ORTHO-PHTHALALDEHYDE DERIVATIVES OF AMINES FOR HIGH-SPEED LIQUID-CHROMATOGRAPHY ELECTROCHEMISTRY
ORTHO-PHTHALALDEHYDE DERIVATIVES OF AMINES FOR HIGH-SPEED LIQUID-CHROMATOGRAPHY ELECTROCHEMISTRY
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DOI：
10.1021/ac00271a010
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发表时间：
1984-01-01
影响因子：
7.4
通讯作者：
SHOUP, RE
中科院分区：
文献类型：
--
作者：
ALLISON, LA;MAYER, GS;SHOUP, RE
在胺与邻苯二甲醛和各种硫醇反应的情况下，传统的衍生化和荧光量子产率问题被液相色谱/电化学法(LCEC)所回避。通过改变邻苯二甲醛试剂中硫醇的体积分数，研究了S取代的异吲哚的降解性。在体积庞大的叔丁基被并入之前，稳定性没有明显的改善，因此半衰期超过几个小时是值得赞赏的。与荧光相反，硫醇对衍生物的电化学影响很小，其特征是异烟肼的氧化非常迅速，不可逆地。通过在短的3微米反相柱上梯度分离，在梯度模式下，LCEC的检测下限低于500fmol。22种氨基酸的分离可以在10分钟内完成，但重新平衡将总分析时间延长到30分钟左右。在等规线模式下，检测下限降低到30-150fmol。不同样品中胺的定量是一个问题，促使了许多分析方案的发展。最成功的方法是那些将胺的衍生化与基于液相色谱的分离相结合的方法，如Spackman，Stein和Moore首次提出的氨基酸方法(1)所说明的那样。他们的氨基酸分析仪基本上是一种特殊的液体
The conventional problems of derivativestability and fluorescence quantum yields In the case of amines reacted with o-phthalaldehyde and various thiols were circumvented by a liquid chromatography/electrochemlstry (LCEC) ap-proach. The degradative hydrolysis of the S-substltuted Iso-Indole was Investigated by varying the sterlc bulk of the thiol used In the o-phthalaldehyde reagent. No appreciable improvement In stability accrued until the bulky tert-butyl group was Incorporated, whereupon half-lives In excess of several hours were appreciated. In contrast to fluorescence, the thiol had little Influence on the electrochemistry of the derivative, which was characterized as a very rapid, Irreversible oxidation of the Isolndole. Gradient separations of both the ß-mercaptoethanol and tert-butyl derivatives on short 3-µ re versed-phase columns permitted LCEC detection limits of less than 500 fmol In the gradient mode. Separations of22 amino acids could be accomplished In under 10 min, but reequilibration lengthened the total analysis time to about 30 min. Detection limits were lowered to 30-150 fmol In the Isocratic mode.The quantitation of amines in varied samples is a problem that has prompted the development of numerous analytical schemes. The most successful approaches havebeen those which couple derivatization of amines with a separation based on liquid chromatography, as illustrated by theamino acid method first proposed by Spackman, Stein, and Moore (1). Their amino acid analyzer was basically a specialized liquid