The authors have no acknowledgements.

1.合成的CMP薄膜通过顺序加入<ol><li>金云母自组装单层（SAM）官能化。 <ol><li>制备11-硫代乙酰基十一烷酸炔丙基酰胺14在乙醇1mM的溶液（SAM-溶液）。混合使用超声波浴，直到解决方案是明确的。用铝箔避光的瓶子。 </li><li>获取在氩气中金云母片。从储存容器撤走后直接浸入云母晶片18小时在SAM的溶液。 </li><li>取所制备的Au-云母晶片出SAM-溶液，冲洗，在氮气流下乙醇和干燥。之后存储从光中，在惰性气体保护基板。 </li></ol></li><li>前体的解决方案。 <ol><li>称量18.64毫克铜催化剂（四（乙腈）铜（I）​​六氟磷酸盐），20.83毫克tetraphenylmethane（TPM）-alkyne和24.22毫克TPM的叠氮化物和填充每个组件到一个单独的Schlenk烧瓶中。参见图1为TPM-炔和TPM叠氮化物，在合成与参考例15所述 。疏散和填充有惰性气体（N 2或氩气）的3倍。 </li><li>加25毫升的水 - 自由四氢呋喃（THF）以每Schlenk烧瓶。用铝箔避光与TPM的叠氮化物和TPM炔烧瓶。 </li></ol></li><li>为CMP制造准备设备。 注意:合成装置示于图2。 <ol><li>使用250ml的单颈圆底烧瓶中。 130毫升THF填写。把准备好的基材涂炔样品室终止SAM。使用一个样本保持器，使得衬底垂直站立。 </li><li>经由在回流冷却器的顶部的交界处连接装置向舒伦克线。 </li><li>疏散和通风用惰性气体的3倍。 </li></ol></li><li>顺序加入在惰性条件下。 <ol><li>加热器设定为90℃，并等到THF为重励磁。 </li><li>让出THF来自出口，在样品室底部的样品室。关闭出口。 </li><li>给予1毫升制备的TPM的叠氮化物溶液和0.5ml经由螺旋盖与隔膜的铜（Ⅰ）催化剂溶液到样品室。使用注射器的中空针的溶液依次从Schlenk烧瓶转移到反应装置。注意:序列没有影响到反应中。 </li><li>等待大约30分钟。 </li><li>让出在样品隔室的底部的反应溶液中的出口。关闭出口并收集冷凝THF冲洗样品。等待大约30分钟。 </li><li>让出了出口处的冲洗溶液在样品隔室的底部。关闭出口。 </li><li>给予1毫升制备的TPM的炔溶液和0.5ml经由螺旋盖与隔膜的铜（Ⅰ）催化剂溶液到样品室。用注射器具有中空针溶液依次从Schlenk烧瓶转移到反应装置。注意:序列没有影响到反应中。 </li><li>等待大约30分钟。 </li><li>让出在样品隔室的底部的反应溶液中的出口。关闭出口并收集冷凝THF冲洗样品。等待大约30分钟。 </li><li>重复步骤1.4.3至1.4.9直至达到各层的期望量。注:一层是约1纳米厚。 </li><li>取出CMP包覆云母基材，以THF，乙醇冲洗并晾干在氮气流。 </li></ol></li></ol> 2.将CMP纳米薄膜的<ol><li>有机玻璃（PMMA）溶液。 <ol><li>制备的4％（重量）聚甲基丙烯酸甲酯（M 996 kDa的）在乙酸乙酯中的溶液。使用聚甲基丙烯酸甲酯超声波浴直到溶液是澄清溶解。 </li></ol></li><li>聚甲基丙烯酸甲酯解旋涂。 <ol><li>设定旋涂至RaMP时间内从0到4000转10秒，保温时间40秒，减速时间10秒，从4000至0 rpm。 </li><li>放置在旋涂器在CMP被覆云母基板和放聚甲基​​丙烯酸甲酯溶液的晶片上，直到它被完全覆盖。启动旋涂机。 </li><li>后旋涂结束后，把样品5分钟的加热板上在90℃。 </li><li>从涂覆的云母基底的每一边缘切断1毫米。使用剪刀切割边缘。 </li></ol></li><li> PMMA转移涂层CMP纳米薄膜。 <ol><li>准备的我2 / KI / H 2溶液0（1:4:40米/ M / M）和Ki / H 2 O（1:10 M / M）。 </li><li>填写150ml的结晶皿中的I 2 / KI H 2 O解决方案，并利用100毫升结晶皿的KI / H 2 O解决方案。把PMMA涂CMP金云母基材，与云母接触到的解决方案，在我2 / KI / H 2 O解决方案之上。要小心，它不下沉。至少等待5分钟。 </li><li>放聚甲基丙烯酸甲酯涂CMP金云母基板从I 2 / KI / H 2 O的溶液在碘化钾/ H 2 O的溶液的上面，云母在接触到溶液中。要小心，它不下沉。至少等待5分钟。 </li><li>填蒸馏水在250毫升结晶皿。剥去从云母的PMMA / CMP /金膜。通过稍微浸入衬底，从一个边缘开始，在蒸馏水中做到这一点。保持基板，使得云母指向的水。注意:程序示于图3。 </li><li>浸涂的PMMA / CMP /在硅晶片上金。通过与晶片接近PMMA / CMP /金缓慢，直到它触及的游泳PMMA / CMP /金膜边缘执行此操作。拉出硅晶片缓慢，一旦Si晶片是在用PMMA / CMP /金膜接触。 </li><li>从硅晶片剥离聚甲基丙烯酸甲酯/ CMP /金薄膜关闭。稍微浸泡基材，从一开始的编辑这样做GE，在我2 / KI / H 2 O解决方案。等待15分钟。 </li><li>后金被完全蚀刻时，通过在硅晶片上的PMMA / CMP膜转移到水中。等待15分钟。 </li><li>重复步骤2.3.7三次，用水洗涤该膜。 </li><li>经洗涤的聚甲基丙烯酸甲酯/ CMP膜转移到所需的基材，例如显微镜载玻片或金涂覆的硅晶片上，通过在步骤2.3.5中提到的方法。让空气中的聚甲基丙烯酸甲酯/ CMP基板干燥至少2小时。 </li></ol></li><li>溶聚甲基丙烯酸甲酯。 <ol><li>放聚甲基丙烯酸甲酯/ CMP衬底丙酮。等待30分钟。取出基板，并用丙酮冲洗。 </li><li>重复步骤2.4.1三次。 </li><li>让CMP基材干燥至少2小时。 </li></ol></li></ol>

<ol>
	<li>Lindemann, P., 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=Preparation+of+Freestanding+Conjugated+Microporous+Polymer+Nanomembranes+for+Gas+Separation.">Preparation of Freestanding Conjugated Microporous Polymer Nanomembranes for Gas Separation.</a> Chemistry of Materials. 26 (24), 7193-71 (2014).</li><li>Kim, M., 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=Preparation+of+Ultrathin+Films+of+Molecular+Networks+through+Layer-by-Layer+Cross-Linking+Polymerization+of+Tetrafunctional+Monomers.">Preparation of Ultrathin Films of Molecular Networks through Layer-by-Layer Cross-Linking Polymerization of Tetrafunctional Monomers.</a> Macromolecules. 44 (18), 7092-7095 (2011).</li><li>Vonh&#246;ren, B., 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=Ultrafast+Layer-by-Layer+Assembly+of+Thin+Organic+Films+Based+on+Triazolinedione+Click+Chemistry.">Ultrafast Layer-by-Layer Assembly of Thin Organic Films Based on Triazolinedione Click Chemistry.</a> ACS Macro Letters. 4 (3), 331-334 (2015).</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&#8722;Organic+Frameworks.">Step-by-Step Route for the Synthesis of Metal&#8722;Organic Frameworks.</a> Journal of the American Chemical Society. 129 (49), 15118-15119 (2007).</li><li>Shekhah, O., Wang, H., Zacher, D., Fischer, R. 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=Growth+Mechanism+of+Metal&#8211;Organic+Frameworks:+Insights+into+the+Nucleation+by+Employing+a+Step-by-Step+Route.">Growth Mechanism of Metal&#8211;Organic Frameworks: Insights into the Nucleation by Employing a Step-by-Step Route.</a> Angewandte Chemie International Edition. 48 (27), 5038-5041 (2009).</li><li>Shekhah, O., Liu, J., Fischer, R. 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. F., Quinn, A., Tjipto, E., Caruso, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Assembly+of+Ultrathin+Polymer+Multilayer+Films+by+Click+Chemistry.">Assembly of Ultrathin Polymer Multilayer Films by Click Chemistry.</a> Journal of the American Chemical Society. 128 (29), 9318-9319 (2006).</li><li>Ai, M., 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=Carbon+Nanomembranes+(CNMs)+Supported+by+Polymer:+Mechanics+and+Gas+Permeation.">Carbon Nanomembranes (CNMs) Supported by Polymer: Mechanics and Gas Permeation.</a> Advanced Materials. 26 (21), 3421-3426 (2014).</li><li>Jiang, J. -. X., Cooper, A. I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=in+Functional+Metal-Organic+Frameworks:+Gas+Storage,+Separation+and+Catalysis.">in Functional Metal-Organic Frameworks: Gas Storage, Separation and Catalysis.</a> Topics in Current Chemistry. (ed Martin Schr&#246;der) Ch. 293, 1-33 (2010).</li><li>Dawson, R., Cooper, A. I., Adams, D. 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. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Covalently+linked+organic+networks.">Covalently linked organic networks.</a> Frontiers in Materials. 2, (2015).</li><li>Kleinert, M., Winkler, T., Terfort, A., Lindhorst, T. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+modular+approach+for+the+construction+and+modification+of+glyco-SAMs+utilizing+1,3-dipolar+cycloaddition.">A modular approach for the construction and modification of glyco-SAMs utilizing 1,3-dipolar cycloaddition.</a> Organic &amp; Biomolecular Chemistry. 6 (12), 2118-2132 (2008).</li><li>Plietzsch, 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=Four-fold+click+reactions:+Generation+of+tetrahedral+methane-+and+adamantane-based+building+blocks+for+higher-order+molecular+assemblies.">Four-fold click reactions: Generation of tetrahedral methane- and adamantane-based building blocks for higher-order molecular assemblies.</a> Organic &amp; Biomolecular Chemistry. 7, (2009).</li><li>Greenler, R. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Infrared+Study+of+Adsorbed+Molecules+on+Metal+Surfaces+by+Reflection+Techniques.">Infrared Study of Adsorbed Molecules on Metal Surfaces by Reflection Techniques.</a> The Journal of Chemical Physics. 44 (1), (1966).</li></ol>

The authors have nothing to disclose.

对于在CMP-膜的合成催化剂的溶液必须是新鲜。破碎的催化剂（即，氧化的）由溶液的蓝色着色指示。新鲜的溶液是无色的。 一个关键点是旋涂PMMA后裁切云母基材的边缘。另外在基板的缺陷应该削减， 即，每个点是聚甲基丙烯酸甲酯可以来缺失金层，因为在与云母基板接触。否则金层不能从云母基板容易剥离。另外关于金层的云母基材支队，支队开始在一个边或角后，应该继续就这一边缘，直到金层完全不沾边。 在聚甲基丙烯酸甲酯/ CMP膜与硅晶片，例如，从水浴到碘溶液或从碘溶液对水的转移，但重要的是膜不涸。一旦膜干燥的硅晶片上，这几乎是不可能的再次分离。 溶解PMMA后，每冲洗步骤应谨慎执行;从膜的重叠边缘可导致去除所述衬底膜。 此刻的样本的大小是由样品隔室的尺寸的限制。所制造的CMP膜的厚度通过反应时间，因为每个循环需要大约2小时的限制。要更少的劳动密集的合成反应装置可以通过添加一个虹吸管被修改;其结果是样品室将被自动清空，可比索氏提取器中。 我们的技术结合超薄轭微孔聚合物膜的处理和使用牺牲衬底，得到CMP纳米薄膜。 CMP纳米薄膜的合成是因为还不可能粉CMP低加工。 相较于其它技术，例如生产SURMOFs 7，我们实现了对溶剂的使用量减少。特别是在壳体SURMOF生产的漂洗步骤具有一个高消费的溶剂，在此情况下，由于使用的回流THF中，我们可降低THF中的消费急剧。 我们预计，所提出的方法将找到的，因为可能应用在气体和液体相分离，以微调的选择性和渗透性超过孔径和化学亲和力的控制。此外，模块化合成从功能构建块适合于其他应用，如催化，感测，或有机电子，CMP材料也可以受益于所描述的处理方法。

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作为大表面积材料已经引起了近来越来越大的兴趣，由于它们的高变异性的官能团的组合掺入其优异的热和化学稳定性，和低的密度。然而，它们的不溶性质会产生问题在它们的处理，因为，如旋涂通常适用技术是不可用的。特别是对于膜应用，其中CMP为薄膜的处理是可取的，则处理问题阻碍他们的商业应用。 这里，我们描述在通过分子层 - 层（LBL）合成官能化基底的CMP薄膜的界面合成。此过程允许具有所需厚度和组成，甚至所需组成梯度的薄膜的制备。 使用牺牲载体允许通过后溶解载体的独立式膜的制备的合成。为了处理这种超薄独立的膜与牺牲涂料的保护表现出极大的承诺，避免了纳米薄膜破裂。到的纳米薄膜转移到期望的基材，所述涂覆的膜upfloated在空气 - 液体界面，然后通过浸涂传送。

膜的特征在于红外反射吸收光谱（IRRAS）。16 图4示出 IRRA谱从在CMP膜转移至金晶片。由芳族骨架的振动典型峰是一千六百○五-1，一千五百十五-1和1412厘米-1。未反应的炔和叠氮基团可通过特征频带在2125厘米-1和一二二七-1可以观察到。 图5显示的扫描电子显微镜（SEM）图像。的独立式膜是清晰可见。 <img alt="图1" src="/files/ftp_upload/53324/53324fig1highres.jpg" width="550" /> 图1.分子构建模块。（一）TPM-炔和（B）TPM叠氮分子结构<a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig1large.jpg" target="_blank">。PL</a>轻松点击此处查看该图的放大版本。 <img alt="图2" src="/files/ftp_upload/53324/53324fig2highres.jpg" width="700" /> 图2.反应装置。设置用于层-层合成在CMP薄膜。该装置由一个单颈圆底烧瓶储器THF中，蒸汽管引领THF蒸气至回流冷却器。将THF缩合物被收集在样品室中。该化学品可以插入在螺丝帽用隔膜。该样品室通过底孔空。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig2large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图3" src="/files/ftp_upload/53324/53324fig3highres.jpg" width="500" /> 图3.取出云母。 </stro纳克&gt;聚甲基丙烯酸甲酯/ CMP膜开始从云母衬底的边缘脱离。聚甲基丙烯酸甲酯/ CMP的半浮在水面上，另一半仍附着于云母基材。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig3large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图4" src="/files/ftp_upload/53324/53324fig4highres.jpg" width="700" /> 图4. IRRA光谱。IRRA谱从在CMP膜转移至金-晶片。从芳香骨干，在1605，1515和1412厘米振动的频段-1的特征为CMP膜。该CD的振动是由于所使用的背景。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig4large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 图5. SEM图像，在CMP膜的SEM-图像。该独立的膜是很好的显示。 （转载自林德曼许可，磷等化学母校 26，7189 - 。7193.版权所有2014年美国化学学会）。 <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53324/53324fig5large.jpg" target="_blank">请点击此处查看该图的放大版本。</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.

层 - 层的合成和独立式共轭微孔聚合物纳米薄膜的转移

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 次观看.  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.

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

Towards Biomimicking Wood: Fabricated Free-standing Films of Nanocellulose, Lignin, and a Synthetic Polycation

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and lignin. Layer-by-layer (LbL) assembly process which relies on the assembly of oppositely charged molecules from aqueous solutions was used to build a freestanding composite film of isolated wood polymers of lignin and oxidized nanofibril cellulose (NFC). To facilitate the assembly of these negatively charged polymers, a positively charged polyelectrolyte, poly(diallyldimethylammomium chloride) (PDDA), was used as a linking layer to create this simplified model cell wall. The layered adsorption process was studied quantitatively using quartz crystal microbalance with dissipation monitoring (QCM-D) and ellipsometry. The results showed that layer mass/thickness per adsorbed layer increased as a function of total number of layers. The surface coverage of the adsorbed layers was studied with atomic force microscopy (AFM). Complete coverage of the surface with lignin in all the deposition cycles was found for the system, however, surface coverage by NFC increased with the number of layers. The adsorption process was carried out for 250 cycles (500 bilayers) on a cellulose acetate (CA) substrate. Transparent free-standing LBL assembled nanocomposite films were obtained when the CA substrate was later dissolved in acetone. Scanning electron microscopy (SEM) of the fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle (PDDA-Lignin-PDDA-NC) was estimated to be 17 nm for two different lignin types used in the study. The data indicates a film with highly controlled architecture where nanocellulose and lignin are spatially deposited on the nanoscale (a polymer-polymer nanocomposites), similar to what is observed in the native cell wall.

The objective of this research was to form synthetic plant cell wall tissue using layer-by-layer assembly of nanocellulose fibrils and isolated lignin assembled from dilute aqueous suspensions.&#160; Surface measurement techniques of quartz crystal microbalance and atomic force microscopy were used to monitor the formation of the polymer-polymer nanocomposite material.

朝仿生学木：纳米纤维素，木质素的装配式自由站立电影和合成聚阳离子

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and ...

科研

化学

A Technique to Functionalize and Self-assemble Macroscopic Nanoparticle-ligand Monolayer Films onto Template-free Substrates

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface.&#160; The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates.&#160; The flow is mediated by a surface tension gradient3,4 and creates macroscopic, high-density, monolayer nanoparticle-ligand films.&#160; This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

A simple, robust and scalable technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates is described in this protocol.

一种技术，功能化和自组装纳米宏观 - 配体单层膜模板上无基材

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and ...

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.

大面积的制造自立性的超薄聚合物薄膜

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

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.

制备热塑性微流体通道

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

生物学

Formation of Biomembrane Microarrays with a Squeegee-based Assembly Method

Lipid bilayer membranes form the plasma membranes of cells and define the boundaries of subcellular organelles. In nature, these membranes are heterogeneous mixtures of many types of lipids, contain membrane-bound proteins and are decorated with carbohydrates. In some experiments, it is desirable to decouple the biophysical or biochemical properties of the lipid bilayer from those of the natural membrane. Such cases call for the use of model systems such as giant vesicles, liposomes or supported lipid bilayers (SLBs). Arrays of SLBs are particularly attractive for sensing applications and mimicking cell-cell interactions. Here we describe a new method for forming SLB arrays. Submicron-diameter SiO2 beads are first coated with lipid bilayers to form spherical SLBs (SSLBs). The beads are then deposited into an array of micro-fabricated submicron-diameter microwells. The preparation technique uses a "squeegee" to clean the substrate surface, while leaving behind SSLBs that have settled into microwells. This method requires no chemical modification of the microwell substrate, nor any particular targeting ligands on the SSLB. Microwells are occupied by single beads because the well diameter is tuned to be just larger than the bead diameter. Typically, more 75% of the wells are occupied, while the rest remain empty. In buffer SSLB arrays display long-term stability of greater than one week. Multiple types of SSLBs can be placed in a single array by serial deposition, and the arrays can be used for sensing, which we demonstrate by characterizing the interaction of cholera toxin with ganglioside GM1. We also show that phospholipid vesicles without the bead supports and biomembranes from cellular sources can be arrayed with the same method and cell-specific membrane lipids can be identified.

Supported lipid bilayers and natural membrane particles are convenient systems that can approximate the properties of cell membranes and be incorporated in a variety of analytical strategies. Here we demonstrate a method for preparing microarrays composed of supported lipid bilayer-coated SiO2 beads, phospholipid vesicles or natural membrane particles.

生物膜的微阵列用刮墨刀型组合方式形成

Lipid bilayer membranes form the plasma membranes of cells and define the boundaries of subcellular organelles. In nature, these membranes are ...

生物工程

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.

通过结合表面接枝和修改后的过程光敏感膜的制备

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

Fabricating Reactive Surfaces with Brush-like and Crosslinked Films of Azlactone-Functionalized Block Co-Polymers

In this paper, fabrication methods that generate novel surfaces using the azlactone-based block co-polymer, poly (glycidyl methacrylate)-block-poly (vinyl dimethyl azlactone) (PGMA-b-PVDMA), are presented. Due to the high reactivity of azlactone groups towards amine, thiol, and hydroxyl groups, PGMA-b-PVDMA surfaces can be modified with secondary molecules to create chemically or biologically functionalized interfaces for a variety of applications. Previous reports of patterned PGMA-b-PVDMA interfaces have used traditional top-down patterning techniques that generate non-uniform films and poorly controlled background chemistries. Here, we describe customized patterning techniques that enable precise deposition of highly uniform PGMA-b-PVDMA films in backgrounds that are chemically inert or that have biomolecule-repellent properties. Importantly, these methods are designed to deposit PGMA-b-PVDMA films in a manner that completely preserves azlactone functionality through each processing step. Patterned films show well-controlled thicknesses that correspond to polymer brushes (~90 nm) or to highly crosslinked structures (~1-10 &#956;m). Brush patterns are generated using either the parylene lift-off or interface directed assembly methods described and are useful for precise modulation of overall chemical surface reactivity by adjusting either the PGMA-b-PVDMA pattern density or the length of the VDMA block. In contrast, the thick, crosslinked PGMA-b-PVDMA patterns are obtained using a customized micro-contact printing technique and offer the benefit of higher loading or capture of secondary material due to higher surface area to volume ratios. Detailed experimental steps, critical film characterizations, and trouble-shooting guides for each fabrication method are discussed.

Surface fabrication methods for patterned deposition of nanometer thick brushes or micron thick, crosslinked films of an azlactone block co-polymer are reported. Critical experimental steps, representative results, and limitations of each method are discussed. These methods are useful for creating functional interfaces with tailored physical features and tunable surface reactivity.

Azlactone 功能块共聚物的刷状和交联膜制备反应表面

In this paper, fabrication methods that generate novel surfaces using the azlactone-based block co-polymer, poly (glycidyl methacrylate)-block-poly (vinyl ...

工程学

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.

超薄高性能金属-有机骨架膜的电泳结晶

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.

聚合物薄膜在多孔基板上的转移程序,具有最小化的缺陷

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

Microscopic Visualization of Porous Nanographenes Synthesized through a Combination of Solution and On-Surface Chemistry

On-surface synthesis has recently been regarded as a promising approach for the generation of new molecular structures. It has been particularly successful in the synthesis of graphene nanoribbons, nanographenes and intrinsically reactive and instable, yet attractive species. It is based on the combination of solution chemistry aimed at preparation of appropriate molecular precursors for further ultra-high vacuum surface assisted transformations. This approach also owes its success to an incredible development of characterization techniques, such as scanning tunneling/atomic force microscopy and related methods, which allow detailed, local characterization at atomic scale. While the surface-assisted synthesis can provide molecular nanostructures with outstanding precision, down to single atoms, it suffers from basing on metallic surfaces and often limited yield. Therefore, the extension of the approach away from metals and the struggle to increase productivity seem to be significant challenges toward wider applications. Herein, we demonstrate the on-surface synthesis approach for generation of non-planar nanographenes, which are synthesized through a combination of solution chemistry and sequential surface-assisted processes, together with the detailed characterization by scanning probe microscopy methods.

<meta charset="utf8"></head><body>通过溶液和表面化学相结合合成的多孔纳米石墨烯的微观可视化

A combination of solution and surface assisted synthesis opens new directions in the atomically precise synthesis of nanostructures. Scanning tunneling microscopy (STM) supplemented by non-contact atomic force microscopy (nc-AFM) enables detailed characterization of newly designed and generated carbon-based nano-objects.