R.E.M. thanks the Royal Society and the E.P.S.R.C. (Grants EP/L014475/1, EP/K025112/1 and EP/K005499/1) for funding work in this area. J.C&#780;. acknowledges the Czech Science Foundation for the project of the Centre of Excellence (P106/12/G015) and the European Union Seventh Framework Programme (FP7/ 2007-&#173;-2013) under grant agreement n&#176;604307. The authors would like to thank P. Chlubn&#225;-Eli&#225;&#353;ov&#225;, W.J. Roth and P. Nachtigall for enlightening discussions.

注意:请查阅所有相关材料安全数据表（MSDS），并在使用前进行的所有过程进行风险评估。几个在该合成过程中使用的化学品是剧毒和致癌性。请这些程序包括工程控制（通风橱）和个人防护设备（安全眼镜，白大褂和适当的化学防护手套）存续期间全部使用适当的安全程序。 1.结构导向剂的制备UTL的合成<ol><li>溶解5.68克氢氧化钠140毫升蒸馏水。 30.66克1,4-二溴丁烷加入到该溶液并搅拌。 </li><li>加热该溶液至回流（油浴110℃）。 </li><li>添加逐滴（〜每秒1滴）16.07克（2R，6S）-2,6-二甲基哌啶并继续回流另外的12小时的。 </li><li>在冰浴中冷却至室温，然后寒意。 </li><li>溶解50克钠氢氧化物在75毫升的蒸馏水中，以制备40重量％的溶液。在冰上冷却。加70毫升冰水中冷却40重量％氢氧化钠溶液，以上述冷却溶液中。 </li><li>过滤白色沉淀物，并在最小的氯仿溶解。 </li><li>提取用氯仿含水残余物（3×200毫升）。结合的氯仿部，并使用约20克无水硫酸钠的干燥。 </li><li>使用滤纸过滤除去硫酸钠，并用氯仿（50毫升）洗涤。 </li><li>使用旋转蒸发直至白色沉淀开始形成部分汽化氯仿。从旋转蒸发器除去，加入乙醚，直到没有进一步沉淀是可见的。 </li><li>通过使用滤纸的漏斗过滤回收白色沉淀物，用乙醚（50毫升）洗涤。 </li><li>干燥白色沉淀在60℃CO / N，得到盐（6R，10S）-6,10 - 二甲基-5-氮鎓螺〔4,5〕癸烷溴化物。 </li><li>溶解25.0克的（6R，10S）-6,10 - 二甲基-5-氮鎓螺〔4,5〕癸烷溴化物在50毫升的蒸馏水。 </li><li>通过使用氢氧根离子交换树脂交换为氢氧根阴离子的溴化物的阴离子。 <ol><li> 25.0克氢氧根离子交换树脂加入到溴化物盐溶液，并搅拌12小时。 </li><li>过滤用滤纸将溶液，将滤液搅拌12小时下重新暴露至25.0克氢氧化离子交换树脂制成。重复暴露于氢氧化物离子交换树脂，直到硝酸银测试为卤素返回一个否定的结果。 注:硝酸银试验是溴离子非常敏感的测试。 <ol><li>酸化0.25毫升的产物溶液与2ml稀硝酸（1.0M）。添加的硝酸银溶液（0.05M）的产物溶液2-3滴。如果形成沉淀，然后重复暴露于氢氧化物离子交换树脂并重新测试，直到没有沉淀可以看到。 </li></ol></li></ol></li><li>确认氢氧化物的浓度e。通过用0.1M（这相当于0.1当量），使用酚酞溶液作为指示剂盐酸滴定。使用滴定管，慢慢的0.1M盐酸小等分添加到产品解决方案的已知体积的一小部分，直到酚酞指示剂只是改变颜色（ 即到达终点）。加入盐酸的总摩尔数等于在初始溶液氢氧化物的摩尔数。 </li><li>用蒸馏水稀释该溶液，得到0.625 M在氢氧化物的浓度。 </li></ol> 2.家长戈UTL分子筛的制备<ol><li>溶解1.08克二氧化锗分成15毫升结构导向剂的溶液（6R，10S）-6,10 - 二甲基-5-氮鎓螺[4,5]癸烷氢氧化物（0.625 1M浓度）。 </li><li>直至形成均匀的溶液分批1.246克热解法二氧化硅添加到上述溶液中，并搅拌另外的30分钟。 注意:将所得的凝胶具有0.8 的 SiO 2的摩尔组成:0.4的GeO 2:0.4 ROH:30 H 2 O，其中ROH为结构导向剂。 </li><li>转移凝胶到聚四氟乙烯内衬的高压釜（30毫升容量）。然后将在10天的烘箱，并加热到175℃。 </li><li> 10天之后，从烘箱中取出高压釜，并允许自然冷却至室温。通过过滤回收白色沸石产品。用大量的水（〜200毫升）洗涤。干燥在70℃CO / N的沸石。 </li><li> 1，之后冷却至RT，以2℃的速率前6小时，在550℃保持-通过以1℃min的速率加热沸石到550℃，除去从沸石的孔中的结构导向剂分钟- 1。 </li><li>获得的粉末X射线衍射光谱使用制造商的方案，以证实结构。 注意:粉末X射线衍射图案应匹配给予n，用于在图2中UTL。 </li><li>获取的 N 2吸附等温线使用制造商的方案，以确认孔隙率。 </li><li>获得使用制造商的方案使用能量色散X射线光谱法元素分析。 </li><li>存储煅烧沸石在干燥的惰性气氛中，以防止材料的水解。 </li></ol> 3.锗UTL的水解形成IPC-1P <ol><li> 1.0克煅烧沸石加至160毫升0.1M盐酸溶液。 </li><li>加热该混合物在95℃下18小时，冷却至RT，并用滤纸过滤回收固体。用大量的水（〜300毫升）中并在70℃CO / N干洗净。 </li><li>获得的粉末X射线衍射光谱使用制造商的方案，以确认的IPC-1P的结构。 注意:粉末X射线衍射图案应匹配在图2 IPC-1P给出的干燥产物被指定。IPC-1P和被存储以进一步使用。 </li></ol> 4 IPC-4分子筛的制备<ol><li>放置0.5克IPC-1P的在陶瓷坩埚中并加热到575℃，在1℃min的加热速率- 1，保持在575℃下6小时之后冷却至RT在2℃min的速度前- 1。 </li><li>获得的粉末X射线衍射光谱使用制造商的方案，以证实结构。 注意:粉末X射线衍射图案应匹配在图2中用于IPC-4给出。 </li><li>获取的 N 2吸附等温线使用制造商的方案，以确认孔隙率。 </li><li>获得使用制造商的方案使用能量色散X射线光谱法元素分析。这会给锗多少保留在结构信息。 </li></ol> 5.准备IPC-2沸石<ol><li> 0.5克IPC-1P添加到10毫升1.0M的硝酸酸溶液。 </li><li> 0.1克diethoxydimethylsilane的（DEDMS）添加到该溶液中。 </li><li>在175℃下将溶液转移到聚四氟乙烯内衬的高压釜和热的烘箱中18小时。 </li><li>从烘箱中取出高压釜并使其自然冷却至室温。 </li><li>通过过滤回收白色产物，用大量的水（约100毫升），在70℃CO / N干洗净。 </li><li>获得的粉末X射线衍射光谱，证实结构。粉末X射线衍射图应与图2中用于IPC-2P给出。 </li><li>放置在陶瓷坩埚中并加热到575℃的产物在1℃min的加热速率- 1，保持在575℃下6小时之后冷却至RT在2℃min的速度前- 1。 </li><li>获得的粉末X射线衍射光谱使用制造商的方案，以证实结构。 注意:衍射图案应符合Ť在图2 IPC-2中给出的帽子。 </li><li>获取的 N 2吸附等温线使用制造商的方案，以确认孔隙率。 </li><li>获得使用制造商的方案使用能量色散X射线光谱法元素分析。 </li></ol>

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The authors have nothing to disclose.

该ADOR过程的实际机制的完整描述超出了本文的范围，但可以在发表的论文中找到引用。3，5，8然而，这是值得推广的过程中的潜在重要性。沸石制剂的ADOR方法从在以何种方式制备最终材料沸石合成的传统方法有很大不同。这方面最重要的结果是，使用该ADOR方法制备的材料具有的潜力是从传统上的沸石根本不同的。特别是有范围使用ADOR法制备是大力独特的材料。这背后的理论在参考文献8中描述。 以上的孔隙率的控制是另一个领域，所述ADOR方法显示不同的性质，以传统的方法。13特别是，它是可能的编写，J再一个全系列沸石与连续可调的孔隙率，这已不是迄今为止可能利用沸石水热合成制得。使系列的变形是在上述方法的步骤3。通过改变从0.1M的使用的酸的浓度一路多达6 M（甚至超越）一种可以根据最终材料的性质。如何可以做到这一点的全部细节在参考文献13给出这既是一个很好的机会和风险。有时，如果所用的酸的浓度，温度和时间留给反应不是最佳所得材料显示的衍射图案，其中最强峰的位置不匹配在图2中所示的那些，但是，在这样的情况这可以通过从与那些在参考文献13中描述的实验比较的粉末X​​射线图案进行识别。 在协议中的关键步骤，以确保一个成功的OUtcome实现是那些与操作。首先，它是重要的，在与该层叠体的中间体接触的任何解决方案不是碱性的，因为这促进了二氧化硅的溶解，特别是在高温下。其次，ADOR过程的不可逆最后步骤是关键因素，因此该材料的适当的组织（步骤3.2和5.2）是用于该过程的成功是至关重要的。如上所述，时间和酸度是在这个过程中都重要的变量，因此确保这些步骤是优化是非常重要的。 如所描述的上面有父沸石是与位于该结构的特定位置的锗一锗的要求。这将限制可被用作母体沸石的数量。沸石UTL是已经显著探索作为父的唯一材料。不过，也有早期迹象表明，其他家长可能会成功AP合股的过程，但进一步的工作是在这方面的需要。 为了确保ADOR方法工作，极大必须小心在操作拆卸步骤之后，以确保中间IPC-1P的层不会溶解或经受显著重排。同样重要的是要获得的权利，以优化最终产品的反应条件的酸度，时间和温度。过度反应条件等精细控制，可在一审相当混乱，是我们的心愿背后的主要驱动力有过程的视频描述。 总之，本过程描述如何沸石合成的ADOR方法可应用于与UTL框架结构的锗以形成两个不同的沸石，IPC-2（OKO）和IPC-4（PCR）。

沸石是一类由角共享四面体的三维开放装置，其中在所述四面体的中心的金属阳离子（传统的硅和铝）由4氧化物阴离子包围的固体。这些角共享四面体导致可以具有各种各样的细孔结构的不同的沸石框架不同的安排。这些孔结构能够容纳的小分子，从而导致他们的应用程序石化，核和医学领域内，等等。需要注意的是沸石拓扑结构和材料，因为识别其拓扑结构（如UTL）或实际材料（ 例如，IPC-2）码-有关更多信息，请参阅国际分子筛协会的网站上，www.iza-online.org 。 沸石的重要特征是它们的孔隙率，其由管辖的量和accessibil定义它们的效用其中，最重要的化学发生的内表面面积的性。这又决定了材料的化学活性和选择性。沸石科学（事实上在所有多孔材料科学）的主要目标是控制孔隙度。 沸石是由水热法，1，2，它几乎没有变化在过去的50年传统的合成。事实上，在过去的重大进展出现在1961年引进季铵盐作为结构导向剂1，并在1982年的磷可以代替硅引起的铝族材料的发现。3鉴于极大效用沸石，有必要制订新的路线，新材料的极大兴趣。这样的路线是最近开发的战略ADOR 4 - 7其中父沸石组装，然后Disassembl编和以这样的方式组织以允许最后重新组装成一个新的固体所得物种。这使得使用已经内置到它的框架，我们可以利用固有的不稳定性事先准备好的沸石。8这个可怜的稳定性从水解不稳定锗掺入了优先位于D4R（双四环）单元中的茎绑定相邻二氧化硅层次丰富起来（ 图1）。这些D4R单元可以使用相对温和的处理从而可以在中间层状材料进行进一步化学处理被选择性地除去。4 传统的水热合成和ADOR之间的主要区别是框架形成的最终方法​​。在水热合成法，这是一个可逆的过程，允许最终结构是结晶的。在ADOR过程，然而，最终的框架形成阶段（重组）是一种不可逆共在高温下的各层的ndensation。以获得高度结晶的最终材料的关键是则组织步骤，其中所述分层的中间体被布置在正确的相对位置，以允许在不可逆凝结成新的框架，以作为最佳的是可能发生的。 在下面的例子中，我们显示如何母体沸石，用UTL沸石拓扑，9一锗，10可以使用预先准备好的有机阳离子作为结构导向剂（SDA）制备（大会工序）。此协议的成功的关键是在沸石，这使得亲GE- UTL到被拆卸和有组织，利用水解在酸以产生层状中间称为IPC-1P特定场所锗的位置。该中间体然后可以在两种不同的方式进行处理。在高温下IPC-1P材料直接重组联TOA沸石与IPC-4的结构，其拓扑是由国际沸石协会（IZA）给出的代码的PCR。然而，在IPC-1P可以不同地通过层之间的含硅种类物质的插层组织。我们称这种操作的IPC-2P的结果。此插和有组织的IPC-2P材料的高温处理导致称为IPC-2新沸石，其拓扑给出IZA代码OKO。所述OKO（IPC-2）和PCR（IPC-4）拓扑结构之间的区别在于，IPC-2包含UTL之间二氧化硅亚基（单个四圈，S4R）样层而IPC-4具有无S4R单元。 沸石是由X射线衍射，N 2吸附和能量色散X射线分析使用扫描电子显微镜表征。

<table border="0" cellpadding="0" cellspacing="0" width="573">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sodium hydroxide</td>
			<td style="width:71px;">Fisher Chemical</td>
			<td style="width:119px;">S/4920/53</td>
			<td align="right" style="width:167px;">99%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">1,4-dibromobutane</td>
			<td>Aldrich</td>
			<td>140805-500G</td>
			<td align="right">99%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">(2R,6S)-2,6-dimethylpiperidine&#160;</td>
			<td>Aldrich</td>
			<td>41470-100ML</td>
			<td>&#62;99%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Paraffin oil</td>
			<td>Fisher Chemical</td>
			<td>P/0320/17</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Chloroform</td>
			<td>Fisher Chemical</td>
			<td>C/4920/17</td>
			<td>&#62;99%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Sodium sulfate (anhydrous)</td>
			<td>Fisher Chemical</td>
			<td>S/6600/60</td>
			<td>&#62;99%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Diethyl ether</td>
			<td>Sigma Aldrich</td>
			<td>24002-2.5L</td>
			<td>&#62;99.5%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Ambersep 900-OH</td>
			<td>Acros Organics</td>
			<td align="right">301340025</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Hydrochloric acid, 0.1N</td>
			<td>Fluka</td>
			<td>318965-500ML</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Phenolphthalein</td>
			<td>Sigma Aldrich</td>
			<td>105945-50G</td>
			<td>ACS Reagent</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Silver nitrate</td>
			<td colspan="2">Ames Goldsmith</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Germanium dioxide</td>
			<td>Alfa Aesar</td>
			<td align="right">11155</td>
			<td align="right">100.00%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">fumed silica (Cab-o-sil M-5)</td>
			<td>Acros Organics</td>
			<td align="right">403731500</td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis of zeolites using the ador (assembly-disassembly-organization-reassembly) route

Zeolites are an important class of materials that have wide ranging applications such as heterogeneous catalysts and adsorbents which are dependent on their framework topology. For new applications or improvements to existing ones, new zeolites with novel pore systems are desirable. We demonstrate a method for the synthesis of novel zeolites using the ADOR route. ADOR is an acronym for Assembly, Disassembly, Organization and Reassembly. This synthetic route takes advantage of the assembly of a relatively poorly stable that which can be selectively disassembled into a layered material. The resulting layered intermediate can then be organized in different manners by careful chemical manipulation and then reassembled into zeolites with new topologies. By carefully controlling the organization step of the synthetic pathway, new zeolites with never before seen topologies are capable of being synthesized. The structures of these new zeolites are confirmed using powder X-ray diffraction and further characterized by nitrogen adsorption and scanning electron microscopy. This new synthetic pathway for zeolites demonstrates its capability to produce novel frameworks that have never been prepared by traditional zeolite synthesis techniques.

粉末X射线衍射图（ 图2）被收集用于生产的所有材料，包括中间层阶段的IPC-1P和IPC-2P。粉末X射线衍射是用于确定存在的沸石相的性质的主要技术。注意，IPC-1P和IPC-2P的晶体结构没有完全表征，为材料总有点无序。然而，每个粉末衍射图案可作为感兴趣的相位的"指纹"。寻找最重要的特征是在图案，这给对晶胞尺寸信息的峰值的位置。每个沸石（和中间体）的具有不同的单位单元尺寸等在每个收集的衍射图案的峰值位置是诊断该特定相的存在，并应与图2所示的参考图案的位置，在汉邦丘拉尔最强峰的位置是看的第一件事。如果该主峰的位置的位置相匹配的参考模式则还要查看是否其它峰也匹配。如果所使用的衍射仪完全一致，并保持那么这场比赛应该是比较好的。存在于样品的X射线衍射图案中不存在在图2的各个图案额外的峰表明，准备好的样品是不相纯的。中的衍射图案的峰的强度是不适合的相位识别程序重要的是，它们可以由于在仪器的不同样本和参考图案之间的不同，以便可以被忽略。在完成全面的结构研究时，得到原子的位置，这是没有必要在这项研究中的信息只强度变得重要。 而X射线衍射是主甲基结构分析，氮吸附等温线（ 图3）的外径，也可用于表征产物沸石。此实验方法首先要求存在于该通道的孔的任何分子（通常是水）通过加热样品，通常是在真空下除去。然后将样品冷却，一般到77 K和氮气的少量施用给系统，要么重量或体积测量用于确定多少氮气已吸附的样品。氮吸附量作图气体的压力，得到在图3所示的等温线，一个成功的合成将显示类似的形状的等温线，以在图1中的那些节目。在总吸附量将成为最大的最佳情况父UTL样品与用于IPC-2和最低量是低级用于IPC-4。这种匹配的孔隙尺寸的变化。由此数据，也可以得到使用BET方程式（ 表1）的表面区域11中元素分析是可以用来确定哪个锗已经从产物中除去的程度的另一种技术。任何适当的化学分析技术可被使用，但我们已经使用能量色散X射线分析（EDX）的扫描型电子显微镜，以确定父锗UTL沸石的组成和最终沸石的IPC-2和-4（ 表1）。 <img alt="图4" src="/files/ftp_upload/53463/53463fig1.jpg" /> 图 1. 拟议机制的原理，从父沸石UTL到最终沸石IPC-2父UTL的-4。D4R单元以红色突出显示。 <a href="https://www.jove.com/files/ftp_upload/53463/53463fig1large.jpg" target="_blank">P</a>租赁点击此处查看该图的放大版本。 <img alt="图4" src="/files/ftp_upload/53463/53463fig2.jpg" /> 图 2. 粉末父&#39;作为造"和煅烧UTL沸石（左）和中间体和最终沸石（右）的X射线衍射图案。的IPC-2P是与现有DEMDA嵌入层状IPC-1P的产物煅烧。 <a href="https://www.jove.com/files/ftp_upload/53463/53463fig2large.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/53463/53463fig3.jpg" /> 图 3。在77K记录UTL（黑）的氮吸附等温线，IPC-2（蓝色）和IPC-4（红色）。吸附等温线显示为未填充的形状和desorpti在等温线填充形状。这个数字是由亲切自然出版集团的许可基准4.转载<a href="https://www.jove.com/files/ftp_upload/53463/53463fig3large.jpg" target="_blank">请点击这里查看该图的放大版本。</a> <table><tbody><tr><td> 沸石 </td><td> 比表面积（米2 /克） </td><td> SI:比戈 </td></tr><tr><td> GE-UTL </td><td> 541.3±1.1 </td><td> 5.8 </td></tr><tr><td> IPC-2 </td><td> 334±1.0 </td><td> &gt; 500 </td></tr><tr><td> IPC-4 </td><td> 236±0.7 </td><td> 90 </td></tr></tbody></table> 表 1。孔隙度值和沸石的元素组成。

Watch this Scientific Journal Video about Synthesis of Zeolites Using the ADOR Assembly-Disassembly-Organization-Reassembly Route at JoVE.com

Synthesis of Zeolites Using the ADOR Assembly-Disassembly-Organization-Reassembly Route

一个由ADOR准备新沸石的协议（A ssembly-ðisassembly-Ørganization- - [R eassembly）合成路线介绍。

沸石使用ADOR（汇编拆卸组织-重组）路线的合成

Zeolites are an important class of materials that have wide ranging applications such as heterogeneous catalysts and adsorbents which are dependent on ...

synthesis-zeolites-using-ador-assembly-disassembly-organization

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Chemistry

Synthesis of Zeolites Using the ADOR (Assembly-Disassembly-Organization-Reassembly) Route

13.2K 次观看.  The University of St Andrews. 一个由ADOR准备新沸石的协议（A ssembly-ðisassembly-Ørganization- - [R eassembly）合成路线介绍。 

视频: Synthesis of Zeolites Using the ADOR Assembly-Disassembly-Organization-Reassembly Route

Anticancer Metal Complexes: Synthesis and Cytotoxicity Evaluation by the MTT Assay

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; therefore their preparation should be conducted under an inert atmosphere. Evaluation of the anticancer activity of these complexes can be achieved by the MTT assay.
The MTT assay is a colorimetric viability assay based on enzymatic reduction of the MTT molecule to formazan when it is exposed to viable cells. The outcome of the reduction is a color change of the MTT molecule. Absorbance measurements relative to a control determine the percentage of remaining viable cancer cells following their treatment with varying concentrations of a tested compound, which is translated to the compound anticancer activity and its IC50 values. The MTT assay is widely common in cytotoxicity studies due to its accuracy, rapidity, and relative simplicity.
Herein we present a detailed protocol for the synthesis of air sensitive metal based drugs and cell viability measurements, including preparation of the cell plates, incubation of the compounds with the cells, viability measurements using the MTT assay, and determination of IC50 values.

A method for synthesis of air-sensitive titanium and vanadium anticancer agents is described, along with the evaluation of their cytotoxic activity towards human cancer cell line by the MTT Assay.

抗癌金属配合物的合成与细胞毒性评价MTT法

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; ...

科研

化学

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

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent reactions with azides to form cyanocarbene intermediates. The synthesis of hypervalent iodonium alkynyl triflates can be facile, but difficulties stem from their isolation and reactivity. In particular, the necessity to use filtration under inert atmosphere at -45 &deg;C for some HIATs requires special care and equipment. Once isolated, the compounds can be stored and used in reactions with azides to form cyanocarbene intermediates. 
The evidence for cyanocarbene generation is shown by visible extrusion of dinitrogen as well as the characterization of products that occur from O-H insertion, sulfoxide complexation, and cyclopropanation. A side reaction of the cyanocarbene formation is the generation of a vinylidene-carbene and the conditions to control this process are discussed. There is also potential to form a hypervalent iodonium alkenyl triflate and the means of isolation and control of its generation are provided. The O-H insertion reaction involves using a HIAT, sodium azide or tetrabutylammonium azide, and methanol as solvent/substrate. The sulfoxide complexation reaction uses a HIAT, sodium azide or tetrabutylammonium azide, and dimethyl sulfoxide as solvent. The cyclopropanations can be performed with or without the use of solvent. The azide source must be tetrabutylammonium azide and the substrate shown is styrene.

Herein is described the synthesis, isolation, and reactions of hypervalent iodonium alkynyl triflates (HIATs) with azides to generate cyanocarbenes. The procedures will involve air-sensitive and cryogen techniques, including cold filtration under an inert atmosphere. Handling and safety of the synthesized compounds will also be discussed.

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 ...

Split-and-pool Synthesis and Characterization of Peptide Tertiary Amide Library

Peptidomimetics are great sources of protein ligands. The oligomeric nature of these compounds enables us to access large synthetic libraries on solid phase by using combinatorial chemistry. One of the most well studied classes of peptidomimetics is peptoids. Peptoids are easy to synthesize and have been shown to be proteolysis-resistant and cell-permeable. Over the past decade, many useful protein ligands have been identified through screening of peptoid libraries. However, most of the ligands identified from peptoid libraries do not display high affinity, with rare exceptions. This may be due, in part, to the lack of chiral centers and conformational constraints in peptoid molecules. Recently, we described a new synthetic route to access peptide tertiary amides (PTAs). PTAs are a superfamily of peptidomimetics that include but are not limited to peptides, peptoids and N-methylated peptides. With side chains on both &#945;-carbon and main chain nitrogen atoms, the conformation of these molecules are greatly constrained by sterical hindrance and allylic 1,3 strain. (Figure 1) Our study suggests that these PTA molecules are highly structured in solution and can be used to identify protein ligands. We believe that these molecules can be a future source of high-affinity protein ligands. Here we describe the synthetic method combining the power of both split-and-pool and sub-monomer strategies to synthesize a sample one-bead one-compound (OBOC) library of PTAs.

Peptide tertiary amides (PTAs) are a superfamily of peptidomimetics that include but are not limited to peptides, peptoids and N-methylated peptides. Here we describe a synthetic method which combines&#160;both split-and-pool and sub-monomer strategies to synthesize a one-bead one-compound library of PTAs.

分裂和池合成及肽叔酰胺图书馆表征

Peptidomimetics are great sources of protein ligands. The oligomeric nature of these compounds enables us to access large synthetic libraries on solid ...

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 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. ...