Name: layer-by-layer synthesis and transfer of freestanding conjugated microporous polymer nanomembranes
Uploaded: 2015-12-15T13:00:00.000+00:00
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Description: Watch this Scientific Journal Video about Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes at JoVE.com

The authors have no acknowledgements.

Sıralı ilavesi yoluyla CMP İnce Filmlerin 1. Sentezi <ol><li> Mika altın Kendinden montajlı tek tabaka (SAM) işlevsellik. <ol><li> Etanol 11-tioasetil-undekan asit-propargyl amid 14 1 mM çözeltisi (SAM-çözüm) hazırlayın. Çözelti berrak olana kadar ultrasonik banyo kullanarak karıştırın. Alüminyum folyo kullanarak ışık şişeyi koruyun. </li><li> Argon altında, altın kaplı mika gofret elde edilir. Depolama kabından çekilmesinden sonra 18 saat boyunca SAM-çözümün doğrudan mika gofret batırmayın. </li><li> SAM-çözümün dışında hazırlanan Au-mika gofret alın azot akımı altında etanol ve kuru ile durulayın. Daha sonra ışık ve inert gaz altında korunan substrat saklayın. </li></ol></li><li> Öncü çözümleri. <ol><li> 18,64 mg Cu-katalizörün (tetrakis (asetonitril) bakır (I) &#39;in sentezi fosfat), 20,83 mg tetraphenylmethane (TPM) -alkyne ve 24,22 mg TPM azid tartılır ve ayrı bir Schlenk şişesi içine, her bir bileşen doldurun.TPM alkin ve TPM azid için bakınız Şekil 1., sentez Başvurusu 15 tarif edilmiştir. Boşaltın ve inert gaz (N2 veya argon) ile 3 kez doldurun. </li><li> Her bir Schlenk şişesine 25 ml su içermeyen tetrahidrofuran (THF) ilave edilir. Alüminyum folyo kullanarak ışık TPM azid ve TPM-alkin ile şişeler koruyun. </li></ol></li><li> CMP imalatı için aparat hazırlayın. Not: Sentez cihazı, Şekil 2 &#39;de gösterilmiştir. <ol><li> Bir 250 ml&#39;lik tek boyunlu, yuvarlak tabanlı bir şişeye kullanın. 130 mi THF içinde doldurun. Alkin ile kaplanmış hazırlanan alt tabaka koymak örnek bölmesine SAM sonlandırıldı. Alt-tabaka dik duran, böylece örnek tutucu kullanın. </li><li> Reflü soğutucusunun üstündeki kavşağında yolu ile savurma hattına cihazı bağlayın. </li><li> 3 kez boşaltın ve inert gaz ile havalandırın. </li></ol></li><li> Soy gaz koşulları altında Sıralı ek. <ol><li> 90 ° C&#39;ye kadar ısıtıcı ayarlayın ve THF yeniden olana kadar bekleyineritken. </li><li> Numune bölmesinin alt kısmındaki çıkışında üzerinde numune bölmesinden THF dışarı edelim. Çıkışını kapatın. </li><li> Hazırlanan TPM azid çözeltisi 1 ml ve septumla vidalı kapakla numune kompartımanı Cu (I) &#39;in katalizör çözeltisi 0,5 ml ver. Reaksiyon aparatı savurma şişesi çözümleri sırayla aktarmak için bir oyuk bir iğne ile bir şırınga kullanın. Not: dizisi reaksiyona herhangi bir etkisi yoktur. </li><li> Yaklaşık 30 dakika bekleyin. </li><li> Numune bölmesinin alt kısmındaki çıkışında üzerinde reaksiyon çözüm olsun. Çıkışını kapatın ve numune durulama özet THF toplamak. Yaklaşık 30 dakika bekleyin. </li><li> Numune bölmesinin alt kısmındaki çıkışında üzerinde durulama çözüm olsun. Çıkışını kapatın. </li><li> Hazırlanan TPM alkin çözeltisi 1 ml ve septumla vidalı kapakla numune kompartımanı Cu (I) &#39;in katalizör çözeltisi 0,5 ml ver. Içi boş bir şırınga kullanınİğne Reaksiyon cihazına bir Schlenk şişesi çözeltiler sıralı olarak aktarmak için kullanılır. Not: dizisi reaksiyona herhangi bir etkisi yoktur. </li><li> Yaklaşık 30 dakika bekleyin. </li><li> Numune bölmesinin alt kısmındaki çıkışında üzerinde reaksiyon çözüm olsun. Çıkışını kapatın ve numune durulama özet THF toplamak. Yaklaşık 30 dakika bekleyin. </li><li> Tekrarlayın tabakalarının istenilen miktara varıncaya kadar 1.4.9 için 1.4.3 adımlar. Not: Bir katman yaklaşık olarak 1 nm kalınlığındadır. </li><li> , CMP-kaplı mika substrat çıkarıp THF, etanol ile durulayın ve azot akımı altında kurutun. </li></ol></li></ol> CMP Nanomembranlar 2. Transferi <ol><li> Poli (metil metakrilat) (PMMA) çözeltisi eklendi. <ol><li> Etil asetat içinde% 4 (ağırlık) PMMA (M 996 kDa) ihtiva eden bir çözelti hazırlayın. Çözelti berrak olana kadar PMMA ultrasonik banyo kullanarak eritin. </li></ol></li><li> PMMA çözümünün Spin kaplama. <ol><li> Ra spin kaplayıcı ayarlamp süresi 0 rpm 4000 ila 10 saniye, saat 40 sn tutup 4,000 0 rpm zamanı 10 sn rampa. </li><li> Spin kaplayıcı CMP kaplı mika substrat yerleştirin ve tamamen kaplıdır kadar gofret PMMA çözümünü koydu. Spin kaplayıcı başlatın. </li><li> Döndürerek kaplama tamamlandıktan sonra, 90 ° C&#39;de bir ısıtma plakası üzerinde 5 dakika boyunca numune koydu. </li><li> Kaplanmış mika substrat her kenarından 1 mm kesti. Kenarları kesmek için bir makas kullanın. </li></ol></li><li> PMMA Devri CMP nanomembrane kaplı. <ol><li> Ve KI / H2O (1:10 a / a) I 2 / KI / H 2 solüsyonu O (: 4 40 a / a / a 1) hazırlayın. </li><li> Çanak kristalleştirilmesi 150 ml I2 / KI H2O çözeltisi doldurun ve çanak kristalleştirilmesi 100 ml KI / H2O çözeltisi doldurun. I 2 / KI / H2O çözeltisi üzerine, çözeltiye temas mika, mika alt tabaka üzerine kaplanmış PMMA CMP altın koyun. O lavabo olmadığını dikkatli olun.En az 5 dakika bekleyin. </li><li> I 2 / KI / H2 çözeltisine temas mika KI / H2O çözeltisi üzerine solüsyon, PMMA kaplı CMP altın mika alt-tabakanın koyun. O lavabo olmadığını dikkatli olun. En az 5 dakika bekleyin. </li><li> Çanak kristalleştirilmesi 250 ml damıtılmış su doldurun. Mika gelen PMMA / CMP / altın filmi atacakmısınız. Hafif damıtılmış su içinde, bir kenarından başlayarak, alt-tabakanın içine daldırılması yapın. Mika suya bakacak şekilde alt tabakayı tutun. Not: süreci Şekil 3 &#39;de gösterilmiştir. </li><li> Dip kat silikon gofret PMMA / CMP / altın. O yüzme PMMA / CMP / altın zarın kenarına temas edene kadar gofret ile yavaş yavaş PMMA / CMP / altın yaklaşarak bunu yapın. Si-gofret PMMA / CMP / altın zar ile temas halinde olduğu zamanlar, yavaş yavaş silikon gofret çekin. </li><li> Silikon gofret PMMA / CMP / altın filmi atacakmısınız. Biraz tek ed itibaren, alt tabakayı daldırarak yapınge, I 2 / KI / H 2 O çözüm. 15 dakika bekleyin. </li><li> Altın tamamen kazınmış sonra silikon vasıtasıyla suya PMMA / CMP zarı aktarın. 15 dakika bekleyin. </li><li> Üç kez adımı yineleyin 2.3.7 suyla membran yıkayın. </li><li> Aşama 2.3.5 belirtilen yöntemle, istenen alt-tabaka, örneğin, bir mikroskop lamı veya altın kaplama silikon yıkanarak PMMA / CMP membran aktarın. En az 2 saat süreyle havada PMMA / CMP substrat kurumasını bekleyin. </li></ol></li><li> PMMA Feshi. <ol><li> Aseton PMMA / CMP substratı koyun. 30 dakika bekleyin. Substrat çıkarın ve aseton ile durulayın. </li><li> Adımı yineleyin 2.4.1 üç kez. </li><li> En az 2 saat CMP substrat kurumasını bekleyin. </li></ol></li></ol>

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The authors have nothing to disclose.

CMP-film oluşturucu sentezi için katalizör çözeltisi taze olarak yer alır. Kırık bir katalizör (örneğin, yükseltgenmiş) çözeltisinin bir mavi rengi ile gösterilir. Taze bir çözüm renksizdir. Bir önemli nokta sıkma kaplama PMMA&#39;nın sonra mika substrat kenarları kesmektir. Ayrıca alt tabaka kusurlar kesilmelidir örneğin, her spot PMMA nedeniyle eksik altın tabakası, mika alt-tabaka ile temas olabilir edildi. Aksi takdirde altın tabakası kolayca mika substrat dan sıyrılıp edilemez. Dekolmanı, bir kenarına veya köşesine başladıktan sonra Ayrıca, mika substrat altın tabakasının ayrılmasını ilişkin altın tabakası tamamen müstakil kadar, kimse bu kenarda devam etmelidir. Iyot çözeltisi veya suya iyot solüsyonu su banyosunda bir silikon, örneğin, PMMA / CMP membranların transferi sırasında, önemli olduğunumembran kuru değil. Membran Si-gofret kurur sonra tekrar ayırmak neredeyse imkansız. PMMA çözüldükten sonra, her durulama adımı dikkatli yapılmalıdır; membranın bir üst üste gelen kenarı, bir alt-tabakadan membran kaldırma yol açabilir. Şu anda numunelerin boyutu numune kompartımanı büyüklüğü ile sınırlıdır. Her bir döngü yaklaşık 2 saat gerektiğinden, imal CMP filmlerin kalınlıkları reaksiyon süresi ile sınırlıdır. Daha az emek yoğun bir sentezi için, reaksiyon cihazı bir sifon eklenerek modifiye edilebilir; Bir sonuç olarak numune kompartımanı, otomatik bir Soxhlet ekstraktörü karşılaştırılabilir boşaltılacaktır. Bizim tekniği ultra ince konjuge mikro gözenekli polimer filmlerin işleme ve CMP Nanomembranlar elde etmek için bir kurban substrat kullanımı birleştiriyor. CMP Nanomembranlar sentezi nedeniyle henüz mümkün değildiToz CMP düşük işlenebilirlik. Diğer tekniklere kıyasla, örneğin SURMOFs 7 üretimi için biz kullanılan çözücü miktarı bir azalma sağlamıştır. Özellikle SURMOF üretimi durumunda durulama aşaması nedeniyle, geri kaynayan THF kullanımı, bu durumda, bir çözücü, yüksek tüketimi biz ölçüde THF tüketimini azaltabilir. Biz sunulan yöntem gözenek büyüklüğüne ve kimyasal afinite üzerinde kontrol ile seçicilik ve gecirgenligi ince ayar çünkü olasılıklar gaz uygulama ve sıvı faz ayrılması bulacaksınız bekliyoruz. Buna ek olarak, kataliz, algılama ya da organik elektronik gibi diğer uygulamalar için, uygun, fonksiyonel bir yapı taşları elde CMP malzeme modüler sentezi de tarif edilen işleme yönteminde yararlı olabilir.

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>Tetrahydrofuran (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&amp;auml;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to &lt;sup&gt;9&lt;/sup&gt;.</td></tr><tr><td>1.1.1.1 Methanetetrayltetrakis(4-ethinylenebenzene) (TPM-alkyne)</td><td></td><td></td><td>Provided by AK Prof. Br&amp;auml;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to &lt;sup&gt;9&lt;/sup&gt;.</td></tr><tr><td>11-thioacetyl-undecaneacid propargylamide</td><td></td><td></td><td>Provided by AK Prof. Br&amp;auml;se. Institute of organic chemistry, Karlsruhe Institute of Technology. Synthesized according to &lt;sup&gt;8&lt;/sup&gt;.</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 gibi büyük yüzey alanlı malzemeler nedeniyle üstün termal ve kimyasal stabilite ile kombinasyon halinde işlevsel gruplar yüksek değişkenlik ve düşük seviyedeki yoğunluklara kadar, son zamanlarda ilgi giderek artan çekmiştir. Böyle sıkma kaplama gibi genellikle uygulanan teknikler mevcut olmadığından Ancak, çözünmeyen doğa kendi işlenmesinde sorunlara neden olmaktadır. Özellikle CMP ince filmlerin işleme arzu edilir membran uygulamaları için, işleme sorunları ticari uygulama engellemiştir. Burada, moleküler katman-katman (Lbl) sentez yoluyla fonksiyonalize yüzeylerde CMP ince filmlerin ara yüzey sentezini tarif eder. Bu işlem, istenen kalınlığı ve kompozisyon ve daha da arzu edilen bir bileşim eğimlere sahip filmlerin hazırlanması sağlar. Kurban desteklerin kullanımı desteği dağılmasından sonra tarafından müstakil membranların hazırlanması veriyorsentez. Böyle ultra-ince müstakil membranlar işlemek için kurban kaplamalarla koruma Nanomembranlar kopma önlemek için, büyük söz gösterdi. İstenen substrata Nanomembranlar aktarmak için, kaplanmış membranlar hava-sıvı arayüzünde upfloated ve daha sonra daldırma ile kaplama yoluyla transfer edilir.

Membranlar 16 Şekil 4, bir altın gofret transfer CMP-membran IRRA-spektrumlarını göstermektedir kızıl ötesi yansıtma absorpsiyon spektroskopisi (IRRAS). Ile karakterize edilir. Aromatik omurga titreşimlerden tipik bantlar 1605 cm -1, 1515 cm -1 ve 1412 cm -1 altındadır. Reaksiyona girmemiş alkin ve azid grupları 2125 cm -1 ve 1227 cm -1 karakteristik bantlar ile görülebilir. 5 taramalı elektron mikroskobu (SEM) görüntüsü göstermektedir. Bağlantısız membran açıkça görülebilir. <img alt="figür 1" src="/files/ftp_upload/53324/53324fig1highres.jpg" width="550" /> Şekil 1. Moleküler yapı blokları. (A) TPM-alkin ve (B) TPM azid Moleküler yapılar. <a href="https://www-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/53324/53324fig1large.jpg" target="_blank">Pl</a>kolaylaştırmak bu rakamın büyük halini görmek için buraya tıklayın. <img alt="Şekil 2," src="/files/ftp_upload/53324/53324fig2highres.jpg" width="700" /> Şekil 2. Reaksiyon aparatı. CMP ince filmlerin katman-katman sentezi için ayarlayın. Cihaz, THF, geri akış soğutucusu THF buharı yol buhar tüpü için rezervuar olarak bir boyunlu yuvarlak tabanlı bir şişeye oluşur. THF kondensatlar numune kompartımanı toplanır. Kimyasal bir septum ile vidalı kapağın üzerine sokulabilmektedir. Numune bölmesi Dipsavaktan boşaltılır. <a href="https://www-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/53324/53324fig2large.jpg" target="_blank">Bu rakamın büyük halini görmek için lütfen buraya tıklayınız.</a> <img alt="Şekil 3," src="/files/ftp_upload/53324/53324fig3highres.jpg" width="500" /> Şekil 3. mika kaldırılıyor. </strong&gt; PMMA / CMP zar mika substrat kenarından ayırmak başlıyor. PMMA / CMP yarısı su üstünde yüzer, diğer yarısı hala mika yüzeye bağlı olduğu. <a href="https://www-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/53324/53324fig3large.jpg" target="_blank">Bu rakamın büyük halini görmek için lütfen buraya tıklayınız.</a> <img alt="Şekil 4," src="/files/ftp_upload/53324/53324fig4highres.jpg" width="700" /> Şekil 4. IRRA-spektrumları. Altın gofret transfer CMP-membran IRRA-spektrumları. 1605, 1515 ve 1412 cm aromatik omurga titreşimlerden bantları -1 CMP-zarın için karakteristiktir. Kullanılan arka. Sebebiyle CD titreşim <a href="https://www-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/53324/53324fig4large.jpg" target="_blank">bu rakamın büyük halini görmek için lütfen buraya tıklayınız.</a> 5. SEM-image Şekil. CMP-membranın SEM-Image. Bağlantısız zar güzel gösterilmiştir. (Lindemann izniyle, P ile yayımlanmaktadır ark Chem Mater 26 7189 -.... 7193. Copyright 2014 American Chemical Society). <a href="https://www-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/53324/53324fig5large.jpg" target="_blank">Bu rakamın büyük halini görmek için lütfen buraya tıklayınız.</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.

Katman-katman Sentezi ve Müstakil Konjuge mikro gözenekli polimer Nanomembranlar Devri

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 Görüntüleme.  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

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.

Geniş alanlı Fabrikasyon Ultrathin Polimer Filmler Serbest ayakta

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

Kimya

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.

Phosphopeptides Gelişmiş Zenginleştirme için Makrogözenekli Polimer Monoliths üzerinde yüksek Gözenekli Koordinasyon Polymer Coatings Hazırlanması

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

Fabrication of the Thermoplastic Microfluidic Channels

In our lab, we have successfully isolated nucleic acids directly from microliter and submicroliter volumes of human blood, urine and stool using polymer/nanoparticle composite microscale lysis and solid phase extraction columns. The recovered samples are concentrated, small volume samples that are PCRable, without any additional cleanup. Here, we demonstrate how to fabricate thermoplastic microfluidic chips using hot embossing and heat sealing. Then, we demonstrate how to use in situ light directed surface grafting and polymerization through the sealed chip to form the composite solid phase columns. We demonstrate grafting and polymerization of a carbon nanotube/polymer composite column for bacterial cell lysis. We then show the lysis process followed by solid phase extraction of nucleic acids from the sample on chip using a silica/polymer composite column. The attached protocols contain detailed instructions on how to make both lysis and solid phase extraction columns.

Here we demonstrate how to fabricate thermoplastic microfluidic chips using hot embossing and heat sealing. Then we demonstrate how to use in situ light directed surface grafting and polymerization through the sealed chip to form the composite solid phase columns.

Termoplastik mikroakışkan Kanallar imalatı

In our lab, we have successfully isolated nucleic acids directly from microliter and submicroliter volumes of human blood, urine and stool using ...

Biyoloji

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Photoredox Katalizörü kullanarak görünür ışık aracılığı ile dispersiyon polimerleştirilmesi ile solucan gibi miseller Facile sentezi

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

Creating Sub-50 Nm Nanofluidic Junctions in PDMS Microfluidic Chip via Self-Assembly Process of Colloidal Particles

Polydimethylsiloxane (PDMS) is the prevailing building material to make microfluidic devices due to its ease of molding and bonding as well as its transparency. Due to the softness of the PDMS material, however, it is challenging to use PDMS for building nanochannels. The channels tend to collapse easily during plasma bonding. In this paper, we present an evaporation-driven self-assembly method of silica colloidal nanoparticles to create nanofluidic junctions with sub-50 nm pores between two microchannels. The pore size as well as the surface charge of the nanofluidic junction is tunable simply by changing the colloidal silica bead size and surface functionalization outside of the assembled microfluidic device in a vial before the self-assembly process. Using the self-assembly of nanoparticles with a bead size of 300 nm, 500 nm, and 900 nm, it was possible to fabricate a porous membrane with a pore size of ~45 nm, ~75 nm and ~135 nm, respectively. Under electrical potential, this nanoporous membrane initiated ion concentration polarization (ICP) acting as a cation-selective membrane to concentrate DNA by ~1,700 times within 15 min. This non-lithographic nanofabrication process opens up a new opportunity to build a tunable nanofluidic junction for the study of nanoscale transport processes of ions and molecules inside a PDMS microfluidic chip.

We propose a simple self-assembly technique of silica colloidal nanoparticles to create a nanofluidic junction between two microchannels in polydimethylsiloxane (PDMS). Using this technique, a nanoporous bead membrane with a pore size down to ~45 nm was built inside a microchannel and applied to electrokinetic preconcentration of DNA samples.

Kolloidal Parçacıkların Öz-Montaj Süreci yoluyla PDMS mikroakışkan Chip Sub-50 Nm Nanofluidic Junctions oluşturma

Polydimethylsiloxane (PDMS) is the prevailing building material to make microfluidic devices due to its ease of molding and bonding as well as its ...

Mühendislik

Preparation of Light-responsive Membranes by a Combined Surface Grafting and Postmodification Process

In order to modify the surface tension of commercial available track-edged polymer membranes, a procedure of surface-initiated polymerization is presented. The polymerization from the membrane surface is induced by plasma treatment of the membrane, followed by reacting the membrane surface with a methanolic solution of 2-hydroxyethyl methacrylate (HEMA). Special attention is given to the process parameters for the plasma treatment prior to the polymerization on the surface. For example, the influence of the plasma-treatment on different types of membranes (e.g.&#160;polyester, polycarbonate, polyvinylidene fluoride) is studied. Furthermore, the time-dependent stability of the surface-grafted membranes is shown by contact angle measurements. When grafting poly(2-hydroxyethyl methacrylate) (PHEMA) in this way, the surface can be further modified by esterification of the alcohol moiety of the polymer with a carboxylic acid function of the desired substance. These reactions can therefore be used for the functionalization of the membrane surface. For example, the surface tension of the membrane can be changed or a desired functionality as the presented light-responsiveness can be inserted. This is demonstrated by reacting PHEMA with a carboxylic acid functionalized spirobenzopyran unit which leads to a light-responsive membrane. The choice of solvent plays a major role in the postmodification step and is discussed in more detail in this paper. The permeability measurements of such functionalized membranes are performed using a Franz cell with an external light source. By changing the wavelength of the light from the visible to the UV-range, a change of permeability of aqueous caffeine solutions is observed.

A plasma-induced polymerization procedure is described for the surface-initiated polymerization on polymer membranes. Further postmodification of the grafted polymer with photochromic substances is presented with a protocol of conducting permeability measurements of light-responsive membranes.

Bir Kombine Yüzey Tırnak ve Postmodification Süreci Işık duyarlı Membranların Hazırlanması

In order to modify the surface tension of commercial available track-edged polymer membranes, a procedure of surface-initiated polymerization is ...

Biyomühendislik

Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and non-porous supports (polymer, ceramic, metal, carbon, and graphene). We developed a novel crystallization technique, which is termed the ENACT approach: the electrophoretic nuclei assembly for the crystallization of highly intergrown thin films (ENACT). This approach allows for a high density of heterogeneous nucleation of MOFs on a chosen substrate via the electrophoretic deposition (EPD) directly from the precursor sol. The growth of well-packed MOF nuclei leads to a highly intergrown polycrystalline MOF film. We show that this simple approach can be used for the synthesis of thin, intergrown zeolite imidazole framework (ZIF)-7 and ZIF-8 films. The resulting 500 nm-thick ZIF-8 membranes show a considerably high H2 permeance (8.3 x 10-6 mol m-2 s-1 Pa-1) and ideal gas selectivities (7.3 for H2/CO2, 15.5 for H2/N2, 16.2 for H2/CH4, and 2655 for H2/C3H8). An attractive performance for C3H6/C3H8 separation is also achieved (a C3H6 permeance of 9.9 x 10-8 mol m-2 s-1 Pa-1 and a C3H6/C3H8 ideal selectivity of 31.6 at 25 &#176;C). Overall, the ENACT process, owing to its simplicity, can be extended to synthesize intergrown thin films of a wide range of nanoporous crystalline materials.

A simple, reproducible, and versatile approach for the synthesis of intergrown, polycrystalline metal-organic framework membranes on a wide range of unmodified porous and non-porous supports is presented.

Elektroforetik kristalizasyon Ultrathin yüksek performanslı Metal organik Framework membranlar

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and ...

Procedure for the Transfer of Polymer Films Onto Porous Substrates with Minimized Defects

The fabrication of devices containing thin film composite membranes necessitates the transfer of these films onto the surfaces of arbitrary support substrates. Accomplishing this transfer in a highly controlled, mechanized, and reproducible manner can eliminate the creation of macroscale defect structures (e.g., tears, cracks, and wrinkles) within the thin film that compromise device performance and the usable area per sample. Here, we describe a general protocol for the highly controlled and mechanized transfer of a polymeric thin film onto an arbitrary porous support substrate for eventual use as a water filtration membrane device. Specifically, we fabricate a block copolymer (BCP) thin film on top of a sacrificial, water-soluble poly(acrylic acid) (PAA) layer and silicon wafer substrate. We then utilize a custom-designed, 3D-printed transfer tool and drain chamber system to deposit, lift-off, and transfer the BCP thin film onto the center of a porous anodized aluminum oxide (AAO) support disc. The transferred BCP thin film is shown to be consistently placed onto the center of the support surface due to the guidance of the meniscus formed between the water and the 3D-printed plastic drain chamber. We also compare our mechanized transfer-processed thin films to those that have been transferred by hand with the use of tweezers. Optical inspection and image analysis of the transferred thin films from the mechanized process confirm that little-to-no macroscale inhomogeneities or plastic deformations are produced, as compared to the multitude of tears and wrinkles produced from manual transfer by hand. Our results suggest that the proposed strategy for thin film transfer can reduce defects when compared to other methods across many systems and applications.

We present a procedure for highly controlled and wrinkle-free transfer of block copolymer thin films onto porous support substrates using a 3D-printed drain chamber. The drain chamber design is of general relevance to all procedures involving transfer of macromolecular films onto porous substrates, which is normally done by hand in an irreproducible fashion.

Polimer filmlerin küçültülmüş kusurlarla gözenekli substratlar üzerine aktarımı için prosedür

The fabrication of devices containing thin film composite membranes necessitates the transfer of these films onto the surfaces of arbitrary support ...

Synthesis of Hydrogels with Antifouling Properties As Membranes for Water Purification

Hydrogels have been widely utilized to enhance the surface hydrophilicity of membranes for water purification, increasing the antifouling properties and thus achieving stable water permeability through membranes over time. Here, we report a facile method to prepare hydrogels based on zwitterions for membrane applications. Freestanding films can be prepared from sulfobetaine methacrylate (SBMA) with a crosslinker of poly(ethylene glycol) diacrylate (PEGDA) via photopolymerization. The hydrogels can also be prepared by impregnation into hydrophobic porous supports to enhance the mechanical strength. These films can be characterized by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) to determine the degree of conversion of the (meth)acrylate groups, using goniometers for hydrophilicity and differential scanning calorimetry (DSC) for polymer chain dynamics. We also report protocols to determine the water permeability in dead-end filtration systems and the effect of foulants (bovine serum albumin, BSA) on membrane performance.

This paper reports practical methods to prepare hydrogels in freestanding films and impregnated membranes and to characterize their physical properties, including water transport properties.

Su Arıtma Membranlar olarak Zehirli Özelliklere Sahip Hidrojeller Sentezi

Hydrogels have been widely utilized to enhance the surface hydrophilicity of membranes for water purification, increasing the antifouling properties and ...

Polimer aşılı metal organik çerçeve tek katmanlarının kendi kendine montajı

Synthesis and Characterization of Self-Assembled Metal-Organic Framework Monolayers Using Polymer-Coated Particles

Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. Attempts to enhance the utility of MOFs have involved the preparation of various composites, including polymer-grafted MOFs. By directly grafting polymers to the external surface of MOFs, issues of incompatibility between polymers and MOFs can be overcome. Polymer brushes grafted from the surface of MOFs can serve to stabilize the MOF while enabling particle assembly into self-assembled metal-organic framework monolayers (SAMMs) via polymer-polymer interactions.
Control over the chemical composition and molecular weight of the grafted polymer can allow for tuning of the SAMM characteristics. In this work, instructions are provided on how to immobilize a chain transfer agent (CTA) onto the surface of the MOF UiO-66 (UiO = Universitetet i Oslo). The CTA&#160;serves as initiation sites for the growth of polymers. Once polymer chains are grown from the MOF surface, the formation of SAMMs is achieved through self-assembly at an air-water interface. The resulting SAMMs are characterized and shown to be freestanding by scanning electron microscopy imaging. The methods presented in this paper are expected to make the preparation of SAMMs more accessible to the research community and thereby expand their potential use as a&#160;MOF-polymer composite.

Yazar Spotlight: Kendinden Montajlı MOF-Polimer Kompozitleri Keşfetmek

A protocol for the synthesis and characterization of self-assembled metal-organic framework monolayers is provided using polymer-grafted, metal-organic framework (MOF) crystals. The procedure shows that polymer-grafted MOF particles can be self-assembled at an air-water interface resulting in well-formed, free-standing, monolayer structures as evidenced by scanning electron microscopy imaging.

Polimer kaplı parçacıklar kullanılarak kendinden montajlı metal-organik çerçeve tek tabakalarının sentezi ve karakterizasyonu

Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. ...