The authors have no acknowledgements.

1. Síntesis de CMP Thin Films través de la adición secuencial <ol><li> Autoensamblada monocapa (SAM) funcionalización de oro sobre mica. <ol><li> Prepare la solución 1 mM de 11-tioacetilo-undecano amida de ácido propargılico 14 en etanol (SAM-solución). Mezclar mediante baño ultrasónico hasta que la solución es clara. Proteja la botella de la luz usando papel de aluminio. </li><li> Obtener oro mica recubierta de obleas en atmósfera de argón. Después de la retirada del recipiente de almacenamiento sumerja la oblea mica directamente a la solución SAM durante 18 h. </li><li> Tome el preparado oblea Au-mica de la solución SAM, enjuagar con etanol y se seca bajo una corriente de nitrógeno. Almacenar Después el sustrato protegido de la luz y bajo gas inerte. </li></ol></li><li> Soluciones precursoras. <ol><li> Pesar 18,64 mg Cu-catalizador (tetraquis (acetonitrilo) de cobre (I) hexafluoro-fosfato), 20,83 mg tetraphenylmethane (TPM) -alkyne y 24,22 mg TPM-azida y llenar cada componente en un matraz Schlenk separado.Ver Figura 1 para TPM-alquino y TPM-azida, la síntesis se describe en la referencia 15. Evacuar y vuelva a llenar con gas inerte (N2 o argón) 3 veces. </li><li> Añadir 25 ml de tetrahidrofurano exento de agua (THF) a cada matraz Schlenk. Proteja los frascos con TPM-azida y TPM-alquino de la luz usando papel de aluminio. </li></ol></li><li> Preparar aparato para la fabricación de CMP. Nota: El aparato de síntesis se muestra en la Figura 2. <ol><li> Use un matraz de fondo redondo de 250 ml un cuello. Rellene 130 ml de THF. Ponga el sustrato preparado revestido con alquino terminado SAM en el compartimiento de la muestra. Utilice un soporte de muestra, de modo que el sustrato está de pie en posición vertical. </li><li> Conectar el aparato a la línea Schlenk través de la unión en la parte superior del refrigerador de reflujo. </li><li> Evacue y ventile con gas inerte 3 veces. </li></ol></li><li> La adición secuencial en condiciones inertes. <ol><li> Ajuste el calentador a 90 ° C y espere hasta que el THF es refundente. </li><li> Vamos a cabo THF desde el compartimento de la muestra sobre la salida en la parte inferior del compartimento de la muestra. Cierre la salida. </li><li> Dar 1 ml de la solución de TPM-azida preparada y 0,5 ml de la solución de Cu (I) catalizador para el compartimento de la muestra a través de la tapa roscada con tabique. Utilice una jeringa con una aguja hueca para transferir la secuencialmente soluciones del matraz Schlenk al aparato de reacción. Nota: La secuencia no tiene ninguna influencia a la reacción. </li><li> Espere aproximadamente 30 min. </li><li> Vamos a cabo la solución de reacción sobre la salida en la parte inferior del compartimento de la muestra. Cierre la salida y recoger el THF condensada para enjuagar la muestra. Espere aproximadamente 30 min. </li><li> Deje que la solución de enjuague sobre la salida en la parte inferior del compartimento de la muestra. Cierre la salida. </li><li> Dar 1 ml de la solución de TPM-alquino preparado y 0,5 ml de la solución de Cu (I) catalizador para el compartimento de la muestra a través de la tapa roscada con tabique. Use una jeringa con un huecoaguja para transferir la secuencialmente soluciones del matraz Schlenk al aparato de reacción. Nota: La secuencia no tiene ninguna influencia a la reacción. </li><li> Espere aproximadamente 30 min. </li><li> Vamos a cabo la solución de reacción sobre la salida en la parte inferior del compartimento de la muestra. Cierre la salida y recoger el THF condensada para enjuagar la muestra. Espere aproximadamente 30 min. </li><li> Repetir los pasos 1.4.3 a 1.4.9 hasta que se alcanza la cantidad deseada de capas. Nota: Una capa es de aproximadamente 1 nm de espesor. </li><li> Saque el sustrato mica recubierta-CMP, enjuagarlo con THF, etanol y se seca bajo una corriente de nitrógeno. </li></ol></li></ol> 2. Transferencia de CMP nanomembranes <ol><li> El poli (metacrilato de metilo) (PMMA) solución. <ol><li> Preparar una solución de 4% (en peso) PMMA (M 996 kDa) en acetato de etilo. Disolver el PMMA utilizando baño ultrasónico hasta que la solución es clara. </li></ol></li><li> Girar recubrimiento de la solución de PMMA. <ol><li> Ajuste el dispositivo de recubrimiento de incremento para la ARtiempo mp 10 segundos de 0 a 4.000 rpm, tiempo de mantenimiento de 40 segundos y el tiempo de rampa 10 s de 4.000 a 0 rpm. </li><li> Coloque el sustrato mica recubierta CMP en el revestidor de giro y poner la solución de PMMA en la oblea hasta que esté completamente cubierto. Inicie el revestidor de giro. </li><li> Una vez finalizada recubrimiento por rotación, se coloca la muestra durante 5 minutos en una placa de calentamiento a 90 ° C. </li><li> Cortar 1 mm de cada borde del sustrato de mica recubierta. Utilice una tijera para cortar los bordes. </li></ol></li><li> Transferencia de PMMA recubierta CMP nanomembrana. <ol><li> Prepare la solución de I2 / KI / H2O (1: 4: 40 m / m / m) y de KI / H2O (01:10 m / m). </li><li> Llene la solución de I2 / KI H2O en unos 150 ml de cristalización plato y rellenar la solución de KI / H2O en 100 ml de cristalización plato. Ponga el oro CMP PMMA recubierta sobre el sustrato de mica, con mica en contacto a la solución, en la parte superior de la I 2 / KI / H 2 O solución. Tenga cuidado de que no se hunde.Espere al menos 5 minutos. </li><li> Ponga el sustrato de mica recubierta de oro CMP PMMA de la I 2 / KI / H 2 O solución en la parte superior de la solución KI / H 2 O, con mica en contacto a la solución. Tenga cuidado de que no se hunde. Espere al menos 5 minutos. </li><li> Llenar de agua destilada en unos 250 ml de cristalización plato. Pele el / CMP película / oro PMMA de la mica. Para ello, mediante la inmersión ligeramente el sustrato, comenzando desde un borde, en agua destilada. Mantenga el sustrato de manera que la mica está apuntando al agua. Nota: El procedimiento se muestra en la Figura 3. </li><li> Dip-capa del PMMA / CMP / oro en la oblea de silicio. Para ello, se acerca el PMMA / CMP / oro lentamente con la oblea hasta que toque el borde de la piscina PMMA / membrana / oro CMP. Tire de la oblea de silicio lentamente, una vez que la oblea de Si-está en contacto con el / la membrana CMP / oro PMMA. </li><li> Pele el / CMP / película de oro PMMA fuera de la oblea de silicio. Haga esto sumergiendo poco el sustrato, a partir de un edge, en el I 2 / KI / H 2 O solución. Espere 15 min. </li><li> Después de que el oro está completamente grabado, transferir la membrana PMMA / CMP al agua a través de la oblea de silicio. Espere 15 min. </li><li> Repita el paso 2.3.7 tres veces para lavar la membrana con agua. </li><li> Transferir la membrana de PMMA / CMP lavado al sustrato deseado, por ejemplo, un portaobjetos de microscopio recubierto de oro o una oblea de silicio, a través del método mencionado en el paso 2.3.5. Deje secar el sustrato de PMMA / CMP al aire durante al menos 2 horas. </li></ol></li><li> Disolución de PMMA. <ol><li> Ponga el sustrato de PMMA / CMP en acetona. Espere 30 min. Saque el sustrato y enjuague con acetona. </li><li> Repita el paso 2.4.1 en tres ocasiones. </li><li> Deje secar el sustrato CMP durante al menos 2 horas. </li></ol></li></ol>

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A., W&#246;ll, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=MOF+thin+films:+existing+and+future+applications.">MOF thin films: existing and future applications.</a> Chemical Society Reviews. 40 (2), 1081-1106 (2011).</li><li>Liu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Deposition+of+Metal-Organic+Frameworks+by+Liquid-Phase+Epitaxy:+The+Influence+of+Substrate+Functional+Group+Density+on+Film+Orientation.">Deposition of Metal-Organic Frameworks by Liquid-Phase Epitaxy: The Influence of Substrate Functional Group Density on Film Orientation.</a> Materials. 5 (9), 1581-1592 (2012).</li><li>Such, G. K., Quinn, J. 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J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanoporous+organic+polymer+networks.">Nanoporous organic polymer networks.</a> Progress in Polymer Science. 37 (4), 530-563 (2012).</li><li>Muller, T., Br&#228;se, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Click+Chemistry+Finds+Its+Way+into+Covalent+Porous+Organic+Materials.">Click Chemistry Finds Its Way into Covalent Porous Organic Materials.</a> Angewandte Chemie International Edition. 50 (50), 11844-11845 (2011).</li><li>Tsotsalas, M., Addicoat, M. 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The authors have nothing to disclose.

Para la síntesis de la CMP-película de la solución del catalizador tiene que ser fresco. Un catalizador roto (es decir, oxidada) se indica mediante una coloración azul de la solución. La solución fresca es incoloro. Un punto crucial es cortar los bordes del sustrato mica después de revestimiento por rotación PMMA. También defectos en el sustrato se deben cortar, es decir, cada punto fuera el PMMA pueda entrar en contacto con el sustrato de mica, a causa de una capa de oro que falta. De lo contrario la capa de oro no puede separarse del sustrato mica fácilmente. También en relación con el desprendimiento de la capa de oro del sustrato mica, después de la separación comenzó en un borde o esquina, se debe continuar por este borde hasta la capa de oro es completamente independiente. Durante la transferencia de las membranas PMMA / CMP con una oblea de silicio, por ejemplo, del baño de agua a la solución de yodo o de la solución de yodo al agua, es importante quela membrana no se seque. Una vez que la membrana se seca en el Si-oblea, es casi imposible separar de nuevo. Después de disolver el PMMA, cada etapa de aclarado debería realizarse con cautela; un borde solapado de la membrana puede conducir a una eliminación de la membrana del sustrato. En el momento en el tamaño de las muestras está limitado por el tamaño del compartimento de la muestra. El espesor de las películas fabricadas CMP está limitada por el tiempo de reacción, ya que cada ciclo necesita alrededor de 2 hr. Para una síntesis de menos mano de obra intensiva el aparato de reacción puede ser modificado mediante la adición de un sifón; Como resultado, el compartimento de la muestra se vacía de forma automática, comparable a un extractor Soxhlet. Nuestra técnica combina el procesamiento de películas de polímeros ultrafinas microporosos conjugados y el uso de un sustrato sacrificial para obtener nanomembranes CMP. La síntesis de nanomembranes CMP aún no era posible debido a labaja capacidad de procesamiento de polvo de CMP. En comparación con otras técnicas, por ejemplo la producción de SURMOFs 7, hemos logrado una reducción de la cantidad de disolvente utilizado. Especialmente la etapa de aclarado en el caso de la producción SURMOF tiene un alto consumo de disolvente, en este caso, debido a la utilización de THF a reflujo, se podría disminuir el consumo de THF drásticamente. Esperamos que el método presentado su aplicación dentro de gas y separación de fases líquido a causa de las posibilidades para ajustar la selectividad y permeabilidad por el control sobre el tamaño de los poros y la afinidad química. Además, la síntesis modular de materiales de CMP a partir de bloques de construcción funcionales adecuados para otras aplicaciones, tales como catálisis, detección, o la electrónica orgánica, también podría beneficiarse de el método de procesamiento descrito.

The preparation of ultra-thin polymer membranes is of high interest for applications in gas separation and nanofiltration. Challenges in the synthesis are represented by (a) the control of the membrane thickness and the homogeneity and (b) transfer of such fragile membranes. To overcome challenge (a), molecular layer-by-layer synthesis1 has shown great promise in controlling the thickness and homogeneity of thin films grown at the solid-liquid interface.2,3 Controlling the number of layers linearly controls the film thickness. The l-b-l method has been successfully used to fabricate surface mounted metal organic frameworks (SURMOFs),4-7 also the synthesis of thin polymer films via l-b-l reaction of polymer chains was demonstrated.8 The challenge (b) concerns the handling of these ultra-thin membranes. To avoid rupture or wrinkling of the nanomembranes sacrificial supports of coatings have shown great promise. 9
Here we will present a detailed protocol for synthesis of conjugated microporous polymer (CMP)10-13 thin films through sequential addition of the molecular building blocks, with desired thickness and composition. The preparation of free-standing CMP nanomembranes is achieved by using a sacrificial support. To handle and transfer the CMP nanomembranes to other supports we will describe a simple protocol to protect the membranes with sacrificial coatings and their upfloating to the liquid air interface and subsequent transfer using dip-coating.

<table>
	<tbody>
		<tr>
			<td>Acetone</td>
			<td>VWR BDH Prolabo</td>
			<td>20066.330</td>
			<td>AnalR NORMAPUR</td>
		</tr>
		<tr>
			<td>Potassium iodide</td>
			<td>VWR BDH Prolabo</td>
			<td>26846.292</td>
			<td>AnalR NORMAPUR</td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>VWR BDH Prolabo</td>
			<td>23882.321</td>
			<td>AnalR NORMAPUR</td>
		</tr>
		<tr>
			<td>Tetrahydrofurane (THF)</td>
			<td>VWR BDH Prolabo</td>
			<td>28559.320</td>
			<td>HiPerSolv CHROMANORM</td>
		</tr>
		<tr>
			<td>THF waterfree</td>
			<td>Merck Millipore</td>
			<td>1.08107.1001</td>
			<td>SeccoSolv</td>
		</tr>
		<tr>
			<td>Iodine</td>
			<td>Sigma-Aldrich</td>
			<td>20,777-2</td>
			<td></td>
		</tr>
		<tr>
			<td>Tetrakis(acetonitrile)copper(I)hexafluoro-phosphate</td>
			<td>Sigma-Aldrich</td>
			<td>346276-5G</td>
			<td></td>
		</tr>
		<tr>
			<td>Poly(methyl methacrylate) 996 kDa (PMMA)</td>
			<td>Sigma-Aldrich</td>
			<td>182265-25G</td>
			<td></td>
		</tr>
		<tr>
			<td>1.1.1.1 Methanetetrayltetrakis(4-azidobenzene) (TPM-azide)</td>
			<td></td>
			<td></td>
			<td>provided by AK Prof. Br&#228;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to9</td>
		</tr>
		<tr>
			<td>1.1.1.1 Methanetetrayltetrakis(4-ethinylenebenzene) (TPM-alkyne)</td>
			<td></td>
			<td></td>
			<td>provided by AK Prof. Br&#228;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to9</td>
		</tr>
		<tr>
			<td>11-thioacetyl-undecaneacid propargylamide</td>
			<td></td>
			<td></td>
			<td>provided by AK Prof. Br&#228;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to8</td>
		</tr>
		<tr>
			<td>gold/titan coated silicium-wafer</td>
			<td>Georg Albert PVD, 76857 Silz, Germany</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>gold coated mica</td>
			<td>Georg Albert PVD, 76857 Silz, Germany</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

layer-by-layer synthesis and transfer of freestanding conjugated microporous polymer nanomembranes

CMP como grandes materiales de área superficial han atraído creciente interés recientemente, debido a su alta variabilidad en la incorporación de grupos funcionales en combinación con su sobresaliente estabilidad térmica y química, y densidades bajas. Sin embargo, su naturaleza insoluble causa problemas en su procesamiento ya que las técnicas generalmente aplicados como recubrimiento por centrifugación no están disponibles. Especialmente para aplicaciones de membrana, en las que es deseable la tramitación de CMP como películas delgadas, los problemas de procesamiento han impedido su aplicación comercial. Aquí se describe la síntesis interfacial de CMP películas delgadas sobre sustratos funcionalizados vía (LBL) la síntesis molecular capa por capa. Este proceso permite la preparación de películas con grosor y la composición deseada y los gradientes de composición incluso deseados. El uso de soportes de sacrificio permite la preparación de membranas Autosoportados por disolución del soporte después dela síntesis. Para manejar este tipo de membranas independientes ultrafinas la protección con recubrimientos de sacrificio mostró una gran promesa, para evitar la rotura de las nanomembranes. Para transferir los nanomembranes al sustrato deseado, las membranas revestidas se upfloated en la interfase aire-líquido y luego se transfieren a través de recubrimiento por inmersión.

Las membranas se caracterizan por espectroscopia de absorción reflexión de infrarrojos (IRRAS). 16 La Figura 4 muestra IRRA-espectros a partir de una CMP-membrana transferido a una oblea de oro. Bandas típicas de las vibraciones de la columna vertebral aromático están a 1.605 cm -1, 1.515 cm -1 y 1.412 cm -1. Grupos alquino y azida sin reaccionar pueden ser observados por bandas características a 2.125 cm -1 y 1.227 cm-1. La figura 5 muestra una imagen de microscopía electrónica de barrido (SEM). La membrana independiente es claramente visible. <img alt="Figura 1" src="/files/ftp_upload/53324/53324fig1highres.jpg" width="550" /> Figura 1. bloques de construcción moleculares. Estructuras moleculares de (A), TPM alquino y (B) TPM-azida. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig1large.jpg" target="_blank">Pl</a>aliviar clic aquí para ver una versión más grande de esta figura. <img alt="Figura 2" src="/files/ftp_upload/53324/53324fig2highres.jpg" width="700" /> Aparato 2. Reacción figura. La configuración de la síntesis de capa por capa de las películas delgadas de CMP. El aparato consiste en una matraz de fondo redondo de cuello como reservorio para el THF, el tubo de vapor para dirigir el vapor de THF al enfriador de reflujo. Los condensados ​​de THF se recogen en el compartimento de la muestra. Los productos químicos se pueden insertar sobre el tapón roscado con un septo. El compartimiento de la muestra se vacía a través de la salida del fondo. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig2large.jpg" target="_blank">Por favor haga clic aquí para ver una versión más grande de esta figura.</a> <img alt="figura 3" src="/files/ftp_upload/53324/53324fig3highres.jpg" width="500" /> Figura 3. Extracción de mica. </strong&gt; La membrana PMMA / CMP está empezando a separar desde el borde de la mica-sustrato. La mitad de la PMMA / CMP está flotando en la superficie del agua, la otra mitad está todavía unido al sustrato de mica. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig3large.jpg" target="_blank">Por favor haga clic aquí para ver una versión más grande de esta figura.</a> <img alt="Figura 4" src="/files/ftp_upload/53324/53324fig4highres.jpg" width="700" /> Figura 4. IRRA-espectros. IRRA-espectros a partir de una CMP-membrana se transfirió a un oro-oblea. Las bandas de las vibraciones de la cadena principal aromática en 1.605, 1.515 y 1.412 cm -1 son característicos para la CMP-membrana. La vibración de CD se debe al fondo utilizado. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig4large.jpg" target="_blank">Haga clic aquí para ver una versión más grande de esta figura.</a> Figura 5. SEM-imagen. SEM-Imagen de la CMP-membrana. La membrana independiente está muy bien muestra. (Reproducido con permiso del Lindemann, P et al Chem Mater 26, 7189 -.... 7193. Derechos de Autor 2014 American Chemical Society.) <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig5large.jpg" target="_blank">Haga clic aquí para ver una versión más grande de esta figura.</a>

Watch this Scientific Journal Video about Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes at JoVE.com

Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes

In this paper we describe the interfacial synthesis of conjugated microporous polymers (CMP) on sacrificial substrates, and the dissolution of the substrate for the preparation of freestanding CMP nanomembranes. In addition, we will describe how the fragile nanomembranes can be transferred to other substrates.

Síntesis de capa por capa y Transferencia de Independientes conjugados microporosas de polímero nanomembranes

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in ...

layer-layer-synthesis-transfer-freestanding-conjugated-microporous

Nanyang Technological University

Research

JoVE Journal

Chemistry

9.3K vistas.  Karlsruhe Institute of Technology. In this paper we describe the interfacial synthesis of conjugated microporous polymers (CMP) on sacrificial substrates, and the dissolution of the substrate for the preparation of freestanding CMP nanomembranes. In addition, we will describe how the fragile nanomembranes can be transferred to other substrates.

Video: Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes

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

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.

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 ...

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 ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

Síntesis y caracterización de supramoleculares Coloides

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

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 ...

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 ...

Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule on the vibrational level of energy. Raman and IR spectroelectrochemistry can be used for advanced characterization of the structural changes in the organic electroactive compounds. Here, the step-by-step analysis by means of Raman and IR spectroelectrochemistry is shown. Raman and IR spectroelectrochemical techniques provide complementary information about structural changes occurring during an electrochemical process, i.e. allows for the investigation of redox processes and their products. The examples of IR and Raman spectroelectrochemical analysis are presented, in which the products of the redox reactions, both in solution and solid state, are identified.

A protocol of step-by-step Raman and IR spectroelectrochemical analysis is presented.

Raman y métodos IR electroquímicas como herramientas para analizar compuestos orgánicos conjugados

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule ...

Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. Conductive polymers, poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT), and a semiconducting polymer, poly(thieno[3,2-b]thiophene) (PTT), were deposited on unconventional highly-disordered and textured substrates with high surface areas, such as paper, towels and fabrics. This reported deposition chamber is an improvement of previous vapor reactors because our system can accommodate both volatile and nonvolatile monomers, such as 3,4-propylenedioxythiophene and thieno[3,2-b]thiophene. Utilization of both solid and liquid oxidants are also demonstrated. One limitation of this method is that it lacks sophisticated in situ thickness monitors. Polymer coatings made by the commonly used solution-based coating methods, such as spin-coating and surface grafting, are often not uniform or susceptible to mechanical degradation. This reported vapor phase deposition method overcomes those drawbacks and is a strong alternative to common solution-based coating methods. Notably, polymer films coated by the reported method are uniform and conformal on rough surfaces, even at a micrometer scale. This feature allows for future application of vapor deposited polymers in electronics devices on flexible and highly textured substrates.

This paper presents a protocol for reactive vapor deposition of poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), and poly(thieno[3,2-b]thiophene) films on glass slides and rough substrates, such as textiles and paper.