Matarese R M, Pecci L, Ricci G, Nardini M, Antonucci A, Cavallini D
Proc Natl Acad Sci U S A. 1987 Aug;84(15):5111-4. doi: 10.1073/pnas.84.15.5111.
Hexahydro-1,4-thiazepine-3,5-dicarboxylic acid and thiomorpholine-3,5-dicarboxylic acid, simply referred to as cyclothionine and TMDA, respectively, are two cyclic sulfur-containing imino acids detected in bovine brain. Human urine has been investigated to establish the occurrence of these imino acids as common constituents under normal conditions. The morning urine of healthy subjects has been analyzed for enrichment of these compounds by using an ion-exchange procedure. Gas/liquid chromatography of the final extracts revealed the presence of peaks coeluting with authentic cyclothionine and TMDA. The latter compound eluted very close to an unknown sulfur-containing compound. A resolved peak of TMDA has been obtained by high-performance liquid chromatography of the final extracts derivatized with phenylisothiocyanate. Selected ion monitoring with multiple-ion detection applied to the compounds separated by gas chromatography revealed the presence of the respective molecular ions and of the decarboxylated fragments, thus confirming the identification of cyclothionine and TMDA in human urine.
六氢-1,4-噻氮杂卓-3,5-二羧酸和硫代吗啉-3,5-二羧酸,分别简称为环硫氨酸和硫代吗啉二羧酸(TMDA),是在牛脑中检测到的两种含硫环状亚氨基酸。人们对人类尿液进行了研究,以确定在正常情况下这些亚氨基酸作为常见成分的存在情况。通过离子交换程序分析了健康受试者的晨尿中这些化合物的富集情况。最终提取物的气相/液相色谱显示存在与 authentic cyclothionine 和 TMDA 共洗脱的峰。后一种化合物的洗脱位置非常接近一种未知的含硫化合物。通过对用异硫氰酸苯酯衍生化的最终提取物进行高效液相色谱,获得了一个分离的 TMDA 峰。对通过气相色谱分离的化合物应用多离子检测的选择离子监测,揭示了各自分子离子和脱羧片段的存在,从而证实了在人类尿液中环硫氨酸和 TMDA 的鉴定。