Popa Iuliana, Solgadi Audrey, Pin Didier, Watson Adrian L, Haftek Marek, Portoukalian Jacques
Analytic and Biological Lipid Systems (Lip(Sys)2), Faculty of Pharmacy, University Paris-Saclay, 92296 Chatenay-Malabry, France.
Technical Platform-Therapeutical Innovation Institute (IPSIT)-UMS 3679 CNRS, Faculty of Pharmacy, University Paris-Saclay, 92290 Chatenay-Malabry, France.
Metabolites. 2021 Nov 26;11(12):803. doi: 10.3390/metabo11120803.
Golden Retrievers may suffer from -related inherited ichthyosis. Our study shows that in the stratum corneum (SC) of ichthyotic dogs, linoleic acid (LA) is also present in the form of 9-keto-octadecadienoic acid (9-KODE) instead of the acylacid form as in normal dogs. The fatty acids purified from SC strips (LA, acylacids) were characterized by liquid chromatography-tandem mass spectrometry (LC-MS) and atmospheric pressure chemical ionization (APCI). Electrospray ionization (ESI) and MS2(MS/MS Tandem mass spectrum/spectra)/M3 (MS/MS/MS Tandem mass spectrum/spectra) fragmentation indicated the positions of the double bonds in 9-KODE. We showed that ichthyotic dogs have a threefold lower LA content in the form of acylacids. The MS2 fragmentation of acyl acids showed in some peaks the presenceof an ion at the / 279, instead of an ion at / 293 which is characteristic of LA. The detected variant was identified upon MS3 fragmentation as 9-keto-octadecadienoic acid (9-KODE), and the level of this keto-derivative was increased in ichthyotic dogs. We showed by the APCI that such keto forms of LA are produced from hydroperoxy-octadecadienoic acids (HpODE) upon dehydration. In conclusion, the free form of 9-KODE was detected in ichthyotic SC up to fivefold as compared to unaffected dogs, and analyses by HPLC (High performance liquid chromatography) and ESI-MS (Electrospray Ionization-Mass Spectrometry) indicated its production via dehydration of native 9-HpODE.
金毛寻回犬可能患有与[具体病因未提及]相关的遗传性鱼鳞病。我们的研究表明,在鱼鳞病犬的角质层(SC)中,亚油酸(LA)是以9-酮基-十八碳二烯酸(9-KODE)的形式存在,而不是像正常犬那样以酰基酸的形式存在。从SC条带中纯化的脂肪酸(LA、酰基酸)通过液相色谱-串联质谱(LC-MS)和大气压化学电离(APCI)进行表征。电喷雾电离(ESI)和MS2(MS/MS串联质谱)/M3(MS/MS/MS串联质谱)碎片化表明了9-KODE中双键的位置。我们发现鱼鳞病犬中酰基酸形式的LA含量低三倍。酰基酸的MS2碎片化在一些峰中显示存在m/z 279的离子,而不是LA特有的m/z 293的离子。在MS3碎片化时检测到的变体被鉴定为9-酮基-十八碳二烯酸(9-KODE),并且这种酮衍生物的水平在鱼鳞病犬中有所增加。我们通过APCI表明,LA的这种酮形式是由氢过氧十八碳二烯酸(HpODE)脱水产生的。总之,与未受影响的犬相比,在鱼鳞病的SC中检测到的9-KODE游离形式高达五倍,并且通过高效液相色谱(HPLC)和电喷雾电离质谱(ESI-MS)分析表明其通过天然9-HpODE的脱水产生。