The chemical identity of arsenosugar phospholipids (As-PL) as mono- (i.e., lyso, L-As-PL) and diacyl-arsenosugar PL in four edible and common marine alga samples, such as nori (Porphyra spp.), wakame (Undaria pinnatifida), dulse (Palmaria palmata), and kombu (Saccharina japonica), was successfully investigated. Adopting negative polarity electrospray ionization (ESI), not common for As-PL, conjugated with hydrophilic interaction liquid chromatography (HILIC) and mass spectrometry (MS), performed either at low resolution using a linear ion trap (LIT) with sequential MSn (n = 2, 3) or at high resolution using a high-resolution/high-accuracy Fourier-transform MS (FTMS), based on an orbital trap instrument, more than 20 As-PL and 2 L-As-PL species were identified. The absence of As-PL standard compounds encouraged us to generate an in-house-built database of As-PL/L-As-PL for a rapid and simple classification. Despite their compositional diversity, tandem MS of deprotonated As-PL and L-As-PL ([M - H]-) demonstrated the occurrence of a highly diagnostic product ion at m/z 389.0 ([AsC10H19O9P]-). The fatty acid composition and distribution of As-PL were easily assigned on the basis of the ratio intensity between sn-1 and sn-2 product ions. Indeed, the preferential formation of [R1C3H5O4P]- ions over [R2C3H5O4P]- ions, both containing the glycerol backbone, enabled the regiochemical assignment of As-PL. These outcomes were confirmed by MSn (n = 2, 3) analyses and using sn-1- and sn-2-regioselective hydrolase enzymes (i.e., phospholipases A1 and A2). The predominant As-PL's in samples of nori (red alga), wakame, and kombu (both brown algae) were identified as containing palmitic acyl chains (i.e., As-PL958 (As-PL 16:0/16:0) with ca. 66 ± 3, 82 ± 4, and 58 ± 3% as relative abundances, respectively), while the main species in dulse (red alga) samples was As-PL982 (As-PL 18:1/16:1) at ca. 38 ± 3%.

中文翻译：

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食用海藻中的砷糖糖（As-PL）：液相色谱与电喷雾电离多级质谱法之间的相互作用以及用于区域化学分配的磷脂酶A1和A2。

在四种可食用和常见的海藻样品（例如紫菜（Porphyra spp。），裙带菜）中，砷糖糖脂（As-PL）作为单（即溶血素，L-As-PL）和二酰基-砷糖PL的化学特征Undaria pinnatifida），dulse（Palmaria palmata）和kombu（Saccharina japonica）已成功进行了调查。采用亲水性液相色谱（HILIC）和质谱（MS）共轭的As-PL不常见的负极电喷雾电离（ESI），可在低分辨率下使用线性离子阱（LIT）和顺序MSn（n = 2，3）或使用高分辨率/高精度傅里叶变换MS（FTMS）在高分辨率下，基于轨道阱仪器，鉴定出20多种As-PL和2种L-As-PL物种。缺乏As-PL标准化合物，这鼓励我们生成内部构建的As-PL / L-As-PL数据库，以便快速，简单地分类。尽管它们的成分多样性，但去质子化的As-PL和L-As-PL（[M-H]-）的串联质谱显示出在m / z 389.0（[AsC10H19O9P]-）上具有高度诊断性的产物离子的发生。根据sn-1和sn-2产物离子之间的比率强度，可以轻松确定As-PL的脂肪酸组成和分布。实际上，[R1C3H5O4P]-离子比[R2C3H5O4P]-离子优先形成，它们都含有甘油主链，使得As-PL的区域化学归属得以实现。这些结果已通过MSn（n = 2、3）分析以及使用sn-1-和sn-2-区域选择性水解酶（即磷脂酶A1和A2）进行了确认。紫菜（红藻）样品中主要的As-PL，裙带菜和海带（均为褐藻）被鉴定为含有棕榈酰基链（即As-PL958（As-PL 16：0/16：0），约66±3、82±4和58±3％分别为相对丰度），而在淡水（红藻）样品中的主要物种是大约在1982年的As-PL982（As-PL 18：1/16：1）。38±3％。