这项工作得到了中国国家自然科学基金 (21502023) 的支持。

1. 合成 1-(Iodoethynyl)-4-甲苯 (2, 1-Iodoalkynes)
<ol><li>添加133毫克 (0.36 毫摩尔) 的 TBAI 和3毫升的 CH3CN 到一个反应管, 其中含有磁性搅拌杆, 这是开放的空气。然后, 用微量泵在混合物中加入 38 μ( 0.3 毫摩尔) 的 tolylethyne。</li>
	<li>添加96.6 毫克 (0.3 毫摩尔) 的 PIDA, 以强力搅拌反应混合物10个部分在20分钟的时间内使用刮刀。</li>
	<li>在室温下搅拌反应混合物3小时。</li>
	<li>将产生的混合物倒入含有30毫升水的部位漏斗中, 用水钠2S2O3 (10%, 0.5 毫升) 淬火。用10毫升醋酸乙酯萃取水层三次。</li>
	<li>用10毫升的饱和盐水和干燥的无水硫酸钠 (0.5 克) 冲洗有机复合层。</li>
	<li>用傅书礼漏斗过滤掉硫酸硫酸钠, 在减压下浓缩滤液以获得原油。</li>
	<li>以己烷为淋洗, 用硅凝胶柱层析法提纯原油产品;纯产物, 1-(iodoethynyl)-4-甲苯, 被获得作为淡黄色液体 (71.9 毫克, 99% 屈服;Rf= 0.79)。</li>
	<li>用1H 和13C 核磁共振波谱分析产品, 高效液相色谱 (HPLC)。</li>
</ol>2. (E)-1-(12-Diiodovinyl)-4-甲苯 (3, 12-Diiodoalkenes) 的合成
<ol><li>加入124.5 毫克 (0.75 毫摩尔) 的基和1毫升的 CH3CN 到一个反应管, 其中含有磁性搅拌杆, 这是开放的空气。然后, 添加 38 ul (0.3 毫摩尔) 对tolylethyne 和3毫升的 H2O 的混合物通过微量泵。</li>
	<li>添加96.6 毫克 (0.3 毫摩尔) 的 PIDA, 以强力搅拌反应混合物10个部分在20分钟的时间内使用刮刀。</li>
	<li>在室温下搅拌反应混合物24小时。</li>
	<li>将所产生的混合物倒入含有30毫升水的部位漏斗中, 用水钠2S2O3 (10% 毫升) 淬火, 并提取含醋酸乙酯1毫升的水层三次。</li>
	<li>用10毫升盐水和干燥的无水硫酸钠 (0.5 克) 冲洗有机复合层。</li>
	<li>用傅书礼漏斗过滤掉硫酸硫酸钠, 在减压下浓缩滤液以获得原油。</li>
	<li>以己烷为淋洗, 用硅凝胶柱层析法提纯粗品。纯产物, (E)-1-(12-diiodovinyl)-4-甲苯, 被获得作为淡黄色液体 (111.9 毫克, 98% 屈服;Rf = 0.84)。</li>
	<li>用1H 和13C 核磁共振波谱分析了该产品, 并进行了 HPLC 测定。</li>
</ol>3. 合成 1-甲基-4-(12, 2-Triiodovinyl) 苯 (4, 11, 2-Triiodoalkenes)
<ol><li>添加133毫克 (0.36 毫摩尔) 的 TBAI 和1毫升的 CH3CN 到一个反应管, 其中含有搅拌杆, 这是开放的空气。然后, 添加 38 ul (0.3 毫摩尔) 的ptolylethyne 使用微量泵。</li>
	<li>添加96.6 毫克 (0.3 毫摩尔) 的 PIDA, 以强力搅拌反应混合物10个部分在20分钟的时间内使用刮刀。在室温下将反应混合物搅拌3小时。</li>
	<li>加入124.5 毫克 (0.75 毫摩尔) 的基在3毫升的 H2O 的反应混合物。</li>
	<li>添加193.2 毫克 (0.6 毫摩尔) 的 PIDA 到反应混合物10个部分在20分钟内使用刮刀。在室温下将反应混合物搅拌3小时。</li>
	<li>再添加124.5 毫克 (0.75 毫摩尔) 的基在3毫升的 H2O 和1毫升的 CH3CN 到反应混合物。</li>
	<li>在20分钟的时间内, 用刮刀将193.2 毫克 (0.6 毫摩尔) 的 PIDA 添加到反应混合物中10部分。在室温下将反应混合物搅拌12小时。</li>
	<li>将所产生的混合物倒入含有30毫升水的部位漏斗中, 用水钠2S2O3 (10% 毫升) 淬火, 并提取含醋酸乙酯2毫升的水层三次。</li>
	<li>用10毫升盐水和干燥的无水硫酸钠 (0.5 克) 冲洗有机复合层。</li>
	<li>用傅书礼漏斗过滤掉硫酸硫酸钠, 在减压下浓缩滤液以获得原油。</li>
	<li>用己烷对硅凝胶柱层析法提纯粗品, 得到纯产物, 1-甲基-4-(1, 2, 2-triiodovinyl) 苯, 作为黄液 (138.4 毫克, 93% 产量;Rf = 0.79)。</li>
	<li>用1H 和13C 核磁共振波谱分析了该产品, 并进行了 HPLC 测定。</li>
</ol>4. HPLC 法测定终端炔烃单、二、三碘的选择性
注: hplc 法测定炔烃的单、二、三碘的选择性。高效液相色谱仪采用 5 μm、4.6 毫米 x 150 毫米柱、CH3CN/H2O = 75/25 (v/v) 作为溶剂, 流速为1.0 毫升/分钟, 以及λ = 254 nm 的探测器波长。
<ol><li>高效液相色谱外标准溶液的制备<ol>
<li>精确地称出 2 (1-(iodoethynyl)-4-甲苯; 9.58 毫克, 39.58×10-3毫摩尔), 3 ((E)-1-(12-diiodovinyl)-4-甲苯; 19.29 毫克, 52.14×10-3毫摩尔) 和4 (1-甲基-4-(12, 2-triiodovinyl) 苯;11.10 毫克, 22.38×10-3毫摩尔)。</li>
		<li>在1毫升的 CH3CN 中混合并溶解这三种化合物, 并在进行 HPLC 分离之前稀释库存溶液100次。</li>
		<li>确定每种产品在 HPLC 色谱上的峰值面积比值 (%)。</li>
		<li>根据以下公式计算每种化合物的摩尔吸收率: ε2 : ε3 : ε4 = a2/n2 : 3/n3 :4/n4 其中ε是摩尔吸收, 一个峰值面积, n 摩尔重量。</li>
	</ol>
</li>
	<li>根据以下公式计算 chemoselectivity: n2 : n3 : n4 = a2/ε2 : 3/ε 3: 4/ε4
</li>
</ol>

作者没有什么特别的东西可以透露。

1-Iodoalkynes, 12-diiodoalkenes 和 11, 2-triiodoalkenes 可 chemoselectively 合成使用高价碘试剂作为有效的调解人氧化碘 (s)。这些 chemoselective 碘协议最关键的因素是碘源的性质和负载, 以及溶剂。例如, 1-iodoalkyne 2被获得作为主要产品 (52% 产量), 当 TBAI (2.5 equiv 装载) 被选择作为碘来源与甲醇结合作为溶剂 (2:3:4= 90:5: 5)。在将碘源转化为基时, 没有观察到这种选择?...

Iodoalkynes 和 iodoalkenes 广泛应用于有机合成1、2、3、4、生物活性物质的重要前体和积木, 并在合成材料和复杂分子给出了转换 C I 键5,6,7,8的容易。近年来, 炔烃的氧化碘越来越多地引起了 iodoalkyne 和 iodoalkene 衍生物的合成。迄今为止, 使用金属催化剂的有效方法9、10、11、12、高价-碘催化剂13、14、阳极氧化系统15、离子液体系统16, 基 (或 I2)-氧化剂组合17,18,19,20, 超声波21, 相转移催化剂22, n-iodosuccinimide9,22,23,24,25, N-邓布利多26,27,28,29,30,31, 格利雅试剂32, 和啉催化剂17,33,24,35已开发为碘的炔烃。最近, 我们报告了一个实用的和 chemoselective 的协议, 合成 1-iodoalkynes, 12-diiodoalkenes, 11, 2-triiodoalkenes36。该方法具有绿色实用的特点: (1) 高价碘催化剂作为氧化功能化试剂的毒性较低, 与其他传统的重金属元素氧化剂37、38、 39,40,41,42, 和 (2) TBAI 和/或基被用作碘源。此外, 在温和的条件下, 我们的系统具有良好的选择性。chemoselective 合成 1-iodoalkynes, 12-diiodoalkenes 和 11, 2 triiodoalkenes 需要精确控制各种因素, 包括组成, 氧化剂, 碘源, 和溶剂。其中, 碘源是反应 chemoselectivity 的最重要因素。在对碘源和溶剂的几种类型和荷载进行筛选后, 确定并建立了三种方法。首先, TBAI 作为碘源结合 PIDA (TBAI PIDA) 是选择性的合成 1-iodoalkynes。或者, 用 PIDA 系统有效地获得 12-diiodoalkenes。两种方法均能提供高产、高 chemoselectivity 的相应产品。相应的三 iodinationproducts, i., 11, 2-triiodoalkenes, 得到了良好的产量从一锅合成, 结合了 TBAI-PIDA 和奇 PIDA 系统36。
在这里, 我们将演示如何从 1-iodoalkynes 到 12-diiodoalkenes 和 11, 2-triiodoalkenes 在类似的反应条件下, chemoselectivity 碘的炔烃, 突出精确的控制, 可以通过明智地选择氧化剂, 碘源, 和溶剂施加。针对这种新型合成技术的发展, 对tolylethyne 作了模型基质。虽然以下协议的重点是合成 1-(iodoethynyl)-4-甲苯, (E)-1-(12-diiodovinyl)-4-甲苯和 1-甲基-4-(12, 2-triiodovinyl) 苯, 这些化合物代表 1-iodoalkynes, 12-diiodoalkenes 和 11, 2-triiodoalkenes,即, 协议是广泛的范围内, 同样的技术可以适用于 chemoselective 碘的芳香和脂肪族终端炔烃36。
使用的试剂在 chemoselective 碘的终端炔烃和小偏差的技术所描述的结果, 对目标产品的显著差异。例如, 从 TBAI 到基的碘源的变化和溶剂的变化从 ch3cn 到 ch3cn-H2O 对碘的 chemoselectivity 产生了戏剧性的影响。详细的议定书旨在帮助外地的新从业者与终端炔烃的 chemoselective 碘, 以避免在合成 1-iodoalkynes、12-diiodoalkenes 和11、2-triiodoalkenes 过程中出现许多常见的缺陷。

<table border="0" cellpadding="0" cellspacing="0" width="860">
	<tbody>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">4-ethynyltoluene,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">D080006</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">phenylacetylene,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">W330041</td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">1-ethynyl-4-methoxybenzene,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">D080007</td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">1-ethynyl-4-fluorobenzene,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">D080005</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:263px;">4-(Trifluoromethyl)phenylacetylene,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">W320273</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:263px;">4-Ethynylbenzoic acid methyl ester,97%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">A020720</td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">3-Aminophenylacetylene,97%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">D080001</td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">3-Butyn-1-ol,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">A040031</td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">Propargylacetate,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">L10031</td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">Tetrabutylammonium Iodide,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">E010070</td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">Potassium iodide,98%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">E010364</td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;width:263px;">(diacetoxyiodo)benzene,99%</td>
			<td style="width:311px;">Energy Chemical</td>
			<td style="width:119px;">A020180</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:263px;">acetonitrile, HPLC grade</td>
			<td style="width:311px;">fischer</td>
			<td style="width:119px;">A998-4</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:263px;">magnetic stirrer</td>
			<td style="width:311px;">IKA</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:263px;">rotary evaporator</td>
			<td style="width:311px;">Buchi</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:263px;">Bruker AVANCE III 400 MHz Superconducting Fourier</td>
			<td style="width:311px;">Bruker</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:263px;">High-performance liquid chromatography</td>
			<td style="width:311px;">Shimadzu</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
	</tbody>
</table>

chemoselective preparation of 1-iodoalkynes, 1,2-diiodoalkenes, and 1,1,2-triiodoalkenes based on the oxidative iodination of terminal alkynes

我们提出了 chemoselective 合成 1-(iodoethynyl)-4-甲苯, 1-(12-diiodovinyl)-4-甲苯, 1-甲基-4-(12, 2-triiodovinyl) 苯作为实际 chemoselective 制备 1-iodoalkynes 的典型例子, 12-diiodoalkenes 和 11, 2-triiodoalkenes 从 chemoselective 碘的终端炔烃介导的高价碘试剂。用p-tolylethyne 作为模型基质筛选各种碘源和/或高价碘试剂, 证实了 chemoselectivity。四丁基碘化 (TBAI) 和 (diacetoxyiodo) 苯 (PIDA) 的组合选择性地产生 1-iodoalkynes, 而基和 PIDA 的组合产生 12-diiodoalkenes。基于 TBAI-PIDA 和 PIDA 的单壶合成, 产生相应的11、2-triiodoalkenes。这些协议随后被应用于合成重要的芳香族和脂质体 1-iodoalkynes, 12-diiodoalkenes 和 11, 2-triiodoalkenes, 得到了良好的产量和优良的 chemoselectivity。

chemoselective 合成 1-iodoalkynes, 12-diiodoalkenes 和 11, 2-triiodoalkenes 的基础上的氧化碘的ptolylethyne 总结在图 1。所有的反应都暴露在空气中。本研究中的所有化合物均采用1H 和13C 核磁共振波谱、质谱和 HPLC 法, 以获得产物的结构和反应的选择性, 并探讨其纯度。所获得的产品稳定后, 在4°c 在一个冰箱四月, i. e., 高效液相色谱和1H ?...

Watch this Scientific Journal Video about Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes at JoVE.com

Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes

基于末端碘氧化炔烃的 1-Iodoalkynes、12-Diiodoalkenes、11、2 Triiodoalkenes 的 Chemoselective 制备

本文介绍了用高价碘试剂对炔烃末氧化碘的详细协议, chemoselectively 提供了 1 iodoalkynes、12 diiodoalkenes、11、2 triiodoalkenes。

We present the chemoselective synthesis of 1-(iodoethynyl)-4-methylbenzene, 1-(1,2-diiodovinyl)-4-methylbenzene, and ...

chemoselective-preparation-1-iodoalkynes-12-diiodoalkenes-112

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Alkynes

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7.6K 次观看.  Guangdong University of Technology. 本文介绍了用高价碘试剂对炔烃末氧化碘的详细协议, chemoselectively 提供了 1 iodoalkynes、12 diiodoalkenes、11、2 triiodoalkenes。

视频: Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes

Methods to Identify the NMR Resonances of the 13C-Dimethyl N-terminal Amine on Reductively Methylated Proteins

Nuclear magnetic resonance (NMR) spectroscopy is a proven technique for protein structure and dynamic studies. To study proteins with NMR, stable magnetic isotopes are typically incorporated metabolically to improve the sensitivity and allow for sequential resonance assignment. Reductive 13C-methylation is an alternative labeling method for proteins that are not amenable to bacterial host over-expression, the most common method of isotope incorporation. Reductive 13C-methylation is a chemical reaction performed under mild conditions that modifies a protein&#39;s primary amino groups (lysine &#949;-amino groups and the N-terminal &#945;-amino group) to 13C-dimethylamino groups. The structure and function of most proteins are not altered by the modification, making it a viable alternative to metabolic labeling. Because reductive 13C-methylation adds sparse, isotopic labels, traditional methods of assigning the NMR signals are not applicable. An alternative assignment method using mass spectrometry (MS) to aid in the assignment of protein 13C-dimethylamine NMR signals has been developed. The method relies on partial and different amounts of 13C-labeling at each primary amino group. One limitation of the method arises when the protein&#39;s N-terminal residue is a lysine because the &#945;- and &#949;-dimethylamino groups of Lys1 cannot be individually measured with MS. To circumvent this limitation, two methods are described to identify the NMR resonance of the 13C-dimethylamines associated with both the N-terminal &#945;-amine and the side chain &#949;-amine. The NMR signals of the N-terminal &#945;-dimethylamine and the side chain &#949;-dimethylamine of hen egg white lysozyme, Lys1, are identified in 1H-13C heteronuclear single-quantum coherence spectra.

Methods to Identify the NMR Resonances of the 13C-Dimethyl N-terminal Amine on Reductively Methylated Proteins

Two methods for assigning the &#945;- and &#949;-dimethylamine nuclear magnetic resonance signals of a reductively 13C-methylated N-terminal lysine are described. One method utilizes the pH-induced selectivity of the reductive methylation reaction, and the other uses aminopeptidase to selectively remove the N-terminal lysine.

Nuclear magnetic resonance (NMR) spectroscopy is a proven technique for protein structure and dynamic studies. To study proteins with NMR, stable magnetic ...

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化学

Determining the Ice-binding Planes of Antifreeze Proteins by Fluorescence-based Ice Plane Affinity

Antifreeze proteins (AFPs) are expressed in a variety of cold-hardy organisms to prevent or slow internal ice growth. AFPs bind to specific planes of ice through their ice-binding surfaces. Fluorescence-based ice plane affinity (FIPA) analysis is a modified technique used to determine the ice planes to which the AFPs bind. FIPA is based on the original ice-etching method for determining AFP-bound ice-planes. It produces clearer images in a shortened experimental time. In FIPA analysis, AFPs are fluorescently labeled with a chimeric tag or a covalent dye then slowly incorporated into a macroscopic single ice crystal, which has been preformed into a hemisphere and oriented to determine the a- and c-axes. The AFP-bound ice hemisphere is imaged under UV light to visualize AFP-bound planes using filters to block out nonspecific light. Fluorescent labeling of the AFPs allows real-time monitoring of AFP adsorption into ice. The labels have been found not to influence the planes to which AFPs bind. FIPA analysis also introduces the option to bind more than one differently tagged AFP on the same single ice crystal to help differentiate their binding planes. These applications of FIPA are helping to advance our understanding of how AFPs bind to ice to halt its growth and why many AFP-producing organisms express multiple AFP isoforms.

Antifreeze proteins (AFPs) bind to specific planes of ice to prevent or slow ice growth. Fluorescence-based ice plane affinity (FIPA) analysis is a modification of the original ice-etching method for determination of AFP-bound ice planes. AFPs are fluorescently labeled, incorporated into macroscopic single ice crystals, and visualized under UV light.

通过荧光基冰平面亲和力确定防冻蛋白的冰结合平面

Antifreeze proteins (AFPs) are expressed in a variety of cold-hardy organisms to prevent or slow internal ice growth. AFPs bind to specific planes of ice ...

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

Here we present a protocol for the synthesis of two distinct carbonyl-decorated carbenes. Both carbenes can be prepared using nearly identical procedures in multi-gram scale quantities. The goal of this manuscript is to clearly detail how to handle and prepare these unique carbenes such that a synthetic chemist of any skill level can work with them. The two carbenes described are a diamidocarbene (DAC, carbene 1) and a monoamidoaminocarbene (MAAC 2). These carbenes are highly electron-deficient and as such display reactivity profiles that are atypical of more traditional N-heterocyclic carbenes. Additionally, these two carbenes only differ in their electrophilic character and not their steric parameters, making them ideal for studying how carbene electronics influence reactivity. To demonstrate this phenomenon, we are also describing the activation of white phosphorus (P4) using these carbenes. Depending on the carbene used, two very different phosphorus-containing compounds can be isolated. When the DAC 1 is used, a tris(phosphaalkenyl)phosphane can be isolated as the exclusive product. Remarkably however, when MAAC 2 is added to P4 under identical reaction conditions, an unexpected carbene-supported P8&#160;allotrope of phosphorus is isolated exclusively. Mechanistic studies demonstrate that this carbene-supported P8allotrope forms via a [2+2] cycloaddition dimerization of a transient diphosphene which has been trapped by treatment with 2,3-dimethyl-1,3-butadiene.

Here, we present a protocol for the synthesis of two carbonyl-decorated carbenes. The protocol makes these interesting compounds readily available to chemists of all skill levels. In addition to the synthesis of these two carbenes, their use in the activation of white phosphorus is also described.

羰基饰卡宾的白色磷的活化制备方法和用途

Here we present a protocol for the synthesis of two distinct carbonyl-decorated carbenes. Both carbenes can be prepared using nearly identical procedures ...

Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process.
The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications.

A procedure for the preparation of porous hybrid separation media composed of a macroporous polymer monolith internally coated by a high surface area microporous coordination polymer is presented.

对磷酸增强富集制备高度多孔配位聚合物涂层的孔聚合物石柱的

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous ...

Preparation of Macroporous Epitaxial Quartz Films on Silicon by Chemical Solution Deposition

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step process based on the preparation of a sol in a one-pot synthesis which is followed by the deposition of a gel film on Si(100) substrates by evaporation induced self-assembly using the dip-coating technique and ends with a thermal treatment of the material to induce the gel crystallization and the growth of the quartz film. The formation of a silica gel is based on the reaction of a tetraethyl orthosilicate and water, catalyzed by HCl, in ethanol. However, the solution contains two additional components that are essential for preparing mesoporous epitaxial quartz films from these silica gels dip-coated on Si. Alkaline earth ions, like Sr2+ act as glass melting agents that facilitate the crystallization of silica and in combination with cetyl trimethylammonium bromide (CTAB) amphiphilic template form a phase separation responsible of the macroporosity of the films. The good matching between the quartz and silicon cell parameters is also essential in the stabilization of quartz over other SiO2 polymorphs and is at the origin of the epitaxial growth.

A protocol is presented for the preparation of piezoelectric macroporous epitaxial films of quartz on silicon by solution chemistry using dip-coating and thermal treatments in air.

化学溶液沉积在硅外延大孔石英薄膜的制备

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step ...

Photochemical Oxidative Growth of Iridium Oxide Nanoparticles on CdSe@CdS Nanorods

We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide (CdSe@CdS) nanorod photocatalysts. Seeded rods are grown using a colloidal hot-injection method and then moved to an aqueous medium by ligand exchange. CdSe@CdS nanorods, an iridium precursor and other salts are mixed and illuminated. The deposition process is initiated by absorption of photons by the semiconductor particle, which results with formation of charge carriers that are used to promote redox reactions. To insure photochemical oxidative growth we used an electron scavenger. The photogenerated holes oxidize the iridium precursor, apparently in a mediated oxidative pathway. This results in the growth of high quality crystalline iridium oxide particles, ranging from 0.5 nm to about 3 nm, along the surface of the rod. Iridium oxide grown on CdSe@CdS heterostructures was studied by a variety of characterization methods, in order to evaluate its characteristics and quality. We explored means for control over particle size, crystallinity, deposition location on the CdS rod, and composition. Illumination time and excitation wavelength were found to be key parameters for such control. The influence of different growth conditions and the characterization of these heterostructures are described alongside a detailed description of their synthesis. Of significance is the fact that the addition of iridium oxide afforded the rods astounding photochemical stability under prolonged illumination in pure water (alleviating the requirement for hole scavengers).

A protocol for the photochemical oxidative growth of small crystalline iridium oxide nanoparticles on the surface of CdSe@CdS seeded rod nanoparticles is presented.

铱氧化物纳米颗粒对硒化镉硫化镉@纳米棒光化学氧化增长

We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide ...

Preparation and In Vitro Characterization of Dendrimer-based Contrast Agents for Magnetic Resonance Imaging

Paramagnetic complexes of gadolinium(III) with acyclic or macrocyclic chelates are the most commonly used contrast agents (CAs) for magnetic resonance imaging (MRI). Their purpose is to enhance the relaxation rate of water protons in tissue, thus increasing the MR image contrast and the specificity of the MRI measurements. Current clinically approved contrast agents are low molecular weight molecules that are rapidly cleared from the body. The use of dendrimers as carriers of paramagnetic chelators can play an important role in the future development of more efficient MRI contrast agents. Specifically, the increase in local concentration of the paramagnetic species results in a higher signal contrast. Furthermore, this CA provides a longer tissue retention time due to its high molecular weight and size. Here, we demonstrate a convenient procedure for the preparation of macromolecular MRI contrast agents based on poly(amidoamine) (PAMAM) dendrimers with monomacrocyclic DOTA-type chelators (DOTA &#8211; 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate). The chelating unit was appended by exploiting the reactivity of the isothiocyanate (NCS) group towards the amine surface groups of the PAMAM dendrimer to form thiourea bridges. Dendrimeric products were purified and analyzed by means of nuclear magnetic resonance spectroscopy, mass spectrometry, and elemental analysis. Finally, high resolution MR images were recorded and the signal contrasts obtained from the prepared dendrimeric and the commercially available monomeric agents were compared.

Preparation and In Vitro Characterization of Dendrimer-based Contrast Agents for Magnetic Resonance Imaging

This protocol describes the preparation and characterization of a dendrimeric magnetic resonance imaging (MRI) contrast agent that carries cyclen-based macrocyclic chelates coordinating paramagnetic gadolinium ions. In a series of MRI experiments in vitro, this agent produced an amplified MRI signal when compared to the commercially available monomeric analogue.

制备及<em&gt;体外</em&gt;磁共振成像基于树状大分子造影剂的表征

Paramagnetic complexes of gadolinium(III) with acyclic or macrocyclic chelates are the most commonly used contrast agents (CAs) for magnetic resonance ...

Preparation of Chitosan-based Injectable Hydrogels and Its Application in 3D Cell Culture

The protocol presents a facile, efficient, and versatile method to prepare chitosan-based hydrogels using dynamic imine chemistry. The hydrogel is prepared by mixing solutions of glycol chitosan with a synthesized benzaldehyde terminated polymer gelator, and hydrogels are efficiently obtained in several minutes at room temperature. By varying ratios between glycol chitosan, polymer gelator, and water contents, versatile hydrogels with different gelation times and stiffness are obtained. When damaged, the hydrogel can recover its appearances and modulus, due to the reversibility of the dynamic imine bonds as crosslinkages. This self-healable property enables the hydrogel to be injectable since it can be self-healed from squeezed pieces to an integral bulk hydrogel after the injection process. The hydrogel is also multi-responsive to many bio-active stimuli due to different equilibration statuses of the dynamic imine bonds. This hydrogel was confirmed as bio-compatible, and L929 mouse fibroblast cells were embedded following standard procedures and the cell proliferation was easily assessed by a 3D cell cultivation process. The hydrogel can offer an adjustable platform for different research where a physiological mimic of a 3D environment for cells is profited. Along with its multi-responsive, self-healable, and injectable properties, the hydrogels can potentially be applied as multiple carriers for drugs and cells in future bio-medical applications.

Here we describe a facile preparation of chitosan-based injectable hydrogels using dynamic imine chemistry. Methods to adjust the hydrogel&#8217;s mechanical strength and its application in 3D cell culture are presented.

糖注射水凝胶的制备及其在3D 细胞培养中的应用

The protocol presents a facile, efficient, and versatile method to prepare chitosan-based hydrogels using dynamic imine chemistry. The hydrogel is ...

Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core

We report a procedure to linearly scale-up the synthesis of 2,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)dibenzothiophene-S,S-dioxide (compound 4) and 2,8-bis(10H-phenothiazin-10-yl)dibenzothiophene-S,S-dioxide (compound 5) using Buchwald-Hartwig cross-coupling reaction conditions. In addition, we demonstrate a scaled-up synthesis of all non-commercially available starting materials that are required for the amination cross-coupling reaction. In the present article, we provide the detailed synthetic procedures for all of the described compounds, alongside their spectral characterization. This work shows the possibility to produce organic molecules for optoelectronic applications on a large scale, which facilitates their implementation into real world devices.

Scale-up synthesis of highly efficient thermally activated delayed fluorescence emitters is described in the presented article.

基于吩 s-二氧化硫核的热活化延迟荧光发射器的放大化学合成

We report a procedure to linearly scale-up the synthesis of 2,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)dibenzothiophene-S,S-dioxide (compound 4) and ...

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic polymers, with the aim of photo-activating oxygen-evolving manganese oxide catalysts, which are important components in artificial photosynthesis. The cross-linking technique was applied to obtain a self-standing membrane with a high PW12O403- content. Incorporation and structure retention of PW12O403- within the polymer matrix were confirmed by FT-IR and micro-Raman spectroscopy, and optical characteristics were investigated by UV-Vis spectroscopy, which revealed successful construction of the metal-to-metal charge transfer (MMCT) unit. After deposition of MnOx oxygen evolving catalysts, photocurrent measurements under visible light irradiation verified the sequential charge transfer, Mn &#8594; MMCT unit &#8594; electrode, and&#160;the photocurrent intensity was consistent with the redox potential of the donor metal (Ce or Co). This method provides a new strategy for preparing integrated systems involving catalysts and photon-absorption parts for use with photo-functional materials.

Here, we present a protocol to prepare charge transfer chromophores based on a polyoxometalate/polymer composite membrane.

氧化锰催化剂光活化 Polyoxometalate 基光响应膜的制备

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic ...