Structural elucidation of molecular species of pacific oyster ether amino phospholipids by normal-phase liquid chromatography/negative-ion electrospray ionization and quadrupole/multiple-stage linear ion-trap mass spectrometry.

Structural elucidation of molecular species of pacific oyster ether amino phospholipids by normal-phase liquid chromatography/negative-ion electrospray ionization and quadrupole/multiple-stage linear ion-trap mass spectrometry.
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DOI:
10.1016/j.aca.2012.05.035
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发表时间:
2012-07-20
影响因子:
6.2
通讯作者:
Subbaiah, Papasani V.
Subbaiah, Papasani V.
中科院分区:
化学1区
文献类型:
--
作者:
Chen, Su;Belikova, Natalia A.;Subbaiah, Papasani V.

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尽管海洋牡蛎含有大量的醚连接氨基磷脂,但各种分子物种的结构鉴定尚未报道。建立了正相硅胶液相色谱/负离子电喷雾/四极杆多级线性离子阱质谱(NPLC-NI-ESI/Q-TRAP-MS 3)方法,用于海洋牡蛎中丝氨酸和乙醇胺磷脂醚类分子的结构鉴定。该方法的主要优点是(i)避免了对衍生自脂质混合物中不同磷脂类别的同量异位前体离子的不正确选择,并产生了用于鉴定sn-1等离子体酰或等离子体酰键的物质的信息丰富且清晰的MSn产物离子质谱,和(ii)通过“浓缩”每种磷脂类的脂质分子以进一步确定次要分子种类的结构来增加前体离子强度。采用NPLC-NI-ESI/MS 3和NPLC-NI-ESI/MS 2相结合的方法,首次解析了美国太平洋牡蛎中二十二碳六烯酰基和二十碳五烯酰基磷脂酰丝氨酸(PS)的化学结构,并区分了多达6种二酰基/烷酰基/烯酰基磷脂酰乙醇胺(PE)的同量异序组分。高含量的ω-3胞浆烯基PS/胞浆烯基PE物质和多种同量异序分子物质异构体的存在是海洋牡蛎的显著特征。简单而稳健的NPLC-NI-ESI/MSn为基础的方法应该是特别有价值的详细表征海洋脂质膳食补充剂方面的omega-3氨基磷脂。
Although marine oysters contain abundant amounts of ether-linked aminophospholipids, the structural identification of the various molecular species has not been reported. We developed a normal-phase silica liquid chromatography/negative-ion electrospray ionization/quadrupole multiple-stage linear ion-trap mass spectrometric (NPLC-NI-ESI/Q-TRAP-MS3) method for the structural elucidation of ether molecular species of serine and ethanolamine phospholipids from marine oysters. The major advantages of the approach are (i) to avoid incorrect selection of isobaric precursor ions derived from different phospholipid classes in a lipid mixture, and to generate informative and clear MSn product ion mass spectra of the species for the identification of the sn-1 plasmanyl or plasmenyl linkages, and (ii) to increase precursor ion intensities by “concentrating” lipid molecules of each phospholipid class for further structural determination of minor molecular species. Employing a combination of NPLC-NI-ESI/MS3 and NPLC-NI-ESI/MS2, we elucidated, for the first time, the chemical structures of docosahexaenoyl and eicosapentaenoyl plasmenyl phosphatidylserine (PS) species and differentiated up to six isobaric species of diacyl/alkylacyl/alkenylacyl phosphatidylethanolamine (PE) in the US pacific oysters. The presence of a high content of both omega-3 plasmenyl PS/plasmenyl PE species and multiple isobaric molecular species isomers is the noteworthy characteristic of the marine oyster. The simple and robust NPLC-NI-ESI/MSn-based methodology should be particularly valuable in the detailed characterization of marine lipid dietary supplements with respect to omega-3 aminophospholipids.
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