The GC-MS detection and characterization of reticuline as a marker of opium use

Reticuline (a precursor of opium alkaloids) was detected and characterised as its trimethylsilyl ethers, acetyl esters and methyl ethers by GC-EIMS and GC-CIMS in opium and the urine of opium users after hydrolysis by acid or beta-glucuronidase as coextractive of morphine. Because this compound cannot be detected in heroin and poppy seeds, it is suggested as a differentiating marker between opium and heroin use, opium and poppy seeds use, or opium and "pharmaceutical" codeine use in cases when opiate use has been confirmed by detection of morphine and codeine in the urine. As well as being a constituent of opium, reticuline in the urine of opium users may also result from the metabolic demethylation of the three other benzyltetrahydroisoquinoline opium alkaloids: codamine, laudanosine and laudanine.     

The GC–MS detection and characterization of reticuline as a marker of opium use

Reticuline (a precursor of opium alkaloids) was detected and characterised as its trimethylsilyl ethers, acetyl esters and methyl ethers by GC–EIMS and GC–CIMS in opium and the urine of opium users after hydrolysis by acid or β-glucuronidase as coextractive of morphine. Because this compound cannot be detected in heroin and poppy seeds, it is suggested as a differentiating marker between opium and heroin use, opium and poppy seeds use, or opium and “pharmaceutical” codeine use in cases when opiate use has been confirmed by detection of morphine and codeine in the urine. As well as being a constituent of opium, reticuline in the urine of opium users may also result from the metabolic demethylation of the three other benzyltetrahydroisoquinoline opium alkaloids: codamine, laudanosine and laudanine.     

Impurities, adulterants and diluents of illicit heroin in Denmark (Jutland and Funen)

The contents of impurities, adulterants and diluents in 77 samples of illicit heroin were determined by a combination of high-performance liquid chromatography and gas chromatography. The origin of each sample was characterized by calculating the content of the opium alkaloids in relation to the heroin content. The routes of distribution were compared by determination of the contents of caffeine, procaine and sugars. The results were used as a "chemical fingerprint" of each sample. The results indicate that it is difficult to prove, with certainty, that two samples are identical. However, in most cases, by determining the amounts of impurities, adulterants and diluents in heroin samples, it will be possible to ascertain whether two samples are different and, in many cases, to determine with reasonable certainty whether two samples are identical.     

Analyse von heroinproben mit der Kapillargaschromatographie. Vergleich von Glaskapillartrennsäule und gepackter Säule

In forensic examination of illicit heroin samples high-resolution capillary gas chromatography is compared with gas chromatography with packed columns. Separation efficiency, reproducibility of qualitative and quantitative determinations and stability of the columns are examined.A practical method with silylation of the samples is presented which allows safe identification and quantification of many various compounds contained in illicit heroin samples. The gas chromatographic data of 35 substances (opium alkaloids and synthetic derivatives, adulterants and diluents) are listed. The method also allows the quantification of morphine, opium, and cocaine samples.     

Hmong folk remedies: limited acetylation of opium by aspirin and acetaminophen.

The traditional folk medicine of the Hmong and other Southeast Asian refugees has accompanied them during their immigration in this country over the past two decades. In two recent cases involving Hmong defendants, unknown solids, resembling charcoal in consistency and purported to be "backache remedies," were analyzed and found to be complex mixtures of aspirin, acetaminophen, caffeine and partly acetylated opium. In particular, significant amounts of acetylacetaminophen, 3-O-acetylmorphine, 6-O-acetylcodeine, 6-O-acetylmorphine, and heroin were identified by gas chromatography/mass spectrometry. Heating approximately equal weights of solid opium, aspirin, and acetaminophen at 130 degrees C for several hours produced a mixture of compounds showing a similar acetylation pattern.     

Heroin Overdose Deaths and Heroin Purity Between 1990 and 2000 in Istanbul,Turkey*

Abstract: Turkey has continuously experienced problems with abuse of, and addiction to, opium derivatives. In this study, we analyzed the relationship between heroin overdose deaths and the characteristics of seized opium derivatives. Data were gathered from the Council of Forensic Medicine of the Ministry of Justice in Istanbul from 1990 to 2000. There were 636 heroin‐related deaths during this period, 595 of which were classified as heroin overdose deaths. Mean crude and weighted heroin purities remained relatively constant and were calculated to be 46% (57–34%) and 51% (39–59%), respectively. The weight of heroin and the number of heroin seizures, but not the heroin purity, were significantly associated with the number of heroin‐related deaths. Prevention strategies are needed to reduce the number of deaths caused by overdoses in countries situated on drug trafficking routes. These strategies should focus on drug trafficking, by providing increased levels of, and support for, law enforcement, stopping the supply of precursor chemicals, and combating corruption among border officials.     

Exploiting expressed sequence tag databases for the development and characterization of gene-derived simple sequence repeat markers in the opium poppy (Papaver somniferum L.) for forensic applications

Simple sequence repeat (SSR) markers in the opium poppy (Papaver somniferum L.) were identified from an expressed sequence tag (EST) database comprised of 20,340 sequences. In total, 2780 SSR-containing sequences were identified. The most frequent microsatellite had an AT/TA motif (37%). Twenty-two opium poppy EST-SSR markers were presently developed and polymorphisms of six markers (psom 2, 4, 12, 13, 17, and 22) were utilized in 135 individuals under narcotic control investigation. An average of three alleles per locus (range: 2-5 alleles) with a mean heterozygosity of 0.167 was detected. Six loci identified 29 unique profiles in 135 individuals. The EST-SSR markers exhibited small degrees of genetic differentiation (fixation index = 0.727, p < 0.001). Other variable markers will be needed to facilitate the forensic identification of the opium poppy for future cases. To determine the potential for cross-species amplification, six markers were tested in five Papaver genera species and two Eschscholzia genera. The psom 4 and psom 17 primer pair was transferable. This is the first study to report SSR markers of the opium poppy.     

Changes in place of origin of heroin seized in Denmark from 1981 to 1986. "Chemical fingerprint" of 138 samples

Hundred thirty-eight samples of heroin weighing more than 0.1 g seized between 1981 and 1986 were characterized according to their contents of opium alkaloids, adulterants, and diluents together with their form and color. The "chemical fingerprint" was used to establish a change in the heroin during the period. As compared to the first few years covered by the survey, a predominant number of the samples at the end of the period were in the base form and contained the opium alkaloids papaverine and noscapine. In particular, the concentration of noscapine as related to the heroin content of each sample had increased considerably, indicating Pakistan or Iran as being the places of origin of most of the heroin seized in Denmark at the end of the period.     

Assay of major and minor constituents of opium samples and studies of their origin

Samples of opium from different countries as well as from various regions of India were studied for their morphine and codeine content by gas-liquid chromatography (GLC) as their silyl ethers in a single step. Non-phenolic alkaloids (thebaine, papaverine and narcotine) were extracted with dichloromethane for GLC after conversion of the meconic acid, morphine and codeine in opium into insoluble salts with lime water. The data on alkaloidal constituents have been utilised in a determination of the origin of seized opium samples in this preliminary study.     

Isolation and identification of unique marker compounds from the Tasmanian poppy Papaver somniferum N. Implications for the identification of illicit heroin of Tasmanian origin

Tasmanian opium accounts for 25% of the world's legal supply of opium straw, and in 1998-99 sufficient numbers of flower pods (66,013) to manufacture ca 500 kg of heroin were stolen. Whilst the heroin signature program has been developed to determine the origin of heroin from other key producers, no such signature currently exists for Tasmanian derived heroin. Tasmanian poppies contain a unique alkaloid, oripavine, which is the source of 'marker' impurities in illicit heroin produced from Tasmanian poppy straw. Treatment of oripavine (500mg) under Thiboumery and Mohr heroin processing conditions, followed by simple evaporative workup afforded 613 mg of a dark orange residue, which upon extensive chromatographic purification yielded oripavine 3-acetate (2) 22 mg; 3-acetyl-N-acetyldesthebaine (3) 35 mg; 3-acetyl-6-methoxy-4,5-epoxyphenanthrene (4) 5.8 mg; 3,4-diacetyl-6-methoxyphenanthrene (5) 27 mg; and 3,4,6-methoxy-5-[2(N-methylacetamido)]ethylphenanthrene (6) 52 mg. Compounds (2-6) are derived from oripavine and are unique to heroin derived from the Tasmanian poppy Papaver somniferum N. Analysis of illicit heroin samples seized from Turkey, Pakistan, Columbia and Myanmar did not reveal any of the aforementioned marker compounds. We have, however, identified four of these marker compounds (3-6) in seized heroin samples from Australia suggesting that they are of Tasmanian origin. Complete details of the isolation and identification of these compounds are provided.     

Fatal intoxications in Denmark following intake of morphine from opium poppies

In Denmark it is legal to grow opium poppies for the production of poppy seeds and until 1986 for decoration purposes, too. Danish poppy capsules contain 0.3-5 mg morphine per capsule and the content of morphine in opium exuded from the capsules may amount to 24%. This has resulted in misuse as both fresh and dried poppy capsules have been used for the production of "opium tea". During the period 1982-1985, seven casualties occurred among drug addicts in Denmark which were solely or partly caused by these opium poppies.     

Noscapine as an adulterant in illicit heroin samples

In this short report the evidence is given (based on the analyses of 22 case samples) that noscapine can be used as an adulterant in illicit heroin samples. In this context, the appearance of illicit heroin samples characterised by a high noscapine content (up to 61%) and a high noscapine/whole morphine ratio (up to 3.5) is highlighted. All samples discussed in the paper (132) were seized in Slovenia, in the period from 1997 to 1999 and were analysed by gas chromatography-mass spectrometry.     

Evaluation of 19 short tandem repeat markers for individualization of Papaver somniferum

Papaver somniferum, commonly known as opium poppy, is the source of natural opiates, which are used as analgesics or as precursors in the creation of semi-synthetic opioids such as heroin. An increase in opioid addiction in the United States has resulted in high rates of illicit opioid use and overdoses. It has recently been shown that P. somniferum DNA suitable for genetic analysis can be recovered from heroin samples. The development of a comprehensive genetic individualization tool for opium poppy could serve to link cases and strengthen programs such as the Drug Enforcement Administration’s (DEA) Heroin Signature Program, which seeks to combat rising opioid use.The purpose of this study was to develop a quantitative real-time PCR (qPCR) method for the quantification of opium poppy DNA, compare three commercial DNA extraction kits for their ability to isolate DNA from poppy seeds, and evaluate nineteen opium poppy short tandem repeat (STR) markers for their use in a forensic identification panel. Such a panel could be used for individualizing samples and determining the geographic origin in heroin or poppy seed tea cases. The qPCR method was proven to be reproducible and reliable, specific for P. somniferum, and sensitive enough for forensic case-type samples. Of the three kits tested, the nexttec™ one-step DNA Isolation Kit for Plants was the optimal method and facilitated rapid extraction of DNA from poppy seeds. The majority of evaluated STR primer sets were unreliable or had low discriminatory power, limiting their use for individualization of poppy samples. A six-locus STR multiplex was developed and evaluated according to Scientific Working Group on DNA Analysis Methods (SWGDAM) and International Society of Forensic Genetics (ISFG) guidelines, including the use of a sequenced allelic ladder. The multiplex was found to have low discriminatory power, with greater than two-thirds of samples analyzed having just two different genotypes. The multiplex was determined to be unsuitable for individualization; however, a genotype map was developed as a proof of concept that these markers may be useful for determining the biogeographical origin of samples. Searching the poppy genome for new STR markers and developing new primer sets may be necessary for the creation of a powerful genetic tool for the individualization of P. somniferum.     

海洛因来源鉴定的新方法

毒品来源的鉴定是指对毒品样品中包含的来源信息进行提取拜分析,这有助于打击毒品犯罪.海洛因是危害我国的主要毒品,它的来源鉴定更引起人们的关注.本文介绍了国际上研究海洛因来源的三种方法,即研究海洛因样品中的各种有机杂质及其相对比例;研究海洛因样品中的痕量无机元素;研究海洛因及吗啡的稳定同位素相对比值.第三种方法能够反映样品的地域性特点,因而在来源鉴定方面有突出的优势.气相色谱-燃烧-同位素比值质谱法是同位素比值测定方法中用于海洛因来源鉴定的最佳手段.这一技术还可用于其他微量物证(如炸药、药品、油品等)的来源鉴别,因而在法庭科学领域内显示了广阔的应用前景.     

Classification of Opium by UPLC‐Q‐TOF Analysis of Principal and Minor Alkaloids

Opium is the raw material for the production of heroin, and the characterization of opium seizures through laboratory analysis is a valuable tool for law enforcement agencies to trace clandestine opium production and trafficking. In this work, a method for opium profiling based on the relative content of five principal and 14 minor opium alkaloids was developed and validated. UPLC‐Q‐TOF was adopted in alkaloid analysis for its high selectivity and sensitivity, which facilitated the sample preparation and testing. The authentic sample set consisted of 100 “Myanmar” and 45 “Afghanistan” opium seizures; based on the data set of the 19 alkaloid variables in them, a partial least squares discriminant analysis classification model was successfully achieved. Minor alkaloids were found to be vitally important for opium profiling, although combined use of both principal and minor alkaloids resulted in the best geographical classification result. The developed method realized a simple and accurate way to differentiate opium from Myanmar and Afghanistan, which may find wide application in forensic laboratories.     

The scourge of opiates: The illicit narcotics trade in the Islamic Republic of Iran

This study seeks to provide an overview of drug trafficking in Iran, particularly as it relates to the Iran–Afghan and Iran–Pakistan border regions. Data were obtained from a systematic review of the academic literature and from open sources, including media reports and official documents. The Iranian government is credited with dedicating substantial resources to combating the drug trafficking. Despite these efforts, Iran continues to be the most significant transit country for opium and heroin from Afghanistan. Several factors are identified that help to explain why Iran, despite its efforts, continues to play a central role in the international drug trade.     

The routine profiling of forensic heroin samples

A method for the routine profiling of illicit heroin samples received in casework has been developed which depends on simple and straightforward sample pretreatment, followed by gas chromatography on a capillary column using flame-ionization detection. The factors affecting the choice of each aspect of the procedure are discussed, as are the statistical data for sampling and the chromatography. Components of illicit heroin derived from opium and other adulterants have been identified. The significance of data from samples examined in 1986 is discussed.     

土制海洛因的薄层色谱扫描快速检验

建立土制海洛因的快速定性和定量检测方法。土制海洛因甲醇溶解,点于GF(254)薄层板上,正庚烷：氯仿：乙酸乙酯：乙醇：氨水（5：2：2：1．5：0．2）非饱和上行展开2次。薄层色谱扫描,Rf值结合斑点光谱扫描定性,色谱扫描定量。结果土制海洛因中主要成分海洛因、单乙酰吗啡、乙酰可待因、吗啡、可待因、蒂巴因、罂粟碱和那可汀分离完全,薄层扫描线性范围为0．2～2或4μg／斑点,最小检出量为0．1μg或0．2μg／斑点。本法可用于土制海洛因和海洛因的定性和定量检测。     

<Emphasis Type="Italic">Maslahat</Emphasis>, the state and the people: opium use in the Islamic Republic of Iran

This article tracks the development of opium use in present day Iran. Investigating how opium use is influenced by ideological change within the country, this paper intimately attempts to understand how Iranian intellectual, religious and national movements affected and still affect opium use. Working from an historicist approach, this paper furthermore investigates the changing response of the state to this opiate addiction. Analyzing the Islamic Republic's response to opiate-drug use is key in understanding how state policy decisions are influenced by and embedded within these ideological movements of a nation, and, specifically, how the Islamic Republic’s constitutional policy of maslahat allows for flexible legal strategies to combat drug control. Such an investigation is important, not only in understanding the etiology of Iranian policies of drug control and criminalization, but also in understanding how ideological movements affect an individual’s choice to use illegal substances.     

Detection of Brodifacoum and other Rodenticides in Drug Mixtures using Thermal Desorption Direct Analysis in Real Time Mass Spectrometry (TD‐DART‐MS)

In recent months, there has been increased reporting of seized drug and toxicology cases containing rodenticides, the active ingredient in rat poisons. Seeing as rodenticides are not scheduled substances, they are not commonly screened for in seized drug analysis. This work investigates the use of TD‐DART‐MS for the simultaneous detection of rodenticides and drugs. Six rodenticides were evaluated, an optimal method was established, and limits of detection in the tens of nanograms were calculated. Additional studies highlight that detection at less than 1% by weight in mixtures with AB‐FUBINACA, cocaine, heroin, or methamphetamine was possible. This work presents an optimized method for detection of these compounds, allowing for the simultaneous detection of drugs and rodenticides, providing drug chemists with a tool for rapid identification of these compounds for forensic or public health purposes.