敞开式激光解吸离子源上的点击化学
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- 英文论文题名：Click Chemistry in Ambient Laser Desorption Ionization Source
- 论文作者：罗海 ; 邱然
- 英文论文作者：Hai Luo ; Ran Qiu ; Beijing National Laboratory for Molecular Sciences ; College of Chemistry and Molecular Engineering ; Peking University
- 年：2016
- 作者机构：北京大学化学与分子工程学院北京分子科学国家实验室;
- 论文关键词：敞开式离子源 ; 激光解吸 ; 点击化学 ; 加速反应 ; 反应监测
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十三分会：质谱分析
- 语种：中文
- 分类号：O643.12;O657.63
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十三分会 ; 质谱分析
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：211k
- 原文格式：D
- 会议级别：全国
摘要
反应质谱方法不仅可检测分子中的特定官能团,提高分析的选择性和灵敏度,而且在捕获反应中间体、研究反应机理,甚至在发现新的化学现象和化合物方面都是一种非常强有力的工具。与烧瓶中的点击化学相比,敞开式激光解吸离子源上的点击反应有其独特的性质。本工作描述了在高电压辅助激光解吸离子源(HALDI)~1上进行的点击反应。~(2,3)激光剥离产生的Cu~+不仅能催化炔烃与叠氮的环加成反应,它还能迅速与两个新生成的三氮唑分子桥接成为一个质谱信号响应高的化合物。对该化合物的离线合成、质谱分析和所获晶体的XRD表征,证实了其三氮唑二聚体的结构。进一步实验显示,这种铜(Ⅰ)三氮唑二聚体在HALDI离子源上的加速生成,是由于激光辐照的热效应以及激光剥离产生的"裸露"的铜(Ⅰ)与三氮唑之间更快的键合。另外,质谱反应监测结果还显示,该铜(Ⅰ)三氮唑二聚体可以催化烧瓶中的点击反应,并为点击反应的"双核机理"~4提供了新的证据。
Reactive mass spectrometry(MS) is a very powerful tool not only for analytical applications but also for discoveries of new chemistry and/or new chemical compounds.Here we describe in-source click chemistry in high-voltage assisted laser desorption ionization(HALDI) MS which shows some unique features comparing with in-flask click reaction.In HALDI-MS,the laser-ablated Cu~+ can catalyze the azide-alkyne cycloaddition and it also quickly bridges two newly formed triazole molecules to produce a copper(Ⅰ) triazole dimer which has an intense MS signal.MS analysis and XRD elucidation of the crystalline obtained by off-line synthesis of the compound confirmed its triazole dimer structure.Further experiments showed that the accelerated formation of the dimer in HALDI source may be ascribed to the effects of the laser heating and the quicker bonding between the "naked" laser-ablated Cu~+ and triazoles.Moreover,the copper(Ⅰ) triazole dimer can also catalyze in-flask click reaction as monitored by MS,and provides a piece of new evidence for the proposed "di-nuclear mechanism" of the click reaction.
Reactive mass spectrometry(MS) is a very powerful tool not only for analytical applications but also for discoveries of new chemistry and/or new chemical compounds.Here we describe in-source click chemistry in high-voltage assisted laser desorption ionization(HALDI) MS which shows some unique features comparing with in-flask click reaction.In HALDI-MS,the laser-ablated Cu~+ can catalyze the azide-alkyne cycloaddition and it also quickly bridges two newly formed triazole molecules to produce a copper(Ⅰ) triazole dimer which has an intense MS signal.MS analysis and XRD elucidation of the crystalline obtained by off-line synthesis of the compound confirmed its triazole dimer structure.Further experiments showed that the accelerated formation of the dimer in HALDI source may be ascribed to the effects of the laser heating and the quicker bonding between the "naked" laser-ablated Cu~+ and triazoles.Moreover,the copper(Ⅰ) triazole dimer can also catalyze in-flask click reaction as monitored by MS,and provides a piece of new evidence for the proposed "di-nuclear mechanism" of the click reaction.
引文
[1]Ren,X.;Liu,J.;Zhang,C.;Luo,H.Rapid Commun.Mass Spectrom.2013,27:613.
[2]Qiu,R.;Luo,H.Analyst 2014,139:3706.
[3]Qiu,R.;Luo,H.RSC Adv.2015,5:96213.
[4]Worrell,B.;Malik,J.;Fokin,V.Science 2013,340:457.
[2]Qiu,R.;Luo,H.Analyst 2014,139:3706.
[3]Qiu,R.;Luo,H.RSC Adv.2015,5:96213.
[4]Worrell,B.;Malik,J.;Fokin,V.Science 2013,340:457.