Garlic (A. sativum) contains a large number of small sulphur (S)-containing metabolites, which are important for its taste and smell and vary with A. sativum variety and growth conditions. This study was designed to investigate the influence of different sulphur-fertilization regimes on low molecular weight S-species by attempting the first sulphur mass balance in A. sativum roots and bulbs using HPLC-ICPMS/MS-ESI-MS/MS. Species unspecific quantification of acid soluble S-containing metabolites was achieved using HPLC-ICP-MS/MS. For identification of the compounds, high resolution ESI-MS (Orbitrap LTQ and q-TOF) was used. The plants contained up to 54 separated sulphur-containing compounds, which constitute about 80% of the total sulphur present in A. sativum. The roots and bulbs of A. sativum contained the same compounds, but not necessarily the same amounts and proportions. The S-containing metabolites in the roots reacted more sensitively to manipulations of sulphur fertilization than those compounds in the bulbs. In addition to known compounds (e.g. γ-glutamyl-S-1-propenylcysteine) we were able to identify and partially quantify 31 compounds. Three as yet undescribed S-containing compounds were also identified and quantified for the first time. Putative structures were assigned to the oxidised forms of S-1-propenylmercaptoglutathione, S-2-propenylmercaptoglutathione, S-allyl/propenyl-containing PC-2 and 2-amino-3-[(2-carboxypropyl)sulfanyl]propanoic acid. The parallel use of ICP-MS/MS as a sulphur-specific detector and ESI-MS as a molecular detector simplifies the identification and quantification of sulphur containing metabolites without species specific standards. This non-target analysis approach enables a mass balance approach and identifies the occurrence of the so far unidentified organosulphur compounds. The experiments showed that the sulphur-fertilization regime does not influence sulphur-speciation, but the concentration of some S-containing compounds in roots is dependent on sulphur fertilization.

中文翻译：

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硫肥的施用会影响大蒜中的硫种类组成：使用HPLC-ICPMS / MS-ESI-MS / MS的硫组学

大蒜（A. sativum）含有大量的少量含硫（S）的代谢产物，这对于其味道和气味很重要，并且会随A. sativum的品种和生长条件而变化。本研究旨在通过尝试使用HPLC-ICPMS / MS-ESI-MS / MS尝试在无根菌根和鳞茎中进行首次硫质量平衡，从而研究不同硫肥施用方式对低分子量S物种的影响。使用HPLC-ICP-MS / MS可实现对酸溶性含S代谢物的非特异性定量分析。为了鉴定化合物，使用了高分辨率的ESI-MS（Orbitrap LTQ和q-TOF）。这些工厂最多包含54种分离的含硫化合物，约占其中总硫含量的80％A.大蒜。番茄的根和鳞茎含有相同的化合物，但不一定相同的含量和比例。与球茎中的那些化合物相比，根部中的含硫代谢产物对硫肥的操纵更敏感。除了已知的化合物（例如， γ-谷氨酰基-S -1-丙烯基半胱氨酸），我们还可以鉴定和部分定量31种化合物。还首次鉴定和定量了三种尚未描述的含S的化合物。推定的结构被分配给S -1-丙烯基巯基谷胱甘肽S -2-丙烯基巯基谷胱甘肽S的氧化形式-含烯丙基/丙烯基的PC-2和2-氨基-3-[（2-羧丙基）硫烷基]丙酸。ICP-MS / MS作为硫磺特异性检测剂与ESI-MS作为分子检测器的并行使用，简化了没有物种特定标准的含硫代谢物的鉴定和定量。这种非目标分析方法可以实现质量平衡方法，并可以识别到目前为止尚未确定的有机硫化合物的存在。实验表明，硫的施肥方式不影响硫的形态，但根中某些含硫化合物的浓度取决于硫的施肥。