资助这项工程由美国化学学会石油研究基金（52488-DNI1）和北卡罗来纳大学格林斯伯勒分校深表感谢。我们还要感谢特里尼罗河博士（联合国宣传小组），以供外借我们适当的玻璃器皿这些实验。视频咨询和编辑由Aaron GLANCY也承认。

1。 HIAT苯的合成<ol><li>装备一个干燥的100毫升的圆底烧瓶中，用磁搅拌器搅拌，并有氩气气氛下的烧瓶中。钳瓶的立场，并将其放入乙腈和固体二氧化碳颗粒冷冻剂洗澡。注意：该制冷剂应为约-45℃。 </li><li>加入10毫升无水二氯甲烷中，冰冷烧瓶，并允许溶剂平衡到冷冻剂的温度。注意：在烧瓶中的过量的顶部空间是用于加入乙醚后，强制沉淀重要。 </li><li>权衡0.35克cyanophenyliodonium三氟甲磺酸酯（1当量），并迅速将其传送到冷烧瓶中。注意：将固体应该是相当不溶在此温度下。 </li><li>去皮的空注射器的质量，然后用它衡量0.37克phenylethynyltributyltin（1当量）。 </li><li>注入phenylethynyltributyltin在冷溶液。注：固体的溶解是一个迹象表明，该HIAT已经形成。大致时间为溶解30分钟。 </li><li>加入乙醚和己烷，迫使产品沉淀。注意：如果沉淀不形成，使溶剂蒸发，在减压下，加入乙醚和己烷，迫使HIAT的沉淀的混合物。 </li><li>装备保温瓶用布氏漏斗和解决方案倒到漏斗过滤。 </li><li>收集固体并存储在寒冷的不透明的容器。 </li></ol> 2。正戊基HIAT合成<ol><li>装备一个250毫升三颈圆底烧瓶中，用磁搅拌器搅拌，并有氩气气氛下的烧瓶中。钳瓶的立场，并将其放入乙腈和固体二氧化碳颗粒冷冻剂洗澡。注意：该制冷剂应为约-45℃。 </li><li>在烧瓶装配在Schlenk过滤装置，使得过滤，可以迅速地进行，并在一个冷统温度。油脂和该装置的每个关节夹紧在一起。注意：该过滤系统可通过几种方法来构造，但它是非常重要的，该系统具有推入惰性气体和拉带通过玻璃过滤器真空的能力。 </li><li>加入10毫升无水二氯甲烷中，冰冷烧瓶，并允许溶剂平衡到冷冻剂的温度。注意：在烧瓶中的过量的顶部空间是用于添加己烷后，强制沉淀重要。 </li><li>权衡0.35克cyanophenyliodonium三氟甲磺酸酯（1当量），并迅速将其传送到冷烧瓶中。注意：将固体应该是相当不溶在此温度下。 </li><li>去皮的空注射器的质量，然后用它衡量0.44克三丁基锡庚炔（1当量）。 </li><li>注入的三丁基庚炔进入冷溶液。注：固体的溶解是一个迹象表明，HIAT已经形成。大致时间为溶解30分钟。 </li><li>注入75毫升十六进制ANE到烧瓶中的额外顶部空间，以形成沉淀物。 </li><li>将收集烧瓶在真空下。 </li><li>从支架上松开的设备和精心倾斜，以解决倒到玻璃过滤器。打开收集瓶真空通过拉液体。注意：不要让真空拉空气进入血管。 </li><li>拆除设备刮固体过滤网一次过滤完成。一旦将固体从滤液中除去它是较少的空气和温度敏感的，并且可以被处理开放于空气中。 </li><li>收集固体并存储在寒冷的不透明的容器。 </li></ol> 3。俄亥俄州Cyanocarbenes制成苯基HIAT的插入<ol><li>装备一个干燥的50ml园底烧瓶用磁搅拌器搅拌，并有氩气气氛下的烧瓶中。夹紧烧瓶中搅拌板和注入20ml无水甲醇中，向烧瓶中。 </li><li>权衡先前甲醇合成为0.300克（1当量）。ZED苯基HIAT并迅速将其添加到烧瓶中。 </li><li>加0.047克的叠氮化钠（1当量）的烧瓶中。注：该解决方案将变暗随着时间的推移和氮​​气由cyanocarbene形成产生。 </li><li>让反应继续进行，只要形成气泡发生。大致完成时间为20分钟。 </li><li>暴露的溶液在空气中，用减压蒸发溶剂。 </li><li>加二氯甲烷的残留液体，并执行水萃取以除去钠三氟甲磺酸酯。收集二氯甲烷和干燥，用无水硫酸钠将有机相。 </li><li>滗出溶液，并用蒸发减压。 </li><li>进行柱层析净化cyanocarbene产品。 </li></ol> 4。使用苯基环丙烷HIAT反应Cyanocarbene <ol><li>称量四丁基铵叠氮化物在手套箱0.125克（1当量），并将其放置在干燥10毫升圆底烧瓶当量uipped用磁搅拌器搅拌。 </li><li>盖上含有叠氮化四丁基铵10毫升圆底烧瓶中，从手套箱中取出，并使用舒伦克线将其放置在搅拌下盘氩气。 </li><li>加入1.0 ml苯乙烯，向烧瓶中，并允许烧瓶搅拌。注：叠氮化物不需要溶解。 </li><li>快速添加0.200克苯基HIAT（1当量）到该浆料中，然后将隔膜背面上被连接到的Schlenk线烧瓶中。注：该解决方案应该立即变暗，由cyanocarbene形成产生氮气。 </li><li>使反应继续下去，只要形成气泡发生。大致完成时间为一分钟。 </li><li>之后，气泡停止后，露出溶液在空气中，进行柱色谱法提纯产物。 </li></ol>

<ol>
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作者宣称，他们有没有竞争的财务权益。

高价碘炔基三氟甲磺酸酯，或HIATs，形成有可与叠氮化物源反应形成cyanocarbenes。这是非常重要的，所有必要的预防措施，因为许多在这个视频显示的试剂和中间体是可能发生爆炸和剧毒。虽然反应性的高的水平可能是危险的，如果准备不足，它表示在该播放该化合物的内在反应性可以通过捕获cyanocarbenes在各种反应如OH插入和环丙烷被利用。 其他HIATs的合成一直试图用不同的成...

有机化学的持续发展取决于新反应的设计和开发。尤其是，新的反应，使以前无法想象的合成路线的发现熊终极意义。为此目的，我们组随意转换炔的两个碳原子和一个叠氮化物的氮成cyanocarbene。1此以前未知的变换将允许在分子复杂显著增加，因为反应性cyanocarbene会迅速进一步反应。最初的努力是使用亲核炔和叠氮化物亲电的，但三唑被有效地形成在该情况下，而不是cyanocarbenes。2使用umpolung方法中，第二种方法是使用亲电炔和亲核叠氮化物和从cyanocarbene反应得到的产物是幸运的形成在该情况下，3有亲核叠氮化物的许多来源，然而，电炔烃是不太常见。本组克劳斯Banert先前报道证明了概念该反应使用炔基-氯，4但本集团与Banert组独立以及同时确定高价碘炔基三氟甲磺酸酯（HIATs）是原因好得多亲电稳定性和反应性。3,6我们这里所描述的合成，分离，和这些HIATs与叠氮化物的形成，并在原位作为cyanocarbenes反应反应。 几个安全预防措施，应继续进行这些实验之前予以考虑。一些高价碘炔基三氟甲磺酸酯是不稳定的，会发生分解，剧烈的某个时候，当暴露在空气和光线。7为了形成cyanocarbene中间，该过程需要使用叠氮化物的来源。叠氮化物是爆炸物和剧毒。8适当的个人防护装备应处理这些材料，特别是有机锡的时候可以穿，和所有操纵试剂应在适当通风罩。该cyanocarbene是一个强大的和不稳定的活性中间体。小心在小范围内开始进行实验，使氮气进化是可控的，从来没有在封闭系统中进行这些反应。如果规模化反应的需要，我们强烈建议使用安全防护罩。 先前已经发表了许多HIATs的合成被包括使用Zefirov的试剂9,10，和Koser试剂，9,11然而，这部影片将使用cyanophenyliodonium三氟甲磺酸酯试剂9,12（ 图1）。合成Cyanophenyliodonium三氟甲磺酸酯基上显示与先前报导的文献制备。与三烷基锡改性炔14 13的试剂反应，形成所需产物。后HIAT合成和分离它可以与叠氮化物反应，形成反应cyanocarbene中间（ 图2）。还有许多其他的方法可以用于合成碘炔烃，如使用炔基硅烷15和炔基硼酸酯16，但在视频的方法的原因是，在我们的经验，它有更好的效率和产率。 我们提出的机制3,5（ 图3），用于本反应包括加入叠氮化物源，以炔的β-碳，由此形成碘鎓盐的分解而碘苯和亚乙烯基碳烯。然后偏卡宾可以通过任一R-基团或酰基叠氮化物，得到炔基-叠氮化物的迁移发生的1,2 -重排。的炔基叠氮化物，然后挤出二氮以形成cyanocarbene可与衬底发生反应。应当指出，有可能是形成高价碘鎓三氟甲磺酸酯的链烯基物质的，这取决于条件。的副产品是利于在质子溶剂如碘鎓盐的质子化比重排的炔酰基叠氮化物更快更低的温度。在OH插入反应发生的另一种可能的产品是其中的偏卡宾的重排的炔基叠氮发生之前被困乙烯基醚。形成这种乙烯基醚的倾向是由R组决定。 之一的，该反应的主要优点是，卡宾反应后，将得到的腈基是一个方便的把手，进一步官能化。许多合成子可以设想用这种方法和不同的产品可以用相同的基板来形成。控制该产物混合物与温度，浓度，和R基团的炔是必要的。3含于cyanocarbenes如何表现适当的洞察，所述方法示出了一种可行的方法以快速增加化学的复杂性，以形成目标分子。如何cyanocarben的例子ë起反应包括OH插入其中的醇的亲核氧原子攻击卡宾，然后质子转移发生，二甲亚砜络合物，其中所述卡宾结合的硫原子，和环丙烷，其中卡宾反应与烯烃。

<table border="1">
<tbody>
 <tr>
 <td></td>
 <td></td>
 <td></td>
 <td>Reagent</td>
 </tr>
 <tr>
 <td>Phenyl acetylene</td>
 <td>Acros</td>
 <td>AC152461000</td>
 <td></td>
 </tr>
 <tr>
 <td>Tri-n-butyltin chloride</td>
 <td>Acros</td>
 <td>139351000</td>
 <td></td>
 </tr>
 <tr>
 <td>Lithium bis(trimethysilyl)amide</td>
 <td>Acros</td>
 <td>347701000</td>
 <td></td>
 </tr>
 <tr>
 <td>Iodobenzene diacetate</td>
 <td>Acros</td>
 <td>176560250</td>
 <td></td>
 </tr>
 <tr>
 <td>Trimethylsilyl cyanide</td>
 <td>Aldrich</td>
 <td>212849</td>
 <td>Extremely toxic. Handle this chemical only in an adequately ventilated hood with extreme caution.</td>
 </tr>
 <tr>
 <td>Trimethylsilyl triflate</td>
 <td>Alfa Aesar</td>
 <td>A12535</td>
 <td></td>
 </tr>
 <tr>
 <td>Sodium Azide</td>
 <td>Sigma-Aldrich</td>
 <td>S8032</td>
 <td>Shock sensitive.</td>
 </tr>
 <tr>
 <td>Tetrabutylammonium azide</td>
 <td>Aldrich</td>
 <td>651664</td>
 <td>If possible, store and handle in a glovebox due to this compound's hygroscopic nature.</td>
 </tr>
 <tr>
 <td>1-Heptyne</td>
 <td>Acros</td>
 <td>223460250</td>
 <td></td>
 </tr>
 <tr>
 <td>Styrene</td>
 <td>Aldrich</td>
 <td>240869</td>
 <td></td>
 </tr>
 <tr>
 <td></td>
 <td></td>
 <td></td>
 <td>[header]</td>
 </tr>
 <tr>
 <td></td>
 <td></td>
 <td></td>
 <td>Material</td>
 </tr>
 <tr>
 <td>Rotary Evaporator (Hei-VAP)</td>
 <td>Heidolph</td>
 <td>517-61000-01-0</td>
 <td></td>
 </tr>
 <tr>
 <td>Glovebox</td>
 <td>MBRAUN</td>
 <td>UL-018</td>
 <td></td>
 </tr>
 </tbody>
</table>

synthesis of hypervalent iodonium alkynyl triflates for the application of generating cyanocarbenes

在这篇文章中所描述的程序涉及的高价碘炔基三氟甲磺酸酯（HIATs）及其与叠氮化物的后续反应的合成和隔离，形成cyanocarbene中间体。的高价碘炔基三氟甲磺酸酯的合成可以是浅显的，但问题是由于隔离和反应性干。特别是，惰性气氛下使用的过滤在-45℃下一些HIATs的必要性，需要特别照顾和设备。一旦分离，所述化合物可被存储和在反应中使用的叠氮化物用于形成cyanocarbene中间体。 的证据cyanocarbene代所表现出的双氮可见挤出以及从俄亥俄州插入，亚砜络合，环丙烷化中发生的产品的特性。该cyanocarbene形成的副反应是偏二卡宾的生成，并控制该过程的条件进行了讨论。有也可能形成一个高价碘鎓三氟甲磺酸烯并进行隔离，其发电的控制手段提供。的OH插入反应包括使用HIAT，叠氮化钠或四丁基铵叠氮化物，和以甲醇为溶剂/基质。亚砜配位反应使用HIAT，叠氮化钠或四丁基铵叠氮化物，和二甲亚砜作为溶剂。该cyclopropanations可以使用或不使用溶剂来进行。叠氮化物源必须是四丁基铵叠氮化物和所示的基板是苯乙烯。

图1示出HIAT的合成通过使用cyanophenyliodonium炔基三氟甲磺酸酯。该HIAT然后可以用来产生cyanocarbenes将经环丙烷的OH插入。与苯基HIAT的OH插入反应产生2 - 甲氧基-2 - 苯基乙腈在高达75％的产率。与苯基HIAT环丙烷反应生成1,2 - diphenylcyclopropanecarbonitrile在多达61％的产量。尽管在视频没有证明，二甲亚砜络合物可以与二甲亚砜进行反应，以产生DMSO-加合物在27％的产率，当与cyanocarbene中间发生...

Watch this Scientific Journal Video about Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes at JoVE.com

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

本文中所描述的合成，分离，和超价碘炔基三氟甲磺酸酯（HIATs）反应，用叠氮化物，以产生cyanocarbenes。该程序将涉及空气敏感和制冷剂的技术，包括在惰性气氛下冷过滤。处理的合成的化合物及安全性也将被讨论。

高价碘鎓炔基三氟甲磺酸酯的生成Cyanocarbenes的合成应用

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent ...

synthesis-hypervalent-iodonium-alkynyl-triflates-for-application

Research

JoVE Journal

Chemistry

10.8K 次观看.  University of North Carolina at Greensboro. 本文中所描述的合成，分离，和超价碘炔基三氟甲磺酸酯（HIATs）反应，用叠氮化物，以产生cyanocarbenes。该程序将涉及空气敏感和制冷剂的技术，包括在惰性气氛下冷过滤。处理的合成的化合物及安全性也将被讨论。 

视频: Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

Synthesis, Cellular Delivery and In vivo Application of Dendrimer-based pH Sensors

The development of fluorescent indicators represented a revolution for life sciences. Genetically encoded and synthetic fluorophores with sensing abilities allowed the visualization of biologically relevant species with high spatial and temporal resolution. Synthetic dyes are of particular interest thanks to their high tunability and the wide range of measureable analytes. However, these molecules suffer several limitations related to small molecule behavior (poor solubility, difficulties in targeting, often no ratiometric imaging allowed). In this work we introduce the development of dendrimer-based sensors and present a procedure for pH measurement in vitro, in living cells and in vivo. We choose dendrimers as ideal platform for our sensors for their many desirable properties (monodispersity, tunable properties, multivalency) that made them a widely used scaffold for several biomedical devices. The conjugation of fluorescent pH indicators to the dendrimer scaffold led to an enhancement of their sensing performances. In particular dendrimers exhibit reduced cell leakage, improved intracellular targeting and allow ratiometric measurements. These novel sensors were successfully employed to measure pH in living HeLa cells and in vivo in mouse brain.

Synthesis, Cellular Delivery and In vivo Application of Dendrimer-based pH Sensors

Fluorescence sensors are powerful tools in life science. Here we describe a methodology to synthesize and use dendrimer-based fluorescent sensors to measure pH in living cells and in vivo. The dendritic scaffold enhances the properties of conjugated fluorescent dyes leading to improved sensing properties.

合成，细胞和交货<em&gt;在体内</em&gt;的树状为基础的pH值传感器应用

The development of  fluorescent indicators represented a revolution for life sciences. Genetically  encoded and synthetic fluorophores with sensing ...

科研

化学

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of trifluoromethoxylated aromatic compounds remains a formidable challenge in organic synthesis. Conventional approaches often suffer from poor substrate scope, or require use of highly toxic, difficult-to-handle, and/or thermally labile reagents. Herein, we report a user-friendly protocol for the synthesis of methyl 4-acetamido-3-(trifluoromethoxy)benzoate using 1-trifluoromethyl-1,2-benziodoxol-3(1H)-one (Togni reagent II). Treating methyl 4-(N-hydroxyacetamido)benzoate (1a) with Togni reagent II in the presence of a catalytic amount of cesium carbonate (Cs2CO3) in chloroform at RT afforded methyl 4-(N-(trifluoromethoxy)acetamido)benzoate (2a). This intermediate was then converted to the final product methyl 4-acetamido-3-(trifluoromethoxy)benzoate (3a) in nitromethane at 120 &#176;C. This procedure is general and can be applied to the synthesis of a broad spectrum of ortho-trifluoromethoxylated aniline derivatives, which could serve as useful synthetic building blocks for the discovery and development of new pharmaceuticals, agrochemicals, and functional materials.

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

An operationally simple procedure for the synthesis of ortho-trifluoromethoxylated aniline derivatives via a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxyacetamide followed by thermally induced intramolecular OCF3-migration is reported.

协议的合成<em&gt;邻</em&gt; -trifluoromethoxylated苯胺类化合物

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of ...

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

科大-1作为香兰素的合成的非均相催化剂

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

蛋白质生物缀合物的合成<em&gt;通过</em&gt;半胱氨酸马来酰亚胺化学

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

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.

使用Photoredox催化剂蠕虫状胶束的简便合成可见光介导的分散聚合

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

Synthesis and Mass Spectrometry Analysis of Oligo-peptoids

Peptoids are sequence-controlled peptide-mimicking oligomers consisting of N-alkylated glycine units. Among many potential applications, peptoids have been thought of as a type of molecular information storage. Mass spectrometry analysis has been considered the method of choice for sequencing peptoids. Peptoids can be synthesized via solid phase chemistry using a repeating two-step reaction cycle. Here we present a method to manually synthesize oligo-peptoids and to analyze the sequence of the peptoids using tandem mass spectrometry (MS/MS) techniques. The sample peptoid is a nonamer consisting of alternating N-(2-methyloxyethyl)glycine (Nme) and N-(2-phenylethyl)glycine (Npe), as well as an N-(2-aminoethyl)glycine (Nae) at the N-terminus. The sequence formula of the peptoid is Ac-Nae-(Npe-Nme)4-NH2, where Ac is the acetyl group. The synthesis takes place in a commercially available solid-phase reaction vessel. The rink amide resin is used as the solid support to yield the peptoid with an amide group at the C-terminus. The resulting peptoid product is subjected to sequence analysis using a triple-quadrupole mass spectrometer coupled to an electrospray ionization source. The MS/MS measurement produces a spectrum of fragment ions resulting from the dissociation of charged peptoid. The fragment ions are sorted out based on the values of their mass-to-charge ratio (m/z). The m/z values of the fragment ions are compared against the nominal masses of theoretically predicted fragment ions, according to the scheme of peptoid fragmentation. The analysis generates a fragmentation pattern of the charged peptoid. The fragmentation pattern is correlated to the monomer sequence of the neutral peptoid. In this regard, MS analysis reads out the sequence information of the peptoids.

A protocol is described for the manual synthesis of oligo-peptoids followed by sequence analysis by mass spectrometry.

寡 peptoids 的合成及质谱分析

Peptoids are sequence-controlled peptide-mimicking oligomers consisting of N-alkylated glycine units. Among many potential applications, peptoids have ...

Synthesis of Substrate-Bound Au Nanowires Via an Active Surface Growth Mechanism

Advancing synthetic capabilities is important for the development of nanoscience and nanotechnology. The synthesis of nanowires has always been a challenge, as it requires asymmetric growth of symmetric crystals. Here, we report a distinctive synthesis of substrate-bound Au nanowires. This template-free synthesis employs thiolated ligands and substrate adsorption to achieve the continuous asymmetric deposition of Au in solution at ambient conditions. The thiolated ligand prevented the Au deposition on the exposed surface of the seeds, so the Au deposition only occurs at the interface between the Au seeds and the substrate. The side of the newly deposited Au nanowires is immediately covered with the thiolated ligand, while the bottom facing the substrate remains ligand-free and active for the next round of Au deposition. We further demonstrate that this Au nanowire growth can be induced on various substrates, and different thiolated ligands can be used to regulate the surface chemistry of the nanowires. The diameter of the nanowires can also be controlled with mixed ligands, in which another &#34;bad&#34; ligand could turn on the lateral growth. With the understanding of the mechanism, Au nanowire-based nanostructures can be designed and synthesized.

We report a solution-based method to synthesize substrate-bound Au nanowires. By tuning the molecular ligands used during the synthesis, the Au nanowires can be grown from various substrates with different surface properties. Au nanowire-based nanostructures can also be synthesized by adjusting the reaction parameters.

通过活性表面生长机制合成基片束缚金纳米线

Advancing synthetic capabilities is important for the development of nanoscience and nanotechnology. The synthesis of nanowires has always been a ...

Synthesis of Soft Polysiloxane-urea Elastomers for Intraocular Lens Application

This study discusses a synthesis route for soft polysiloxane-based urea (PSU) elastomers for their applications as accommodating intraocular lenses (a-IOLs). Aminopropyl-terminated polydimethylsiloxanes (PDMS) were previously prepared via the ring-chain equilibration of the cyclic siloxane octamethylcyclotetrasiloxane (D4) and 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS). Phenyl groups were introduced into the siloxane backbone via the copolymerization of D4 and 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-cyclotetrasiloxane (D4Me,Ph). These polydimethyl-methyl-phenyl-siloxane-block copolymers were synthesized for increasing the refractive indices of polysiloxanes. For applications as an a-IOL, the refractive index of the polysiloxanes must be equivalent to that of a young human eye lens. The polysiloxane molecular weight is controlled by the ratio of the cyclic siloxane to the endblocker APTMDS. The transparency of the PSU elastomers is examined by the transmittance measurement of films between 200 and 750 nm, using a UV-Vis spectrophotometer. Transmittance values at 750 nm (upper end of the visible spectrum) are plotted against the PDMS molecular weight, and &#62; 90% of the transmittance is observed until a molecular weight of 18,000 g&#183;mol&#8722;1. Mechanical properties of the PSU elastomers are investigated using stress-strain tests on die-cut dog-bone-shaped specimens. For evaluating mechanical stability, mechanical hysteresis is measured by repeatedly stretching (10x) the specimens to 5% and 100% elongation. Hysteresis considerably decreases with the increase in the PDMS molecular weight. In vitro cytotoxicity of some selected PSU elastomers is evaluated using an MTS cell viability assay. The methods described herein permit the synthesis of a soft, transparent, and noncytotoxic PSU elastomer with a refractive index approximately equal to that of a young human eye lens.

This study describes synthetic routes for aminopropyl-terminated polydimethylsiloxanes and polydimethyl-methyl-phenyl-siloxane-block copolymers and for soft polysiloxane-based urea (PSU) elastomers. It presents the application of PSUs as accommodating an intraocular lens. An evaluation method for in vitro cytotoxicity is also described.

软聚聚硅氧烷-尿素弹性体在人工晶体中的应用

This study discusses a synthesis route for soft polysiloxane-based urea (PSU) elastomers for their applications as accommodating intraocular lenses ...

Synthesis and Bioconjugation of Thiol-Reactive Reagents for the Creation of Site-Selectively Modified Immunoconjugates

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. Yet maleimide-based conjugates display limited stability in vivo because the succinimidyl thioether linkage can undergo a retro-Michael reaction. This, of course, can lead to the release of the radioactive payload or its exchange with thiol-bearing biomolecules in circulation. Both of these processes can produce elevated activity concentrations in healthy organs as well as decreased activity concentrations in target tissues, resulting in reduced imaging contrast and lower therapeutic ratios. In 2018, we reported the creation of a modular, stable, and easily accessible phenyloxadiazolyl methyl sulfone reagent &#8212; dubbed &#8216;PODS&#8217; &#8212; as a platform for thiol-based bioconjugations. We have clearly demonstrated that PODS-based site-selective bioconjugations reproducibly and robustly create homogenous, well-defined, highly immunoreactive, and highly stable radioimmunoconjugates. Furthermore, preclinical experiments in murine models of colorectal cancer have shown that these site-selectively labeled radioimmunoconjugates exhibit far superior in vivo performance compared to radiolabeled antibodies synthesized via maleimide-based conjugations. In this protocol, we will describe the four-step synthesis of PODS, the creation of a bifunctional PODS-bearing variant of the ubiquitous chelator DOTA (PODS-DOTA), and the conjugation of PODS-DOTA to the HER2-targeting antibody trastuzumab.

In this protocol, we will describe the synthesis of PODS, a phenyoxadiazolyl methyl sulfone-based reagent for the site-selective attachment of cargos to the thiols of biomolecules, particularly antibodies. In addition, we will describe the synthesis and characterization of a PODS-bearing bifunctional chelator and its conjugation to a model antibody.

硫醇反应试剂的合成与生物共轭作用--用于原位选择性修饰免疫共轭的生成

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. ...

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

The conjugate addition of organometallic reagents to &#945;,&#946;-unsaturated carbonyls represents an important method to generate C&#8211;C bonds in the preparation of all-carbon quaternary centers. Though conjugate additions of organometallic reagents are typically performed utilizing highly reactive organolithium or Grignard reagents, organozinc reagents have garnered attention for their enhanced chemoselectivity and mild reactivity. Despite numerous recent advances with more reactive diorganozinc and mixed diorganozinc reagents, the generation of all-carbon quaternary centers via the conjugate addition of functionalized monoorganozinc reagents remains a challenge. This protocol details a convenient and mild &#8220;one-pot&#8221; preparation and copper mediated conjugate addition of functionalized monoorganozinc bromides to cyclic &#945;,&#946;-unsaturated carbonyls to afford a broad scope of all-carbon quaternary centers in generally excellent yield and diastereoselectivity. Key to the development of this technology is the utilization of DMA as a reaction solvent with TMSCl as a Lewis acid. Notable advantages to this methodology include the operational simplicity of the organozinc reagent preparation afforded by the utilization of DMA as a solvent, as well as an efficient conjugate addition mediated by various Cu(I) and Cu(II) salts. Moreover, an intermediate silyl enol ether can be isolated utilizing a modified workup procedure. The substrate scope is limited to cyclic unsaturated ketones, and the conjugate addition is impeded by stabilized (e.g., allyl, enolate, homoenolate) and sterically encumbered (e.g., neopentyl, o-aryl) monoorganozinc reagents. Conjugate additions to five- and seven-membered rings were effective, albeit in lower yields compared with six-membered ring substrates.

A simple and practical protocol for the efficient conjugate addition of functionalized monoorganozinc bromides to cyclic &#945;,&#946;-unsaturated carbonyls to furnish all-carbon quaternary centers was developed.

功能化单有机硼化合物共轭法高效合成全碳第四纪中心

The conjugate addition of organometallic reagents to &#945;,&#946;-unsaturated carbonyls represents an important method to generate C&#8211;C bonds in the ...