Khoury Spiro, El Banna Nadine, Tfaili Sana, Chaminade Pierre
Lip(Sys)²- Chimie Analytique Pharmaceutique (FKA EA4041 Groupe de Chimie Analytique de Paris-Sud), Univ. Paris-Sud, Université Paris-Saclay, F-92290, Châtenay-Malabry, France.
Anal Bioanal Chem. 2016 Feb;408(5):1453-65. doi: 10.1007/s00216-015-9245-6. Epub 2016 Jan 15.
Phospholipid quantification in biological samples is crucial and is increasingly studied in lipidomics. Quantitative studies are often performed using commercially available standards of phospholipid classes in order to mimic the composition of biological samples. For this, studies are conducted by liquid chromatography coupled to electrospray ionization-mass spectrometry. In liquid chromatography coupled to mass spectrometry (LC-MS) analysis, the matrix components and the co-elution of several phospholipid species lead to the phenomenon of ion suppression. As a result, a decrease in the response of phospholipid species in mass spectrometry MS is observed. In fact, inter-species ion suppression affects the efficiency of phospholipid (PL) ionization and might also influence the quantitative results. The aim of this work is to study the PL inter-species ion suppression phenomenon in electrospray ionization (ESI)-mass spectrometry on a triple quadrupole TQ and an LTQ-Orbitrap in order to improve quantification in natural and biological samples. Thus, the phospholipid MS response was evaluated to study the effect of acyl chain length, the degree, and the position of unsaturation on acyl chain and the effect of the polar head group structure. A number of saturated and unsaturated phospholipid species and mixtures were analyzed in different ionization modes to a better understanding of inter-species ion suppression phenomenon. PL molecular species responded differently according to the length of fatty acid chains, the number of unsaturation, and the nature of the polar head group. Fatty acid chain length showed to have the most marked effect on MS response.
生物样品中的磷脂定量至关重要,并且在脂质组学中受到越来越多的研究。定量研究通常使用市售的磷脂类标准品来模拟生物样品的组成。为此,通过液相色谱与电喷雾电离-质谱联用进行研究。在液相色谱与质谱联用(LC-MS)分析中,基质成分和几种磷脂种类的共洗脱会导致离子抑制现象。结果,观察到质谱(MS)中磷脂种类的响应降低。事实上,种间离子抑制会影响磷脂(PL)的电离效率,也可能影响定量结果。这项工作的目的是在三重四极杆TQ和LTQ-轨道阱上研究电喷雾电离(ESI)-质谱中的PL种间离子抑制现象,以提高天然和生物样品中的定量分析。因此,评估了磷脂MS响应,以研究酰基链长度、酰基链不饱和度的程度和位置以及极性头部基团结构的影响。分析了许多饱和和不饱和磷脂种类及其混合物在不同电离模式下的情况,以更好地理解种间离子抑制现象。PL分子种类根据脂肪酸链的长度、不饱和度的数量以及极性头部基团的性质表现出不同的响应。脂肪酸链长度对MS响应的影响最为显著。