我们感谢美国国家科学基金会（CHE0910597）和美国国立卫生研究院（P50-GM067982）为支持这项工作。我们非常感谢有益的讨论，关于荧光测量教授迈克尔·Trakselis的（匹兹堡大学）。我们承认克里斯蒂Gogick和罗宾·斯隆（匹兹堡大学），他们协助收集荧光数据。

1。微波辅助脱氢DA反应<ol><li>添加的对 - 氯苯乙烯衍生物（0.045克，0.18毫摩尔）和1,2 - 二氯乙烷（3毫升），以2-5毫升微波照射小瓶装有搅拌棒，以创建一个0.060 M溶液。这种浓度被使用，因为较高的浓度会导致形成不希望的产品。 </li><li>盖上盖子的的微波辐射小瓶，并将其放置在微波合成腔。 </li><li>照射该溶液在180℃下，在搅拌下与固定的保持时间为200分钟。保持时间是多长时间的照射下会出现在指定的温度。反应混合物会变成金黄色。较长的反应时间，是不利于反应的收率。 </li><li>确认反应完成后采用5％乙酸乙酯/己烷作为洗脱剂，用薄层色谱法（TLC）。可视化UV光的TLC板和高锰酸钾染色。的反应物的 R ft和产品，分别为0.2和0.25。 </li><li>转移反应，用1毫升的1,2 - 二氯乙烷中的闪烁瓶中冲洗的微波反应瓶中。这结果在约3毫升的闪烁小瓶中的溶液中。 </li><li>浓缩的闪烁小瓶的内容在40℃下在减压下用旋转蒸发器（10-30毫米汞柱）。蒸发的溶剂的，将需要5-10分钟，和45 mg将得到的粗制的褐色油。原油是稳定的，并可以无限期储存而不分解。 </li><li>纯化粗油状物通过硅胶吸移管，用5％乙酸乙酯/己烷作为洗脱剂，获得41毫克的富马酸二甲酯，为白色固体，通过过滤。 </li><li> 1 H核的磁共振（NMR）谱作为溶剂使用氘代氯仿（CDCl 3），该产品经确认的身份。对于一个300 MHz的NMR波谱仪，在萘的1 H NMR谱如下所示：7.80（四，J = 1.8赫兹，1H），7.72（四，J = 9.0赫兹，1H），7.70（，1H），7.38（西元，J = 1.8，9.0赫兹，1H），3.07（，J = 7.1赫兹吨，4H），2.66（3H），2.1​​8（P，J = 7.1赫兹，2H）ppm的。 </li></ol> 2。布赫瓦尔德哈特维希钯催化交叉偶联反应<ol><li>加入RuPhos钯化合物（3毫克，0.004毫摩尔），以烘箱干燥的0.5-2毫升Biotage公司微波照射小瓶装有搅拌棒和帽小瓶。 </li><li>疏散和笔芯小瓶用氮气三次通过刺穿隔垫的盖用小的针头。一旦清除的小瓶完成后，取出针。的微波照射小瓶将作为密封管中，在反应过程中，最好的结果是最小的空气是在反应容器中存在时获得。 </li><li>通过隔膜，锂，双（三甲基甲硅烷基）酰胺（0.32毫升的1.0M的THF溶液，0.32毫摩尔）在搅拌下，通过注射器添加。该解决方案将变成红色。 </li><li>搅拌2-10分钟后，加入焦（0.038克，0.16毫摩尔）在0.3毫升无水四氢呋喃（THF）通过注射器。可以使用附加的THF（高达0.2毫升），充分溶解的富马酸二甲酯。 </li><li>搅拌2-10分钟后，加入二甲胺（0.12毫升的2.0M的THF溶液，0.24毫摩尔），通过注射器，并降低反应容器到预热85℃油浴中。 </li><li>将反应混合物加热3小时，在85℃，或直至反应完成通过TLC。反应混合物的颜色是深褐色。对于薄层色谱法，利用20％乙酸乙酯/己烷溶液作为洗脱剂，并可视化用UV光所得到的板和高锰酸钾染色。反应物和产物的 R f分别是0.5和0.4。 </li><li>冷却反应至室温，取出小瓶帽，并用饱和氯化铵水溶液淬灭反应，（10毫升）。 </li><li>使用60毫升的分液漏斗中，从有机层中分离水层。萃取水层用乙酸乙酯萃取三次（12毫升）。 </li><li>在分液漏斗中，并合并有机层，用食盐水（15毫升）洗一次。 </li><li>硫酸钠干燥合并的有机层干燥10分钟，然后通过重力过滤除去硫酸钠。 </li><li>使用旋转蒸发器，所得的溶液在减压下浓缩，在30℃（10〜30毫米汞柱）。蒸发的溶剂的，将需要5-10分钟，和将得到粗制的褐色油。 </li><li>与一个1.5厘米的色谱柱和5％乙酸乙酯/己烷作为洗脱剂，通过硅胶柱色谱法纯化粗产物。的染料，将得到的黄色固体为27毫克。 </li><li>确认的身份的产品由1 H NMR光谱使用CDCl 3作为溶剂。对于一个400 MHz的NMR光谱仪，1 H NMR谱的染料如下：7.64（D，J = 9.0赫兹，1H），7.56（，1H），7.11（，J = 2.5，9.0赫兹，1H西元），6.87（D，J = 2.5赫兹，1H），3.02（6H），3.02 - 2.87（4H），2.65（3H），2.12（P，J = 7.3赫兹，2H）ppm的。 </li></ol> 3。制备染料溶液中的光物理研究<ol><li> 1毫克的染料转移到一个干净的，干燥的10毫升容量瓶中，并稀释至体积用二氯甲烷（DCM），得到了0.4×10 -3 M的储备溶液的染料。 </li><li>第二个10 mL容量瓶中，稀释的原液253μl的准备1×10 -5 M解决方案的染料量与DCM。此解决方案将被用于收集的UV-Vis和染料的荧光数据。 </li></ol> 4。紫外 - 可见吸收光谱<ol><li>填写两个石英分光光度计细胞与DCM。这些都是空白样品。把它们放入紫外 - 可见分光光度计腔。切勿接触光学器件表面的细胞。处理细胞的侧面板的顶部，不面对光轴。 </li><li>设置仪器参数的狭缝宽度为2和采集速率为480nm /分钟。选择样品的名称，并选择收购的范围从600到200纳米。 </li><li>收集背景的光谱，从仪器中取出样品细胞，把它倒空，然后用清水冲洗1×10 -5 M染料溶液灌装前的几个部分。避免溢出细胞。在插入样品细胞放回持有人之前，用干净的镜头纸仔细擦拭牢房窗户。 </li><li>收集样品的吸收光谱。观察到的最大吸收波长为377 nm。 </li><li>仔细清洁石英与水，丙酮，乙醇，然后再运行分析其他样品的UV-Vis吸收分光光度计细胞。 </li><li>使用Excel或Origin软件绘制和分析收集到的数据。 </li></ol> 5。荧光发射光谱<ol><li>填充石英的1×10 -5 M染料溶液的荧光细胞，并将其放置到spectrofluoromet呃。避免与皮肤接触的光学表面的细胞。 </li><li>设置仪器参数：激发波长为334 nm处，狭缝宽度为2，以0.1nm /秒的采集速率，采集范围从390至750纳米。甲390 nm的切口过滤器需要以除去散射光从发射源。 </li><li>收集的样品的荧光发射光谱。观察到在510 nm处的荧光发射最大值。 </li><li>清洁的石英荧光细胞与水，丙酮，和乙醇在运行前对其它样品的荧光分析。 </li><li>使用Excel或Origin软件绘制和分析收集到的数据。 </li></ol>

<ol>
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作者宣称，他们没有竞争的金融利益。

微波辅助脱氢DA反应 DA反应的分子内脱氢，苯乙烯基前体的微波辐射（MWI）在71-100％的高收益率和较短的反应时间产生不同的萘结构，需要短短的30分钟（ 图1）18。最困难的方面的进行脱氢DA反应是溶剂的选择，这往往是复杂的，因为需要考虑到各种溶剂的特性，以确保最佳的加热。第一和最重要的是，一个成功的反应必须有可能在溶剂中，是与微波条件兼?...

小分子设计和合成一系列的科学领域，包括医药，农药，有机染料和多1的发展是至关重要的。 （DDA）的Diels-Alder（DA）和脱氢的Diels-Alder反应是在小的环状和芳族化合物2-4的合成，尤其是强大的工具。此外，热脱氢DA反应苯乙烯二烯，炔烃的亲二烯体的芳族化合物的合成提供了一种潜在的有利的路线通过初步形成双环[2.2.2]辛烯酮类化合物，可以进一步在氧化条件下芳香5。通过采用分子内的热脱氢DA苯乙烯二烯与炔反应，利用苯乙烯作为二烯，如不需要的[2 +2]环加成5,6和聚合反应7和区域选择性差，减轻和萘化合物的问题通常与可以生成。 苯乙烯与炔烃分子内的热脱氢DA反应也不是没有相当大的问题。首先，大多数反应受到产量低，长的反应时间，和高的反应温度8-11。此外，很多反应不提倡纯形成的萘产品，萘和二氢生产，往往分不开的混合物通过柱层析11,12。的前体的苯乙烯 - ynes系绳也仅限于包括的杂原子和/或羰基部分。仅是一个示例报告所有含碳的系绳，要求的条件为250℃下48小时整洁，以便取得萘生成10。 除了有限的各种内的系绳的起始原料，这种方法的最严重的限制之一是在常规的热条件下的耐受性的功能的缺乏。的炔末端的原料或者是未取代的或附加的苯基或三甲基甲硅烷基（TMS）基团8-13。 在一个实例中，示出在炔烃末端酯进行脱氢的DA反应，但这个结果萘，二氢萘产品11的混合物中。后来的提案建议，TMS组附加炔末端是必要的，实现独家萘形成的高收益率10。 热脱氢DA反应报告的各种功能的不足，严重限制了潜在的这种反应对装配独特的萘结构。 萘结构的变化源于它们的功能，在多个科学领域，特别是有机荧光染料14,15的小分子构建模块的愿望。出色的空间分辨率和响应时间的小组织ANIC染料监测实时事件16已经导致数百市售的荧光化合物的发展。许多这些染料是萘与分立的光物理和化学性质15。 选择的荧光染料具有特殊性能的监视单个的功能，从而导致不​​断增长的需求提供更多样化的光物理性质的荧光基团为新的类是具有挑战性的。为此目的，热分子内脱氢DA反应的苯乙烯与炔烃，允许多样化的一个独特的萘骨架将是潜在的有利开发新的萘的含有荧光染料中的应用。 作为一种替代方法，常规加热，微波辅助化学是有利的，因为它提供的化学样品的更均匀的加热，从而导致更高的化学产率，更快的反应速率，温和的反应条件下s，而往往是不同的选择性的产品17。 采用微波辅助与传统加热条件下的反应时间从几天减少到几分钟，增加以前差收益，降低反应温度，并提供更多的选择性形成的分子内的苯乙烯脱氢DA反应，消除的方法与此相关的问题所需的富马酸二甲酯产物。微波辅助的反应条件下，也可能会更容易，更多样化的功能，以方便将进入富马酸二甲酯的产品，这是前所未有的。只有一个现有的例子已被报道利用脱氢DA的反应，其中的90％产率的富马酸二甲酯和二氢化萘中得到尽可能少为15分钟，在170°C 12的微波辅助的条件。 在这里报道了微波辅助分子内脱氢酶本地DA反应的苯乙烯基衍生工具的专属形成的官能化和多样化的富马酸二甲酯的产品，在短短的30分钟，高定量的产率18。此协议进一步证明该实用程序的萘产品的一个步骤转换成一种新型的溶致变色荧光染料的光物理性质的对手流行的商用染料普罗丹19。

<table border="1">
	<tbody>
		<tr>
			<td>Reagent/Material</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>1,2-Dichloroethane, ACS reagent &ge;99.0%</td>
			<td>Sigma-Aldrich</td>
			<td>319929</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>SiliaPlate G TLC - glass-backed, 250 &mu;m</td>
			<td>Silicycle</td>
			<td>TLG-R10011B-323</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Ethyl acetate, certified ACS &ge;99.5%</td>
			<td>Fisher Scientific</td>
			<td>E14520</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Hexanes, certified ACS &ge;98.5%</td>
			<td>Fisher Scientific</td>
			<td>H29220</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Silica gel, standard grade</td>
			<td>Sorbent Technologies</td>
			<td>30930M</td>
			<td>60 A, 40-63 &mu;M (230 x 400 mesh)</td>
		</tr>
		<tr>
			<td>RuPhos palladacycle</td>
			<td>Strem</td>
			<td>46-0266</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Nitrogen gas</td>
			<td>Matheson TRIGAS</td>
			<td>NI304</td>
			<td>Nitrogen 304cf, industrial</td>
		</tr>
		<tr>
			<td>Lithium bis(trimethylsilyl) amide solution</td>
			<td>Sigma-Aldrich</td>
			<td>225770</td>
			<td>1.0 M solution in THF</td>
		</tr>
		<tr>
			<td>Tetrahydrofuran anhydrous &ge;99.9%</td>
			<td>Sigma-Aldrich</td>
			<td>401757</td>
			<td>Inhibitor-free</td>
		</tr>
		<tr>
			<td>Dimethylamine solution</td>
			<td>Sigma-Aldrich</td>
			<td>391956</td>
			<td>2.0 M solution in THF</td>
		</tr>
		<tr>
			<td>Ammonium chloride</td>
			<td>Fisher Scientific</td>
			<td>A661-500</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Sodium sulfate, anhydrous (granular)</td>
			<td>Fisher Scientific</td>
			<td>S421-500</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Chromatography column</td>
			<td>Chemglass</td>
			<td>CG-1188-04</td>
			<td>&frac12; in ID x 18in E.L.</td>
		</tr>
		<tr>
			<td>Cyclohexane, &ge;99.0%</td>
			<td>Fisher Scientific</td>
			<td>C556-1</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Toluene anhydrous, 99.8%</td>
			<td>Sigma-Aldrich</td>
			<td>24451</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>1,4-Dioxane anhydrous, 99.8%</td>
			<td>Sigma-Aldrich</td>
			<td>296309</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Tetrahydrofuran anhydrous, &ge;99.9%</td>
			<td>Sigma-Aldrich</td>
			<td>186562</td>
			<td>250 ppm BHT as inhibitor</td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Sigma-Aldrich</td>
			<td>650463</td>
			<td>Chromasolv Plus</td>
		</tr>
		<tr>
			<td>Chloroform, &ge;99.8%</td>
			<td>Fisher Scientific</td>
			<td>C298-1</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Acetonitrile anhydrous, 99.8%</td>
			<td>Sigma-Aldrich</td>
			<td>271004</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Dimethyl sulfoxide, &ge;99.9%</td>
			<td>Fisher Scientific</td>
			<td>D128</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Ethyl alcohol</td>
			<td>Pharmco-AAPER</td>
			<td>11ACS200</td>
			<td>Absolute</td>
		</tr>
		<tr>
			<td>Equipment</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Synthesizer</td>
			<td>Biotage</td>
			<td>Biotage Initiator Exp</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Vial</td>
			<td>Biotage</td>
			<td>352016</td>
			<td>0.5 - 2 ml</td>
		</tr>
		<tr>
			<td>Microwave Vial</td>
			<td>Biotage</td>
			<td>351521</td>
			<td>2 - 5 ml</td>
		</tr>
		<tr>
			<td>Microwave Vial Cap</td>
			<td>Biotage</td>
			<td>352298</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Synthesizer</td>
			<td>Anton Paar</td>
			<td>Monowave 300</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Vial G4</td>
			<td>Anton Paar</td>
			<td>99135</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Vial Cap</td>
			<td>Anton Paar</td>
			<td>88882</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>NMR Spectrometer</td>
			<td>Bruker</td>
			<td>Avance</td>
			<td>300 or 400 MHz</td>
		</tr>
		<tr>
			<td>UV-Visible Spectrometer</td>
			<td>PerkinElmer</td>
			<td>Lamda 9</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Spectrophotometer cell</td>
			<td>Starna Cells</td>
			<td>29B-Q-10</td>
			<td>Spectrosil quartz, path length 10 mm, semi-micro, black wall</td>
		</tr>
		<tr>
			<td>Spectrofluorometer</td>
			<td>HORIBA Jobin Yvon</td>
			<td>FluoroMax-3 S4</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Fluorometer cell</td>
			<td>Starna Cells</td>
			<td>29F-Q-10</td>
			<td>Spectrosil quartz, path length 10 mm, semi-micro</td>
		</tr>
	</tbody>
</table>

microwave-assisted intramolecular dehydrogenative diels-alder reactions for the synthesis of functionalized naphthalenes/solvatochromic dyes

功能化萘的应用程序在不同的研究领域，从天然或生物活性分子的合成新型有机染料的制备。虽然众多的策略已被报告给访问萘棚架，许多程序在结合功能，这反过来又变窄的范围内可用的基板方面仍然存在局限性。因此，通用的方法直接访问取代的萘的发展是非常必要的。 的Diels-Alder（DA）的环加成反应是一个强大的和有吸引力的方法，从容易得到的起始原料，形成饱和的和不饱和的环系统。本文描述一种新的微波辅助分子内脱氢DA反应的苯乙烯基衍生物生成多种官能化的环戊二烯并[b]萘，无法使用现有的合成方法来制备第当比常规加热，微波辐射加速反应速率，提高产量，并限制了不希望的副产物的形成。 此协议的实用程序进一步证明由转换的DA环加成到一种新型的溶致变色荧光染料经由布赫瓦尔德-哈特威格钯催化的交叉偶联反应。荧光光谱法，作为一个信息和灵敏的分析技术，研究领域包括环境科学，医学，药理学，细胞生物学中起着关键的作用。获得各种新的有机荧光团所提供的微波辅助的脱氢DA反应允许在这些领域的进一步提高。

照射微波（MWI）的苯乙烯基衍生物，在180℃结果完全环戊二烯并[b]萘形成在低至30分钟，并在高至定量的产率（ 图1）18。 无二氢萘副产品是观察，并通过1 H NMR光谱的产品，而不需要额外的纯化照射后（ 图2）出现纯。耐受性良好的富马酸二甲酯框架的各种变化利用这些热的条件下，包括该系绳的变化和替代图案的萘环，吸电子基团的一个?...

Watch this Scientific Journal Video about Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes at JoVE.com

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

微波辅助分子内的脱氢的Diels-Alder反应（DA）提供简洁的访问功能化环戊[<em&gt; B</em&gt;]萘积木。一个步骤转换成脱氢DA双环[2.2.2]辛烯酮类化合物的新型溶致变色荧光染料通过布赫瓦尔德-哈特维希钯催化交叉偶联反应证明了这种方法的效用。

微波辅助分子内Diels-Alder反应的功能化萘/变色染料的合成脱氢

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to ...

microwave-assisted-intramolecular-dehydrogenative-diels-alder

Research

Education

JoVE Core

JoVE Journal

Organic Chemistry

Chemistry

Unit 1

Dienes, Conjugated Pi Systems, and Pericyclic Reactions

SCIENTISTS IN ACTION

16.8K 次观看.  University of Pittsburgh. 微波辅助分子内的脱氢的Diels-Alder反应（DA）提供简洁的访问功能化环戊[ B]萘积木。一个步骤转换成脱氢DA双环[2.2.2]辛烯酮类化合物的新型溶致变色荧光染料通过布赫瓦尔德-哈特维希钯催化交叉偶联反应证明了这种方法的效用。

视频: Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan &#948; solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials&#39; morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by St&#246;ber&#39;s methods, which have smooth surfaces.

Silica nanoparticles were prepared using acid-catalysis of a siloxane precursor and microwave-assisted synthetic techniques resulting in the controlled growth of nanomaterials ranging from 30-250 nm in diameter. The growth dynamics can be controlled by varying the initial silicic acid concentration, time of the reaction, and temperature of reaction.

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle ...

科研

化学

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

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 ...

The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified with furfurylamine to graft furan groups to the rubber backbone. These pendant furan groups are then cross-linked with a bis-maleimide via a Diels-Alder coupling reaction. Both reactions can be performed under a broad range of experimental conditions and can easily be applied on a large scale. The material properties of the resulting Diels-Alder cross-linked rubbers are similar to a peroxide-cured ethylene/propylene/diene rubber (EPDM) reference. The cross-links break at elevated temperatures (&#62; 150 &#176;C) via the retro-Diels-Alder reaction and can be reformed by thermal annealing at lower temperatures (50-70 &#176;C). Reversibility of the system was proven with infrared spectroscopy, solubility tests and mechanical properties. Recyclability of the material was also shown in a practical way, i.e., by cutting a cross-linked sample into small parts and compression molding them into new samples displaying comparable mechanical properties, which is not possible for conventionally cross-linked rubbers.

A simple two-step approach involving rubber modification and cross-linking yields fully reworkable, elastic rubber products.

热可逆交联橡胶通过的Diels-Alder反应的化学制备与性能

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ...

Synthesis of Plant Phenol-derived Polymeric Dyes for Direct or Mordant-based Hair Dyeing

Effective hair dyeing through in situ incubation of keratin hair with the products of fungal laccase-catalyzed polymerization of plant phenols has been previously demonstrated. However, the dyeing process takes a long time to complete compared to commercial hair-dyeing products. To overcome this bottleneck, pre-synthesized polymeric products of the oxidative reaction of Trametes versicolor laccase on catechin and catechol, either with or without mordant agents (e.g., FeSO4), were here employed to achieve permanent keratin hair dyeing in various colors and shades. The laccase action in acidic sodium acetate buffer led to a deep black coloration after coupling reactions between the plant phenols. The colored dye products were then desalted and concentrated with ultrafiltration. The dyes, with or without mordant agents, caused a significant increase in &#916;E values (i.e., color difference value) in gray human hair within 2.5 hours. In addition, different keratin colors and shades were induced depending upon the mordanting and pH changes. The dyed hair also exhibited a strong resistance to detergent treatments, indicating that our methods can give rise to permanent hair dyeing.&#160;Overall, our work has provided novel insight into developing eco-friendly hair-dyeing methods as alternatives to commercial toxic diamine-based dyes.

Here, we present a protocol to use pre-synthesized polymeric products derived from fungal laccase-catalyzed polymerization of plant phenols, either with or without mordant agents (e.g., FeSO4), to induce detergent-resistant keratin hair dyeing within 2.5 hours.

对于直接或媒介为基础的头发染色厂苯酚衍生的高分子染料的合成

Effective hair dyeing through in situ incubation of keratin hair with the products of fungal laccase-catalyzed polymerization of plant phenols has been ...

One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate glycosyl donor. Following azido-nitration of a glycal, the product 2-azido-1-nitrate ester can be hydrolyzed under microwave-assisted irradiation. This transformation is usually achieved using strongly nucleophilic reagents and extended reaction times. Microwave irradiation induces hydrolysis, in the absence of reagents, with short reaction times. Following denitration, the intermediate anomeric alcohol is converted, in the same pot, to the corresponding 2-azido-1-trichloroacetimidate.

A 2-azido-1-nitrate-ester can be converted to the corresponding 2-azido-1-trichloroacetimidate in a one-pot procedure. The goal of the manuscript is to demonstrate utility of the microwave reactor in carbohydrate synthesis.

硝酸酯 Anomeric Trichloroacetimidates 的单锅微波辅助转化

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate ...

Enzymatic Cascade Reactions for the Synthesis of Chiral Amino Alcohols from L-lysine

Amino alcohols are versatile compounds with a wide range of applications. For instance, they have been used as chiral scaffolds in organic synthesis. Their synthesis by conventional organic chemistry often requires tedious multi-step synthesis processes, with difficult control of the stereochemical outcome. We present a protocol to enzymatically synthetize amino alcohols starting from the readily available L-lysine in 48 h. This protocol combines two chemical reactions that are very difficult to conduct by conventional organic synthesis. In the first step, the regio- and diastereoselective oxidation of an unactivated C-H bond of the lysine side-chain is catalyzed by a dioxygenase; a second regio- and diastereoselective oxidation catalyzed by a regiodivergent dioxygenase can lead to the formation of the 1,2-diols. In the last step, the carboxylic group of the alpha amino acid is cleaved by a pyridoxal-phosphate (PLP) decarboxylase (DC). This decarboxylative step only affects the alpha carbon of the amino acid, retaining the hydroxy-substituted stereogenic center in a beta/gamma position. The resulting amino alcohols are therefore optically enriched. The protocol was successfully applied to the semipreparative-scale synthesis of four amino alcohols. Monitoring of the reactions was conducted by high performance liquid chromatography (HPLC) after derivatization by 1-fluoro-2,4-dinitrobenzene. Straightforward purification by solid-phase extraction (SPE) afforded the amino alcohols with excellent yields (93% to &#62;95%).

Chiral amino alcohols are versatile molecules for use as scaffolds in organic synthesis. Starting from L-lysine, we synthesize amino alcohols by an enzymatic cascade reaction combining diastereoselective C-H oxidation catalyzed by dioxygenase followed by cleavage of the carboxylic acid moiety of the corresponding hydroxyl amino acid by a decarboxylase.

酶联反应合成 l-赖氨酸手性氨基醇的研究

Amino alcohols are versatile compounds with a wide range of applications. For instance, they have been used as chiral scaffolds in organic synthesis. ...

Reducing Willow Wood Fuel Emission by Low Temperature Microwave Assisted Hydrothermal Carbonization

Biomass is a sustainable fuel, as its CO2 emissions are reintegrated in biomass growth. However, the inorganic precursors in the biomass cause a negative environmental impact and slag formation. The selected short rotation coppice (SRC) willow wood has a high ash content (<img alt="Equation 1" src="/files/ftp_upload/58970/58970eq1.jpg" /> = 1.96%) and, therefore, a high content of emission and slag precursors. Therefore, the reduction of minerals from SRC willow wood by low temperature microwave assisted hydrothermal carbonization (MAHC) at 150 &#176;C, 170 &#176;C, and 185 &#176;C is investigated. An advantage of MAHC over conventional reactors is an even temperature conductance in the reaction medium, as microwaves penetrate the whole reactor volume. This allows a better temperature control and a faster cooldown. Therefore, a succession of depolymerization, transformation and repolymerization reactions can be analyzed effectively. In this study, the analysis of the mass loss, ash content and composition, heating values and molar O/C and H/C ratios of the treated and untreated SCR willow wood showed that the mineral content of the MAHC coal was reduced and the heating value increased. The process water showed a decreasing pH and contained furfural and 5-methylfurfural. A process temperature of 170 &#176;C showed the best combination of energy input and ash component reduction. The MAHC allows a better understanding of the hydrothermal carbonization process, while a large-scale industrial application is unlikely because of the high investment costs.

A protocol for the emission precursor depletion from low quality biomass by low temperature microwave assisted hydrothermal carbonization treatment is presented. This protocol includes the microwave parameters and the analysis of the biocoal product and process water.

低温微波辅助热液碳化降低柳树燃料排放

Biomass is a sustainable fuel, as its CO2 emissions are reintegrated in biomass growth. However, the inorganic precursors in the biomass cause a negative ...

Pretargeted Radioimmunotherapy Based on the Inverse Electron Demand Diels-Alder Reaction

While radioimmunotherapy (RIT) is a promising approach for the treatment of cancer, the long pharmacokinetic half-life of radiolabeled antibodies can result in high radiation doses to healthy tissues. Perhaps not surprisingly, several different strategies have been developed to circumvent this troubling limitation. One of the most promising of these approaches is pretargeted radioimmunotherapy (PRIT). PRIT is predicated on decoupling the radionuclide from the immunoglobulin, injecting them separately, and then allowing them to combine in vivo at the target tissue. This approach harnesses the exceptional tumor-targeting properties of antibodies while skirting their pharmacokinetic drawbacks, thereby lowering radiation doses to non-target tissues and facilitating the use of radionuclides with half-lives that are considered too short for use in traditional radioimmunoconjugates. Over the last five years, our laboratory and others have developed an approach to in vivo pretargeting based on the inverse electron-demand Diels-Alder (IEDDA) reaction between trans-cyclooctene (TCO) and tetrazine (Tz). This strategy has been successfully applied to pretargeted positron emission tomography (PET) and single-photon emission computed tomography (SPECT) imaging with a variety of antibody-antigen systems. In a pair of recent publications, we have demonstrated the efficacy of IEDDA-based PRIT in murine models of pancreatic ductal adenocarcinoma and colorectal carcinoma. In this protocol, we describe protocols for PRIT using a 177Lu-DOTA-labeled tetrazine radioligand ([177Lu]Lu-DOTA-PEG7-Tz) and a TCO-modified variant of the colorectal cancer targeting huA33 antibody (huA33-TCO). More specifically, we will describe the construction of huA33-TCO, the synthesis and radiolabeling of [177Lu]Lu-DOTA-PEG7-Tz, and the performance of in vivo biodistribution and longitudinal therapy studies in murine models of colorectal carcinoma.

This protocol describes the synthesis and characterization of a trans-cyclooctene (TCO)-modified antibody and a 177Lu-labeled tetrazine (Tz) radioligand for pretargeted radioimmunotherapy (PRIT). In addition, it details the use of these two constructs for in vivo biodistribution and longitudinal therapy studies in a murine model of colorectal cancer.

基于逆电子需求函数-alder 反应的隐形放射免疫治疗

While radioimmunotherapy (RIT) is a promising approach for the treatment of cancer, the long pharmacokinetic half-life of radiolabeled antibodies can ...

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 ...

Microwave-Assisted Preparation of 1-Aryl-1H-pyrazole-5-amines

A synthetic process for the preparation of a variety of 1-aryl-1H-pyrazole-5-amines was developed. The microwave-mediated nature of this method makes it efficient in both time and resources and utilizes water as the solvent. 3-Aminocrotononitrile or an appropriate &#945;-cyanoketone is combined with an aryl hydrazine and dissolved in 1 M HCl. The mixture is then heated in a microwave reactor at 150 &#176;C, typically for 10-15 min. The product can be readily obtained by basifying the solution with 10% NaOH and isolating the desired compound with a simple vacuum filtration. The use of water as a solvent in this reaction lends to its ease and utility in production, and this method is easily reproducible with a variety of functional groups. Typical isolated yields range from 70-90%, and reactions can be performed on the milligram to gram scale with little to no change in observed yields. Some of the applications of these molecules and their derivatives include pesticides, anti-malarials, and chemotherapeutics, among many others.

Microwave-Assisted Preparation of 1-Aryl-1H-pyrazole-5-amines

1-Aryl-1H-pyrazole-5-amines are prepared from aryl hydrazines combined with either 3-aminocrotononitrile or an &#945;-cyanoketone in a 1 M HCl solution using a microwave reactor. Most reactions are done in 10-15 minutes and pure product can be obtained via vacuum filtration with typical isolated yields of 70-90%.

微波辅助制备1-Aryl-1 H-pyrazole-5胺

A synthetic process for the preparation of a variety of 1-aryl-1H-pyrazole-5-amines was developed. The microwave-mediated nature of this method makes it ...