这项研究得到了欧洲联盟的2020居里夫人-居里赠款协议 H2020-MSCA-ITN-2015/674990 项目 "EXCILIGHT" 下的研究和创新计划的资助。睡衣感谢皇家学会的沃尔夫森研究优异奖。

警告: 请在使用之前检查所有相关的材料安全数据表 (MSDS)。合成中使用的几种化学物质具有剧毒和致癌性。使用硅胶时, 必须佩戴保护性呼吸面罩, 以防吸入微粒。在进行化学反应时, 请遵守所有适当的安全规则, 包括使用工程控制 (通风柜) 和个人防护设备 (安全眼镜、手套、实验室大衣、全长长裤、双脚趾鞋). 
 所有试剂和溶剂都是在商业上购买的, 没有任何进一步的纯化。 1 用 CDCl 3 作为溶剂, 在400兆赫核磁共振光谱仪上记录了 H 和 13 C 核磁共振谱。质子核磁共振化学位移报告为和 #948; 相对于氘溶剂的 ppm 值: CDCl 3 (7.26)。数据显示如下: 化学位移, 多重性和耦合常数 (s) ( J ) 在赫兹. 多被报告在范围 (在 ppm) 他们出现了。碳核磁共振数据收集相对于相应的溶剂信号 CDCl 3 (77.16)。熔点是用熔点仪测量的。基质辅助激光解吸电离-飞行时间 (MALDI) 质谱是运行在津 Axima-CFR 光谱仪 (质量范围 1-150 000 Da). 
 1. 所报告化合物的合成 <ol> <li> 合成化合物 1 (36-二叔丁基-9 h 咔唑) 19 <ol> <li> 使用500毫升三颈圆底烧瓶, 溶解 9-H 咔唑 (10.0 克, 60 摩尔) 在硝基 (300 毫升) 在氮气大气之下。然后, 加入锌 (II) 氯化物 (24.3 克, 180 摩尔) 的解决方案. </li>
		<li> 将 2-氯-2-丙烷 (19.5 毫升, 180 摩尔) 倒入100毫升加法漏斗, 并在剧烈搅拌下加入滴. </li>
		<li> 将产生的混合物在室温下搅拌6小时. </li>
		<li> 通过薄层层析 (TLC) 监测反应的完成情况, 使用二氯甲烷: 己烷 1:1 v/v 作为淋洗混合物。在消耗了 9-H 咔唑后, 加入100毫升的水来中和溶液. </li>
		<li> 每次使用150毫升的二氯甲烷提取产品三次。将有机层从水中分离出来, 另外用150毫升水冲洗两次。
		<ol> <li> 用15克硫酸镁干燥产生的有机层, 并在减压下蒸发溶剂以获得灰色粉末. </li>
		</ol> </li> <li> 用二氯甲烷提纯柱层析法: 己烷 1:1 v/v 溶剂混合物作为淋洗提供了13.1 克 (79%) 化合物1作为白色粉末. 
		化合物1特性: 1 H 核磁共振 (400 MHz, CDCl 3 , 25 和 #176; C, ppm): 8.12 (d, J = 1.9 Hz, 2H), 7.78 (s b, 1H), 7.5 (dd, J = 8.5, 1.9 hz, 2H), 7.33 (dd, j = 5.6, 0.5 hz, 2H), 1.49 (s, 18H). 
		 13 c 核磁共振 (400 兆赫, CDCl 3 , 25 和 #176; c, ppm): 142.4, 138.2, 123.7, 123.4, 116.3, 110.2, 34.9, 32.2. 
		MS: m/z 279.4 (m +). 
		熔点: 233-235 和 #176; C. </li>
	</ol> </li> <li> 合成化合物 2 (28-dibromodibenzothiophene) 20 <ol> <li> 使用500毫升三颈圆底烧瓶, 在氮气下溶解吩 (15.0 毫升, 81.3 摩尔), 在氯仿 (100 ml) 下气氛.其次, 在0和 #176 添加滴溴 (9.3 毫升, 180 摩尔); C 在剧烈搅拌下. </li>
		<li> 在完全添加溴后, 将温度提高到室温, 并将反应混合物搅拌18小时. </li>
		<li> 过滤掉产生的白色沉淀物, 然后用50毫升水反复洗涤, 然后用15毫升的甲醇分离 28-dibromodibenzothiophene, 以23克 (83%) 的产量作为白色粉末. 
		化合物2表征: 1 H 核磁共振 (400 兆赫, CDCl 3 , 25 和 #176; C, ppm): 8.24 (d, J = 2.0 Hz, 2H), 7.71 (d, j = 8.0 Hz, 2H), 7.58 (d, J = 2.0 hz, 2H). 
		 13 c 核磁共振 (400 兆赫, CDCl 3 , 25 和 #176; c, ppm): 138.8, 136.3, 130.5, 124.9, 124.3, 118.8. 
		MS: m/z 342.1 (m +). 
		熔点: 227-229 和 #176; C. </li>
	</ol> </li> <li> 合成化合物 3 (28-dibromodibenzothiophene-5-二氧化物) 21 <ol> <li> 加载500毫升的一颈圆底烧瓶, 悬挂 28-dibromodibenzothiophene (21.3 g, 60 摩尔) 和过氧化氢溶液 (30 毫升 30% (w/w) 在 H 2 O) 在冰河乙酸 (250 毫升) 和反流为 2 h 在氮气气氛下. </li>
		<li> 将产生的混合物冷却到室温, 并过滤掉白色沉淀. </li>
		<li> 用15毫升的水冲洗三次, 然后用10毫升的甲醇洗涤, 获得19.3 克 (85%) 的白色粉末. 
		化合物3表征: 1 H 核磁共振 (400 兆赫, CDCl 3 , 25 和 #176; C, ppm): 8.22 (d, J = 1.6 Hz, 2H), 7.70 (d, j = 8.0 Hz, 2H), 7.57 (d, J = 2 hz, 2H). 
		 13 c 核磁共振 (400 兆赫, CDCl 3 , 25 和 #176; c, ppm): 133.3, 130.4, 129.1, 125.6, 124.8, 124.3. 
		MS: m/z 374.1 (m +). 
		熔点: 360-362 和 #176; C. </li>
	</ol> </li> <li> 合成化合物 4 (28-双 (36-二叔丁基-9 h-咔-9-基) 吩 s 二氧化物) 22 <ol> 使用500毫升三颈圆底烧瓶, 溶解28在无水甲苯 (0.80 毫升) 中, dibromodibenzothiophene (0.45 克, 1.2 摩尔) 和36二叔丁基-9 h 咔唑 (2.86 克, 250 摩尔) 和加气, 在剧烈搅拌下, 通过氮气冒泡15分钟. </li>
		<li> 在此之后, 添加三 (丙酮) 乙酸 (0) (0.025 克, 0.03 摩尔) 和 2-基-2 & #8242;, 4 和 #8242;, 6 和 #8242;-triisopropylbiphenyl (XPhos, 0.06 克, 0.12 摩尔) 到反应混合物和加气的解决方案为另15分钟。</li> <li> 添加叔丁醇 (0.32 克, 0.834 摩尔) 和叔丁醇 (6 毫升), 加气为 15 min. </li>
		<li> 热反应溶液在110和 #176; C 在氮气气氛下 18 h. </li>
		<li> 冷却到室温, 加水 (150 毫升), 并将有机产品提取为二氯甲烷 (250 毫升), 并用150毫升水冲洗两次有机层. </li>
		<li> 用15克硫酸镁干燥产生的有机层, 并在减压下除去溶剂以获得原油. </li>
		<li> 用柱层析法提纯粗料 (使用混合溶剂作为淋洗: 二氯甲烷: 石油醚1:1 伏/伏) 以产生化合物4为白色固体 (0.58 克, 63%). 
		化合物4特性: 1 H 核磁共振 (400 MHz, CDCl 3 , 25 & #176; C, ppm): 8.13 (d, J = 1.6 Hz, 4H), 8.11 (d, J = 8.2 hz, 2H), 7.99 (d, J = 1.7 hz, 2H), 7.82 (dd, j = 8.2, 1.8 Hz, 2H), 7.48 (dd, j =8.7, 1.9 hz, 4H), 7.40 (d, J = 8.6 Hz, 4H), 1.45 (s, 36H). 
		 13 c 核磁共振 (400 兆赫, CDCl 3 , 25 和 #176; c, ppm): 144.4, 144.2, 138.5, 135.8, 133.4, 128.4, 124.4, 124.3, 119.5, 116.8, 109.2, 35.0, 32.2. 
		MS: m/z 769.97 (m +). 
		熔点: 351-353 和 #176; C. </li>
	</ol> </li> <li> 合成化合物 5 (28-双 (10 phenothiazin-10-基) 吩 s, s-二氧化物) 23 <ol> <li> Using 250 毫升三-颈圆底烧瓶, 溶解 28-dibromodibenzothiophene s, s-二氧化物 (0.67 g, 1.8 摩尔) 和嗪 (0.75 克, 3.77 摩尔) 在无水甲苯 (60 毫升) 和加气通过起泡通过氮气在剧烈搅拌下15分钟. </li>
		<li> 在此之后, 添加三 (丙酮) 乙酸 (0) (0.11 克, 0.12 摩尔) 和 2-基-2 & #8242;, 4 和 #8242;, 6 和 #8242;-triisopropylbiphenyl (XPhos, 0.12 克, 0.23 摩尔) 到反应混合物和加气的解决方案为另15分钟。</li> <li> 添加叔丁醇 (0.38 克, 3.94 摩尔) 和德加, 由此产生的混合物增加 15 min. </li>
		<li> 将反应溶液加热到110和 #176; C 在氮气气氛下为 18 h. </li>
		<li> 冷却反应混合物到室温, 加水 (150 毫升), 并提取有机产品成二氯甲烷 (250 毫升) 和另外洗两次与150毫升的水. </li>
		<li> 干燥产生的有机层是用15克硫酸镁, 并在减压下除去溶剂, 以给予原油产品. </li>
		<li> 通过柱层析 (用溶剂混合物作为淋洗: 二氯甲烷: 己烷2:1 伏/五) 以获得化合物5为白色固体 (0.9 克, 55%). 
		化合物5特性: 1 H 核磁共振 (400 MHz, CDCl 3 , 25 & #176; C, ppm): 7.71 (d, J = 8.2 Hz, 2H), 7.36 (dd, J = 7.7, 1.5 hz, 4H), 7.28-7. 19 (m, 8H), 7.16 (dd, J = 7.7, 1.3 hz, 4H), 7.02 (dd, j = 8.1, 1.3 hz, 4H). 
		 13 c 核磁共振 (400 兆赫, CDCl 3 , 25 和 #176; c, ppm): 148.8, 141.1, 133.2, 131.8, 129.7, 128.1, 126.9, 125.1, 125.3, 123.1, 121.2, 111.7. 
		MS: m/z 610.08 (m +). 
		熔点: 353-355 和 #176; C. </li>
	</ol>
	</li>
</ol>

<ol>
	<li>Tang, C. W., VanSlyke, S. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Organic+electroluminescent+diodes.">Organic electroluminescent diodes.</a> Appl.Phys. Lett. 51, 913-915 (1987).</li><li>Pope, M., Kallmann, H. P., Magnante, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electroluminescence+in+Organic+Crystals.">Electroluminescence in Organic Crystals.</a> J. Chem. Phys. 38, 2042-2043 (1963).</li><li>Friend, R. H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electroluminescence+in+conjugated+polymers.">Electroluminescence in conjugated polymers.</a> Nature. 397, 121-128 (1999).</li><li>Rothberg, L. J., Lovinger, A. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Status+of+and+prospects+for+organic+electroluminescence.">Status of and prospects for organic electroluminescence.</a> J. Mater. Res. 11, 3174-3187 (1996).</li><li>Brown, A. R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Poly(p-phenylenevinylene)+light-emitting+diodes:+Enhanced+electroluminescent+efficiency+through+charge+carrier+confinement.">Poly(p-phenylenevinylene) light-emitting diodes: Enhanced electroluminescent efficiency through charge carrier confinement.</a> Appl. Phys. Lett. 61, 2793-2795 (1992).</li><li>Wang, Q., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Non-Doped+Phosphorescent+Organic+Light-Emitting+Device+with+Above+31%+External+Quantum+Efficiency.">A Non-Doped Phosphorescent Organic Light-Emitting Device with Above 31% External Quantum Efficiency.</a> Adv. Mater. 26, 8107-8113 (2014).</li><li>Wang, X., Gong, S. L., Song, D., Lu, Z. H., Wang, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+Efficient+and+Robust+Blue+Phosphorescent+Pt(II)+Compounds+with+a+Phenyl-1,2,3-triazolyl+and+a+Pyridyl-1,2,4-triazolyl+Chelate+Core.">Highly Efficient and Robust Blue Phosphorescent Pt(II) Compounds with a Phenyl-1,2,3-triazolyl and a Pyridyl-1,2,4-triazolyl Chelate Core.</a> Adv. Funct. Mater. 24, 7257-7271 (2014).</li><li>Ulbricht, C., Beyer, B., Friebe, C., Winter, A., Schubert, U. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+Developments+in+the+Application+of+Phosphorescent+Iridium+(III)+Complex+Systems.">Recent Developments in the Application of Phosphorescent Iridium (III) Complex Systems.</a> Adv. Mater. 21, 4418-4441 (2009).</li><li>Adachi, C., Baldo, M. A., Thompson, M. E., Forrest, S. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nearly+100%+internal+phosphorescence+efficiency+in+an+organic+light-emitting+device.">Nearly 100% internal phosphorescence efficiency in an organic light-emitting device.</a> J. Appl. Phys. 90, 5048-5051 (2001).</li><li>Park, Y. S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Exciplex-Forming+Co-host+for+Organic+Light-Emitting+Diodes+with+Ultimate+Efficiency.">Exciplex-Forming Co-host for Organic Light-Emitting Diodes with Ultimate Efficiency.</a> Adv. Funct. Mater. 23, 4914-4920 (2013).</li><li>Xu, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+progress+in+metal-organic+complexes+for+optoelectronic+applications.">Recent progress in metal-organic complexes for optoelectronic applications.</a> Chem. Soc. Rev. 43, 3259-3302 (2014).</li><li>Uoyama, H., Goushi, K., Shizu, K., Nomura, H., Adachi, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+efficient+organic+light-emitting+diodes+from+delayed+fluorescence.">Highly efficient organic light-emitting diodes from delayed fluorescence.</a> Nature. 492, 234-238 (2012).</li><li>Zhang, Q., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficient+Blue+Organic+Light-Emitting+Diodes+Employing+Thermally+Activated+Delayed+Fluorescence.">Efficient Blue Organic Light-Emitting Diodes Employing Thermally Activated Delayed Fluorescence.</a> Nat. Photonics. 8, 326-332 (2014).</li><li>Hirata, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+Efficient+Blue+Electroluminescence+based+on+Thermally+Activated+Delayed+Fluorescence.">Highly Efficient Blue Electroluminescence based on Thermally Activated Delayed Fluorescence.</a> Nat. Mater. 14, 330-335 (2015).</li><li>Yang, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+Advances+in+Organic+Thermally+Activated+Delayed+Fluorescence+Materials.">Recent Advances in Organic Thermally Activated Delayed Fluorescence Materials.</a> Chem. Soc. Rev. 46, 915-1016 (2017).</li><li>Im, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecular+Design+Strategy+of+Organic+Thermally+Activated+Delayed+Fluorescence+Emitters.">Molecular Design Strategy of Organic Thermally Activated Delayed Fluorescence Emitters.</a> Chem. Mater. 29, 1946-1963 (2017).</li><li>Wong, M. Y., Zysman-Colman, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Purely+Organic+Thermally+Activated+Delayed+Fluorescence+Materials+for+Organic+Light-Emitting+Diodes.">Purely Organic Thermally Activated Delayed Fluorescence Materials for Organic Light-Emitting Diodes.</a> Adv. Mater. 1605444, (2017).</li><li>Dias, F. B., Penfold, T. J., Monkman, A. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photophysics+of+thermally+activated+delayed+fluorescence+molecules.">Photophysics of thermally activated delayed fluorescence molecules.</a> Methods Appl. Fluoresc. 5, 012001 (2017).</li><li>Liu, Y., Nishiura, M., Wang, Y., Hou, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=&#960;-Conjugated+Aromatic+Enynes+as+a+Single-Emitting+Component+for+White+Electroluminescence.">&#960;-Conjugated Aromatic Enynes as a Single-Emitting Component for White Electroluminescence.</a> J. Am. Chem. Soc. 128, 5592-5593 (2006).</li><li>Neumoyer, C. R., Amstutz, E. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Studies+in+the+Sulfone+Series.+I.+The+Preparation+of+2,8-Diaminodibenzothiophene-5-dioxide.">Studies in the Sulfone Series. I. The Preparation of 2,8-Diaminodibenzothiophene-5-dioxide.</a> J. Am. Chem. Soc. 69, 1920-1921 (1947).</li><li>Gilman, H., Nobis, J. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rearrangement+with+4-Iododibenzothiophene+in+Amination+by+Sodamide.">Rearrangement with 4-Iododibenzothiophene in Amination by Sodamide.</a> J. Am. Chem. Soc. 67, 1479-1480 (1945).</li><li>Dias, F. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Triplet+Harvesting+with+100%+Efficiency+by+Way+of+Thermally+Activated+Delayed+Fluorescence+in+Charge+Transfer+OLED+Emitters.">Triplet Harvesting with 100% Efficiency by Way of Thermally Activated Delayed Fluorescence in Charge Transfer OLED Emitters.</a> Adv. Mater. 25, 3707-3714 (2013).</li><li>Dias, F. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+role+of+local+triplet+excited+states+and+D-A+relative+orientation+in+thermally+activated+delayed+fluorescence:+photophysics+and+devices.">The role of local triplet excited states and D-A relative orientation in thermally activated delayed fluorescence: photophysics and devices.</a> Adv. Sci. 3, 1600080 (2016).</li><li>Moss, K. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tuning+the+Intramolecular+Charge+Transfer+Emission+from+Deep+Blue+to+Green+in+Ambipolar+Systems+Based+on+Dibenzothiophene+S,S-Dioxide+by+Manipulation+of+Conjugation+and+Strength+of+the+Electron+Donor+Units.">Tuning the Intramolecular Charge Transfer Emission from Deep Blue to Green in Ambipolar Systems Based on Dibenzothiophene S,S-Dioxide by Manipulation of Conjugation and Strength of the Electron Donor Units.</a> J. Org. Chem. 75, 6771-6781 (2010).</li></ol>

我们没有什么要透露的。

本文的目的是展示 large-scale 合成的高效有机材料 (图 1) 的 OLED 应用从商业可用的起始材料。由于以前的报告只描述最后的交叉反应步骤, 并提到一些过时的出版物, 我们报告了详细的 step-by 步骤合成所有的材料连同他们的全核磁共振和质谱用于改进实验重现性的表征。
两个发射器承担相同的 dibenzothiophene-5-dioxide 电子受体核。在合成 3 (图 2) 的第一步是溴的商业可用的吩分子。20大范围的反应发生在隔夜, 收益率为83%。所产生的 dibrominated 化合物2可以进一步氧化的解决过氧化氢的冰乙酸, 产量19.3 克的白色粉末过滤和洗涤后。在交叉反应中使用了21化合物 3, 无需进一步纯化。
化合物4和5之间的光特性的差异在于胺单元的电子捐献特性。其中一个化合物有外围烷基化咔唑单位, 而另一种则有嗪组。嗪分子可以购买从化学供应商和使用没有任何修改。然而, 在化合物4叔丁基基团的情况下, 需要引入咔唑装置的芳香环上, 以提高有机溶剂的溶解度。据报道, 在没有合适的烷基基团的情况下, 产品的溶解度下降, 导致反应收率明显降低。24烷基基团可引入到每个苯基环中, 利用叔丁基氯化物和 9-H-咔唑在硝基中存在锌 (II) 的弗里德尔工艺反应, 基于亲芳香替代机理。19结果发现, 产物的纯度不够高, 在混合物中存在几个 by-products;因此, 用柱层析法对粗灰色粉末进行提纯, 分离出13.1 克化合物 1, 作为白色粉末回收。
所需的 TADF 发射器4和5通过钯催化的碳氮交叉反应合成, 使用以前描述的文献程序。22,23我们发现, 增加起始物料的数量不会对所需产品的产量产生负面影响, 这表明可能会进一步增加反应量。化合物4和5可分别获得63% 和55% 的产量。
最后, 详细介绍了如何为发光应用制备高效有机分子的详细指南, 从现成的材料开始, 并有可能扩大整个合成程序。通过这项工作, 意图是, large-scale 合成许多其他 TADF 发射器将确保技术从实验室工作台快速过渡到工业应用。

在过去的几十年里, 研究人员研究了有机分子及其衍生物在有机发光二极管 (oled) 自1987年首次引入以来的应用。1发现电致发光 (EL) 导致有机材料在显示和照明领域得到广泛的应用。2对生产新的有机化合物和研究其光特性的巨大兴趣是由 oled 对现有技术的优势驱动的;最值得注意的是, 他们更节能, 可以提供优异的设备性能, 同时保持高灵活性, 小厚度, 低重量。然而, 与无机发光二极管 (led) 相比, oled 仍然受到不利影响, 无法从大规模的商业生产中得到这种技术, 包括寿命缩短, 效率低下。直到最近, 大多数的研究都是以第一代 oled 为基础的, 而排放依赖于有机材料的荧光。由于荧光只能从单线态发生, 因此该器件的最大理论内部量子效率 (IQE) 只有25%。3,4,5通过利用含有重金属的有机配合物 (如 Ir、Pt), 研究人员可以通过辐射过渡过程从单线态和三重态中捕获电子, 从而克服25% 的效率障碍。6,7,8因此, 第二代磷光 oled (PHOLEDs) 的最大理论效率可高达100%。9,10目前, 许多商用 OLED 器件利用铱为基础的绿色和红色磷光发光金属络合物。11尽管这些材料在移动显示器和其他电子应用中得到了广泛的应用, 但重金属前体盐的成本及其短暂的寿命已经促使研究人员寻找替代品。
OLED 技术的广泛商业化必须实现多种目标, 如高稳定性、高效率的功耗和设备的低生产成本。近年来, 有研究表明, 热活化延迟荧光 (TADF) 发射器可以有效替代 PHOLED 材料达到相同的 IQE 值, 这些材料现在被认为是第三代 OLED 材料。12,13,14纯有机 TADF 发射器可以在几个步骤, 从现成的开始材料, 使整个设备制造商业吸引力的市场。到目前为止, 有几个全面的文献综述涵盖从材料合成到器件制造的所有方面。15,16,17,18 TADF 材料制备的主要问题是使用含钯催化剂的交叉反应。为了显示 TADF 材料准备的潜力在增加的规模。我们将 TADF 发射器的合成从起始物料扩大到所需产品4和 5 (图 1)。22,23此详细的协议旨在帮助该领域的新从业者了解与合成 TADF 材料相关的信息。

<table border="0" cellpadding="0" cellspacing="0" width="973">
	<tbody>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">2-Chloro-2-methylpropane, 99+%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">19780</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">2-Dicyclohexylphosphino-2&#8242;,4&#8242;,6&#8242;-triisopropylbiphenyl (XPhos), 97%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">638064</td>
			<td style="width:167px;">Air sensitive</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">9-H-carbazole, 95%</td>
			<td style="width:163px;">Alfa Aesar</td>
			<td style="width:164px;">A11448</td>
			<td style="width:167px;">Air sensitive</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Bromine, 99.5%</td>
			<td style="width:163px;">Fisher</td>
			<td style="width:164px;">10452553</td>
			<td style="width:167px;">Highly toxic</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Chloroform, anhydrous, 99%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">288306</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Dibenzothiophene, 98%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">D32202</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Dichloromethane, anhydrous, 99.8%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">270997</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Glacial acetic acid, 99.7+%</td>
			<td style="width:163px;">Alfa Aesar</td>
			<td style="width:164px;">36289</td>
			<td style="width:167px;">Corrosive to skin</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Hexane, anhydrous, 95%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">296090</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="26">
			<td height="26" style="height:26px;width:480px;">Hydrogen peroxide solution (30 % (w/w) in H2O)</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">H1009</td>
			<td style="width:167px;">Corrosive to skin</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Magnesium sulfate, 99.5%</td>
			<td style="width:163px;">Alfa Aesar</td>
			<td style="width:164px;">33337</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Nitromethane, 98+%</td>
			<td style="width:163px;">Alfa Aesar</td>
			<td style="width:164px;">A11806</td>
			<td style="width:167px;">Highly explosive</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Phenothiazine, 98+%</td>
			<td style="width:163px;">Alfa Aesar</td>
			<td style="width:164px;">A12517</td>
			<td style="width:167px;">Air sensitive</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Sodium tert-butoxide, 97%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">359270</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Tert-butanol, anhydrous, 99.5%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">471712</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Toluene, anhydrous, 99.8%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:164px;">244511</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Tris(dibenzylideneacetone) dipalladium(0), Pd 21.5% min</td>
			<td style="width:163px;">Alfa Aesar</td>
			<td style="width:164px;">12760-03</td>
			<td style="width:167px;">Air sensitive</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:480px;">Zinc (II) chloride, anhydrous, 98+%</td>
			<td style="width:163px;">Alfa Aesar</td>
			<td style="width:164px;">A16281</td>
			<td style="width:167px;"></td>
		</tr>
	</tbody>
</table>

scale-up chemical synthesis of thermally-activated delayed fluorescence emitters based on the dibenzothiophene-s,s-dioxide core

我们报告的程序, 线性放大合成28双 (36-二叔丁基-9 咔-9-基) 吩-S, 二氧化硫 (化合物 4) 和 28-双 (10 phenothiazin 10 基) 吩 s 二氧化物 (化合物 5) 使用布赫瓦尔德-Hartwig 交叉反应条件。此外, 我们展示了扩大合成的所有非可用的起始材料, 是所需的胺化交叉反应。在本篇文章中, 我们为所有被描述的化合物提供详细的合成程序, 以及它们的光谱表征。这项工作表明有可能大规模生产用于光电应用的有机分子, 这有助于它们在现实世界的设备中实现。

最后的 TADF 发射器 (图 1) 的化学结构被标记为蓝色为电子捐赠的小组和红色为电子撤退的核心。烷基化咔唑衍生物和 dibrominated dibenzothiopene s 二氧化物受体分子可以从廉价的起始材料 (图 2) 中制备。最终产品可以由钯催化的胺化交叉反应的 large-scale 版制备 (图 3)。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56501/56501fig1.jpg"> 
图 1.基于 28-吩-5-二氧化物电子受体核 (红色示) 轴承 36-叔丁基-9 h-咔-9-基和 10 h-phenothiazin-10-基的热活化延迟荧光发射器的化学结构化合物4和化合物5分别。电子捐赠组以蓝色显示。<a href="//ecsource.jove.com/files/ftp_upload/56501/56501fig1large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56501/56501fig2.jpg"> 
图 2.由 9-H 咔唑和 28-dibromodibenzothiophene-5-二氧化物 (化合物 3) 的烷基化反应制备36二叔丁基-9 h 咔唑 (化合物 1) 的化学反应途径, 从商业上可利用的吩开始两步。<a href="//ecsource.jove.com/files/ftp_upload/56501/56501fig2large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56501/56501fig3.jpg"> 
图 3.布赫瓦尔德-Hartwig 28-dibromodibenzothiophene-5-二氧化物 (化合物 3) 和相应的二次胺之间的交叉耦合反应, 产生化合物4和5。<a href="//ecsource.jove.com/files/ftp_upload/56501/56501fig3large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>

Watch this Scientific Journal Video about Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core at JoVE.com

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

本文介绍了高效热激活延迟荧光发射器的放大合成。

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 ...

scale-up-chemical-synthesis-thermally-activated-delayed-fluorescence

Research

JoVE Journal

Chemistry

9.5K 次观看.  University of Strathclyde. 本文介绍了高效热激活延迟荧光发射器的放大合成。

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

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 ...

科研

化学

Synthesis, Characterization, and Functionalization of Hybrid Au/CdS and Au/ZnS Core/Shell Nanoparticles

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large extinction coefficients which can be tuned across the visible spectrum. Research into the plasmonic enhancement of optical transitions has become popular, due to the possibility of altering and in some cases improving photo-absorption or emission properties of nearby chromophores such as molecular dyes or quantum dots. The electric field of the plasmon can couple with the excitation dipole of a chromophore, perturbing the electronic states involved in the transition and leading to increased absorption and emission rates. These enhancements can also be negated at close distances by energy transfer mechanism, making the spatial arrangement of the two species critical. Ultimately, enhancement of light harvesting efficiency in plasmonic solar cells could lead to thinner and, therefore, lower cost devices. The development of hybrid core/shell particles could offer a solution to this issue. The addition of a dielectric spacer between a gold nanoparticles and a chromophore is the proposed method to control the exciton plasmon coupling strength and thereby balance losses with the plasmonic gains. A detailed procedure for the coating of gold nanoparticles with CdS and ZnS semiconductor shells is presented. The nanoparticles show high uniformity with size control in both the core gold particles and shell species allowing for a more accurate investigation into the plasmonic enhancement of external chromophores.

The synthesis of uniform gold nanoparticles coated with semiconductor shells of CdS or ZnS is performed. The semiconductor coating is conducted by first depositing a silver sulfide shell and exchanging the silver cations for zinc or cadmium cations.

合成，表征和混合金/硫化镉和Au / ZnS核/壳纳米颗粒功能化

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large ...

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 ...

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2&#215;1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

锗通过原子层沉积钙钛矿型钛酸锶的外延生长

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and ...

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 ...

Hydroquinone Based Synthesis of Gold Nanorods

Gold nanorods are an important kind of nanoparticles characterized by peculiar plasmonic properties. Despite their widespread use in nanotechnology, the synthetic methods for the preparation of gold nanorods are still not fully optimized. In this paper we describe a new, highly efficient, two-step protocol based on the use of hydroquinone as a mild reducing agent. Our approach allows the preparation of nanorods with a good control of size and aspect ratio (AR) simply by varying the amount of hexadecyl trimethylammonium bromide (CTAB) and silver ions (Ag+) present in the "growth solution". By using this method, it is possible to markedly reduce the amount of CTAB, an expensive and cytotoxic reagent, necessary to obtain the elongated shape. Gold nanorods with an aspect ratio of about 3 can be obtained in the presence of just 50 mM of CTAB (versus 100 mM used in the standard protocol based on the use of ascorbic acid), while shorter gold nanorods are obtained using a concentration as low as 10 mM.

This paper describes a protocol for the synthesis of gold nanorods, based on the use of hydroquinone as reducing agent, plus the different mechanisms for controlling their size and aspect ratio.

金纳米棒基于对苯二酚合成

Gold nanorods are an important kind of nanoparticles characterized by peculiar plasmonic properties. Despite their widespread use in nanotechnology, the ...

Microfluidic-based Synthesis of Covalent Organic Frameworks (COFs): A Tool for Continuous Production of COF Fibers and Direct Printing on a Surface

Covalent Organic Frameworks (COFs) are a class of porous covalent materials which are frequently synthesized as unprocessable crystalline powders. The first COF was reported in 2005 with much effort centered on the establishment of new synthetic routes for its preparation. To date, most available synthetic methods for COF synthesis are based on bulk mixing under solvothermal conditions. Therefore, there is increasing interest in developing systematic protocols for COF synthesis that provide for fine control over reaction conditions and improve COF processability on surfaces, which is essential for their use in practical applications. Herein, we present a novel microfluidic-based method for COF synthesis where the reaction between two constituent building blocks, 1,3,5-benzenetricarbaldehyde (BTCA) and 1,3,5-tris(4-aminophenyl)benzene (TAPB), takes place under controlled diffusion conditions and at room temperature. Using such an approach yields sponge-like, crystalline fibers of a COF material, hereafter called MF-COF. The mechanical properties of MF-COF and the dynamic nature of the approach allow the continuous production of MF-COF fibers and their direct printing onto surfaces. The general method opens new potential applications requiring advanced printing of 2D or 3D COF structures on flexible or rigid surfaces.

Microfluidic-based Synthesis of Covalent Organic Frameworks COFs: A Tool for Continuous Production of COF Fibers and Direct Printing on a Surface

We present a novel microfluidic-based method for synthesis of covalent organic frameworks (COFs). We demonstrate how this approach can be used to produce continuous COF fibers, and also 2D or 3D COF structures on surfaces.

基于微流体的共价有机骨架（COFs）的合成:用于连续生产COF纤维和直接印刷在表面上的工具

Covalent Organic Frameworks (COFs) are a class of porous covalent materials which are frequently synthesized as unprocessable crystalline powders. The ...

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 ...

Synthesis of Core-shell Lanthanide-doped Upconversion Nanocrystals for Cellular Applications

Lanthanide-doped upconversion nanocrystals (UCNs) have attracted much attention in recent years based on their promising and controllable optical properties, which allow for the absorption of near-infrared (NIR) light and can subsequently convert it into multiplexed emissions that span over a broad range of regions from the UV to the visible to the NIR. This article presents detailed experimental procedures for high-temperature co-precipitation synthesis of core-shell UCNs that incorporate different lanthanide ions into nanocrystals for efficiently converting deep-tissue penetrable NIR excitation (808 nm) into a strong blue emission at 480 nm. By controlling the surface modification with biocompatible polymer (polyacrylic acid, PAA), the as-prepared UCNs acquires great solubility in buffer solutions. The hydrophilic nanocrystals are further functionalized with specific ligands (dibenzyl cyclooctyne, DBCO) for localization on the cell membrane. Upon NIR light (808 nm) irradiation, the upconverted blue emission can effectively activate the light-gated channel protein on the cell membrane and specifically regulate the cation (e.g., Ca2+) influx in the cytoplasm. This protocol provides a feasible methodology for the synthesis of core-shell lanthanide-doped UCNs and subsequent biocompatible surface modification for further cellular applications.

A protocol is presented for the synthesis of core-shell lanthanide-doped upconversion nanocrystals (UCNs) and their cellular applications for channel protein regulation upon near-infrared (NIR) light illumination.

核壳镧系掺杂转换纳米晶的合成及其在蜂窝中的应用

Lanthanide-doped upconversion nanocrystals (UCNs) have attracted much attention in recent years based on their promising and controllable optical ...

Synthesis and Evaluation of a Ruthenium-based Mitochondrial Calcium Uptake Inhibitor

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of this compound commences from [Ru(NH3)5Cl]Cl2 in 1 M NH4OH in a closed container, yielding a green solution. Purification is accomplished with cation-exchange chromatography. This compound is characterized and verified to be pure by UV-vis and IR spectroscopy. The mitochondrial calcium uptake inhibitory properties are assessed in permeabilized HeLa cells by fluorescence spectroscopy.

A protocol for the synthesis, purification, and characterization of a ruthenium-based inhibitor of mitochondrial calcium uptake is presented. A procedure to evaluate its efficacy in permeabilized mammalian cells is demonstrated.

钌线粒体钙吸收抑制剂的合成与评价

We detail the synthesis and purification of a mitochondrial calcium uptake inhibitor, [(OH2)(NH3)4Ru(&#181;-O)Ru(NH3)4(OH2)]5+. The optimized synthesis of ...