This work has been performed at the Molecular Foundry, Lawrence Berkeley National Laboratory and supported by the Office of Science, Office of Basic Energy Sciences, Scientific User Facilities Division of the US Department of Energy, under Contract No. DE-AC02&#8211;05CH11231. The financial support of F.M. by a ME-Fulbright fellowship and A.S. by Higher Education Commission of Pakistan are gratefully acknowledged.

NOTA: Antes de comenzar, compruebe todas las hojas de datos de materiales pertinentes (MSDS). Varios de los productos químicos utilizados en los procedimientos de síntesis y de aplicación son tóxicos. Siga todas las prácticas de seguridad apropiadas y utilizar el equipo adecuado de protección (bata, pantalones largos, zapatos cerrados, gafas de seguridad, guantes). Utilice todo el equipo de protección personal al manipular criogénica de nitrógeno líquido para las medidas de adsorción de nitrógeno (guantes aislantes, careta). 1. poroso polímero Preparación Monolito a Granel y Formato de columna capilar <ol><li> Bulk Polymer Monolith para la caracterización <ol><li> Purificar estireno, divinilbenceno y ácido metacrílico a través de una columna de alúmina básica, con el fin de eliminar los inhibidores de la polimerización. Colocar 10 g de alúmina básica en un ml jeringa de plástico desechable 25 con una torunda de lana de vidrio de envasado en la punta de la jeringa. Hacer pasar aproximadamente 10 ml de monómero a través de la columna. </li><li> Cargar los monómeros (50 mg estireno, divinilbenceno 100 mg y 50 mg de ácido metacrílico) y los agentes formadores de poros (300 mg de tolueno y 300 mg isooctano) en un vial de vidrio de 1 ml. Añadir el iniciador de la polimerización, 4 mg de 2,2&#39;-azobisisobutironitrilo (AIBN, 1% con respecto a los monómeros). </li><li> Homogeneizar por sonicación durante 10 min. Eliminar el oxígeno disuelto por burbujeo de nitrógeno a través del líquido durante 10 min. Sellar la tapa del frasco con la película de parafina y colocarlo en un baño de agua a 60 ° C durante 6 horas para polimerizar la mezcla. </li><li> Enfriar a temperatura ambiente y romper el frasco con cuidado. Transferir el monolito de polímero en un dedal de extracción de celulosa. Colocar el cartucho de extracción en una cámara de extracción Soxhlet y ensamblar a un matraz de fondo redondo que contiene un volumen de metanol, que es al menos tres veces el volumen de la cámara de extracción. Montar un condensador a la parte superior de la cámara de extracción. Realizar la extracción Soxhlet por ebullición del metanoldurante 16 h, asegurando la eliminación completa de los monómeros sin reaccionar y agentes formadores de poros. </li><li> Secar durante la noche en un horno de vacío a 60 ° C. Confirmar la presencia de grupos funcionales carboxílicos para unir el PCP por Fourier Transform Infrared Spectroscopy (FT-IR). Medir el área de superficie por porosimetría de adsorción de nitrógeno. </li></ol></li><li> La funcionalización de sílice Capilares para la Preparación de columnas monolíticas <ol><li> Cortar 2 m de 100 micras Identificación del capilar de sílice fundida de poliamida recubierto. Conéctelo a una jeringa de vidrio desde 0,25 hasta 0,50 ml y lavar el capilar con acetona. Eliminar la acetona por aclarado el capilar con agua. </li><li> Con el fin de activar el recubrimiento de sílice interna del capilar, utilizar una bomba de jeringa a fluir una solución 0,2 M acuosa de NaOH a 0,25 l / min durante 30 min. Enjuague con agua hasta que el efluente es neutral. </li><li> Utilice tiras de papel de pH para comprobar el pH del efluente. Con el fin de protonar los grupos silanol del capilar, bombear un aqueo 0,2 Msolución de HCl nosotros a través del capilar a 0,25 l / min durante 30 min. Enjuague con agua hasta que el efluente es neutral. Enjuague con etanol. </li><li> Bombear un 20% (w / w) solución de etanol de 3- (trimetoxisilil) propil metacrilato (pH 5 ajustado con ácido acético) en 0,25 l / min durante 1 hora. En este paso, el capilar de sílice está funcionalizado con grupos vinilo con el fin de fijar el monolito de polímero a la superficie interior capilar. </li><li> Enjuague con acetona y seco, en una corriente de nitrógeno y dejar a temperatura ambiente durante la noche antes de su uso. Cortar el capilar en pedazos más cortos de longitud 20 cm. </li></ol></li><li> Preparación de columnas monolíticas capilares <ol><li> Preparar una mezcla de polimerización idénticas como para el monolito de polímero a granel (sección 1.1) en un vial de vidrio de 1 ml con un septo de caucho. Añadir iniciador AIBN 1% con respecto a los monómeros. Homogeneizar por sonicación durante 10 min. </li><li> Purgar la mezcla de polimerización con nitrógeno mediante el acoplamiento de un capilar de sílice no funcionalizadoa una corriente de nitrógeno. <ol><li> Insertar el capilar corriente de nitrógeno a través del septo de caucho del vial y sumergirlo en la mezcla de polimerización de manera que el nitrógeno burbujas a través del líquido. Deje la tapa del frasco ligeramente suelto para evitar sobrepresiones. Purgar durante 10 min. </li><li> Levantar el capilar corriente de nitrógeno de la mezcla de polimerización para el espacio de cabeza del vial, y cerrar herméticamente la tapa. Insertar un capilar funcionalizado a través del septo en la mezcla de polimerización. El exceso de presión generada en el capilar a través del nitrógeno inyectado en el espacio de cabeza bombea la mezcla de polimerización a través del capilar funcionalizado. </li><li> Recoger varias gotas de mezcla de polimerización a partir del efluente del capilar para asegurarse de que está completamente lleno y cerrarlo con un tapón de caucho. Tome el capilar fuera del vial muy cuidadosamente y cerrar la entrada del capilar con un septum de goma. </li></ol></li><li> Polimerizar la mezclatura contenida en el capilar en un baño de agua a 60 ° C durante 6 horas. Enfriar a temperatura ambiente y cortar unos pocos milímetros de ambos extremos del capilar. Eliminar los monómeros sin reaccionar y agentes formadores de poros mediante el lavado de la columna con acetonitrilo utilizando una bomba de HPLC a 3 l / min durante 30 min. Compruebe contrapresión de la columna capilar. </li></ol></li></ol> 2. Crecimiento del Hierro-benzenetrycarboxylate (FeBTC) PCP <ol><li> Crecimiento del FeBTC MSP en un polímero a granel Monolito para la caracterización <ol><li> Moler el monolito previamente secado utilizando un mortero. </li><li> Sumergir 100 mg del polvo monolito en 5 ml de 2 mM FeCl 3 · 6H 2 O en etanol durante 15 min. Filtro de vacío usando un filtro de nylon (0,22 micras) y se lava el polvo con etanol. Sumergir el polvo monolito en 5 ml de 2 mM de ácido 1,3,5-bencenotricarboxílico (BTC) en etanol durante 15 min. Filtro de vacío usando un filtro de nylon (0,22 micras) y se lava el polvo con etanol.</li><li> Repita el paso número 2 como se desee. El crecimiento de la capa de metal-orgánica final será definido por el número de ciclos aplicados. Típicamente, se realizan entre 10 y 30 ciclos. Confirmar la presencia de nuevos poros por porosimetría de adsorción de nitrógeno. Medir la cantidad de sitios de metal adicionales por análisis termogravimétrico (TGA). </li></ol></li><li> Crecimiento de la FeBTC Ministerio de Salud Pública en una columna monolítica capilar para el enriquecimiento de fosfopéptidos <ol><li> El uso de una bomba de jeringa. Enjuague el monolito capilar con 2 mM FeCl 3 · 6H 2 O en etanol durante 15 min a 2 l / min. Lavar con etanol durante 15 min a 2 l / min. Enjuague el monolito capilar con una mM BTC 2 en etanol durante 15 min a 2 l / min. Lavar con etanol durante 15 min a 2 l / min. </li><li> Repita el paso 1 como se desee. El crecimiento de la capa de metal-orgánica final será definido por el número de ciclos realizados. </li></ol></li></ol> 3. La proteína de digestión y Enrichment de Phosphopeptides <ol><li> La digestión de proteínas <ol><li> Disolver 0,5 ml de leche desnatada en 1 ml de agua y se divide en 200 l fracciones. </li><li> Para la digestión de las proteínas añadir bicarbonato de amonio 160 l 1 M y ditiotreitol 50 l 45 mM de cada fracción, con el fin de escindir los enlaces disulfuro. Incubar a 50 ° C en un termomezclador durante 15 min. </li><li> Añadir poco a poco 50 l de una solución acuosa de yodoacetamida 100 mM, mientras que la solución se enfrió a temperatura ambiente. Yodoacetamida evitará la formación de nuevos enlaces disulfuro. </li><li> Incubar en la oscuridad durante 15 min a temperatura ambiente. Añadir 1 ml de agua desionizada. Añadir 2 g de tripsina y digerir las proteínas en un termomezclador a 37 ° C durante 14 horas. </li><li> Terminar la digestión por acidificación con 10 l de ácido trifluoroacético al 1%, y colocándolo en el termomezclador durante 5 min a temperatura ambiente. Guarde las proteínas digeridas a -20 ° C. </li></ol></li><li> Enriquecimiento de fosfopéptidos utilizando una columna capilar Ministerio de Salud Pública. <ol><li> Lavar la columna con 100 l de una mezcla 4: 1 de acetonitrilo que contiene un ácido trifluoroacético al 0,1% durante 10 min a un caudal de 1 l / min. Bombear la digestión de la proteína a través de la columna a 2 l / min durante 30 min. </li><li> Lavar los péptidos no fosforilados de nuevo con una mezcla 4: 1 de acetonitrilo que contiene un ácido trifluoroacético al 0,1% durante 10 min a un caudal de 1 l / min. Lavar con agua durante 10 min a un caudal de 1 l / min. </li><li> Fosfopéptidos eluir utilizando una solución tampón de pH 7 de fosfato 250 mM bombeado a 1 l / min durante 15 min. Recoger el eluyente en un vial y desalar la solución utilizando un protocolo estándar 19. Preparar un ácido / ml de 2,5-dihidroxibenzoico 2 mg de utilizarlo como la matriz para la espectrometría de láser asistida por matriz de desorción / ionización tiempo de vuelo de masas (MALDI-TOF-MS). Dibujado 2 l de ácido 2,5-dihidroxibenzoico en la punta para eluir el phosphopeptides y detectar directamente sobre la placa de MALDI. </li><li> Analizar las manchas por MALDI-TOF-MS y regenerar la columna mediante el lavado a fondo con agua y luego metanol. </li></ol></li></ol>

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The authors have nothing to disclose.

El monolito de polímero original contiene grupos funcionales carboxílicos capaces de unirse a los metales. La coordinación de los sitios de metal iniciales sobre el material original, somos capaces de hacer crecer una capa PCP (Figura 1), la incorporación de una serie de sitios de metales adicionales que configuran una red microporosa. Esto hace que los materiales presentados MSP atractivos para los procedimientos de extracción o purificación donde están involucrados especies metálicas, tales co...

Polímeros de coordinación poroso (PCP) son compuestos de coordinación basado en centros metálicos unidos por ligandos orgánicos con la repetición de las entidades de coordinación que se extienden en 1, 2 o 3 dimensiones que pueden ser amorfo o cristalino 1-3. En los últimos años, esta clase de materiales porosos ha atraído una gran atención debido a su alta porosidad, tunability química de ancho, y su estabilidad. PCP se han explorado para una gama de aplicaciones, incluyendo el almacenamiento de gas, separación de gas, y la catálisis 3-6, y muy recientemente, las primeras aplicaciones analíticas de los PCP se han descrito 7. Debido a su mayor funcionalidad química y alta porosidad PCP han sido blanco por su enorme potencial para la mejora de los procesos de purificación y separaciones cromatográficas, y una serie de informes sobre este tema se han publicado 7-13. Sin embargo, el rendimiento de los PCP no se encuentra actualmente en un Equivalenivel nt con materiales cromatográficos existentes probablemente debido a la rápida difusión a través de grandes huecos entre partículas en lechos de relleno de estos sólidos debido a sus morfologías normalmente de forma irregular de sus partículas o cristales. Este embalaje distribuida irregularmente conduce a un rendimiento menor de lo esperado, así como contrapresiones alta columna e indeseables morfologías forma de pico 14,15. Con el fin de resolver el problema de la rápida difusión a través de los huecos entre las partículas y concomitantemente mejorar el rendimiento de los PCP para aplicaciones analíticas, el desarrollo de un material híbrido basado en un monolito de polímero macroporoso 16 que contiene el PCP en la superficie de los macroporos haría ser deseable. Monolitos de polímeros son materiales de una sola pieza que puedan sostener el flujo convectivo a través de sus poros, lo que los convierte en una de las alternativas más eficientes para cordón de envases y se han comercializado con éxito por varios c autónomo<html> as empresas 17,18. Monolitos polímero poroso se basan generalmente en la polimerización de un monómero y un reticulante en presencia de porógenos, que son típicamente mezclas binarias de solventes orgánicos. Los materiales monolíticos obtenidos tienen una estructura microglobular y una alta porosidad y el flujo de permeabilidad. Un enfoque simple para unificar estos materiales para preparar un monolito de polímero que contiene un PCP se basa en la adición directa de los PCP tal como se sintetizan en la mezcla de polimerización del monolito. Este enfoque dio lugar a los PCP enterrado en su mayoría dentro de un esqueleto de polímero, y no ser activo para la aplicación ulterior del material final 14,15. Un enfoque sintético diferente es claramente necesario con el fin de, por ejemplo, desarrollar películas uniformes de PCP, o marcos de metal-orgánicos cristalinos (MOF) donde la mayoría de los poros contenidos en el cristal son accesibles desde los macroporos del monolito de polímero. t &quot;&gt; Aquí nos presenta un protocolo simple para la preparación de un material híbrido de metal-polímero orgánico (MSP), basado en un soporte de polímero macroporoso con grupos funcionales adecuados para la unión de PCP, que pueden ser implementados fácilmente como un auto-contenida sola monolito de polímero -piece en un formato de columna con propiedades óptimas para aplicaciones de flujo continuo. El procedimiento de síntesis de polímeros es seguido por una solución basada en la temperatura ambiente sencillo &#160; método para hacer crecer un recubrimiento de PCP en la superficie interna de los poros de la monolito 19-20. Como el primer ejemplo, se describe la preparación de un hierro (III) benzenetricarboxylate (FeBTC) película de polímero de coordinación dentro de un poli macroporoso (ácido estireno-divinilbenceno-metacrílico) monolito. Este método es eficaz para la preparación de polvos a granel, así como columnas capilares y el protocolo descrito es fácilmente implementable a otros PCP. Como un ejemplo del potencial de MOPHs como materiales funcionales para el flujo-throuaplicaciones gh, que aplican los países desarrollados FeBTC Ministerio de Salud Pública, que contiene una capa densa de Fe (III) centros para enriquecer fosfopéptidos de mezclas de proteínas digeridas explotan la afinidad de unión de fosfopéptidos a Fe (III). El protocolo desarrollado 21 se compone de tres partes principales: Preparación del soporte monolito de polímero orgánico macroporoso; el crecimiento del revestimiento PCP en la superficie de los poros de la monolito; aplicación para el enriquecimiento de fosfopéptidos.

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>Polyimide-coated capillaries</td>
			<td>Polymicro Technologies</td>
			<td>TSP100375</td>
			<td>100 &#956;m i.d.</td>
		</tr>
		<tr>
			<td>3-(trimethoxysilyl)propyl methacrylate, 98%</td>
			<td>Sigma-Aldrich</td>
			<td>440159</td>
			<td></td>
		</tr>
		<tr>
			<td>Styrene, 99%</td>
			<td>Sigma-Aldrich</td>
			<td>W323306</td>
			<td>Technical grade</td>
		</tr>
		<tr>
			<td>Divinylbenzene, 80%</td>
			<td>Sigma-Aldrich</td>
			<td>414565</td>
			<td></td>
		</tr>
		<tr>
			<td>Methacrylic acid, 98%</td>
			<td>Mallinckrodt</td>
			<td>MK150659</td>
			<td></td>
		</tr>
		<tr>
			<td>Toluene, &#8805;99.5%</td>
			<td>EMD chemicals</td>
			<td>MTX0735-6</td>
			<td></td>
		</tr>
		<tr>
			<td>Isooctane, &#8805;99.5%</td>
			<td>Sigma-Aldrich</td>
			<td>650439</td>
			<td></td>
		</tr>
		<tr>
			<td>2,2&#39;-azobisisobutyronitrile, 98%</td>
			<td>Sigma-Aldrich</td>
			<td>441090</td>
			<td></td>
		</tr>
		<tr>
			<td>Aluminium oxide (basic alumina)</td>
			<td>Sigma-Aldrich</td>
			<td>199443</td>
			<td></td>
		</tr>
		<tr>
			<td>Iron (III) chloride hexahydrate, 97%</td>
			<td>Sigma-Aldrich</td>
			<td>236489</td>
			<td></td>
		</tr>
		<tr>
			<td>1,3,5-benzenetrycarboxylic acid, 95%</td>
			<td>Sigma-Aldrich</td>
			<td>482749</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetonitrile, &#8805;99.5%</td>
			<td>Sigma-Aldrich</td>
			<td>360457</td>
			<td></td>
		</tr>
		<tr>
			<td>Ammonium bicarbonate, &#8805;99.5%</td>
			<td>Sigma-Aldrich</td>
			<td>9830</td>
			<td></td>
		</tr>
		<tr>
			<td>Trifluoroacetic acid, &#8805;99%</td>
			<td>Sigma-Aldrich</td>
			<td>302031</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethanol, &#8805;99.8%</td>
			<td>Sigma-Aldrich</td>
			<td>2854</td>
			<td></td>
		</tr>
		<tr>
			<td>Iodoacetamide, &#8805;99%</td>
			<td>Sigma-Aldrich</td>
			<td>I1149</td>
			<td></td>
		</tr>
		<tr>
			<td>Dithiothreitol, &#8805;99%</td>
			<td>Sigma-Aldrich</td>
			<td>43819</td>
			<td></td>
		</tr>
		<tr>
			<td>Monobasic sodium phosphate dihydrate, &#8805;99%</td>
			<td>Sigma-Aldrich</td>
			<td>71505</td>
			<td></td>
		</tr>
		<tr>
			<td>Dibasic sodium phosphate dihydrate, &#8805;99%</td>
			<td>Sigma-Aldrich</td>
			<td>71643</td>
			<td></td>
		</tr>
		<tr>
			<td>Phosphoric acid, &#8805;85%</td>
			<td>Sigma-Aldrich</td>
			<td>438081</td>
			<td></td>
		</tr>
		<tr>
			<td>2,5-dihydroxybenzoic acid, &#8805;99%</td>
			<td>Sigma-Aldrich</td>
			<td>85707</td>
			<td></td>
		</tr>
		<tr>
			<td>Trypsin</td>
			<td>Sigma-Aldrich</td>
			<td>T8003</td>
			<td>Bovine pancreas</td>
		</tr>
		<tr>
			<td>&#946;-casein</td>
			<td>Sigma-Aldrich</td>
			<td>C6905</td>
			<td>Bovine milk</td>
		</tr>
		<tr>
			<td>ZipTip pipette tips</td>
			<td>Merck Millipore</td>
			<td>ZTC18S096</td>
			<td>C18 resin</td>
		</tr>
	</tbody>
</table>

preparation of highly porous coordination polymer coatings on macroporous polymer monoliths for enhanced enrichment of phosphopeptides

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process.
The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications.

Una ilustración esquemática de la PCP crecimiento en la superficie de los poros del monolito de polímero orgánico se muestra en la Figura 1. En esta figura, se ilustra el inicial Fe (III) átomos retenidas en la superficie de los poros del monolito de polímero original, coordinado a grupos funcionales carboxílicos . Utilizando el protocolo descrito en el presente documento ligando orgánico adicional y Fe iones (III) se añaden a la superficie, la conformación de una red de coordinación poroso d...

Watch this Scientific Journal Video about Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides at JoVE.com

Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

A procedure for the preparation of porous hybrid separation media composed of a macroporous polymer monolith internally coated by a high surface area microporous coordination polymer is presented.

Preparación de altamente poroso Coordinación Polymer Coatings en macroporosas Polymer Monolitos de Enriquecimiento mejorada de Phosphopeptides

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous ...

preparation-highly-porous-coordination-polymer-coatings-on

Research

JoVE Journal

Chemistry

10.0K vistas.  E. O. Lawrence Berkeley National Laboratory. A procedure for the preparation of porous hybrid separation media composed of a macroporous polymer monolith internally coated by a high surface area microporous coordination polymer is presented.

Video: Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

Confocal Imaging of Confined Quiescent and Flowing Colloid-polymer Mixtures

The behavior of confined colloidal suspensions with attractive interparticle interactions is critical to the rational design of materials for directed assembly1-3, drug delivery4, improved hydrocarbon recovery5-7, and flowable electrodes for energy storage8. Suspensions containing fluorescent colloids and non-adsorbing polymers are appealing model systems, as the ratio of the polymer radius of gyration to the particle radius&#160;and concentration of polymer control the range and strength of the interparticle attraction, respectively. By tuning the polymer properties and the volume fraction of the colloids, colloid fluids, fluids of clusters, gels, crystals, and glasses can be obtained9.&#160;Confocal microscopy, a variant of fluorescence microscopy, allows an optically transparent and fluorescent sample to be imaged with high spatial and temporal resolution in three dimensions. In this technique, a small pinhole or slit blocks the emitted fluorescent light from regions of the sample that are outside the focal volume of the microscope optical system. As a result, only a thin section of the sample in the focal plane is imaged. This technique is particularly well suited to probe the structure and dynamics in dense colloidal suspensions at the single-particle scale: the particles are large enough to be resolved using visible light and diffuse slowly enough to be captured at typical scan speeds of commercial confocal systems10. Improvements in scan speeds and analysis algorithms have also enabled quantitative confocal imaging of flowing suspensions11-16,37.&#160;In this paper, we demonstrate confocal microscopy experiments to probe the confined phase behavior and flow properties of colloid-polymer mixtures. We first prepare colloid-polymer mixtures that are density- and refractive-index matched. Next, we report a standard protocol for imaging quiescent dense colloid-polymer mixtures under varying confinement in thin wedge-shaped cells. Finally, we demonstrate a protocol for imaging colloid-polymer mixtures during microchannel flow.

Confocal microscopy is used to image quiescent and flowing colloid-polymer mixtures, which are studied as model systems for attractive suspensions. Image analysis algorithms are used to calculate structural and dynamic metrics for the colloidal particles that measure changes due to geometric confinement.

Imagen confocal de Confinados en reposo y que fluye mezclas de coloide y polímeros

The behavior of confined colloidal suspensions with attractive interparticle interactions is critical to the rational design of materials for directed ...

Investigación

Química

Fabrication of Large-area Free-standing Ultrathin Polymer Films

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films. Typically, ultrathin films are prepared using either sacrificial layers, which may damage the film or affect its mechanical properties, or they are made on freshly cleaved mica, a substrate that is difficult to scale. Further, the size of ultrathin film is typically limited to a few square millimeters. In this method, we modify a surface with a polyelectrolyte that alters the strength of adhesion between polymer and deposition substrate. The polyelectrolyte can be shown to remain on the wafer using spectroscopy, and a treated wafer can be used to produce multiple films, indicating that at best minimal amounts of the polyelectrolyte are added to the film. The process has thus far been shown to be limited in scalability only by the size of the coating equipment, and is expected to be readily scalable to industrial processes. In this study, the protocol for making the solutions, preparing the deposition surface, and producing the films is described.

We describe a method for the fabrication of large-area (up to 13 cm diameter) and ultrathin (as thin as 8 nm) polymer films. Instead of using a sacrificial interlayer to delaminate the film from its substrate, we use a self-limiting surface treatment suitable for arbitrarily large areas.

La fabricación de superficies de gran autoportante ultrafinos Polymer Films

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films.  Typically, ultrathin films are prepared ...

Photodynamic Therapy with Blended Conducting Polymer/Fullerene Nanoparticle Photosensitizers

In this article a method for the fabrication and reproducible in-vitro evaluation of conducting polymer nanoparticles blended with fullerene as the next generation photosensitizers for Photodynamic Therapy (PDT) is reported. The nanoparticles are formed by hydrophobic interaction of the semiconducting polymer MEH-PPV (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]) with the fullerene PCBM (phenyl-C61-butyric acid methyl ester) in the presence of a non-compatible solvent. MEH-PPV has a high extinction coefficient that leads to high rates of triplet formation, and efficient charge and energy transfer to the fullerene PCBM. The latter processes enhance the efficiency of the PDT system through fullerene assisted triplet and radical formation, and ultrafast deactivation of MEH-PPV excited stated. The results reported here show that this nanoparticle PDT sensitizing system is highly effective and shows unexpected specificity to cancer cell lines.

This protocol describes a method for the fabrication of conducting polymer nanoparticles blended with fullerene. These nanoparticles were investigated for their potential use as a next generation photosensitizers for Photodynamic Therapy (PDT).

Terapia fotodinámica con Blended polímero conductor / Fullerene nanopartículas fotosensibilizadores

In this article a method for the fabrication and reproducible in-vitro evaluation of conducting polymer nanoparticles blended with fullerene as the next ...

Preparation of Macroporous Epitaxial Quartz Films on Silicon by Chemical Solution Deposition

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step process based on the preparation of a sol in a one-pot synthesis which is followed by the deposition of a gel film on Si(100) substrates by evaporation induced self-assembly using the dip-coating technique and ends with a thermal treatment of the material to induce the gel crystallization and the growth of the quartz film. The formation of a silica gel is based on the reaction of a tetraethyl orthosilicate and water, catalyzed by HCl, in ethanol. However, the solution contains two additional components that are essential for preparing mesoporous epitaxial quartz films from these silica gels dip-coated on Si. Alkaline earth ions, like Sr2+ act as glass melting agents that facilitate the crystallization of silica and in combination with cetyl trimethylammonium bromide (CTAB) amphiphilic template form a phase separation responsible of the macroporosity of the films. The good matching between the quartz and silicon cell parameters is also essential in the stabilization of quartz over other SiO2 polymorphs and is at the origin of the epitaxial growth.

A protocol is presented for the preparation of piezoelectric macroporous epitaxial films of quartz on silicon by solution chemistry using dip-coating and thermal treatments in air.

Preparación de macroporosas Epitaxial cuarzo Films en silicio por la solución de deposición química

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step ...

Functionalization of Single-walled Carbon Nanotubes with Thermo-reversible Block Copolymers and Characterization by Small-angle Neutron Scattering

We demonstrate a protocol for single-walled carbon nanotube functionalization using thermo-sensitive PEO-PPO-PEO triblock copolymers in an aqueous solution. In a carbon nanotube/PEO105-PPO70-PEO105 (poloxamer 407) aqueous solution, the amphiphilic poloxamer 407 adsorbs onto the carbon nanotube surfaces and self-assembles into continuous layers, driven by intermolecular interactions between constituent molecules. The addition of 5-methylsalicylic acid changes the self-assembled structure from spherical-micellar to a cylindrical morphology. The fabricated poloxamer 407/carbon nanotube hybrid particles exhibit thermo-responsive structural features so that the density and thickness of poloxamer 407 layers are also reversibly controllable by varying temperature. The detailed structural properties of the poloxamer 407/carbon nanotube particles in suspension can be characterized by small-angle neutron scattering experiments and model fit analyses. The distinct curve shapes of the scattering intensities depending on temperature control or addition of aromatic additives are well described by a modified core-shell cylinder model consisting of a carbon nanotube core cylinder, a hydrophobic shell, and a hydrated polymer layer. This method can provide a simple but efficient way for the fabrication and in-situ characterization of carbon nanotube-based nano particles with a structure-tunable encapsulation.

A method for the functionalization of carbon nanotubes with structure-tunable polymeric encapsulation layers and structural characterization using small-angle neutron scattering is presented.

Funcionalización de pared simple nanotubos de carbono con Thermo-reversibles copolímeros de bloque y Caracterización de ángulo pequeño dispersión de neutrones

We demonstrate a protocol for single-walled carbon nanotube functionalization using thermo-sensitive PEO-PPO-PEO triblock copolymers in an aqueous ...

The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified with furfurylamine to graft furan groups to the rubber backbone. These pendant furan groups are then cross-linked with a bis-maleimide via a Diels-Alder coupling reaction. Both reactions can be performed under a broad range of experimental conditions and can easily be applied on a large scale. The material properties of the resulting Diels-Alder cross-linked rubbers are similar to a peroxide-cured ethylene/propylene/diene rubber (EPDM) reference. The cross-links break at elevated temperatures (&#62; 150 &#176;C) via the retro-Diels-Alder reaction and can be reformed by thermal annealing at lower temperatures (50-70 &#176;C). Reversibility of the system was proven with infrared spectroscopy, solubility tests and mechanical properties. Recyclability of the material was also shown in a practical way, i.e., by cutting a cross-linked sample into small parts and compression molding them into new samples displaying comparable mechanical properties, which is not possible for conventionally cross-linked rubbers.

A simple two-step approach involving rubber modification and cross-linking yields fully reworkable, elastic rubber products.

La preparación y propiedades de termo-reversible reticulado Química Caucho Vía de Diels-Alder

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ...

Monitoring the Effects of Illumination on the Structure of Conjugated Polymer Gels Using Neutron Scattering

We demonstrate a protocol to effectively monitor the gelation process of a high concentration solution of conjugated polymer both in the presence and absence of white light exposure. By instituting a controlled temperature ramp, the gelation of these materials can be precisely monitored as they proceed through this structural evolution, which effectively mirrors the conditions experienced during the solution deposition phase of organic electronic device fabrication. Using small angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) along with appropriate fitting protocols we quantify the evolution of select structural parameters throughout this process. Thorough analysis indicates that continued light exposure throughout the gelation process significantly alters the structure of the ultimately formed gel. Specifically, the aggregation process of poly(3-hexylthiophene-2,5-diyl) (P3HT) nano-scale aggregates is negatively affected by the presence of illumination, ultimately resulting in the retardation of growth in conjugated polymer microstructures and the formation of smaller scale macro-aggregate clusters.

A protocol for the analysis of gels formed from the optoelectronic conjugated polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) using small and ultra-small angle neutron scattering in both the presence and absence of illumination is presented.

Supervisar los efectos de iluminación en la estructura de los geles de polímero conjugado mediante dispersión de neutrones

We demonstrate a protocol to effectively monitor the gelation process of a high concentration solution of conjugated polymer both in the presence and ...

Microfluidic Dry-spinning and Characterization of Regenerated Silk Fibroin Fibers

The protocol demonstrates a method for mimicking the spinning process of silkworm. In the native spinning process, the contracting spinning duct enables the silk proteins to be compact and ordered by shearing and elongation forces. Here, a biomimetic microfluidic channel was designed to mimic the specific geometry of the spinning duct of the silkworm. Regenerated silk fibroin (RSF) spinning doped with high concentration, was extruded through the microchannel to dry-spin fibers at ambient temperature and pressure. In the post-treated process, the as-spun fibers were drawn and stored in ethanol aqueous solution. Synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) technology was used to investigate the microstructure of single RSF fibers, which were fixed to a sample holder with the RSF fiber axis normal to the microbeam of the X-ray. The crystallinity, crystallite size, and crystalline orientation of the fiber were calculated from the WAXD data. The diffraction arcs near the equator of the two-dimensional WAXD pattern indicate that the post-treated RSF fiber has a high orientation degree.

A protocol for the microfluidic spinning and microstructure characterization of regenerated silk fibroin monofilament is presented.

Seco de microfluidos-spinning y caracterización de las fibras regeneradas fibroína de seda

The protocol demonstrates a method for mimicking the spinning process of silkworm. In the native spinning process, the contracting spinning duct enables ...

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). ...

Time-resolved Photophysical Characterization of Triplet-harvesting Organic Compounds at an Oxygen-free Environment Using an iCCD Camera

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables the acquisition of photoluminescence spectra covering the time regime from nanoseconds up to 0.1 s. This enables us to follow the changes in the intensity (decay) and emission of the spectra over time. Using this method, it is possible to study diverse photophysical phenomena, such as the emission of phosphorescence, and the contributions of prompt and delayed fluorescence in molecules showing thermally activated delayed fluorescence (TADF). Remarkably, all spectra and decays are obtained in a single experiment. This can be done for solids (thin film, powder, crystal) and liquid samples, where the only limitations are the spectral sensitivity of the camera and the excitation wavelength (532 nm, 355 nm, 337 nm, and 266 nm). This technique is, thus, very important when investigating the excited state dynamics in organic emitters for their application in organic light-emitting diodes and other areas where triplet harvesting is of paramount importance. Since triplet states are strongly quenched by oxygen, emitters with efficient TADF luminescence, or those showing room temperature phosphorescence (RTP), must be correctly prepared in order to remove any dissolved oxygen from solutions and films. Otherwise, no long-lived emission will be observed. The method of degassing solid samples as presented in this work is basic and simple, but the degassing of liquid samples creates additional difficulties and is particularly interesting. A method of minimizing solvent loss and changing the sample concentration, while still enabling to remove oxygen in a very efficient and a repeatable manner, is presented in this work.

Here, we present a method of the spectroscopic characterization of organic molecules by means of time-resolved photoluminescence spectroscopy on the nanosecond-to-millisecond timescale in oxygen-free conditions. Methods to efficiently remove oxygen from the samples and, thus, limit luminescence quenching are also described.

Tiempo-resolved fotofísicas caracterización de trío cosecha compuestos orgánicos en un libre de oxígeno ambiente usando un iCCD cámara

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables ...