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Quantifying Sphingomyelin in Dairy through Infusion-Based Shotgun Mass Spectrometry with Lithium-Ion-Induced Fragmentation
Journal of Agricultural and Food Chemistry ( IF 5.7 ) Pub Date : 2022-10-14 , DOI: 10.1021/acs.jafc.2c04587 Andrew D Magnuson 1 , Michael R Bukowski 2 , Thad A Rosenberger 3 , Matthew J Picklo 1
Journal of Agricultural and Food Chemistry ( IF 5.7 ) Pub Date : 2022-10-14 , DOI: 10.1021/acs.jafc.2c04587 Andrew D Magnuson 1 , Michael R Bukowski 2 , Thad A Rosenberger 3 , Matthew J Picklo 1
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Quantifying sphingomyelin (SM) species by infusion-based mass spectrometry (MS) is complicated by the presence of isobaric phosphatidylcholine (PC) species, which generate a common m/z 184 product ion in the presence of ammonium ions as a result of the phosphocholine headgroup. Lithium ion adducts of SM undergo a selective dehydration [Li + H2O + (CH3)3NC2H4PO4] with a corresponding neutral loss of −207 Da. This neutral loss was employed to create a SM-selective method for identifying target species, which were quantitated using multiple reaction monitoring (MRM). SM-selective fragments in MS3 were used to characterize the sphingosine base and acyl chain. These methods were used to identify 50 individual SM species in bovine milk ranging from SM 28:1 to SM 44:2, with d16:1, d17:1, d18:1, d19:1, and d20:1 bases, and acyl fatty acids ranging from 10 to 25 carbons and 0–1 desaturations. Spiked SM standards into milk had a recovery of 99.7%, and endogenous milk SM had <10% coefficient of variation for both intra- and interday variability, with limits of detection of 1.4–5.55 nM and limits of quantitation of 11.8–178.1 nM. This MS–MRM method was employed to accurately and precisely quantify SM species in dairy products, including bovine-derived whole milk, half and half, whipping cream, and goat milk.
中文翻译：
通过基于输液的霰弹枪质谱法和锂离子诱导碎裂法定量乳制品中的鞘磷脂
由于存在同量异位磷脂酰胆碱 (PC) 物质，通过基于输液的质谱 (MS) 对鞘磷脂 (SM) 物质进行定量变得复杂，由于磷酸胆碱的存在，在铵离子存在的情况下，该物质会产生一个常见的m / z 184 产物离子头组。SM 的锂离子加合物经历选择性脱水 [Li + H 2 O + (CH 3 ) 3 NC 2 H 4 PO 4 ]，相应的中性损失为 -207 Da。这种中性损失用于创建用于识别目标物种的 SM 选择性方法，使用多反应监测 (MRM) 对其进行定量。MS 3中的 SM 选择性片段用于表征鞘氨醇碱基和酰基链。这些方法用于鉴定牛奶中 50 种单独的 SM 物种，范围从 SM 28:1 到 SM 44:2，具有 d16:1、d17:1、d18:1、d19:1 和 d20:1 碱基和酰基脂肪酸范围从 10 到 25 个碳和 0-1 个去饱和度。将 SM 标准添加到牛奶中的回收率为 99.7%，内源性牛奶 SM 的日内和日间变异系数均小于 10%，检测限为 1.4-5.55 nM，定量限为 11.8-178.1 nM。这种 MS-MRM 方法用于准确定量乳制品中的 SM 种类，包括牛源性全脂奶、半奶、鲜奶油和山羊奶。
更新日期：2022-10-14
中文翻译：
通过基于输液的霰弹枪质谱法和锂离子诱导碎裂法定量乳制品中的鞘磷脂
由于存在同量异位磷脂酰胆碱 (PC) 物质，通过基于输液的质谱 (MS) 对鞘磷脂 (SM) 物质进行定量变得复杂，由于磷酸胆碱的存在，在铵离子存在的情况下，该物质会产生一个常见的m / z 184 产物离子头组。SM 的锂离子加合物经历选择性脱水 [Li + H 2 O + (CH 3 ) 3 NC 2 H 4 PO 4 ]，相应的中性损失为 -207 Da。这种中性损失用于创建用于识别目标物种的 SM 选择性方法，使用多反应监测 (MRM) 对其进行定量。MS 3中的 SM 选择性片段用于表征鞘氨醇碱基和酰基链。这些方法用于鉴定牛奶中 50 种单独的 SM 物种，范围从 SM 28:1 到 SM 44:2，具有 d16:1、d17:1、d18:1、d19:1 和 d20:1 碱基和酰基脂肪酸范围从 10 到 25 个碳和 0-1 个去饱和度。将 SM 标准添加到牛奶中的回收率为 99.7%，内源性牛奶 SM 的日内和日间变异系数均小于 10%，检测限为 1.4-5.55 nM，定量限为 11.8-178.1 nM。这种 MS-MRM 方法用于准确定量乳制品中的 SM 种类，包括牛源性全脂奶、半奶、鲜奶油和山羊奶。
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