Name: synthesis of a thiol building block for the crystallization of a semiconducting gyroidal metal-sulfur framework
Uploaded: 2018-04-09T13:00:00.000+00:00
Duration: 12 min 30 s
Description: Watch this Scientific Journal Video about Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework at JoVE.com

这项工作得到了中国国家自然科学基金 (21471037)、广东省杰出青年学者基金 (15ZK0307)、广东科技规划项目 (2017A050506051) 和香港特区研究资助委员会 [GRF 11303414]。

警告: 使用前请查阅所有相关的材料安全数据表。二硫化甲和 thiomethoxide 钠是强烈的恶臭, 应在通风罩中处理。金属钠具有极强的反应性, 对潜在的火灾和爆炸危险需要特别的安全措施。除使用油烟机外, 个人防护设备 (安全眼镜、手套、实验室大衣、全长长裤和闭趾鞋) 应适当采用。以下程序的一部分涉及标准的无空气处理技术。
1. Thiomethoxide 钠的制备 (CH3SNa)
<ol><li>将200毫升 Schlenk 烧瓶连接到真空气体歧管。疏散烧瓶, 然后用 N2三次回填它, 这样瓶子里就充满了一个稍正的 N2压力。 注意: 文献中简要提到了一种类似的编写 CH3SNa 的方法, 但没有提供详细的程序27,28。</li>
	<li>从煤油油藏取出一大块金属钠。用纸巾擦拭表面的残余油, 用刀子刮掉表面上的氧化物层。快速切割6.7 克的金属钠 (0.29 摩尔) 成小块 (e. g, 约大豆大小), 并立即将小块转移到200毫升 Schlenk 瓶下的计数器流 N2。立即用隔膜封住烧瓶。 注: 为了减少对空气的接触, 你可以从6.7 克的数量中切出钠, 并根据实际使用的钠量调整 THF 和二甲硫的含量。</li>
	<li>将80毫升无水、无气的 THF 从 Schlenk 线置于 N2保护下的烧瓶中通过套管。提取14.0 毫升二甲硫 (0.158 摩尔; 用 n2预先清除) 放入注射器中, 并将其注入到在 N2保护下的烧瓶中滴下。 注意: 二甲基二硫恶臭, 应在通风罩中处理。</li>
	<li>用地面玻璃塞子代替隔膜。将反应混合物在室温下搅拌24小时, 然后在60摄氏度处搅动3小时。 注: 反应混合物在室温下搅拌时粘性变稠;当加热到60摄氏度时, 混合物可以更容易搅拌, 从而加快反应完成。</li>
	<li>当温度保持在60摄氏度左右时, 使用 N2 (0.2 升/分钟) 的流来吹散 THF 溶剂和过量二甲基二硫醚, 直到出现干固体。使用冷阱 (e. g, 丙酮/干冰) 收集流出的 THF 和二甲硫。</li>
	<li>将剩余的固体混合物与油泵一起疏散约2小时, 除去残留的 THF 和二甲硫, 然后用 N2将其回填, 以获得淡黄色固体 (19.8 克, 97%)。将固态产品 CH3SNa 存储在黑暗中的氮气气氛中。 注: 为了保护真空泵, 在泵浦过程中应使用冷阱。</li>
</ol>2. 制备23、67、1011-hexakis (pentanoylthio) 苯并菲 (HVaTT) 作为受保护的硫醇链接器
<ol><li>将 0.664 g 的 CH3SNa (9.0 毫摩尔) 加载到50毫升 Schlenk 烧瓶中, 在 n 2 ( i.e) 的计数器流下, 在 n 2 保护下连接到真空气体歧管. 注意: CH3SNa 对空气敏感, 容易吸收水分。为了尽量减少对空气的接触, 你可以快速地称量出特定的量并将其添加到烧瓶中, 然后调整其他反应物的数量, 23, 67, 1011-hexabromotriphenylene (HBT), 相应地。 警告: 实心 CH3SNa 具有强烈的气味, 应在通风罩中处理。</li>
	<li>在 N2的计数器流下, 向烧瓶中添加0.216 克 HBT (0.30 毫摩尔), 并用隔膜封住烧瓶。</li>
	<li>将10毫升无水和无气 13-二甲基 2 imidazolidinone (DMEU) 从 Schlenk 线的 N2保护下通过套管转移到烧瓶中。</li>
	<li>用普通的玻璃塞子代替隔膜, 搅拌反应混合物, 用盐浴将其加热到240摄氏度, 在 N2下加48小时。</li>
	<li>对反应进展的薄层监测: 在 N2下, 使用玻璃吸管提取反应混合物的小整除 (约0.1 毫升), 并立即将其注入 valeroyl 氯化物 (约0.1 毫升) 在塑料中的整齐液体样品中。离心瓶, 然后摇1分钟;混合物应立即变成混浊与灰白色的颜色。加入0.4 毫升去离子水和0.1 毫升醋酸乙酯, 关闭瓶盖, 摇晃几秒钟。 注: 如果反应已经完成, 就不会出现在水层和乙酸乙酯之间的任何东西。如果不是, 将出现两层之间的白色不溶物。</li>
	<li>吸管上半部分, 并用它来发现薄层色板。用1:4 乙酸乙酯/石油醚开发薄层色谱板。对于一个完整的反应, 目标分子显示为一个规则点围绕 Rf = 0.4 在紫外线灯下。</li>
	<li>关掉暖气, 把反应瓶从盐浴中冷却到室温, 然后用冰浴把瓶子冷却到摄氏0摄氏度。</li>
	<li>用注射器在 N2下注入1.5 毫升的 valeroyl 氯 (12.6 毫摩尔) 到烧瓶中 (在大约2分钟的时间内)。保持搅拌在0°c 为2小时注: 在低温下添加 valeroyl 氯化物, 有助于减少副产品的生成。</li>
	<li>将混合物倒入50毫升的冰水中, 用醋酸乙酯 (3 30 毫升) 提取。然后用水 (6 60 毫升) 清洗复合有机层, 干燥过无水 MgSO4, 并通过旋转蒸发器去除挥发物。</li>
	<li>以1:10 乙酸乙酯/石油醚为淋洗, 用柱层析分离油性原油产品, 在溶剂的回转蒸发后提供淡黄色油性产物。用1:4 乙酸乙酯/石油醚开发薄层色谱板, Rf = 0.4。使用下面的研磨步骤进一步净化油性产品。</li>
	<li>添加5毫升的 methanolto 的油性产品, 油脂实验2分钟收集的结果白色固体使用吸滤 (产量: 59%)。</li>
</ol>3. HTT-铅骨架材料单晶的制备
<ol><li>混合11.4 毫克的 PbOAc·3H2O (0.030 毫摩尔) 在1.0 毫升乙烯二胺在一瓶, 以作出明确的解决办法。</li>
	<li>负载9.1 毫克的 HVaTT (0.010 毫摩尔), 2.0 毫升的脱气甲醇溶液的氢氧化钠 (70 毫摩尔/升), 和1.0 毫升乙烯二胺成空10毫升瓶和油脂实验5分钟。</li>
	<li>将 PbOAc 溶液添加到微气泡 HVaTT 混合物中。然后用 N2将反应混合物泡在1分钟内, 然后戴上螺钉盖密封瓶子。</li>
	<li>加热瓶在90°c 在一个烤箱48小时, 其次是自然冷却到室温, 在此期间形成了黄橙, 八面体单晶, 适合单晶 x 射线衍射研究 (产量: 45%)。</li>
	<li>吸入过滤掉晶体并迅速用甲醇清洗。用玻璃吸管将晶体转移到含有无气甲醇 (5 毫升) 的瓶子中, 以存放在室温下。</li>
</ol>4. 百草枯二碘化与 HTT 铅晶体的相互作用
<ol><li>使用玻璃巴斯德吸管从甲醇的股票中提取出几粒 HTT Pb 单晶, 并将其放到培养皿上 (直径35毫米和深度10毫米)。用纸巾或滤纸 (或让甲醇自然干燥) 吸收甲醇液体, 然后落到晶体上几滴水溶液的百草枯二碘化 (0.1%, w/w)。</li>
	<li>用眼睛或显微镜观察晶体的颜色变化。</li>
</ol>

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W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Early+metal+thiolato+species+as+metalloligands+in+the+formation+of+early/late+heterobimetallic+complexes:+syntheses+and+molecular+structures+of+Cp2Ti(SMe)2,+Cp2V(SMe)2,+(Cp2Ti(&#181;-SMe)2)2Ni+and+(Ni(&#181;-SMe)2)6.">Early metal thiolato species as metalloligands in the formation of early/late heterobimetallic complexes: syntheses and molecular structures of Cp2Ti(SMe)2, Cp2V(SMe)2, (Cp2Ti(&#181;-SMe)2)2Ni and (Ni(&#181;-SMe)2)6.</a> Organometallics. 8 (12), 2836-2843 (1989).</li><li>Chakraborty, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sodium+methanethiolate.">Sodium methanethiolate.</a> e-EROS Encycl Reagents Org Synth. , 1-5 (2014).</li><li>Huang, 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=A+semiconducting+gyroidal+metal-sulfur+framework+for+chemiresistive+sensing.">A semiconducting gyroidal metal-sulfur framework for chemiresistive sensing.</a> J Mater Chem A. 5 (31), 16139-16143 (2017).</li><li>He, 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=Building+thiol+and+metal-thiolate+functions+into+coordination+nets:+Clues+from+a+simple+molecule.">Building thiol and metal-thiolate functions into coordination nets: Clues from a simple molecule.</a> J Solid State Chem. 182 (7), 1821-1826 (2009).</li><li>Yee, K. -. K., 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=Effective+Mercury+Sorption+by+Thiol-Laced+Metal-Organic+Frameworks:+in+Strong+Acid+and+the+Vapor+Phase.">Effective Mercury Sorption by Thiol-Laced Metal-Organic Frameworks: in Strong Acid and the Vapor Phase.</a> J Am Chem Soc. 135 (21), 7795-7798 (2013).</li><li>Yee, K. -. K., 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=Room-temperature+acetylene+hydration+by+a+Hg(II)-laced+metal-organic+framework.">Room-temperature acetylene hydration by a Hg(II)-laced metal-organic framework.</a> Chem Commun. 51 (54), 10941-10944 (2015).</li><li>Gui, 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=Tackling+poison+and+leach:+catalysis+by+dangling+thiol-palladium+functions+within+a+porous+metal-organic+solid.">Tackling poison and leach: catalysis by dangling thiol-palladium functions within a porous metal-organic solid.</a> Chem Commun. 51 (32), 6917-6920 (2015).</li><li>He, J., Zeller, M., Hunter, A. D., Xu, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Functional+shakeup+of+metal-organic+frameworks:+the+rise+of+the+sidekick.">Functional shakeup of metal-organic frameworks: the rise of the sidekick.</a> CrystEngComm. 17 (48), 9254-9263 (2015).</li></ol>

作者没有什么可透露的。

溴组与 thiomethoxide 阴离子的反应显然首先产生了甲基硫醚类, 然后 demethylated 过量 thiomethoxide 提供 thiolate 负离子产品。为了确保完全转化为所需的 thiolate 阴离子 (特别是 polybromide 基板如 HBT), 长时间加热的旺盛条件 (例如, 240 °c 超过48小时) 与大量过量钠 thiomethoxide (例如, 超过三倍的摩尔的溴组) 是必不可少的。防止反应物和产物的 thiolate 种类的氧化也需要氮气保护。酰化步骤 (例?...

目前有极大的兴趣使用强, 极化金属硫 (e. g., 金属 thiolate) 链接, 用于构造具有增强电催化和导电性能的开放框架材料1,2,3,4,5,6,7,8,9,10. 除了在延长的状态下促进电子相互作用和运输外, 软和共价键金属硫的连接也给水环境中的应用提供了更好的稳定性。在含硫的积木中, 对称的, 多齿多环芳烃积木, 如 23, 67, 1011-苯并菲 hexathiol (HTT)9,11,12, 13,14不仅提供高度极化的π电子, 而且在框架设计和合成方面也提供了明显的优势。首先, 刚性和对称的苯并菲核心, 结合螯合 dithiolene 组的 HTT, 有助于锁定金属离子在常规的粘合图案, 简化预期网络的结构预测7,15. 与硫磺连接器的刚性和开放几何结合, 具有大量孔隙特征的框架结构通常可以在固态中实现。
在组装硫醇设备金属 orangic 框架 (MOF) 材料的一个主要挑战是植根于有机链接分子的合成。在经典的协议中, 硫醇基团必须是从苯酚组中提取的, 使用纽曼-Kwart 重排O-芳 thiocarbamate 前体16,17,18。然而, 这种方法涉及对苯酚前体分子的精心制备步骤以及高温固相转化的潜在并发症。另一种制造硫醇的方法是在苛刻的条件下使用 thioethers 的还原脱, 例如, 液态氨水中的钠金属 19, 20, 21, 22, 而不是与羧基和其他许多捐助函数兼容, 用于网络建设。
相比之下, 此处提出的协议具有多种优点: 安全性、方便性、成本效益以及与其他功能组 (e. g、carbonitrile 和吡啶) 的兼容性。通过大力加热一般廉价的芳香卤化物 (e. g, hexabromotriphenylene) 和 thiomethoxide 阴离子, thiolate 负离子产生 (通过甲基硫醚类中间产物), 然后酰给稳定和易于处理的硫酯产品-所有在一个锅。
我们还将描述一个程序, 利用硫酯分子作为连接器的蒙面形式, 以获取单一晶体半导体和多孔金属 dithiolene 网络。不同于高度反应自由站立的硫醇, 它倾向于分解和复杂化金属 thiolate 开放框架的结晶, 硫酯可以容易地被切开(e. g, 由氢氧化钠或乙二胺)就地提供硫醇类, 有助于减轻硫醇单位和金属中心之间的反应, 从而改善结晶。
这种制备硫醇/硫酯的议定书尚未被其他群体广泛用于金属-硫框架的新兴领域, 尽管 thiolate 阴离子的烷基芳 thioethers 的亲核 dealkylations 已经被有机化学家23,24,25,26。通过展示这种有效的 thioesters 合成方法及其用于促进金属硫网络的结晶, 我们希望进一步努力弥合合成有机化学与固态化学, 有助于快速、健康地发展多孔骨架。

<table><tbody><tr><td>Bromine</td><td>DAMAO CHEMICAL REAGENT FACTORY</td><td>7726-95-6</td><td>Highly toxic</td></tr><tr><td>Triphenylene&amp;nbsp;&amp;nbsp;</td><td>HWRK Chem</td><td>HWG45510</td><td></td></tr><tr><td>Iron powder</td><td>Sigma-Aldrich</td><td>12310</td><td></td></tr><tr><td>Nitrobenzene</td><td>DAMAO CHEMICAL REAGENT FACTORY</td><td>2934</td><td></td></tr><tr><td>Diethyl ether&amp;nbsp;</td><td>DAMAO CHEMICAL REAGENT FACTORY</td><td>48</td><td></td></tr><tr><td>Dichloromethane</td><td>DAMAO CHEMICAL REAGENT FACTORY</td><td>3067</td><td></td></tr><tr><td>Sodium metal</td><td>J&amp;amp;K</td><td>WM-NMS-54-25X-50G</td><td>Air sensitive</td></tr><tr><td>Tetrahydrofuran</td><td>J&amp;amp;K</td><td>315353</td><td></td></tr><tr><td>Dimethyl disulfide</td><td>INTERNATIONAL LABORATORY USA</td><td>726415</td><td></td></tr><tr><td>1,3-Dimethyl-2-imadazolidinone</td><td>J&amp;amp;K</td><td>50483</td><td>Dried over 4&amp;Aring; sieves</td></tr><tr><td>Valeryl&amp;nbsp; chloride</td><td>J&amp;amp;K</td><td>99590</td><td></td></tr><tr><td>Methanol</td><td>Guangzhou Chemical Reagent Factory</td><td>2334</td><td></td></tr><tr><td>Sodium hydroxide</td><td>Guangzhou Chemical Reagent Factory</td><td>1588</td><td></td></tr><tr><td>Ethylene diamine</td><td>Riedel-de Ha&amp;euml;n</td><td>15070</td><td></td></tr><tr><td>Lead acetate trihydrate</td><td>PEKING CHEMICAL WORKE</td><td>861218</td><td></td></tr></tbody></table>

synthesis of a thiol building block for the crystallization of a semiconducting gyroidal metal-sulfur framework

我们提出了一种制备硫酯分子的方法, 作为硫醇连接器的掩蔽形式及其在高度有序的单晶态中获取半导体和多孔金属 dithiolene 网络的利用。不同于高度反应自由站立的硫醇, 它倾向于分解和复杂化金属 thiolate 开放框架的结晶, 硫酯反应原位提供硫醇种类, 为缓和之间的反应硫醇单位和金属中心, 从而改善结晶。具体地说, 硫酯是在一锅工序中合成的: 芳香溴 (hexabromotriphenylene) 在剧烈的条件下与过量 thiomethoxide 反应, 首先形成硫醚类中间产物。硫醚类然后 demethylated 过剩的 thiomethoxide 提供 thiolate 负离子, 酰形成硫酯产品。用标准柱层析法对硫酯进行了简便纯化, 然后直接在骨架合成中使用, 其中氢氧化钠和乙二胺用于恢复原位硫酯到硫醇连接器组装单晶 Pb (II)-dithiolene 网络。与其他的硫醇合成方法 (e. g) 相比, 用钠金属和液态氨裂解烷基硫醚类, 这里的硫酯合成使用简单的条件和经济试剂。此外, 硫酯产品稳定, 可以方便地处理和储存。更重要的是, 与访问水晶金属 thiolate 开放框架的一般困难相反, 我们证明使用硫酯进行原位的硫醇连接器的形成大大提高了固态的结晶度. 产品。我们打算通过披露硫酯的合成协议以及水晶骨架固体, 鼓励在技术上重要的金属硫框架方面开展更广泛的研究工作。

HVaTT 分子的红外光谱 (由 KBr 颗粒法收集) 以其最大吸收率为1700厘米-1, 按照硫酯官能团的羰基拉伸。1HVaTT (400 MHz、CDCl3) 的 H 核磁共振谱显示了δ8.47 中的一个单线, 从芳香氢, 连同 4 multiplets 从脂肪族质子: δ 8.47 (s, 6H, CHAr), 2.75-2.72 (t, J = 7.4, 12H, CH2), 1.81-1. 77 (m,12H, ch2), 1.50-1. 45 (dd, J = 7.4, 12H, CH2), 1.00-0. 97 (t, J</em...

Watch this Scientific Journal Video about Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework at JoVE.com

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

在这里, 我们提出了一锅, 过渡无金属合成的硫醇和 thioesters 从芳香卤化物和 thiomethoxide 钠, 其次是制备的单一晶体的金属 dithiolene 网络使用硫醇物种产生的就地从更稳定和易于驾驭的硫酯。

半导体回转金属硫框架结晶的硫醇构建块的合成

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

synthesis-thiol-building-block-for-crystallization-semiconducting

Research

Education

JoVE Journal

JoVE Core

Organic Chemistry

Chemistry

Unit 1

Ethers, Epoxides, Sulfides

SCIENTISTS IN ACTION

9.0K 次观看.  Guangdong University of Technology. 在这里, 我们提出了一锅, 过渡无金属合成的硫醇和 thioesters 从芳香卤化物和 thiomethoxide 钠, 其次是制备的单一晶体的金属 dithiolene 网络使用硫醇物种产生的就地从更稳定和易于驾驭的硫酯。

视频: Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template&#39;s channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

This article describes the preparation of well-ordered nickel nanofoams via electroless metal deposition onto nanoporous templates obtained from self-assembled diblock copolymer based supramolecules.

Gyroid镍纳米结构的嵌段共聚物超分子

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, ...

科研

化学

Seeded Synthesis of CdSe/CdS Rod and Tetrapod Nanocrystals

We demonstrate a method for the synthesis of multicomponent nanostructures consisting of CdS and CdSe with rod and tetrapod morphologies. A seeded synthesis strategy is used in which spherical seeds of CdSe are prepared first using a hot-injection technique. By controlling the crystal structure of the seed to be either wurtzite or zinc-blende, the subsequent hot-injection growth of CdS off of the seed results in either a rod-shaped or tetrapod-shaped nanocrystal, respectively. The phase and morphology of the synthesized nanocrystals are confirmed using X-ray diffraction and transmission electron microscopy, demonstrating that the nanocrystals are phase-pure and have a consistent morphology. The extinction coefficient and quantum yield of the synthesized nanocrystals are calculated using UV-Vis absorption spectroscopy and photoluminescence spectroscopy. The rods and tetrapods exhibit extinction coefficients and quantum yields that are higher than that of the bare seeds. This synthesis demonstrates the precise arrangement of materials that can be achieved at the nanoscale by using a seeded synthetic approach.

A protocol for the seeded synthesis of rod-shaped and tetrapod-shaped multicomponent nanostructures consisting of CdS and CdSe is presented.

硒化镉/硫化镉棒和纳米四脚合成种子

We demonstrate a method for the synthesis of multicomponent nanostructures consisting of CdS and CdSe with rod and tetrapod morphologies. A seeded ...

Synthesis of Ligand-free CdS Nanoparticles within a Sulfur Copolymer Matrix

Aliphatic ligands are typically used during the synthesis of nanoparticles to help mediate their growth in addition to operating as high-temperature solvents. These coordinating ligands help solubilize and stabilize the nanoparticles while in solution, and can influence the resulting size and reactivity of the nanoparticles during their formation. Despite the ubiquity of using ligands during synthesis, the presence of aliphatic ligands on the nanoparticle surface can result in a number of problems during the end use of the nanoparticles, necessitating further ligand stripping or ligand exchange procedures. We have developed a way to synthesize cadmium sulfide (CdS) nanoparticles using a unique sulfur copolymer. This sulfur copolymer is primarily composed of elemental sulfur, which is a cheap and abundant material. The sulfur copolymer has the advantages of operating both as a high temperature solvent and as a sulfur source, which can react with a cadmium precursor during nanoparticle synthesis, resulting in the generation of ligand free CdS. During the reaction, only some of the copolymer is consumed to produce CdS, while the rest remains in the polymeric state, thereby producing a nanocomposite material. Once the reaction is finished, the copolymer stabilizes the nanoparticles within a solid polymeric matrix. The copolymer can then be removed before the nanoparticles are used, which produces nanoparticles that do not have organic coordinating ligands. This nascent synthesis technique presents a method to produce metal-sulfide nanoparticles for a wide variety of applications where the presence of organic ligands is not desired.

Herein we present a method to synthesize ligand-free cadmium sulfide (CdS) nanoparticles based on a unique sulfur copolymer. The sulfur copolymer operates as a high temperature solvent and a sulfur source during the nanoparticle synthesis and stabilizes the nanoparticles after the reaction.

a硫磺共聚物基质内的免费配体硫化镉纳米粒子的合成

Aliphatic ligands are typically used during the synthesis of nanoparticles to help mediate their growth in addition to operating as high-temperature ...

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, 1,4-benzene-bis(iminoguanidinium) (BBIG), is demonstrated. The ligand is synthesized as the chloride salt (BBIG-Cl) by in situ imine condensation of terephthalaldehyde with aminoguanidinium chloride in water, followed by crystallization as the sulfate salt (BBIG-SO4). Alternatively, BBIG-Cl is synthesized ex situ in larger scale from ethanol. The sulfate separation ability of the BBIG ligand is demonstrated by selective and quantitative crystallization of sulfate from seawater. The ligand can be recycled by neutralization of BBIG-SO4 with aqueous NaOH and crystallization of the neutral bis-iminoguanidine, which can be converted back into BBIG-Cl with aqueous HCl and reused in another separation cycle. Finally, 35S-labeled sulfate and &#946; liquid scintillation counting are employed for monitoring the sulfate concentration in solution. Overall, this protocol will instruct the user in the necessary skills to synthesize a ligand, employ it in the selective crystallization of sulfate from aqueous solutions, and quantify the separation efficiency.

A protocol for in situ aqueous synthesis of a bis(iminoguanidinium) ligand and its utilization in selective separation of sulfate is presented.

分离硫酸选择性结晶用双 -  iminoguanidinium配体

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, ...

The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a sterically demanding ligand, has increased in recent years. The metastable Sn(I) halide is synthesized at&#160;&#34;outer space conditions&#34; via the preparative co-condensation technique. Thereby, the subhalide is synthesized in an oven at high temperatures, around 1,300 &#176;C, and at reduced pressure by the reaction of elemental tin with hydrogen halide gas (e.g., HCl). The subhalide (e.g., SnCl) is trapped within a matrix of an inert solvent, like toluene at -196 &#176;C. Heating the solid matrix to -78 &#176;C gives a metastable solution of the subhalide. The metastable subhalide solution is highly reactive but can be stored at -78 &#176;C for several weeks. On heating the solution to room temperature, a disproportionation reaction occurs, leading to elemental tin and the corresponding dihalide. By applying bulky ligands like Si(SiMe3)3, the intermediate metalloid cluster compounds can be trapped before complete disproportionation to elemental tin. Hence, the reaction of a metastable Sn(I)Cl solution with Li-Si(SiMe3)3 gives [Sn10(Si(SiMe3)3)4]2- 1 as black crystals in high yield. 1 is formed via a complex reaction sequence including salt metathesis, disproportionation, and degradation of larger clusters. Further, 1 can be analyzed by various methods like NMR or single crystal X-ray structure analysis.

The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique

The disproportionation reaction of a metastable Sn(I) chloride solution, obtained via the preparative co-condensation technique, is used for the synthesis of a metalloid tin cluster compound.

的合成[锡<sub&gt; 10</sub&gt;（SI（SIME<sub&gt; 3</sub&gt;）<sub&gt; 3</sub&gt;）<sub&gt; 4</sub&gt;]<sup&gt; 2</sup<sup&gt; -</sup&gt;使用亚稳锡（I）卤溶液通过共缩聚合成技术

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a ...

Preparation of Large-area Vertical 2D Crystal Hetero-structures Through the Sulfurization of Transition Metal Films for Device Fabrication

We have demonstrated that through the sulfurization of transition metal films such as molybdenum (Mo) and tungsten (W), large-area and uniform transition metal dichalcogenides (TMDs) MoS2 and WS2 can be prepared on sapphire substrates. By controlling the metal film thicknesses, good layer number controllability, down to a single layer of TMDs, can be obtained using this growth technique. Based on the results obtained from the Mo film sulfurized under the sulfur deficient condition, there are two mechanisms of (a) planar MoS2 growth and (b) Mo oxide segregation observed during the sulfurization procedure. When the background sulfur is sufficient, planar TMD growth is the dominant growth mechanism, which will result in a uniform MoS2 film after the sulfurization procedure. If the background sulfur is deficient, Mo oxide segregation will be the dominant growth mechanism at the initial stage of the sulfurization procedure. In this case, the sample with Mo oxide clusters covered with few-layer MoS2 will be obtained. After sequential Mo deposition/sulfurization and W deposition/sulfurization procedures, vertical WS2/MoS2 hetero-structures are established using this growth technique. Raman peaks corresponding to WS2 and MoS2, respectively, and the identical layer number of the hetero-structure with the summation of individual 2D materials have confirmed the successful establishment of the vertical 2D crystal hetero-structure. After transferring the WS2/MoS2 film onto a SiO2/Si substrate with pre-patterned source/drain electrodes, a bottom-gate transistor is fabricated. Compared with the transistor with only MoS2 channels, the higher drain currents of the device with the WS2/MoS2 hetero-structure have exhibited that with the introduction of 2D crystal hetero-structures, superior device performance can be obtained. The results have revealed the potential of this growth technique for the practical application of 2D crystals.

Through the sulfurization of pre-deposited transition metals, large-area and vertical 2D crystal hetero-structures can be fabricated. The film transferring and device fabrication procedures are also demonstrated in this report.

硫化过渡金属膜制备大面积垂直2D 晶体杂化结构

We have demonstrated that through the sulfurization of transition metal films such as molybdenum (Mo) and tungsten (W), large-area and uniform transition ...

工程学

Constructing Thioether/Vinyl Sulfide-tethered Helical Peptides Via Photo-induced Thiol-ene/yne Hydrothiolation

Here, we describe a detailed protocol for the preparation of thioether-tethered peptides using on-resin intramolecular/intermolecular thiol-ene hydrothiolation. In addition, this protocol describes the preparation of vinyl-sulfide-tethered peptides using in-solution intramolecular thiol-yne hydrothiolation between amino acids that possess alkene/alkyne side chains and cysteine residues at i, i+4 positions. Linear peptides were synthesized using a standard Fmoc-based solid-phase peptide synthesis (SPPS). Thiol-ene hydrothiolation is carried out using either an intramolecular thio-ene reaction or an intermolecular thio-ene reaction, depending on the peptide length. In this research, an intramolecular thio-ene reaction is carried out in the case of shorter peptides using on-resin deprotection of the trityl groups of cysteine residues following the complete synthesis of the linear peptide. The resin is then set to UV irradiation using photoinitiator 4-methoxyacetophenone (MAP) and 2-hydroxy-1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-1-propanone (MMP). The intermolecular thiol-ene reaction is carried out by dissolving Fmoc-Cys-OH in an N,N-dimethylformamide (DMF) solvent. This is then reacted with the peptide using the alkene-bearing residue on resin. After that, the macrolactamization is carried out using benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop), 1-hydroxybenzotriazole (HoBt), and 4-Methylmorpholine (NMM) as activation reagents on the resin. Following the macrolactamization, the peptide synthesis is continued using standard SPPS. In the case of the thio-yne hydrothiolation, the linear peptide is cleaved from the resin, dried, and subsequently dissolved in degassed DMF. This is then irradiated using UV light with photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA). Following the reaction, DMF is evaporated and the crude residue is precipitated and purified using high-performance liquid chromatography (HPLC). These methods could function to simplify the generation of thioether-tethered cyclic peptides due to the use of the thio-ene/yne click chemistry that possesses superior functional group tolerance and good yield. The introduction of thioether bonds into peptides takes advantage of the nucleophilic nature of cysteine residues and is redox-inert relative to disulfide bonds.

We present a protocol for the construction of thioether/vinyl sulfide-tethered helical peptides using photo-induced thiol-ene/thiol-yne hydrothiolation.

利用光致硫醇-烯/yne Hydrothiolation 构造硫醚类/乙烯基硫化物栓系螺旋肽

Here, we describe a detailed protocol for the preparation of thioether-tethered peptides using on-resin intramolecular/intermolecular thiol-ene ...

Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in Poly(S-Divinylbenzene)

Elemental sulfur (S8) is a byproduct of the petroleum industry with millions of tons produced annually. Such abundant production and limited applications lead to sulfur as a cost-efficient reagent for polymer synthesis. Inverse vulcanization combines elemental sulfur with a variety of monomers to form functional polysulfides without the need for solvents. Short reaction times and straight forward synthetic methods have led to rapid expansion of inverse vulcanization. However, high reaction temperatures (&#62;160 &#176;C) limit the types of monomers that can be used. Here, the dynamic sulfur bonds in poly(S-divinylbenzene) are used to initiate polymerization at much lower temperatures. The S-S bonds in the prepolymer are less stable than S-S bonds in S8, allowing radical formation at 90 &#176;C rather than 159 &#176;C. A variety of allyl and vinyl ethers have been incorporated to form terpolymers. The resulting materials were characterized by 1H NMR, gel permeation chromatography, and differential scanning calorimetry, as well as examining changes in solubility. This method expands on the solvent-free, thiyl radical chemistry utilized by inverse vulcanization to create polysulfides at mild temperatures. This development broadens the range of monomers that can be incorporated thus expanding the accessible material properties and possible applications.

Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in PolyS-Divinylbenzene

The goal of this protocol is to initiate polymerization using dynamic sulfur bonds in poly(S-divinylbenzene) at mild temperatures (90 &#176;C) without using solvents. Terpolymers are characterized by GPC, DSC and 1H NMR, and tested for changes in solubility.

在高温下利用聚苯 (s-二硝基苯) 动态硫键合成三聚体

Elemental sulfur (S8) is a byproduct of the petroleum industry with millions of tons produced annually. Such abundant production and limited applications ...

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. However, the synthesis of single-crystalline core-shell MOFs is very challenging, and thus a limited number of examples have been reported. Here, we suggest a method of synthesizing single-crystalline HKUST-1@MOF-5 core-shells, which is HKUST-1 at the center of MOF-5. Through the computational algorithm, this pair of MOFs was predicted to have the matched lattice parameters and chemical connection points at the interface. To construct the core-shell structure, we prepared the octahedral- and cubic-shaped HKUST-1 crystals as a core MOF, in which the (111) and (001) facets were mainly exposed, respectively. Via the sequential reaction, the MOF-5 shell was well-grown on the exposed surface, showing a seamless connect interface, which resulted in the successful synthesis of single-crystalline HKUST-1@MOF-5. Their pure phase formation was proved by optical microscopic images and powder X-ray diffraction (PXRD) patterns. This method presents the potential of and insights into the single-crystalline core-shell synthesis with different kinds of MOFs.

Here, we demonstrate a protocol for the two-step synthesis of single-crystalline core-shells using a non-isostructural metal-organic framework (MOF) pair, HKUST-1 and MOF-5, which have well-matched crystal lattices.

单晶核壳金属有机骨架的合成

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

从多主题膦接头合成低价 MOF

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

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, energy, and catalysis. Recently, low-valent MOFs (LVMOFs) have been explored for their potential use as heterogeneous catalysts, and multitopic phosphine linkers have been shown to be a useful building block for the formation of LVMOFs. However, the synthesis of LVMOFs using phosphine linkers requires conditions that are distinct from those in the majority of the MOF synthetic literature, including the exclusion of air and water and the use of unconventional modulators and solvents, making it somewhat more challenging to access these materials. This work serves as a general tutorial for the synthesis of LVMOFs with phosphine linkers, including information on the following: 1) the judicious choice of the metal precursor, modulator, and solvent; 2) the experimental procedures, air-free techniques, and required equipment; 3) the proper storage and handling of the resultant LVMOFs; and 4) useful characterization methods for these materials. The intention of this report is to lower the barrier to this new subfield of MOF research and facilitate advancements toward novel catalytic materials.

作者聚焦:从多主题膦接头合成低价金属有机框架的实验方法  

Here, we describe a protocol for the synthesis of low-valent metal-organic frameworks (LVMOFs) from low-valent metals and multitopic phosphine linkers under air-free conditions. The resulting materials have potential applications as heterogeneous catalyst mimics of low-valent metal-based homogeneous catalysts.

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, ...

半导体回转金属硫框架结晶的硫醇构建块的合成

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