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><tbody><tr><td>2-Chloro-2-methylpropane, 99+%</td><td>Sigma Aldrich</td><td>19780</td><td></td></tr><tr><td>2-Dicyclohexylphosphino-2&amp;prime;,4&amp;prime;,6&amp;prime;-triisopropylbiphenyl (XPhos), 97%</td><td>Sigma Aldrich</td><td>638064</td><td>Air sensitive</td></tr><tr><td>9-H-carbazole, 95%</td><td>Alfa Aesar</td><td>A11448</td><td>Air sensitive</td></tr><tr><td>Bromine, 99.5%</td><td>Fisher</td><td>10452553</td><td>Highly toxic</td></tr><tr><td>Chloroform, anhydrous, 99%</td><td>Sigma Aldrich</td><td>288306</td><td></td></tr><tr><td>Dibenzothiophene, 98%</td><td>Sigma Aldrich</td><td>D32202</td><td></td></tr><tr><td>Dichloromethane, anhydrous, 99.8%</td><td>Sigma Aldrich</td><td>270997</td><td></td></tr><tr><td>Glacial acetic acid, 99.7+%</td><td>Alfa Aesar</td><td>36289</td><td>Corrosive to skin</td></tr><tr><td>Hexane, anhydrous, 95%</td><td>Sigma Aldrich</td><td>296090</td><td></td></tr><tr><td>Hydrogen peroxide solution (30 % (w/w) in H&lt;sub&gt;2&lt;/sub&gt;O)</td><td>Sigma Aldrich</td><td>H1009</td><td>Corrosive to skin</td></tr><tr><td>Magnesium sulfate, 99.5%</td><td>Alfa Aesar</td><td>33337</td><td></td></tr><tr><td>Nitromethane, 98+%</td><td>Alfa Aesar</td><td>A11806</td><td>Highly explosive</td></tr><tr><td>Phenothiazine, 98+%</td><td>Alfa Aesar</td><td>A12517</td><td>Air sensitive</td></tr><tr><td>Sodium tert-butoxide, 97%</td><td>Sigma Aldrich</td><td>359270</td><td></td></tr><tr><td>Tert-butanol, anhydrous, 99.5%</td><td>Sigma Aldrich</td><td>471712</td><td></td></tr><tr><td>Toluene, anhydrous, 99.8%</td><td>Sigma Aldrich</td><td>244511</td><td></td></tr><tr><td>Tris(dibenzylideneacetone) dipalladium(0), Pd 21.5% min</td><td>Alfa Aesar</td><td>12760-03</td><td>Air sensitive</td></tr><tr><td>Zinc (II) chloride, anhydrous, 98+%</td><td>Alfa Aesar</td><td>A16281</td><td></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

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

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to the preparation of new organic dyes. Although numerous strategies have been reported to access naphthalene scaffolds, many procedures still present limitations in terms of incorporating functionality, which in turn narrows the range of available substrates. The development of versatile methods for direct access to substituted naphthalenes is therefore highly desirable.
The Diels-Alder (DA) cycloaddition reaction is a powerful and attractive method for the formation of saturated and unsaturated ring systems from readily available starting materials. A new microwave-assisted intramolecular dehydrogenative DA reaction of styrenyl derivatives described herein generates a variety of functionalized cyclopenta[b]naphthalenes that could not be prepared using existing synthetic methods. When compared to conventional heating, microwave irradiation accelerates reaction rates, enhances yields, and limits the formation of undesired byproducts.
The utility of this protocol is further demonstrated by the conversion of a DA cycloadduct into a novel solvatochromic fluorescent dye via a Buchwald-Hartwig palladium-catalyzed cross-coupling reaction. Fluorescence spectroscopy, as an informative and sensitive analytical technique, plays a key role in research fields including environmental science, medicine, pharmacology, and cellular biology. Access to a variety of new organic fluorophores provided by the microwave-assisted dehydrogenative DA reaction allows for further advancement in these fields.

Microwave-assisted intramolecular dehydrogenative Diels-Alder (DA) reactions provide concise access to functionalized cyclopenta[b]naphthalene building blocks. The utility of this methodology is demonstrated by one-step conversion of the dehydrogenative DA cycloadducts into novel solvatochromic fluorescent dyes via Buchwald-Hartwig palladium-catalyzed cross-coupling reactions.

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 ...

科研

化学

Electroactive Polymer Nanoparticles Exhibiting Photothermal Properties

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step process that finishes with Negishi coupling. Negishi coupling is a cross-coupling process in which a chemical precursor is first lithiated, followed by transmetallation with ZnCl2. The resultant organozinc compound can be coupled to a dibrominated aromatic precursor to give the conjugated monomer. Polymer films can be prepared via electropolymerization of the monomer and characterized using cyclic voltammetry and ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. Nanoparticles (NPs) are prepared via emulsion polymerization of the monomer using a two-surfactant system to yield an aqueous dispersion of the polymer NPs. The NPs are characterized using dynamic light scattering, electron microscopy, and UV-Vis-NIR-spectroscopy. Cytocompatibility of NPs is investigated using the cell viability assay. Finally, the NP suspensions are irradiated with a NIR laser to determine their effectiveness as potential materials for photothermal therapy (PTT).

A protocol is presented for the synthesis and preparation of nanoparticles consisting of electroactive polymers.

电活性聚合物纳米粒子参展光热特性

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step ...

工程学

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

环状聚合物的合成及其在熔融状态扩散运动的表征在单分子水平

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

A facile method for the preparation of polycarbodiimide-based secondary structures (e.g., nano-rings, &#34;craters,&#34; fibers, looped fibers, fibrous networks, ribbons, worm-like aggregates, toroidal structures, and spherical particles) is described. These aggregates are morphologically influenced by extensive hydrophobic side chain-side chain interactions of the singular polycarbodiimide strands, as inferred by atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques. Polycarbodiimide-g-polystyrene copolymers (PS-PCDs) were prepared by a combination of synthetic methods, including coordination-insertion polymerization, copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) &#34;click&#34; chemistry, and atom transfer radical polymerization (ATRP). PS-PCDs were found to form specific toroidal architectures at low concentrations in CHCl3. To determine the influence of a more polar solvent medium (i.e., THF and THF/EtOH) on polymer aggregation behavior, a number of representative PS-PCD composites have been tested to show discrete concentration-dependent spherical particles. These fundamental studies are of practical interest to the development of experimental procedures for desirable architectures by directed self-assembly in thin film. These architectures may be exploited as drug carriers, whereas other morphological findings represent certain interest in the area of novel functional materials.

Here, we present a protocol to prepare and visualize secondary structures (e.g., fibers, toroidal architectures, and nano-spheres) derived from helical polycarbodiimides. The morphology characterized by both atomic force microscopy (AFM) and scanning electron microscopy (SEM) was shown to depend on molecular structure, concentration, and the solvent of choice.

从螺旋聚碳化二亚胺共聚物及其三唑衍生物获得自组装形貌

A facile method for the preparation of polycarbodiimide-based secondary structures (e.g., nano-rings, &#34;craters,&#34; fibers, looped fibers, fibrous ...

Time-resolved Photophysical Characterization of Triplet-harvesting Organic Compounds at an Oxygen-free Environment Using an iCCD Camera

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables the acquisition of photoluminescence spectra covering the time regime from nanoseconds up to 0.1 s. This enables us to follow the changes in the intensity (decay) and emission of the spectra over time. Using this method, it is possible to study diverse photophysical phenomena, such as the emission of phosphorescence, and the contributions of prompt and delayed fluorescence in molecules showing thermally activated delayed fluorescence (TADF). Remarkably, all spectra and decays are obtained in a single experiment. This can be done for solids (thin film, powder, crystal) and liquid samples, where the only limitations are the spectral sensitivity of the camera and the excitation wavelength (532 nm, 355 nm, 337 nm, and 266 nm). This technique is, thus, very important when investigating the excited state dynamics in organic emitters for their application in organic light-emitting diodes and other areas where triplet harvesting is of paramount importance. Since triplet states are strongly quenched by oxygen, emitters with efficient TADF luminescence, or those showing room temperature phosphorescence (RTP), must be correctly prepared in order to remove any dissolved oxygen from solutions and films. Otherwise, no long-lived emission will be observed. The method of degassing solid samples as presented in this work is basic and simple, but the degassing of liquid samples creates additional difficulties and is particularly interesting. A method of minimizing solvent loss and changing the sample concentration, while still enabling to remove oxygen in a very efficient and a repeatable manner, is presented in this work.

Here, we present a method of the spectroscopic characterization of organic molecules by means of time-resolved photoluminescence spectroscopy on the nanosecond-to-millisecond timescale in oxygen-free conditions. Methods to efficiently remove oxygen from the samples and, thus, limit luminescence quenching are also described.

利用 iccd 摄像机对无氧环境下的三重收集有机化合物进行光物理表征

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables ...

Constructing Thioether/Vinyl Sulfide-tethered Helical Peptides Via Photo-induced Thiol-ene/yne Hydrothiolation

Here, we describe a detailed protocol for the preparation of thioether-tethered peptides using on-resin intramolecular/intermolecular thiol-ene hydrothiolation. In addition, this protocol describes the preparation of vinyl-sulfide-tethered peptides using in-solution intramolecular thiol-yne hydrothiolation between amino acids that possess alkene/alkyne side chains and cysteine residues at i, i+4 positions. Linear peptides were synthesized using a standard Fmoc-based solid-phase peptide synthesis (SPPS). Thiol-ene hydrothiolation is carried out using either an intramolecular thio-ene reaction or an intermolecular thio-ene reaction, depending on the peptide length. In this research, an intramolecular thio-ene reaction is carried out in the case of shorter peptides using on-resin deprotection of the trityl groups of cysteine residues following the complete synthesis of the linear peptide. The resin is then set to UV irradiation using photoinitiator 4-methoxyacetophenone (MAP) and 2-hydroxy-1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-1-propanone (MMP). The intermolecular thiol-ene reaction is carried out by dissolving Fmoc-Cys-OH in an N,N-dimethylformamide (DMF) solvent. This is then reacted with the peptide using the alkene-bearing residue on resin. After that, the macrolactamization is carried out using benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop), 1-hydroxybenzotriazole (HoBt), and 4-Methylmorpholine (NMM) as activation reagents on the resin. Following the macrolactamization, the peptide synthesis is continued using standard SPPS. In the case of the thio-yne hydrothiolation, the linear peptide is cleaved from the resin, dried, and subsequently dissolved in degassed DMF. This is then irradiated using UV light with photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA). Following the reaction, DMF is evaporated and the crude residue is precipitated and purified using high-performance liquid chromatography (HPLC). These methods could function to simplify the generation of thioether-tethered cyclic peptides due to the use of the thio-ene/yne click chemistry that possesses superior functional group tolerance and good yield. The introduction of thioether bonds into peptides takes advantage of the nucleophilic nature of cysteine residues and is redox-inert relative to disulfide bonds.

We present a protocol for the construction of thioether/vinyl sulfide-tethered helical peptides using photo-induced thiol-ene/thiol-yne hydrothiolation.

利用光致硫醇-烯/yne Hydrothiolation 构造硫醚类/乙烯基硫化物栓系螺旋肽

Here, we describe a detailed protocol for the preparation of thioether-tethered peptides using on-resin intramolecular/intermolecular thiol-ene ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

半导体回转金属硫框架结晶的硫醇构建块的合成

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

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

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

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

硫醇反应试剂的合成与生物共轭作用--用于原位选择性修饰免疫共轭的生成

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

Synthesis and Calibration of Phosphorescent Nanoprobes for Oxygen Imaging in Biological Systems

Oxygen measurement by phosphorescence quenching [1, 2] consists of the following steps: 1) the probe is delivered into the medium of interest (e.g. blood or interstitial fluid); 2) the object is illuminated with light of appropriate wavelength in order to excite the probe into its triplet state; 3) the emitted phosphorescence is collected, and its time course is analyzed to yield the phosphorescence lifetime, which is converted into the oxygen concentration (or partial pressure, pO2). The probe must not interact with the biological environment and in some cases to be 4) excreted from the medium upon the measurement completion. Each of these steps imposes requirements on the molecular design of the phosphorescent probes, which constitute the only invasive component of the measurement protocol. Here we review the design of dendritic phosphorescent nanosensors for oxygen measurements in biological systems. The probes consist of Pt or Pd porphyrin-based polyarylglycine (AG) dendrimers, modified peripherally with polyethylene glycol (PEG's) residues. For effective two-photon excitation, termini of the dendrimers may be modified with two-photon antenna chromophores, which capture the excitation energy and channel it to the triplet cores of the probes via intramolecular FRET (F&ouml;rster Resonance Energy Transfer). We describe the key photophysical properties of the probes and present detailed calibration protocols.

We present principles of oxygen measurements by phosphorescence quenching and review design of porphyrin-based dendritic nanosensors for oxygen imaging in biological systems.

氧成像在生物系统中的磷光纳米探针的合成和校准

Oxygen measurement by phosphorescence quenching [1, 2] consists of the following steps: 1) the probe is delivered into the medium of interest (e.g. blood ...

生物学

Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach

Methine-bridged conjugated bicyclic aromatic compounds are common constituents of a range of biologically relevant molecules such as porphyrins, dipyrrinones, and pharmaceuticals. Additionally, restricted rotation of these systems often results in highly to moderately fluorescent systems as observed in 3H,5H-dipyrrolo[1,2-c:2',1'-f]pyrimidin-3-ones, xanthoglows, pyrroloindolizinedione analogs, BODIPY analogs, and the phenolic and imidazolinone ring systems of Green Fluorescent Protein (GFP). This manuscript describes an inexpensive and operationally simple method of performing a Claisen-Schmidt condensation to generate a series of fluorescent pH dependent pyrazole/imidazole/isoindolone dipyrrinone analogs. While the methodology illustrates the synthesis of dipyrrinone analogs, it can be translated to produce a wide range of conjugated bicyclic aromatic compounds. The Claisen-Schmidt condensation reaction utilized in this method is limited in scope to nucleophiles and electrophiles that are enolizable under basic conditions (nucleophile component) and non-enolizable aldehydes (electrophile component). Additionally, both the nucleophilic and electrophilic reactants must contain functional groups that will not inadvertently react with hydroxide. Despite these limitations, this methodology offers access to completely novel systems that can be employed as biological or molecular probes.

The Claisen-Schmidt condensation reaction is an important methodology for the generation of methine-bridged conjugated bicyclic aromatic compounds. Through utilizing a base-mediated variant of the aldol reaction, a range of fluorescent and/or biologically relevant molecules can be accessed through a generally inexpensive and operationally simple synthetic approach.