Direct chiral separation of abscisic acid by high‐performance liquid chromatography with a phenyl column and a mobile phase containing γ‐cyclodextrin
Direct chiral separation of abscisic acid by high‐performance liquid chromatography with a phenyl column and a mobile phase containing γ‐cyclodextrin
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苯基柱和含γ-环糊精流动相高效液相色谱法直接手性分离脱落酸
DOI：
10.1002/jssc.202200827
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发表时间：
2023
影响因子：
3.1
通讯作者：
Kodama Shuji
中科院分区：
文献类型：
--
作者：
Terashima Hiroyuki;Mutoh Yui;Aizawa Sen‐ichi;Taga Atsushi;Mikami Ikko;Itabashi Yutaka;Tsutsumiuchi Kaname;Yamamoto Atsushi;Kodama Shuji
脱落酸（2‐顺式，4‐反式）是一种具有不对称碳原子的植物激素。采用高效液相色谱法，采用苯基柱和含γ -环糊精的手性流动相分离天然脱落酸对映体。最佳流动相为0.8% (w/v) γ‐环糊精，4% （v/v）乙腈，20 mM磷酸盐缓冲液（pH 6.0）。发现(R)‐脱落酸比(S)‐脱落酸更早被检测到。由于γ‐环糊精几乎不保留在苯基柱上，因此表明(R)‐脱落酸与γ‐环糊精形成的配合物比(S)‐脱落酸更稳定。用该方法成功地分离了相思蜜样品中的脱落酸，并且只检测到(S)‐脱落酸。用发光二极管灯在365 nm处照射脱落酸制备了具有生物活性的2 -反式，4 -反式脱落酸，并用该方法对其进行了部分对映分离。由于(S)脱落酸的辐照诱导顺式到反式异构化产生一种2 -反式、4 -反式脱落酸对映体，因此在顺式到反式异构化过程中没有发生外消旋是合理的。在蜂蜜样品中检测到(S)‐Abscisic acid和(S)‐2‐trans,4‐trans - Abscisic acid，其中(S)‐Abscisic acid的峰面积比(S)‐2‐trans，4‐trans - Abscisic acid的峰面积大7倍。
Abscisic acid (2‐cis,4‐trans‐abscisic acid) is a plant hormone that has an asymmetric carbon atom. We tried to separate the enantiomers of native abscisic acid by HPLC using a phenyl column and a chiral mobile phase containing γ‐cyclodextrin. The optimum mobile phase conditions were found to be 0.8% (w/v) γ‐cyclodextrin, 4% (v/v) acetonitrile, and 20 mM phosphate buffer (pH 6.0). It was found that (R)‐abscisic acid was earlier detected than (S)‐abscisic acid. Since γ‐cyclodextrin is hardly retained on a phenyl column, it was suggested that (R)‐abscisic acid formed a more stable complex with γ‐cyclodextrin than the (S)‐abscisic acid. Abscisic acid in an acacia honey sample was successfully enantioseparated with the proposed method and only (S)‐abscisic acid was detected. A biologically inactive 2‐trans,4‐trans‐abscisic acid, which was prepared by irradiation of abscisic acid with a light‐emitting diode lamp at 365 nm, was partially enantioseparated by the proposed method. Since the irradiation of (S)‐abscisic acid‐inducedcis‐to‐transisomerization to produce one 2‐trans,4‐trans‐abscisic acid enantiomer, it is reasonable that racemization did not proceed during thecis‐to‐transisomerization. (S)‐Abscisic acid and probably (S)‐2‐trans,4‐trans‐abscisic acid were detected in a honey sample, where the peak area of (S)‐abscisic acid was 7 times larger than that of (S)‐2‐trans,4‐trans‐abscisic acid.