Name: development of heterogeneous enantioselective catalysts using chiral metal-organic frameworks (mofs)
Uploaded: 2020-01-17T15:00:00
Description: Watch this Scientific Journal Video about Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs at JoVE.com

这项工作得到了韩国国家研究基金会（NRF）基础科学研究计划NRF-2019R1A2C4070584和由韩国政府资助的NRF-2016R1A5A1009405科学研究中心的支持。S. Kim 获得 NRF 全球博士奖学金 （NRF-2018H1A2A1062013） 的支持。

1. 三种尺寸的 （S） -KUMOF-1 晶体的制备
注：每一步都遵循前一份报告2、24、27的实验部分和补充资料。三种不同尺寸的（S） -KUMOF-1：大 （S） -KUMOF-1-（L）， 中等 （S） -KUMOF-1-（M） 和小（S）-KUMOF-1-（S） 粒径 >100 μm， >20 ?...

<ol>
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在合成 （S） -KUMOF-1后， 一些小瓶中的晶体似乎是粉末状的， 不适合用于催化.因此， 需要选择适当的晶体 （S） -KUMOF-1.（S） -KUMOF-1的收率仅使用成功合成的小瓶计算。当从溶剂中抽离时， （S） -KUMOF-1拆除.因此，晶体应始终保持湿润。因此， 称称完整 （S） -KUMOF-1晶体浸入溶剂中是很困难的.（...

MoFs 被认为是化学反应的有用异构催化剂。有许多不同的报告使用MoF用于抗选择性催化1，2，3，4，5，6，7，8，9，10，11，12，13，14，15，16，17 ，18，19.不过，目前尚不清楚这些反应是发生在MoFs的内表面还是外表面。最近的研究提出了关于利用可用表面和减少扩散20，21，22，23的问题。一个更引人注目的问题是，手性环境随MOF晶体中每个腔的位置而变化。手性环境的这种异质性意味着反应产物的立体选择性取决于反应位24。因此，设计一个高效的抗选择性催化剂需要确定反应发生的位置。为此，必须确保反应仅在内表面或仅在 MOF 的外表面发生，同时保持内部完好无损。MoF的多孔结构及其含有手性环境活性位点的较大表面积可用于内选性催化。因此，MoFs是固体支持异构催化剂25的极佳替代品。如果MoF内部没有反应，则需要重新考虑使用MoF作为异构催化剂。反应部位的位置很重要，以及腔的大小。在多孔材料中，型腔的大小根据基板的大小决定基板的大小。有一些关于基于MOF的催化剂的报告，它忽视型腔尺寸问题25。许多基于MOF的催化剂将笨重的催化种类（例如，Ti（O-i Pr）4）引入到原来的框架结构3，8，13。在原始框架结构中采用笨重的催化品种时，腔体尺寸发生变化。笨重的催化种类导致的腔体尺寸减小，使得基材无法完全扩散到MoFs中。因此，在这些情况下，需要考虑按 MoF 的空腔大小对基板大小进行区分。MOF的催化反应往往难以支持MOF腔内发生反应的证据。一些研究表明，比MOF腔体更大的基板很容易转化为预期产品，这似乎是矛盾的8，13。这些结果可以解释为基板的功能组与启动催化反应的催化位点之间的接触。在这种情况下，无需基板扩散到 MoF;反应发生在MOF晶体26的表面，腔体大小不直接参与基材根据其尺寸的区分。
为了确定MoFs的反应部位，选择了一种已知的刘易斯酸促进碳基-ene反应2。以3-甲基甲酸酯及其同系物为基质，研究了四种类型的苯丙基-烯反应（图1）。此前报道的反应分为两类：使用Zn试剂的化学计量反应和使用Ti试剂27的催化反应。最小基质的反应需要锌/KUMOF-1（KUMOF + 韩国大学金属-有机框架）;据报道，这种反应发生在晶体27内部。该方法使用了两种MoF，即用于化学计量反应的Zn/KUMOF-1和用于催化反应的Ti/KUMOF-1。由于这两种MoF的不同反应机制，反应速率与基板大小的比较是可能的2，28，29。颗粒大小对碳基-ene反应的影响与Zn/KUMOF-127表明，如前一份报告所示，外表面的手性环境不同于MOF晶体24的内侧。本文演示了一种通过比较三种基材与两类催化剂的反应和颗粒大小效应的方法，如上文27所述。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Acetone</td>
			<td>Daejung</td>
			<td>1009-4110</td>
			<td></td>
		</tr>
		<tr>
			<td>Analytical Balance</td>
			<td>Sartorius</td>
			<td>CP224S</td>
			<td></td>
		</tr>
		<tr>
			<td>Copper(II) nitrate trihydrate</td>
			<td>Sigma Aldrich</td>
			<td>61194</td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Daejung</td>
			<td>3030-4465</td>
			<td></td>
		</tr>
		<tr>
			<td>Dimethyl zinc</td>
			<td>Acros</td>
			<td>377241000</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Daejung</td>
			<td>4016-4410</td>
			<td></td>
		</tr>
		<tr>
			<td>Filter paper</td>
			<td>Whatman</td>
			<td>WF1-0900</td>
			<td></td>
		</tr>
		<tr>
			<td>Methanol</td>
			<td>Daejung</td>
			<td>5558-4410</td>
			<td></td>
		</tr>
		<tr>
			<td>Microwave synthesizer</td>
			<td>CEM</td>
			<td></td>
			<td>Discover SP</td>
		</tr>
		<tr>
			<td>Microwave synthesizer 10 mL Vessel Accessory Kit</td>
			<td>CEM</td>
			<td>909050</td>
			<td></td>
		</tr>
		<tr>
			<td>N,N-Diethylformamide</td>
			<td>TCI</td>
			<td>D0506</td>
			<td></td>
		</tr>
		<tr>
			<td>N,N-Dimethylaniline</td>
			<td>TCI</td>
			<td>D0665</td>
			<td></td>
		</tr>
		<tr>
			<td>n-Hexane</td>
			<td>Daejung</td>
			<td>4081-4410</td>
			<td></td>
		</tr>
		<tr>
			<td>Normject All plastic syringe 5 mL luer tip 100/pk</td>
			<td>Normject</td>
			<td>A5</td>
			<td></td>
		</tr>
		<tr>
			<td>Pasteur Pipette 150 mm</td>
			<td>Hilgenberg</td>
			<td>HG.3150101</td>
			<td></td>
		</tr>
		<tr>
			<td>PTFE tape</td>
			<td>KDY</td>
			<td>TP-75</td>
			<td></td>
		</tr>
		<tr>
			<td>Rotary Evaporator</td>
			<td>Eyela</td>
			<td>243239</td>
			<td></td>
		</tr>
		<tr>
			<td>Shaker</td>
			<td>DAIHAN Scientific</td>
			<td>DH.WSO04010</td>
			<td></td>
		</tr>
		<tr>
			<td>Silica gel 60 (230-400 mesh)</td>
			<td>Merck</td>
			<td>109385</td>
			<td></td>
		</tr>
		<tr>
			<td>Synthetic Oven</td>
			<td>Eyela</td>
			<td>NDO-600ND</td>
			<td></td>
		</tr>
		<tr>
			<td>Titanium isopropoxide</td>
			<td>Sigma Aldrich</td>
			<td>87560</td>
			<td></td>
		</tr>
		<tr>
			<td>Vial (20 mL)</td>
			<td>SamooKurex</td>
			<td>SCV2660</td>
			<td></td>
		</tr>
		<tr>
			<td>Vial (5 mL)</td>
			<td>SamooKurex</td>
			<td>SCV1545</td>
			<td></td>
		</tr>
	</tbody>
</table>

development of heterogeneous enantioselective catalysts using chiral metal-organic frameworks (mofs)

基底尺寸由反应部位手性环境的孔径和均匀性进行区分，是金属-有机框架（MOF）中基于的催化剂在抗选择性催化反应中验证反应位点的重要问题系统。因此，有必要用一种验证基于MOF的催化剂反应位的方法来研究这个问题。通过将基板大小与两种不同类型的碳基-ene反应的的反应速率与两种 MoF 进行比较，实现了基底尺寸按孔径尺寸进行区分。MOF催化剂用于比较两种反应类型（锌介导的化学计量和Ti催化碳基-ene反应）在两种不同介质中的性能。采用该方法，观察到整个MOF晶体参与了反应，当反应是气算计时，晶体孔的内部在施加手性控制方面发挥了重要作用。MOF催化剂手性环境的均质性，通过锌介导的化学计量反应系统中使用的粒子的尺寸控制方法确定。为催化反应提出的方案表明，无论基质大小如何，反应主要发生在催化剂表面，揭示了MOF异构催化剂中的实际反应位点。该方法用于MOF催化剂的反应现场验证，为开发异构异构选择性MOF催化剂提出了各种考虑。

使用锌试剂的苯基-ene反应是化学计量的，因为甲氧基和碳基组与金属结合亲和力的差异（图2）。因此，基板在反应部位被转换成产品并保留在那里。如协议第4节所述，通过拆除晶体获得所需的产品。锌/（S）-KUMOF-1（表1）对基材的异构异构化碳基-ene反应结果表明，最小基质（1a）可以在晶体内扩散，以高收率（92%）转化为产物?...

Watch this Scientific Journal Video about Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs at JoVE.com

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs

在这里，我们提出了一个协议，通过比较化学计量和催化碳基-ene反应，以找出反应是否发生在金属-有机框架的内表面或外表面，金属-有机框架的活性现场验证。

使用气性金属-有机框架 （MoF） 开发异构异构选择性催化剂

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of ...

我们关于基于MOF的催化剂反应场验证的想法提供了关于MOF内表面还是外表面发生反应的可靠数据。这些方法可用于评估反应位点，这对于基于MOF的催化剂的设计至关重要。开发基于MOF的催化剂的研究可以使用这些方法实现催化剂特性的客观视角。这些方法的可视化演示至关重要，因为这些技术很难仅通过文本教学进行。演示这个程序的将是吉焕汉，一个研究生，从我的研究团队。对于小尺寸的KUMOF-1合成，在甲醇中溶解0.2毫克铜（II）硝酸盐，0.24毫克二甲酸结合。用PTFE盖盖反应电池，将反应器放在65摄氏度、每平方英寸100磅和50瓦的微波反应器中，20分钟。在反应结束时，用一个小铲子轻轻搅拌，使所得的蓝色立方晶体浮动，将晶体倒在滤纸上。每次洗涤用三毫升的热 DEF 洗三次，每次洗涤用三毫升无水 DCM 清洗三毫升，然后再将晶体转移到新鲜的无水 DCM 中进行储存。对于中等大小的KUMOF-1合成，将7.2毫克硝酸铜溶解在1.5毫升甲醇中，在1.5毫升的 DEF 中溶解9毫克二甲酸结合体。用针刺破胶带，将四毫升小瓶放入20毫升小瓶中。在小瓶和大瓶之间的空间中加入一毫升DMA。在65摄氏度的烤箱中，将大瓶紧紧盖住，进行24小时的孵育。第二天，用一个小铲子轻轻搅拌配方升小瓶溶液，将产生的蓝色立方晶体浮动，将晶体倒在一块滤纸上。在将晶体储存在三毫升新鲜DCM中之前，用三毫升新鲜热 DEF 和甲醇清洗三次晶体。对于锌/KUMOF-1晶体制备，在零下78摄氏度的DCM两毫升中，将680微升二甲基锌加入180毫克的KUMOF-1悬浮液。在此温度下，以每分钟 180 次旋转摇动混合物三个小时。在孵化结束时，将上清液除掉，用三毫升冷DCM洗涤所得产品数次，以完全去除任何未反应的二甲基锌。并遵循KUMOF-1晶体制备方案，如证明获得小、中、大尺寸锌/KUMOF-1晶体。合成钛/KUMOF-1晶体，在DCM的两毫升中，将59微升的异丙胺钛加入24毫克悬浮量。在室温下每分钟180次旋转时摇动混合物5小时。在孵育结束时，将上清液除掉，用三毫升冷DCM洗涤所得产品数次，以完全去除任何残留的异丙胺。并遵循KUMOF-1晶体制备方案，如证明获得小、中、大尺寸钛/KUMOF-1晶体。对于锌/KUMOF-1的异质碳基-烯反应，在零下78摄氏度的2毫升DCM中，将100微升DCM基板溶液加入102毫克悬浮锌/KUMOF-1。将反应混合物放入低温冷却浴中三个半小时，并摇动。在孵育结束时，用水性6法兰酸溶液的三毫升解，并通过硅藻硅垫过滤由此产生的混合物。对于钛/KUMOF-1的异质催化碳基-烯反应，在零摄氏度的2毫升DCM中加入100微升的基板溶液，加入钛/KUMOF-1的12毫克悬浮液中。在此温度下，以每分钟 180 次旋转的速度摇动溶液 36 小时。在孵育结束时，收集上清液，每次洗涤用三毫升新鲜DCM清洗三次。由于烷氧碳基组与金属的结合亲和力的差异，使用锌试剂进行抗性碳基-ene反应是计量的。锌/KUMOF-1基板异质碳基-ene反应结果表明，最小的基材可以扩散到晶体内部，并在高产量中转化为产品，证明金属有机框架的所有反应位点均可用。随着基板尺寸的增加，产量和抗异体过剩率下降，表明较大的基板无法进入金属有机框架晶体内的反应位点。最大的基板没有在此系统中发生反应，可能是因为反应通道被相应的反应产品阻断。如果基板尺寸太大，表面反应位点进行第一次接触并直接阻塞通道入口，因此其他基板无法穿透。当基板的大小与空隙的大小相比足够小时，额外的基板可以穿透晶体。与锌介质系统不同，钛催化系统提供了更多关于催化反应场址发生的事件的信息，不受基板尺寸的影响。事实上，大多数反应发生在表面或表面之下，产品被立即移除到溶液中。如所证明，请仔细遵循碳化-烯反应程序的步骤，对获得可靠的实验结果非常重要。双光子显微镜测量将为各种基于MOF的催化剂的实际反应场提供额外的数据。作为MOF催化剂反应场的验证程序是必要的。我们的方法可以作为仔细检查结果的手段。

Research

JoVE Journal

Chemistry

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

增强型氟烷烃的化学气相沉积等离子通过疏水金属 - 有机骨架的制备氨的去除

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

科研

化学

Synthesis and Characterization of Functionalized Metal-organic Frameworks

功能化的合成与表征金属 - 有机骨架

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

Synthesis of a Water-soluble MetalÃƒÆ’Ã‚Â¢ÃƒÂ¢Ã¢â‚¬Å¡Ã‚Â¬ÃƒÂ¢Ã¢â€šÂ¬Ã…â€œOrganic Complex Array

一个水溶性金属 - 有机络合物阵列合成

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

金属-有机框架的表面功能化改善防潮性能

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. ...

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

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 ...

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Because of their designability and unprecedented synergistic effects, core-shell metal-organic frameworks (MOFs) have been actively examined recently. ...

A Technical Guide for Performing Spectroscopic Measurements on Metal-Organic Frameworks

对金属有机骨架进行光谱测量的技术指南

Metal-organic frameworks (MOFs) offer a unique platform to understand light-driven processes in solid-state materials, given their high structural ...

Synthesis of Low-Valent MOFs from Multitopic Phosphine Linkers

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers (Video) | JoVE 

多位膦接头合成低价金属有机骨架的实验方法

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, ...

Triazole and Tetrazole Functionalized Zr-MOFs Synthesis and Characterization

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange

Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange (Video) | JoVE

通过合成后配体交换合成三唑和四唑功能化Zr基金属有机骨架

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. ...

Magnetometric Characterization of Redox-Active MOFs Solid-State Electrochemistry

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks (Video) | JoVE 

氧化还原-活性金属-有机骨架固态电化学中中间体的磁力表征

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs ...

使用气性金属-有机框架 （MoF） 开发异构异构选择性催化剂

使用气性金属-有机框架（MoF）开发异构异构选择性催化剂