UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry.

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry.
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紫外灯作为一种简便的臭氧源,通过电喷雾电离质谱法对不饱和脂质进行结构分析。

DOI:
10.1007/s13361-017-1861-2
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发表时间:
2018
影响因子:
3.2
通讯作者:
Xia,Yu
Xia,Yu
中科院分区:
化学3区
文献类型:
--
作者:
Stinson,CraigA;Zhang,Wenpeng;Xia,Yu

文献摘要

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烯烃官能团的臭氧化反应是一种高效、特异的化学反应,与质谱联用技术在不饱和脂类结构分析中的应用日益广泛。在这项工作中,我们利用低压汞灯(6 W)启动臭氧分解内电喷雾电离(ESI)源。通过将灯放置在部分透射来自灯的185 nm紫外(UV)发射的nanoESI发射器附近,将喷雾溶液中溶解的分子氧转化为臭氧,其随后裂解脂质的脂肪酰基内的双键。溶剂条件,如水和酸溶液的pH值的存在下,被发现是关键的优化臭氧分解产率。快速(秒的时间尺度)和有效的(50%-100%产率)臭氧分解模型不饱和磷脂和脂肪酸与紫外灯诱导臭氧分解纳入静态和输液nanoESI源。该方法能够区分双键位置异构体,并根据产率确定双键的几何形状。紫外灯诱导臭氧分解的分析效用进一步证明了液相色谱(LC)-MS平台上的实施。臭氧分解是在一个流动的微反应器,这是由臭氧可渗透的管道,使环境中的臭氧产生的灯照射可以扩散到反应器中,并诱导在线臭氧分解后LC分离和前ESI-MS。
Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%–100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS.