Reconocemos el Instituto Militar de Virginia (VMI) Departamento de Química para el apoyo de experimentos electroquímicos e instrumentación (LSC y JTH). La Oficina VMI del Decano de la Facultad apoyado cuotas de producción asociados a las publicaciones JoVE. Reconocemos la UNC EFRC: Centro de Combustibles Solares, un centro de investigación de vanguardia de la Energía, financiado por el Departamento de Energía, Oficina de Ciencia, Oficina de Energía de Ciencias Básicas bajo Premio número DE-SC0001011, Estados Unidos para el apoyo de la síntesis y caracterización de materiales compuestos (DPH ).

1. Sintetizar 1 Sintetizar 1 (PhTpy es 4 &#39;-fenil-2,2&#39;: 6 &#39;, 2&#39; &#39;- terpiridina; 5,5&#39;-dvbpy es 5,5&#39;-divinil-2,2&#39;-bipiridina; Figura 4) de acuerdo con el procedimiento descrito anteriormente. 18 2. Preparar 1,3 mM de monómero Solución de 1 en una solución de electrolito <ol><li> Preparar una solución electrolítica 0,1 m stock de tetra hexafluorfosfato n -butilamonio, TBAPF 6, en acetonitrilo, MeCN. <ol><li> Coloque MeCN durante activada 3 tamices moleculares A o K 2 CO 3, durante 24 horas para eliminar H 2 O. accidental </li><li> Coloque TBAPF 6 (0,969 g, 2,50 mmol) en una llama 25,00 ml secado matraz volumétrico. </li><li> Se filtra el tamiz molecular o CO K 2 3 partículas de la MeCN seca y llevar el matraz aforado de 25,00 ml que contiene TBAPF <sub&gt; 6 a volumen. </li></ol></li><li> Coloque 1 (0,0049 g, 5,2 x 10 -6 mol) en seco y vial 4 dram o un matraz de fondo redondo de 10 ml y añadir 4,00 ml de la solución madre de 0,1 M TBAPF 6 en MeCN. </li><li> Transferencia de 3,5-4,0 ml de la solución electrolítica de color rojo-naranja de 1 en el compartimiento central de una celda de 3 compartimentos, con cada compartimento separado por una frita de vidrio de porosidad media. </li><li> Llenar rápidamente los compartimentos exteriores de la célula 3-compartimento a una altura igual como la solución de stock compartimento central, con algunos de los restantes seco 0,1 M TBAPF 6 en MeCN para evitar la fuga de los compartimentos exteriores. Nota: El tiempo es un factor importante porque las soluciones en los diferentes compartimentos se mezcle lentamente y cambiar significativamente la concentración del compartimiento principal, si las alturas de disolventes no son los mismos. </li></ol> 3. Electropolymerize 1 en un diámetro de 3 mm de cristaly Carbon electrodo o una 1,0 cm 2 FTO electrodo <ol><li> Preparar septos para tubos de desgasificación de nitrógeno / argón y para los electrodos. <ol><li> Haga un corte en cada uno de los tabiques 3 caucho y guiar una delgada politetrafluoroetileno, PTFE, tubo a través de la rendija. </li><li> Deslice el electrodo 3 referencia Ag / AgNO través de uno de los tabiques, colocar el electrodo de referencia / PTFE tubo / tabique en uno de los compartimentos exteriores, y sellar el compartimiento con el tabique. </li><li> Guía el contador de electrodo de alambre de platino / gasa través de un lugar diferente del tabique de platino de alambre / tubo de PTFE / septum en uno de los compartimentos exteriores, y sellar el compartimiento con el septum. Si la ranura no es lo suficientemente grande o alambre suficientemente rígida para evitar que se doble el alambre, utilizar una aguja de calibre ancho para guiar el contador de electrodo de alambre de platino a través del septo. </li><li> Conduce a un 3 mm electrodo de carbono vítreo recién pulida a través del septo restante y colocarlo de tal manera que el electrodo es SUSPEnded en la solución o, para una diapositiva FTO, guiar un cable conectado a una pinza de conexión a través del septo, y luego sujetar la corredera FTO con la pinza de cocodrilo y asegúrese de que el lado conductor de la corredera es perpendicular a la contra-electrodo cuando está sumergido . <ol><li> Antes de insertar el electrodo de carbono vítreo: pulir el carbono vítreo mediante la colocación de alúmina (0,5 micras) sobre una almohadilla de pulido mojada y, a continuación, mover el electrodo en una figura-8 movimiento durante 30 segundos mientras se mantiene el electrodo perpendicular a la almohadilla - para pulir todos los lados del electrodo de manera uniforme - y aclarar cualquier alúmina restante con una H 2 O botella con atomizador de agua seguido de una botella con atomizador enjuague MeCN. </li><li> Antes de la corredera de sujeción FTO: envolver varias capas de no conductor de cinta Kapton alrededor de la parte central de una diapositiva FTO 30 x 10 mm de tal manera que una porción 10 x 10 mm de la corredera está expuesto. </li><li> Recoge un espectro UV-Vis de la diapositiva FTO colocando / sosteniendo el carro FTO en un positION en la trayectoria del haz del espectrómetro que ha sido predeterminado para garantizar la coherencia. </li></ol></li></ol></li><li> Desairear las soluciones en la celda electroquímica de 3 compartimientos. <ol><li> Conectar un extremo del tubo de Tygon al nitrógeno / suministro de argón y conectar el otro extremo a un lavador de gases que contiene MeCN. </li><li> Corte otro pedazo de tubo Tygon, conecte un extremo a la emanación MeCN lavado de nitrógeno / argón, y conecte el otro extremo a un divisor de 4 vías. </li><li> Conecte los tubos de PTFE a las 3 conexiones remanentes del 4 vías. </li><li> Sumergir los tubos de PTFE en las soluciones en cada uno de los compartimentos y encienda el flujo de nitrógeno / argón de tal manera que un rápido burbujeo de la solución comienza. </li><li> Continuar de-airear la solución durante 5-10 min, a continuación, tirar de los tubos de PTFE justo encima de la superficie de la solución, dejando el flujo de nitrógeno / argón sobre el fin de mantener una presión positiva de gas inerte en el sistema y para prevenir la solución convection causado por burbujeo. </li></ol></li><li> Realizar experimentos electroquímicos. <ol><li> Conectar los electrodos desde el potenciostato a los electrodos apropiados en la celda 3-compartimiento. </li><li> Realice una voltametría cíclica, CV, experimentar con los siguientes parámetros: potencialidades de conmutación = 0 V y -1,81 V; escanear / velocidad de barrido = 100 mV / seg; número de ciclos = 5. </li><li> Cuando el experimento CV, retire el electrodo de trabajo (FTO carbono vítreo o) a partir de la solución de polimerización y enjuagar suavemente la superficie del electrodo con MeCN de una pipeta o una botella con atomizador para eliminar cualquier solución de monómero restante. </li></ol></li></ol> 4. Superficie Determinación de cobertura <ol><li> Coloque el electrodo de trabajo se enjuaga en una solución recién preparada de 0,1 M TBAPF 6 / MeCN en una celda electroquímica que contiene un contraelectrodo y un electrodo de referencia (preferiblemente el mismo electrodo de referencia utilizado en la electropolymerization). </li><li> Realice una voltametría cíclica, CV, experimentar con los siguientes parámetros: potencialidades de conmutación = 0 y 1,5 V; escanear / velocidad de barrido = 100 mV / seg; número de ciclos = 15. </li><li> Integrar el cargo bajo los picos anódicos y catódicos para la electropolymer adsorbido Ru (III / II) par, en promedio la carga bajo la anódica y catódica picos, y utilizando la ecuación 1 a determinar la cobertura de la superficie. </li><li> Para la diapositiva FTO: Lugar / mantener la corredera FTO en la posición predeterminada en la parte delantera del soporte de la muestra, tales UV-Vis que la trayectoria del haz pasa a través de la película coloreada. El portaobjetos FTO puede estar húmedo o seco, pero hacer comparaciones bajo las mismas condiciones que los espectros de blanco se recogió bajo. </li><li> Restar el espectro obtenido para el espectro FTO que se recogió para esa diapositiva determinada antes de electropolimerización a partir del espectro de la película-on-FTO con el fin de producir un espectro de absorción de la película en sí. </li></ol>

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No conflicts of interest declared.

Electropolimerización ofrece una amplia gama de variables controlables que no son comunes a otras técnicas. Además de las variables de reacción estándar como concentración de reactivo (monómero), temperatura, disolvente, etc., electropolimerización puede ser controlado adicionalmente por parámetros del experimento electroquímicos comunes a los métodos electroquímicos. Tasas CV escaneo, potenciales conmutación, y el número de ciclos afectan la deposición de electropolymers. Por ejemplo, a medida q...

Electropolimerización es una técnica de polimerización que utiliza un potencial aplicado para iniciar la polimerización de los precursores monoméricos directamente en la superficie de un electrodo y se ha explotado para producir electroactivo delgada y / o fotoquímicamente películas polypyridyl activos en el electrodo y semiconductores superficies. 1-4 Electrocatálisis, 5-10 de transferencia de electrones, 11, 12 fotoquímica, 13-16 electrochromism, 17 y coordinación química 18 han sido investigados en películas electroquímicamente. Esta técnica fue desarrollada por primera vez en la Universidad de Carolina del Norte en una colaboración Meyer-Murray por el electropolimerización de vinilo 3, 5, 7, 8, 11 a 15, 19, y 20 pirrol 6, 9, 21 a 24 me derivatizarsecomplejos am- sobre una variedad de sustratos realización. La figura 1 presenta una serie de ligandos basados ​​piridilo común que, cuando se coordina a complejos metálicos, han producido electropolymers. En electropolimerización reductora, electropolimerización de compuestos de vinilo que contienen se produce tras la reducción de ligandos piridilo conjugados con grupos vinilo, mientras que con ligandos de pirrol-funcionalizado, electropolimerización se inicia por la oxidación de los restos de pirrol, resultando en electropolimerización oxidativo (Figura 2). Tecnología electropolimerización fue desarrollado con el objetivo de proporcionar una metodología generalizada para unir directamente prácticamente cualquier complejo de metal de transición a cualquier electrodo. La versatilidad del método abre la puerta a numerosas investigaciones de electropolymer electrodos modificados. En contraste con otras estrategias de fijación, que implican contacto directo con el electrodo, electropolimerización ofrece la advantage de no requerir superficie del electrodo pre-modificación. . Por lo tanto, se puede aplicar a cualquier número de sustratos que llevan a cabo, independientemente de la composición superficial o la morfología 4, 10, 25, 26 Esta versatilidad es un resultado del cambio de las propiedades físicas como la duración de polímero crece; los monómeros son solubles en la solución electrolítica pero a medida que se produce la polimerización y la reticulación rigidiza la película, la precipitación y adsorción física se produce la superficie del electrodo (Figura 3). 27 En comparación con carboxilato unido a la superficie de óxido, que son inestables en las superficies de óxido en el agua, o complejos de fosfonato derivatizados, que son inestables a valores de pH elevados, comúnmente utilizados en la investigación de combustibles solar, estas estructuras de película de electrodo de polímero interfaciales ofrecen el beneficio añadido de la estabilidad en una variedad de medios, incluyendo disolventes orgánicos y agua en un intervalo de pH de gran tamaño (0-14).28-30 electropolimerización también puede depositar películas con grandes gamas de coberturas superficiales aparentes, a partir de sub-monocapa a decenas o cientos de equivalentes monocapa, mientras que las estructuras de carboxilato o fosfonato derivatizado complejos de interfaz se limitan a las coberturas de superficie monocapa. Aunque cualquier número de compuestos que contienen piridilo y polypyridyl de vinilo o de pirrol son capaces de polimerización, [Ru II (PhTpy) (5,5&#39;-dvbpy) (MeCN)] (PF 6) 2, (1; PhTpy es 4 &#39;fenil- 2,2 &#39;: 6&#39;, 2 &#39;&#39; - terpiridina; 5,5&#39;-dvbpy es 5,5&#39;-divinil-2,2&#39;-bipiridina; Figura 4) se utilizará como complejo modelo para demostrar electropolimerización reductiva sobre carbón vítreo y óxido de estaño dopado con flúor, FTO, electrodos en este informe. 1 es un ejemplo de un precursor electropolymer moderna que tiene aplicaciones potenciales electrocatalíticas y, debido a su metal a li-transferencia de carga gand, MLCT, espectro de absorción de la mentira en la región visible del espectro de luz, se puede investigar con UV-Vis. 18, 30 Tenga en cuenta que algunos de los resultados presentados aquí por 1 ya han sido publicados en una forma ligeramente modificada. 18

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

Modificación de la superficie del electrodo controlable es importante en un número de campos, especialmente aquellos con aplicaciones de combustibles solares. Electropolimerización es una técnica de modificación de la superficie que electrodepósitos un película polimérica en la superficie de un electrodo utilizando un potencial aplicada para iniciar la polimerización de los sustratos en la capa de Helmholtz. Esta técnica útil se estableció por primera vez por una colaboración Murray-Meyer de la Universidad de Carolina del Norte en Chapel Hill, en la década de 1980 y utilizado para estudiar numerosos fenómenos físicos de películas que contienen complejos inorgánicos como el sustrato monomérico. Aquí, seleccionamos a un procedimiento para electrodos de recubrimiento con un complejo inorgánico mediante la realización de electropolimerización reductiva del complejo poli-piridilo contiene vinilo en electrodos recubiertos de carbono vítreo y flúor óxido de estaño dopado. Se incluyen recomendaciones sobre las configuraciones de células electroquímicas y los procedimientos de solución de problemas. Aunque no explicitly describe aquí, electropolimerización oxidativa de compuestos que contienen pirrol sigue procedimientos similares a electropolimerización reductora a base de vinilo, pero son mucho menos sensibles a oxígeno y agua.

Crecimiento Electropolymer se reconoce más fácilmente al observar el progreso de la CV experimento prescrito (Protocolo de texto PASO 3.3.2). La figura 5 ejemplifica el crecimiento electropolymer en un 0,071 cm 2 (3 mm de diámetro) de electrodo de carbono vítreo con 1. El primer ciclo del experimento produce un voltamograma más o menos parecida a la que se espera de una solución de rutenio de concentración similar (Figura 5, vestigios negro) sino en ci...

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.

Reductiva electropolimerización de un poli-piridilo Complex contiene vinilo sobre carbón vítreo y dopado con flúor óxido de estaño Electrodos

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 vistas.  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.

Mejora En-gel β-eliminación para ligada al O y exhaustiva sulfo-glycomics reductoras de Espectrometría de Masas

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

Investigación

Química

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.

Plantillas Atómicamente definidos para crecimiento epitaxial de óxido complejo Películas Delgadas

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.

Transporte de nanotubos de carbono modificado en la superficie a través de una columna de suelo

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.

Fotoquímico oxidativo Crecimiento de iridio nanopartículas de óxido de 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.

Análisis on-line de compuestos que contienen nitrógeno en matrices complejas de hidrocarburos

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.

Las investigaciones en el complejo Ga (III) de EOB-DTPA y su<sup&gt; 68</sup&gt; Ga radiomarcados analógica

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.

Injerto de nanotubos de carbono pirólisis con poliestireno para permitir uno mismo-Asamblea y pliegues anisotrópico

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.

Espectroscopia de impedancia electroquímica como herramienta para la valoración constante de tipo electroquímico

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.

Síntesis de Solvothermal de 96 MIL y UiO-66-NH2 de capa atómica deposita recubrimientos de óxido de Metal en esteras de la 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.

Fabricación aditiva negativa del complejo en forma de carburos de boro

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