The GC-MS quantification of biogenic monoamines (BMAs), together with their acidic metabolites (ACMEs), in a single step, is presented here for the first time. This novel principle is based on the exceptional reactivity of the hexamethyldisilazane (HMDS) and perfluorocarboxylic acid (PFCA) couples [1,2], resulting in the simultaneous trimethylsilylation and acylation of BMAs and ACMEs. For this basic study, tyramine (TYR), 3-methoxytyramine (3-MeTYR), dopamine (DA), epinephrine (EP), normetanephrine (NORMNE), norepinephrine (NOREP), tryptamine (T), 3,4-dihydroxyphenylalanine (L-DOPA), 5-methoxytryptamine (5-MeT), serotonin (ST), and their ACMEs, such as homovanillic acid (HVA), vanillylmandelic acid (VMA), and 5-hydroxyindoleacetic acid (5-HIAA) were selected. These three ACMEs were derived from 3-MeTYR, NORMNE and ST, respectively. The mass fragmentation properties of the fully derivatized products proved to be of stoichiometric distribution. Informative high masses were obtained: such as the molecular ions [M]+= and/or their [M-CH3]+ alternatives. The exceptions were EP and NOREP which decomposed to the same specific, abundant mass of m/z 355 representing the C7H3-tri-OTMS ions formed by the loss of their nitrogen-containing moieties. The general rule of this new principle was confirmed by using trifluoroacetic acid (TFA), pentafluoropropionic acid (PFPA), or heptafluorobutyric acid (HFBA) with HMDS in parallel tests. In all three cases, derivatives of close retention properties in a stoichiometric manner were obtained. On the basis of the optimum separation characteristics between the BMA-ACME pairs, the HMDS & PFPA couple was preferred as the reagent of choice. Method validation was carried out, both with model solutions and in the presence of the urine matrices (without any preliminary extraction). Analytical performance characteristics for the model solutions like repeatability (RSD% 3.88-6.4), linearity (R2 0.991-0.999) and limit of quantitation (LOQ 8.8-103 ng/mL) were determined. Analytical performance characteristics for urine matrices were calculated by using the standard addition method applying the urine of a healthy volunteer and also analyzing urines of patients diagnosed with neurological diseases.

中文翻译：

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直接样品制备和同时全氟酰化 - 生物单胺及其酸性代谢物的三甲基硅烷化，用于通过 GC-MS 进行单步分析

此处首次介绍了在一个步骤中对生物单胺 (BMA) 及其酸性代谢物 (ACME) 进行 GC-MS 定量。这一新原理基于六甲基二硅氮烷 (HMDS) 和全氟羧酸 (PFCA) 对 [1,2] 的特殊反应性，导致 BMA 和 ACME 同时发生三甲基甲硅烷基化和酰化。对于这项基础研究，酪胺 (TYR)、3-甲氧基酪胺 (3-MeTYR)、多巴胺 (DA)、肾上腺素 (EP)、去甲变肾上腺素 (NORMNE)、去甲肾上腺素 (NOREP)、色胺 (T)、3,4-二羟基苯丙氨酸 (选择了 L-DOPA)、5-甲氧基色胺 (5-MeT)、5-羟色胺 (ST) 及其 ACME，如高香草酸 (HVA)、香草扁桃酸 (VMA) 和 5-羟基吲哚乙酸 (5-HIAA)。这三个 ACME 分别来自 3-MeTYR、NORMNE 和 ST。完全衍生的产品的质量碎裂特性证明是化学计量分布的。获得了信息丰富的高质量：例如分子离子 [M]+= 和/或它们的 [M-CH3]+ 替代物。例外是 EP 和 NOREP，它们分解成相同的特定质量数，质量数相同的 m/z 355，代表因失去含氮部分而形成的 C7H3-tri-OTMS 离子。通过在平行试验中使用三氟乙酸 (TFA)、五氟丙酸 (PFP​​A) 或七氟丁酸 (HFBA) 与 HMDS，证实了这一新原理的一般规则。在所有三种情况下，都以化学计量方式获得了接近保留特性的衍生物。基于 BMA-ACME 对之间的最佳分离特性，HMDS 和 PFPA 对是首选试剂。使用模型溶液和存在尿液基质（没有任何初步提取）进行了方法验证。确定了模型溶液的分析性能特征，如重复性 (RSD% 3.88-6.4)、线性 (R2 0.991-0.999) 和定量限 (LOQ 8.8-103 ng/mL)。尿液基质的分析性能特征是通过使用标准加法方法计算的，该方法适用于健康志愿者的尿液，并分析诊断出患有神经系统疾病的患者的尿液。8-103 ng/mL) 被确定。尿液基质的分析性能特征是通过使用标准加法方法计算的，该方法适用于健康志愿者的尿液，并分析诊断出患有神经系统疾病的患者的尿液。8-103 ng/mL) 被确定。尿液基质的分析性能特征是通过使用标准加法方法计算的，该方法适用于健康志愿者的尿液，并分析诊断出患有神经系统疾病的患者的尿液。