV / sec; numero di cicli = 5. </li><li> Quando l&#39;esperimento CV, rimuovere il lavoro (carbonio vetroso o FTO) elettrodo dalla soluzione di polimerizzazione e risciacquare delicatamente la superficie dell&#39;elettrodo con MeCN da una pipetta o uno spruzzatore per rimuovere qualsiasi soluzione monomero residuo. </li></ol></li></ol> 4. Determinazione della superficie di copertura <ol><li> Inserire l&#39;elettrodo risciacquato lavorare in una soluzione preparata di 0,1 M TBAPF 6 / MeCN in una cella elettrochimica contenente un elettrodo contatore e un elettrodo di riferimento (preferibilmente lo stesso elettrodo di riferimento utilizzato nel electropolymerization). </li><li> Eseguire un voltammetria ciclica, CV, esperimento con i seguenti parametri: potenzialità di commutazione = 0 e +1,5 V; scansione / velocità di scansione = 100 mV / sec; numero di cicli = 15. </li><li> Integrare la carica sotto le cime anodica e catodica per il electropolymer adsorbito Ru (III / II) coppia, media la carica sotto il anodica e picchi catodica, e con l&#39;equazione 1 determinare la copertura della superficie. </li><li> Per la diapositiva FTO: luogo / tenere la diapositiva FTO nella posizione predeterminata fronte del supporto del campione UV-Vis tale che il fascio percorso passa attraverso il film colorato. La slitta FTO può essere bagnato o asciutto ma fare confronti nelle stesse condizioni come spettri bianco è stato raccolto sotto. </li><li> Sottrarre spettro ottenuto per lo spettro FTO che è stato raccolto per quel particolare diapositiva prima elettropolimerizzazione dallo spettro del film-on-FTO per produrre uno spettro di assorbimento del film stesso. </li></ol>

<ol>
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No conflicts of interest declared.

Elettropolimerizzazione offre una vasta gamma di variabili controllabili che non sono comuni ad altre tecniche. Oltre alle variabili di reazione standard come reagente (monomero) concentrazione, temperatura, solventi, ecc, elettropolimerizzazione può essere ulteriormente controllata da parametri dell&#39;esperimento elettrochimici comuni metodi elettrochimici. Tassi CV scansione, potenzialità di commutazione, e il numero di cicli influenzano la deposizione di electropolymers. Ad esempio, il numero di cicli at...

Elettropolimerizzazione è una tecnica di polimerizzazione che utilizza un potenziale applicato di avviare la polimerizzazione dei precursori monomerici direttamente sulla superficie di un elettrodo ed è stato sfruttato per produrre elettroattivi sottile e / o fotochimicamente film polypyridyl attivi sulle superfici degli elettrodi e dei semiconduttori. 1-4 Elettrocatalisi, 5-10 trasferimento di elettroni, 11, 12 fotochimica, 13-16 electrochromism, 17 e chimica di coordinazione 18 sono state studiate in film electropolymerized. Questa tecnica è stata sviluppata presso la University of North Carolina in una collaborazione Meyer-Murray per il elettropolimerizzazione di vinile 3, 5, 7, 8, 11-15, 19, 20 e pirrolo 6, 9, 21-24 me derivatizzataTal complessi su una varietà di substrati conduzione. La Figura 1 presenta una serie di leganti a base piridile comune che, quando coordinato a complessi metallici, hanno prodotto electropolymers. In elettropolimerizzazione riduttiva, elettropolimerizzazione di composti vinilici contenenti verifica sulla riduzione leganti piridinici coniugati con gruppi vinilici, mentre con ligandi pirrolo-funzionalizzato, elettropolimerizzazione viene iniziata mediante ossidazione delle frazioni pirrolo, conseguente ossidativo elettropolimerizzazione (Figura 2). Elettropolimerizzazione tecnologia è stata sviluppata con l&#39;obiettivo di fornire una metodologia generalizzata per collegare direttamente qualsiasi complesso di metallo di transizione per qualsiasi elettrodo. La versatilità del metodo apre la porta a numerose ricerche di electropolymer elettrodi modificati. In contrasto con altre strategie di attaccamento, che comportano legame diretto dell&#39;elettrodo, elettropolimerizzazione offre la advantage di non richiedere superficie dell&#39;elettrodo pre-modifica. . Quindi può essere applicato a qualsiasi numero di substrati conduttivi, indipendentemente composizione superficiale o morfologia 4, 10, 25, 26 Questa versatilità è il risultato di modificare le proprietà fisiche come la lunghezza del polimero cresce; i monomeri sono solubili nella soluzione elettrolitica, ma come si verifica polimerizzazione e reticolazione irrigidisce il film, precipitazione e adsorbimento fisico si verifica la superficie dell&#39;elettrodo (Figura 3). 27 Rispetto ai ossido carbossilato-bound superficie, che sono instabili sulle superfici di ossido in acqua, o complessi fosfonato-derivatizzato, instabili pH elevati di, comunemente utilizzati nella ricerca combustibili solare, queste strutture interfacciali pellicola elettrodo-polimero offrono il vantaggio di stabilità in una varietà di supporti, tra cui i solventi organici e acqua su un ampio intervallo di pH (0-14).28-30 elettropolimerizzazione può anche depositare film con grandi intervalli di coperture superficie apparente, dal sub-monostrato a decine o centinaia di equivalenti monostrato, mentre strutture carbossilato o fosfonato-derivatizzata complessi-interfaccia sono limitati a coperture superficiali monostrato. Anche se un numero qualsiasi di vinile o pirrolici contenenti piridil e polypyridyl composti sono in grado di polimerizzazione, [Ru II (PhTpy) (5,5&#39;-dvbpy) (MeCN)] (PF 6) 2, (1; PhTpy è 4&#39;-fenil -2,2 &#39;: 6&#39;, 2 &#39;&#39; - terpyridine; 5,5&#39;-dvbpy è 5,5&#39;-divinil-2,2&#39;-bipiridina, Figura 4) sarà utilizzata come un complesso modello per dimostrare elettropolimerizzazione riduttiva su carbone vetroso e ossido di stagno drogato con fluoro, FTO, elettrodi in questa relazione. 1 è un esempio di un moderno precursore electropolymer che ha potenziali applicazioni elettrocatalitici e, grazie alla sua metallo-ligand trasferimento di carica, MLCT, spettro di assorbimento che giace nella regione visibile dello spettro di luce, può essere analizzata con la spettroscopia UV-Vis. 18, 30 Si prega di notare che alcuni risultati presentati qui per 1 sono già stati pubblicati in una forma leggermente modificata. 18

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			<td height="20" style="height:20px;">Tetrabutylammonium hexafluorophosphate for electrochemical analysis, &#8805;99.0%,&#160;</td>
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			<td height="20" style="height:20px;width:384px;">Acetonitrile&#160;(Optima LC/MS), Fisher Chemical</td>
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			<td height="20" style="height:20px;">3 mm dia. Glassy Carbon Working Electrode</td>
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			<td height="20" style="height:20px;">Non-Aqueous Ag/Ag+ Reference Electrode w/ porous Teflon Tip</td>
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			<td>Chemglass</td>
			<td>CG-1114-15</td>
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			<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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reductive electropolymerization of a vinyl-containing poly-pyridyl complex on glassy carbon and fluorine-doped tin oxide electrodes

Controllabile modifica della superficie dell&#39;elettrodo è importante in numerosi campi, in particolare quelli con applicazioni combustibili solari. Elettropolimerizzazione è una tecnica di modificazione superficiale che elettrodepositi un film polimerico sulla superficie di un elettrodo utilizzando un potenziale applicato di avviare la polimerizzazione di substrati nello strato Helmholtz. Questa tecnica utile è stata fondata da una collaborazione Murray-Meyer presso la University of North Carolina a Chapel Hill nei primi anni 1980 e utilizzato per studiare numerosi fenomeni fisici di film contenenti complessi inorganici come il substrato monomero. Qui, si evidenzia una procedura per gli elettrodi di rivestimento con un complesso inorganico eseguendo elettropolimerizzazione riduttiva del complesso poli-piridil vinile contenente sul carbonio vetroso e fluoro ossido di stagno drogato elettrodi rivestiti. Raccomandazioni su configurazioni cella elettrochimica e le procedure di risoluzione dei problemi sono inclusi. Anche se non equi xplicitly descritto, elettropolimerizzazione ossidativa di composti contenenti pirrolici segue procedure simili a base di vinile elettropolimerizzazione riduttivo, ma sono molto meno sensibili a ossigeno e acqua.

Crescita Electropolymer è più facilmente riconoscibile osservando il progresso dell&#39;esperimento CV prescritta (protocollo Text STEP 3.3.2). Figura 5 esemplifica electropolymer crescita su 0,071 centimetri (diametro 3 mm) 2 elettrodo di carbone vetroso con 1. Il primo ciclo dell&#39;esperimento produce un voltammogramma approssimativamente simile a quella che si prevede una soluzione di rutenio concentrazione simile (figura 5, tracce nero), quando cicli ...

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.

Riduttiva elettropolimerizzazione di un Poly-piridil Complex-vinile contenente on Glassy carbonio e fluoro-drogato Tin Oxide Elettrodi

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

Research

JoVE Journal

Chemistry

11.7K Views.  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. 

Video: 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.

Miglioramento in gel riduttive solfo-glycomics β-eliminazione completa per O-linked e di spettrometria di massa

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

Ricerca

Chimica

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.

Modelli atomicamente definiti per epitassiale crescita di ossido Complex Thin Films

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.

Trasporto di nanotubi di carbonio modificati superficie attraverso una colonna di terreno

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.

Fotochimica ossidativa crescita di Iridium ossido di nanoparticelle su 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.

Analisi on-line dei composti contenenti azoto in matrici idrocarburi complessi

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.

Indagini su GA (III) Complesso di EOB-DTPA e la sua<sup&gt; 68</sup&gt; Ga marcata radioattivamente analogico

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.

L'innesto Multiwalled Carbon Nanotubes con polistirolo per abilitare l'auto-assemblaggio e discromie anisotropo

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.

Spettroscopia di impedenza elettrochimica come uno strumento per la stima della costante tasso elettrochimica

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.

Sintesi di Solvothermal di MIL-96 e UiO-66-NH2 su strato atomico depositato rivestimenti in ossido di metallo su stuoie di fibra

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.

Produzione additiva negativa del complesso a forma di carburi di boro

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