Porphyroxine

UHPLC-MS/MS quantitation of porphyroxine in opium and application of porphyroxine-acetylated products as signature markers for heroin.[Pubmed:30835929]

Drug Test Anal. 2019 Jul;11(7):999-1008.

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(14) -desmethyl-epi-Porphyroxine (B) and N,O(8) -diacetyl-O(14) -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 ( per thousand) and the relative concentrations to morphine were in the range of 1x10(-4) and 1x10(-2) 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.

Characterization and origin of the 'B' and 'C' compounds in the acid/neutral forensic signatures of heroin - products from the acylation of porphyroxine and subsequent hydrolysis.[Pubmed:26593749]

Drug Test Anal. 2017 Mar;9(3):462-469.

Two significant compounds often found in the gas chromatographic analysis of the acid/neutral extracts from illicit heroin have remained uncharacterized for 30 years. The unknown compounds are referred to as the 'B' and 'C' compounds. It has been postulated that these compounds arise from acetylation of Porphyroxine, a rhoeadine alkaloid found at trace levels in the opium poppy, Papaver somniferum. Porphyroxine was isolated from opium and acetylated to produce N,O(8) -diacetylPorphyroxine. Mild hydrolysis produced N,O(8) -diacetyl-O(14) -desmethyl-epi-Porphyroxine (the C compound) and N-acetyl-O(14) -desmethyl-epi-Porphyroxine (the B compound). Both N,O(8) -diacetyl-O(14) -desmethyl-epi-Porphyroxine and N-acetyl-O(14) -desmethyl-epi-Porphyroxine were determined to be C-14 epimers of Porphyroxine and N,O(8) -diacetylPorphyroxine. The non-epimerized isomers of the B and C compounds were also detected in illicit heroin, but at much lower levels. Chromatographic and spectroscopic data are presented for the aforementioned compounds. The presence/absence and relative concentrations of these compounds is presented for the four types of heroin (Southwest Asian, South American, Southeast Asian, and Mexican). The prevalence of detection for the B and C compounds are Southwest Asian = 92-93%, South American = 64-72%, Southeast Asian = 45-49%, and Mexican South American > Southeast Asian, each by an order of magnitude. These compounds were rarely detected in Mexican heroin. The presence/absence and relative concentrations of these compounds provide pertinent forensic signature characteristics that significantly enhance the final regional classifications. Copyright (c) 2015 John Wiley & Sons, Ltd.