Special Testing and Research Laboratory, U.S. Drug Enforcement Administration, 22624 Dulles Summit Court, Dulles, Virginia, 20166, USA.
Drug Test Anal. 2019 Jul;11(7):999-1008. doi: 10.1002/dta.2581. Epub 2019 Apr 3.
Porphyroxine, a trace alkaloid in opium, was identified in the early 1800s and isolated/characterized in the 1960s. Recently, two significant porphyroxine-related byproducts found in the acidic and neutral extracts of illicit heroin were characterized by this laboratory as the N-acetyl-O -desmethyl-epi-porphyroxine (B) and N,O -diacetyl-O -desmethyl-epi-porphyroxine (C). The prevalence of the B and C compounds has been consistent in the following order of abundance for the thousands of authentic heroin samples analyzed: Southwest Asia (SWA) > South America (SA) > Southeast Asia (SEA) > Mexico (MEX). In this research, a rapid and efficient ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed to determine the content of porphyroxine and five primary alkaloids (morphine, codeine, thebaine, noscapine, and papaverine) in opium after extraction with methanol/water (50/50). The method was validated in terms of linearity, accuracy, recovery, and precision for porphyroxine. The limit of quantitation (LOQ) for porphyroxine was 2.5 ng/mL. The developed method was successfully applied to a total of 114 authentic opium samples from the major poppy-growing regions. The amount of porphyroxine was determined at the level of part per thousand (‰) and the relative concentrations to morphine were in the range of 1x10 and 1x10 with an order of SWA > SEA, SA > MEX for its average abundance, which is consistent with the order of the average abundance of its acetylated products (B, C) in illicit heroin. This study reveals the significance of porphyroxine and its acylated compounds in classifying heroin and opium samples to major geographical regions of production.
卟咯啉是鸦片中的一种痕量生物碱，于 19 世纪早期被鉴定，并于 20 世纪 60 年代被分离/表征。最近，本实验室在非法海洛因的酸性和中性提取物中鉴定出两种重要的卟咯啉相关副产物，即 N-乙酰-O-去甲基-表-卟咯啉（B）和 N,O-二乙酰-O-去甲基-表-卟咯啉（C）。在对数千个真实海洛因样本进行分析后，B 和 C 化合物的流行程度按照以下丰度顺序排列：西南亚（SWA）> 南美洲（SA）> 东南亚（SEA）> 墨西哥（MEX）。在这项研究中，开发了一种快速高效的超高效液相色谱-串联质谱（UHPLC-MS/MS）方法，用于在甲醇/水（50/50）提取后测定鸦片中卟咯啉和五种主要生物碱（吗啡、可待因、蒂巴因、那可丁和罂粟碱）的含量。该方法在卟咯啉的线性、准确性、回收率和精密度方面进行了验证。卟咯啉的定量限（LOQ）为 2.5ng/mL。该方法成功应用于来自主要罂粟种植地区的 114 个真实鸦片样本。卟咯啉的含量以千分比（‰）的水平确定，其与吗啡的相对浓度范围为 1x10 和 1x10，平均丰度顺序为 SWA>SEA、SA>MEX，与非法海洛因中其乙酰化产物（B、C）的平均丰度顺序一致。本研究揭示了卟咯啉及其酰化化合物在对主要生产地区的海洛因和鸦片样本进行分类方面的重要性。
