Department of Clinical Pharmaceutics, School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan; Laboratory of Clinical Pharmacokinetics, the Medical Frontier Center, Shizuoka General Hospital, 4-27-1 Kita Ando, Aoi-ku, Shizuoka 420-8527, Japan.
Department of Clinical Pharmaceutics, School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan.
Chem Phys Lipids. 2023 Aug;254:105305. doi: 10.1016/j.chemphyslip.2023.105305. Epub 2023 May 6.
The lipid composition and organization of the stratum corneum (SC) in patients with psoriasis and healthy subjects were compared using X-ray diffraction, Fourier-transform infrared spectroscopy (FT-IR), and ultraperformance liquid chromatography, combined with time-of-flight mass spectrometry (UPLC-TOFMS). In healthy SC (HSC), SC lipids formed two lamellar phases (long and short periodicity phases). Hexagonal and orthorhombic hydrocarbon-chain packing were observed in the lateral lipid organization at 30 °C via X-ray diffraction. In HSC, the lamellar phases and the hydrocarbon-chain packing organizations changed with elevated temperatures and finally disappeared. In these behaviors, the high-temperature hexagonal hydrocarbon-chain packing organization, which appeared above the orthorhombic hydrocarbon-chain packing organization, transformed to the liquid phase at about 90 °C in HSC. In psoriatic SC (PSC), hexagonal hydrocarbon-chain packing organization disappeared at about 65 °C with elevated temperatures. No high-temperature hexagonal hydrocarbon-chain packing organization were observed in PSC during heating process. Disorder of the hydrocarbon-chain packing of SC lipids was observed in PSC via FT-IR. In UPLC-TOFMS, free fatty acid (FFA) and ceramide (CER) compositions differed between patients with PSC and HSC. Specifically, the levels of ultra-long chain fatty acids containing CER and phytosphingosine-containing CER were decreased, while those of sphingosine and dihydrosphingosine-containing CER and unsaturated FFA were increased in PSC. Furthermore, FFA and CER carbon chain lengths decreased in patients with PSC. These results suggest that the alteration of SC lipid composition and the reduction of carbon chain lengths in PSC lowered the structural transformation temperature, thereby reducing barrier function.
采用 X 射线衍射、傅里叶变换红外光谱(FT-IR)和超高效液相色谱-飞行时间质谱联用技术(UPLC-TOFMS)比较了银屑病患者和健康受试者的角质层(SC)的脂质组成和组织。在健康 SC(HSC)中,SC 脂质形成两个层状相(长周期和短周期相)。通过 X 射线衍射在 30°C 下观察到侧向脂质组织中存在六方和正交烃链堆积。在 HSC 中,随着温度的升高,层状相和烃链堆积组织发生变化,最终消失。在这些行为中,高于正交烃链堆积组织的高温六方烃链堆积组织在 HSC 中约 90°C 时转变为液相。在银屑病 SC(PSC)中,随着温度的升高,六方烃链堆积组织在约 65°C 时消失。在 PSC 的加热过程中未观察到高温六方烃链堆积组织。FT-IR 观察到 SC 脂质烃链堆积的无序。在 UPLC-TOFMS 中,PSC 患者与 HSC 患者的游离脂肪酸(FFA)和神经酰胺(CER)组成不同。具体而言,含有 CER 的超长链脂肪酸和含有植物鞘氨醇的 CER 的水平降低,而含有神经鞘氨醇和二氢神经鞘氨醇的 CER 和不饱和 FFA 的水平升高。此外,PSC 患者的 FFA 和 CER 碳链长度降低。这些结果表明,PSC 中 SC 脂质组成的改变和碳链长度的减少降低了结构转化温度,从而降低了屏障功能。