Department of Chemistry, University of Washington, Seattle, WA.
Department of Pediatrics, University of Washington, Seattle, WA.
Clin Chem. 2018 Apr;64(4):690-696. doi: 10.1373/clinchem.2017.282251. Epub 2018 Jan 16.
Deficiency of lysosomal acid lipase (LAL) causes Wolman disease and cholesterol ester storage disease. With the recent introduction of enzyme replacement therapy to manage LAL deficiency comes the need for a reliable assay of LAL enzymatic activity that can be applied to dried blood spots (DBS).
We prepared and tested a library of analogs of palmitoyl 4-methylumbelifferyl esters to find a highly active and specific substrate for LAL in DBS. The LAL assay was optimized leading to both LC-MS/MS and fluorometric assay of LAL. We tested the new assay on DBS from healthy and LAL-deficient patients.
The ester formed between palmitic acid and 4-propyl-8-methyl-7-hydroxycoumarin (P-PMHC) was found to be >98% selective for LAL in DBS based on the sensitivity of its activity to the LAL-specific inactivator Lalistat-2 and the fact that the activity was close to zero using DBS from patients previously shown to be LAL-deficient. Use of P-PMHC and heavy isotope-labeled internal standard with optimized assay conditions led to an approximately 2-fold increase in the specific activity of LAL compared with the previously reported LAL assay. Patients deficient in LAL were readily distinguished from normal persons with the new LAL assay using UPLC-MS/MS or fluorometric assay platforms.
The new assay can measure LAL in DBS with a single measurement compared with the previous method involving 2 assays done in parallel.
溶酶体酸性脂肪酶 (LAL) 的缺乏会导致沃曼病和胆固醇酯贮积症。随着最近酶替代疗法的引入,需要有一种可靠的 LAL 酶活性测定方法,可应用于干血斑 (DBS)。
我们制备并测试了一系列棕榈酰 4-甲基伞形酮酯类似物的文库,以在 DBS 中找到一种对 LAL 具有高活性和特异性的底物。对 LAL 测定法进行了优化,从而可以对 LAL 进行 LC-MS/MS 和荧光测定。我们在健康和 LAL 缺乏症患者的 DBS 上测试了新的测定法。
在 DBS 中,棕榈酸和 4-丙基-8-甲基-7-羟基香豆素(P-PMHC)之间形成的酯被发现对 LAL 具有>98%的选择性,这是基于其活性对 LAL 特异性失活剂 Lalistat-2 的敏感性以及先前显示为 LAL 缺乏症的患者的 DBS 活性接近零的事实。使用 P-PMHC 和优化测定条件下的重同位素标记内部标准,与之前报道的 LAL 测定法相比,LAL 的比活性增加了约 2 倍。使用新的 LAL 测定法,使用 UPLC-MS/MS 或荧光测定平台,很容易将 LAL 缺乏症患者与正常人区分开来。
与之前涉及 2 个平行测定的方法相比,新的测定法可以单次测量 DBS 中的 LAL。