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 começar, verifique todas as fichas de dados de materiais relevantes (MSDSs). Muitos dos produtos químicos usados ​​nos procedimentos de síntese e de aplicação são tóxicos. Por favor, siga todas as práticas de segurança apropriadas e utilizar equipamentos adequados de proteção (jaleco, calças compridas, sapatos fechados, óculos de segurança, luvas). Por favor, use todos os equipamentos de protecção individual criogênico ao manusear nitrogênio líquido para as medições de adsorção de nitrogênio (luvas isolantes, protetor facial). 1. Porous Polymer Monolith Preparação em massa e Capilar formato de coluna <ol><li> Massa de polímero Monolith para Caracterização <ol><li> Purifica-se o estireno, divinilbenzeno e ácido metacrílico através de uma coluna de alumina básica, de modo a remover os inibidores de polimerização. Colocar 10 g de alumina básica em 25 ml de uma seringa de plástico descartável com um tampão de lã de vidro embalado na ponta da seringa. Fazer passar cerca de 10 ml do monómero através da coluna. </li><li> Carregar os monómeros de estireno (50 mg, 100 mg de divinilbenzeno e 50 mg de ácido metacrílico) e os agentes de formação de poros (300 mg de tolueno e 300 mg de isooctano) em um frasco de vidro de 1 ml. Adicionar o iniciador da polimerização, 4 mg de 2,2&#39;-azobisisobutironitrilo (AIBN, 1% em relação aos monómeros). </li><li> Homogeneizar a mistura por ultra-sons durante 10 min. Remover o oxigénio dissolvido por borbulhamento de azoto através do líquido durante 10 min. Fecha-se o frasco com tampa de película de parafina e colocá-lo num banho de água a 60 ° C durante 6 horas para polimerizar a mistura. </li><li> Arrefecer à temperatura ambiente e quebrar o frasco cuidadosamente. Transferir o monólito de polímero em um cartucho de extracção de celulose. Colocar o dedal de extracção para uma câmara de extracção de Soxhlet e montá-lo para um balão de fundo redondo que contém um volume de metanol, que é pelo menos três vezes o volume da câmara de extracção. Montar um condensador para a parte superior da câmara de extracção. Realizar a extração Soxhlet fervendo o metanoldurante 16 h, assegurando a completa remoção dos monómeros que não reagiram e agentes de formação de poro. </li><li> Secar durante a noite numa estufa de vácuo a 60 ° C. Confirmar a presença de grupos funcionais carboxílicos para anexar o PCP por Fourier Transform Infrared Spectroscopy (FT-IR). Medir a área de superfície por adsorção de porosimetria de azoto. </li></ol></li><li> Funcionalização da sílica Capilares para a preparação de colunas monolíticas <ol><li> Corte de 2 m de uma ID de 100 uM capilar de sílica fundida revestido com poliimida. Ligue-o a uma seringa de vidro de 0,25-0,50 ml e lava-se o capilar com acetona. Remover a acetona por lavagem da coluna capilar com água. </li><li> A fim de activar o revestimento de sílica interno do capilar, utilizar uma bomba de seringa a fluir uma solução aquosa de NaOH 0,2 M em 0,25 mL / min durante 30 min. Lavar com água até o efluente estar neutro. </li><li> Use tiras de papel de pH para verificar efluente pH. Em ordem para protonar os grupos silanol do capilar, uma bomba aqueo 0,2 Msolução de HCl-nos através do capilar em 0,25 mL / min durante 30 min. Lavar com água até o efluente estar neutro. Enxágüe com etanol. </li><li> Bombear a 20% (w / w) de uma solução de etanol 3- (trimetoxisilil) metacrilato de propilo (pH 5 ajustado com ácido acético) a 0,25 mL / min durante 1 hora. Neste passo, o capilar de sílica funcionalizado com grupos de vinil, a fim de fixar o monólito de polímero para a superfície interior dos capilares. </li><li> Lavar com acetona e seco numa corrente de azoto e deixar à temperatura ambiente durante a noite antes da utilização. Corte o capilar em pedaços mais curtos de comprimento 20 cm. </li></ol></li><li> Preparação das colunas capilares Monolithic <ol><li> Prepara-se uma mistura de polimerização idêntico para o monólito de polímero a granel (secção 1.1), num frasco de vidro de 1 ml com um septo de borracha. Adicionar iniciador AIBN 1% em relação aos monómeros. Homogeneizar a mistura por ultra-sons durante 10 min. </li><li> Purgar a mistura com azoto polimerização por acoplamento de um capilar de sílica não-funcionalizadoa um fluxo de azoto. <ol><li> Inserir o capilar corrente de azoto, através do septo de borracha do frasco e mergulhá-lo na mistura de polimerização, de modo que o azoto bolhas através do líquido. Deixe a tampa do frasco levemente solto para evitar excesso de pressão. Purgar para 10 min. </li><li> Levantar o capilar corrente de azoto a partir da mistura de polimerização para o espaço superior do frasco, e fechar firmemente a tampa. Inserir um capilar funcionalizada através do septo para dentro da mistura de polimerização. O excesso de pressão gerada no capilar através do azoto injectado na câmara de expansão bombeia a mistura de polimerização através do capilar funcionalizado. </li><li> Recolha algumas gotas de mistura de polimerização a partir do efluente do capilar para assegurar que ele está completamente cheio e fechá-lo com um septo de borracha. Aqui o capilar para fora do frasco com muito cuidado e fechar a entrada do tubo capilar com um septo de borracha. </li></ol></li><li> Polimerizar o mixtura contido no capilar em um banho de água a 60 ° C durante 6 h. Arrefecer à temperatura ambiente e corte de alguns milímetros de ambas as extremidades do capilar. Remover os monómeros não reagidos e agentes de formação de poros através de lavagem da coluna com acetonitrilo utilizando uma bomba de HPLC em 3 mL / min durante 30 min. Verifique contrapressão da coluna capilar. </li></ol></li></ol> 2. Crescimento da Ferro-benzenetrycarboxylate (FeBTC) PCP <ol><li> Crescimento do FeBTC MOPH em um polímero Monolith massa para Caracterização <ol><li> Moer o monólito previamente seca utilizando um almofariz e pilão. </li><li> Imergir 100 mg do pó monólito em 5 ml de 2 mM de FeCl 3 .6H 2 O em etanol durante 15 min. Filtro de vácuo utilizando um filtro de nylon (0,22 um) e lava-se o pó com etanol. Mergulha-se o pó monólito em 5 ml de mM de ácido benzeno- 1,3,5-2 (BTC) em etanol durante 15 min. Filtro de vácuo utilizando um filtro de nylon (0,22 um) e lava-se o pó com etanol.</li><li> Repita o passo número 2 como desejar. O crescimento do revestimento orgânico-metálico final será definido pelo número de ciclos aplicados. Normalmente, entre 10 e 30 ciclos são realizados. Confirmar a presença de novos poros por porosimetria de adsorção de azoto. Medir a quantidade de locais adicionais de metal por análise termogravimétrica (TGA). </li></ol></li><li> Crescimento do FeBTC MOPH numa coluna capilar monolítico para o enriquecimento de fosfopéptidos <ol><li> Utilizando uma bomba de seringa. Lavar o monólito capilar com 2 mM de FeCl 3 .6H 2 O em etanol durante 15 minutos a 2 uL / min. Lava-se com etanol durante 15 minutos a 2 uL / ​​min. Lavar o monólito capilar com uma BTC 2 mM em etanol durante 15 minutos a 2 uL / ​​min. Lava-se com etanol durante 15 minutos a 2 uL / ​​min. </li><li> Repita o passo 1 se o desejar. O crescimento do revestimento orgânico-metálico final será definido pelo número de ciclos realizados. </li></ol></li></ol> 3. Proteína A digestão e Enrichment de Fosfopeptídeos <ol><li> A digestão de proteínas <ol><li> Dissolve-se 0,5 ml de leite não gordo em 1 ml de água e dividi-lo em fracções de 200 uL. </li><li> Para a digestão de proteínas adicionar 160 ul de 1 M de bicarbonato de amónio e 50 ul de 45 mM de ditiotreitol a cada fracção, a fim de clivar as ligações dissulfureto. Incubar a 50 ° C num Thermomixer durante 15 min. </li><li> Adicionar gradualmente 50 mL de uma solução aquosa de iodoacetamida 100 mM, enquanto que a solução foi arrefecida até à temperatura ambiente. Iodoacetamida irá evitar a formação de novas ligações dissulfureto. </li><li> Incubar no escuro durante 15 min à temperatura ambiente. Adicionar 1 ml de água desionizada. Adicionar 2 mg de tripsina e digerir proteínas num termomisturador a 37 ° C durante 14 h. </li><li> Terminar a digestão por acidificação com 10 ul de ácido trifluoroacético a 1% e colocando-o no termomisturador durante 5 min à temperatura ambiente. Armazenar as proteínas digeridas a -20 ° C. </li></ol></li><li> Enriquecimento de fosfopéptidos usando uma coluna capilar MOPH. <ol><li> Lavar a coluna com 100 mL de uma mistura 4: 1 de acetonitrilo contendo um ácido trif luoroacético a 0,1% durante 10 min a um caudal de 1 mL / min. Bombear a digestão da proteína através da coluna a 2 mL / min durante 30 min. </li><li> Lavar os peptídeos não fosforilados novamente com uma mistura 4: 1 de acetonitrilo contendo um ácido trif luoroacético a 0,1% durante 10 min a um caudal de 1 mL / min. Lava-se com água durante 10 min a um caudal de 1 mL / min. </li><li> Fosfopéptidos eluir usando uma solução tampão de pH 7 fosfato 250 mM bombeada a 1 mL / min durante 15 min. Recolhe-se o eluente num frasco e dessalinizar a solução utilizando um protocolo padrão de 19. Preparar um ácido / ml 2,5-di-hidroxibenzóico 2 mg a usá-lo como a matriz para a espectrometria de massa de laser assistida por matriz dessorção / ionização de tempo-de-voo (MALDI-TOF-MS). Tirado 2 ul de ácido 2,5-di-hidroxibenzóico em ponta para eluir o phosphopeptides e identificá-los diretamente sobre a placa MALDI. </li><li> Analisar as manchas por MALDI-TOF-MS e regenerar a coluna por lavagem com água e em seguida com metanol. </li></ol></li></ol>

<ol>
	<li>Li, H., Eddaoudi, M., O&#8217;Keeffe, M., Yaghi, O. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Design+and+synthesis+of+an+exceptionally+stable+and+highly+porous+metal-organic+framework.">Design and synthesis of an exceptionally stable and highly porous metal-organic framework.</a> Nature. 402, 276-279 (1999).</li><li>Kitagawa, S., Kitaura, R., Noro, S. i. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Functional+porous+coordination+polymers.">Functional porous coordination polymers.</a> Angew. Chem. Int. Ed. 43, 2334-2375 (2004).</li><li>Furukawa, H., Cordova, K. E., O&#8217;Keeffe, M., Yaghi, O. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+chemistry+and+applications+of+metal-organic+frameworks.">The chemistry and applications of metal-organic frameworks.</a> Science. 341, 974 (2013).</li><li>Ma, S., Zhou, H. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Gas+storage+in+porous+metal-organic+frameworks+for+clean+energy+applications.">Gas storage in porous metal-organic frameworks for clean energy applications.</a> Chem. Commun. 46, 44-53 (2010).</li><li>Li, J. R., Sculley, J., Zhou, H. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-organic+frameworks+for+separations.">Metal-organic frameworks for separations.</a> Chem. Rev. 112, 869-932 (2012).</li><li>Lee, J., Farha, O. K., Roberts, J., Scheidt, K. A., Nguyen, S. T., Hupp, J. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-organic+framework+materials+as+catalysts.">Metal-organic framework materials as catalysts.</a> Chem. Soc. Rev. 38, 1450-1459 (2009).</li><li>Gu, Z. Y., Yang, C. X., Chang, N., Yan, X. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-organic+frameworks+for+analytical+chemistry:+From+sample+collection+to+chromatographic+separation.">Metal-organic frameworks for analytical chemistry: From sample collection to chromatographic separation.</a> Acc. Chem. Res. 45, 734-745 (2012).</li><li>Ahmad, R., Wong-Foy, A. G., Matzger, A. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Microporous+coordination+polymers+as+selective+sorbents+for+liquid+chromatography.">Microporous coordination polymers as selective sorbents for liquid chromatography.</a> Langmuir. 25, 11977-11979 (2009).</li><li>Yang, C. X., Yan, X. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-organic+framework+MIL-101(Cr)+for+high-performance+liquid+chromatographic+separation+of+substituted+aromatics.">Metal-organic framework MIL-101(Cr) for high-performance liquid chromatographic separation of substituted aromatics.</a> Anal. Chem. 83, 7144-7150 (2011).</li><li>Fu, Y. Y., Yang, C. X., Yan, X. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Control+of+the+coordination+status+of+the+open+metal+sites+in+metal-organic+frameworks+for+high+performance+separation+of+polar+compounds.">Control of the coordination status of the open metal sites in metal-organic frameworks for high performance separation of polar compounds.</a> Langmuir. 28, 6802-6810 (2012).</li><li>Gu, Z. Y., Yan, X. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-organic+framework+MIL-101+for+high-resolution+gas-chromatographic+separation+of+xylene+isomers+and+ethylbenzene.">Metal-organic framework MIL-101 for high-resolution gas-chromatographic separation of xylene isomers and ethylbenzene.</a> Angew. Chem. Int. Ed. 49, 1477-1480 (2010).</li><li>Chang, N., Gu, Z. Y., Yan, X. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Zeolitic+imidazolate+framework-8+nanocrystal+coated+capillary+for+molecular+sieving+of+branched+alkanes+from+linear+alkanes+along+with+high-resolution+chromatographic+separation+of+linear+alkanes.">Zeolitic imidazolate framework-8 nanocrystal coated capillary for molecular sieving of branched alkanes from linear alkanes along with high-resolution chromatographic separation of linear alkanes.</a> J. Am. Chem. Soc. 132, 13645-13647 (2010).</li><li>Yu, L. Q., Xiong, C. X., Yan, X. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Room+temperature+fabrication+of+post-modified+zeolitic+imidazolate-90+as+stationary+phase+for+open-tubular+capillary+electrochromatography.">Room temperature fabrication of post-modified zeolitic imidazolate-90 as stationary phase for open-tubular capillary electrochromatography.</a> J. Chromatogr. A. 1343, 188-194 (2014).</li><li>Fu, Y. Y., Yang, C. X., Yan, X. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Incorporation+of+metal-organic+framework+UiO-66+into+porous+polymer+monoliths+to+enhance+the+liquid+chromatographic+separation+of+small+molecules.">Incorporation of metal-organic framework UiO-66 into porous polymer monoliths to enhance the liquid chromatographic separation of small molecules.</a> Chem. Commun. 49, 7162-7164 (2013).</li><li>Lin, C. L., Lirio, S., Chen, Y. T., Lin, C. H., Huang, H. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+novel+hybrid+metal-organic+framework-polymeric+monolith+for+solid-phase+extraction.">A novel hybrid metal-organic framework-polymeric monolith for solid-phase extraction.</a> Chem. Eur. J. 20, 3317-3321 (2014).</li><li>Svec, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Porous+polymer+monoliths:+Amazingly+wide+variety+of+techniques+enabling+their+preparation.">Porous polymer monoliths: Amazingly wide variety of techniques enabling their preparation.</a> J. Chromatogr. A. 1217, 902-924 (2010).</li><li>Shekhah, O., 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=Step-by-step+route+for+the+synthesis+of+metal-organic+frameworks.">Step-by-step route for the synthesis of metal-organic frameworks.</a> J. Am. Chem. Soc. 129, 15118-15119 (2007).</li><li>Shekhah, O., Fu, L., Belmabkhout, Y., Cairns, A. J., Giannelis, E. P., Eddaoudi, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Successful+implementation+of+the+stepwise+layer-by-layer+growth+of+MOF+thin+films+on+confined+surfaces:+mesoporous+silica+foam+as+a+first+case+study.">Successful implementation of the stepwise layer-by-layer growth of MOF thin films on confined surfaces: mesoporous silica foam as a first case study.</a> Chem. Commun. 48, 11434-11436 (2012).</li><li>Saeed, A., Maya, F., Xiao, D. J., Naham-ul-Haq, M., Svec, F., Britt, D. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Growth+of+a+highly+porous+coordination+polymer+on+a+macroporous+polymer+monolith+support+for+enhanced+immobilized+metal+ion+affinity+chromatographic+enrichment+of+phosphopeptides.">Growth of a highly porous coordination polymer on a macroporous polymer monolith support for enhanced immobilized metal ion affinity chromatographic enrichment of phosphopeptides.</a> Adv. Funct. Mater. 24, 5797-5710 (2014).</li><li>Krenkova, J., Lacher, N. A., Svec, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Control+of+selectivity+via+nanochemistry:+Monolithic+capillary+column+containing+hydroxyapatite+nanoparticles+for+separation+of+proteins+and+enrichment+of+phosphopeptides.">Control of selectivity via nanochemistry: Monolithic capillary column containing hydroxyapatite nanoparticles for separation of proteins and enrichment of phosphopeptides.</a> Anal. Chem. 82, 8335-8341 (2010).</li><li>Jabeen, F., 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=Silica-lanthanum+oxide:+Pioneer+composite+of+rare-earth+metal+oxide+in+selective+phosphopeptides+enrichment.">Silica-lanthanum oxide: Pioneer composite of rare-earth metal oxide in selective phosphopeptides enrichment.</a> Anal. Chem. 84, 10180-10185 (2012).</li><li>Hussain, D., 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=Functionalized+diamond+nanopowder+for+phosphopeptides+enrichment+from+complex+biological+fluids.">Functionalized diamond nanopowder for phosphopeptides enrichment from complex biological fluids.</a> Anal. Chim. Acta. 775, 75-84 (2013).</li><li>Aprilita, N. H., 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=Poly(glycidyl+methacrylate/divinylbenzene)-IDA-FeIII+in+phosphoproteomics.">Poly(glycidyl methacrylate/divinylbenzene)-IDA-FeIII in phosphoproteomics.</a> J. Proteom. Res. 4, 2312-2319 (2005).</li><li>Lo, C. Y., Chen, W. Y., Chen, C. T., Chen, Y. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rapid+enrichment+of+phosphopeptides+from+tryptic+digests+of+proteins+using+iron+oxide+nanocomposites+of+magnetic+particles+coated+with+zirconia+as+the+concentrating+probes.">Rapid enrichment of phosphopeptides from tryptic digests of proteins using iron oxide nanocomposites of magnetic particles coated with zirconia as the concentrating probes.</a> J. Proteom. Res. 6, 887-893 (2007).</li><li>Aryal, U. K., Ross, A. R. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enrichment+and+analysis+of+phosphopeptides+under+different+experimental+conditions+using+titanium+dioxide+affinity+chromatography+and+mass+spectrometry.">Enrichment and analysis of phosphopeptides under different experimental conditions using titanium dioxide affinity chromatography and mass spectrometry.</a> Rapid Commun. Mass. Spectrom. 24, 219-231 (2010).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Select Iron Affinity Gel Technical Bulletin. , (2015).</li></ol>

The authors have nothing to disclose.

O monólito de polímero original contém grupos funcionais carboxílicos capazes de ligar-se a metais. Coordenando os locais de metal iniciais sobre o material original, somos capazes de crescer um revestimento PCP (Figura 1A), que incorpora uma série de sites de metal adicionais moldando uma rede microporosa. Isso faz com que os materiais apresentados MOPH atraentes para os procedimentos de extracção ou purificação, onde estão envolvidas as espécies metálicas, tais como a técnica de cromatogr...

Polímeros de coordenação poroso (PCPS) são compostos de coordenação com base em centros metálicos ligados por ligantes orgânicos com repetição de entidades de coordenação que se estende em uma, duas ou três dimensões, que pode ser amorfa ou cristalina 1-3. Nos últimos anos, esta classe de materiais porosos tem atraído a atenção geral devido à sua elevada porosidade, de largura tunability química, e a sua estabilidade. PCP têm sido explorados para uma gama de aplicações incluindo a armazenagem de gás, a separação de gás, e catálise 3-6 e, muito recentemente, as primeiras aplicações analíticas de PCP têm sido descritos 7. Por causa de sua funcionalidade química e alta porosidade PCP avançados têm sido alvo de seu enorme potencial para a melhoria dos processos de purificação e separações cromatográficas, e uma série de relatórios sobre este assunto têm sido publicados 7-13. No entanto, o desempenho de PCP não está neste momento a um equivalenível nt com materiais cromatográficos existentes provavelmente devido à rápida difusão através de grandes espaços vazios interpartículas em camadas preenchidas com estes sólidos devido às suas morfologias tipicamente de forma irregular de suas partículas ou cristais. Esta embalagem irregularmente distribuída leva a um desempenho inferior ao esperado, assim como contrapressões alta coluna e indesejáveis ​​morfologias formato de pico 14,15. A fim de resolver o problema da rápida difusão através dos espaços vazios entre partículas e concomitantemente aumentar o desempenho de PCP para aplicações analíticas, o desenvolvimento de um material híbrido baseado em um monólito de polímero macroporoso 16 que contém o PCP na superfície dos macroporos seria ser desejável. Monólitos de polímero são auto-suficientes, materiais de peça única que possam sustentar fluxo convectivo através de seus poros, o que os torna uma das alternativas mais eficientes para talão de embalagens e têm sido comercializados com sucesso por vários c<html> ompanies 17,18. Monólitos polímero poroso são geralmente baseados na polimerização de um monómero e um agente de reticulação na presença de porogénios, que são tipicamente misturas binárias de solventes orgânicos. Os materiais monolíticos obtidos têm uma estrutura microglobular e uma porosidade elevada e permeabilidade ao fluxo. Uma abordagem simples para unificar destes materiais para preparar um monólito de polímero contendo um PCP baseia-se na adição directa de PCP tal como sintetizada na mistura de polimerização do monólito. Esta abordagem resultou em PCPs principalmente enterrado dentro de um andaime do polímero, e não estar ativo para a continuação da aplicação do material final 14,15. Uma abordagem sintética diferente é claramente necessário, a fim de, por exemplo, desenvolver filmes uniformes de PCP, ou estruturas de metal-orgânicos cristalinos (MOF) onde a maioria dos poros contidos no interior do cristal são acessíveis a partir dos macroporos do monólito de polímero. t &quot;&gt; Aqui relatamos um protocolo simples para a preparação de um material híbrido de polímero orgânico-metálico (MOPH) com base num suporte de polímero macroporosas com grupos funcionais adequados para a ligação do PCP, que podem ser facilmente implementados como um auto-contido única monólito de polímero -Peça num formato de coluna com propriedades óptimas para aplicações de escoamento. O procedimento de síntese do polímero é seguida por uma solução com base em temperatura ambiente simples &#160; método para crescer um revestimento PCP sobre a superfície interna dos poros do monólito 19-20. Como primeiro exemplo, descreve-se a preparação de uma película de polímero de coordenação de ferro (III) benzenotricarboxilato (FeBTC) dentro de um poli macroporosa (estireno-ácido metacrílico-divinilbenzeno) monólito. Este método é eficaz para a preparação de pós a granel, bem como a coluna capilar e o protocolo descrito é facilmente exequível a outros PCP. Como um exemplo do potencial de MOPHs como materiais funcionais para o fluxo atra-aplicações gh, aplicou-se o desenvolvido FeBTC MOPH que contém um revestimento denso de Fe (III) para enriquecer fosf centros de misturas de proteínas digeridas que exploram a afinidade de ligação de fosfopéptidos a Fe (III). O protocolo desenvolvido 21 compreende três partes principais: Preparação do suporte macroporous monólito de polímero orgânico; crescimento do revestimento PCP sobre a superfície dos poros do monolito; aplicação para o enriquecimento de fosfopeptídeos.

<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.

Uma ilustração esquemática do crescimento PCP sobre a superfície dos poros do monólito de polímero orgânico é mostrado na Figura 1. Nesta figura, ilustra-se o inicial de Fe (III) átomos retido sobre a superfície dos poros do monólito de polímero original é coordenado com grupos funcionais carboxílicos . Utilizando o protocolo descrito aqui ligando orgânico adicional e iões Fe (III) são adicionados à superfície, formação de uma rede de coordenação porosa dentro do monólito de pol?...

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.

Preparação de altamente poroso Coordenação Polymer Revestimentos em macroporosas Polymer Monólitos para o enriquecimento avançado de Fosfopeptídeos

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 visualizações.  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.

Vídeo: 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.

Imagem confocal de Confinado repouso e fluindo Misturas colóide-polímero

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

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.

Fabricação de grande-área royalty-pé 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 Fotodinâmica com Blended polímero condutor / Fullerene Nanoparticle Fotossensibilizadores

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.

Preparação de macroporosas Epitaxial quartzo Filmes sobre Silicon Chemical Solution Deposition por

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.

Funcionalização da murada-Single nanotubos de carbono com termo-reversível copolímeros em bloco e caracterização por 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 ...

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.

A preparação e propriedades de termo-reversível reticulada Química Rubber Via 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.

Monitorização dos efeitos de iluminação sobre a estrutura do polímero conjugado géis usando 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 ...

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.

Microfluidic seco-fiação e caracterização de fibras regeneradas da 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 impedância eletroquímica como uma ferramenta para estimativa de constante taxa eletroquímica

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.

Tempo-resolvido compostos orgânicos de Photophysical caracterização dos Triplet-colheita em um livre de oxigênio ambiente usando uma câmera de iCCD

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