Enantioselective syntheses and X-ray structures of (S)- and (R)-N-norlaudanidine: trace opium constituents

The enantioselective synthesis of each of the enantiomers of N-norlaudanidine, a minor Papaver somniferum opium benzyltetrahydoisoquinoline alkaloid is described. This was achieved using a chiral auxiliary-mediated Bischler-Napieralski cyclization-sodium borohydride reduction strategy. The X-ray crystal structures of each of these secondary amines are reported.     

Determination of thebaine in water samples, biological fluids, poppy capsule, and narcotic drugs, using electromembrane extraction followed by high-performance liquid chromatography analysis

Opium determination is of great importance from toxicological and pharmaceutical standpoints. In present work, electromembrane extraction (EME) coupled with high-performance liquid chromatography (HPLC) and ultraviolet (UV) detection was developed for determination of thebaine as a natural alkaloid, in different matrices containing water, urine, poppy capsule, street heroine, and codeine tablet. Thebaine migrated from 3 mL of sample solutions, through a thin layer of 2-nitrophenyl octyl ether (NPOE) immobilized in the pores of a porous hollow fiber, and into a 15 μL acidic aqueous acceptor solution present inside the lumen of the fiber. The variables of interest, such as chemical composition of the organic liquid membrane, stirring speed, extraction time and voltage, pH of donor and acceptor phases and salt effect in the EME process were optimized. Under optimal conditions, thebaine was effectively extracted from different matrices with recoveries in the range of 45–55%, which corresponded to preconcentration factors in the range of 90–110. Good linearity was achieved for calibration curves with a coefficient of estimation higher than 0.997. Detection limits and intra-day precision (n = 3) were less than 15 μg L⁻¹ and 8.9%, respectively.     

Application of a simple and sensitive GC–MS method for determination of morphine in the hair of opium abusers

Thirty hair samples were collected from male opioid abusers for whom the presence of morphine in their urine samples was confirmed by thin layer chromatography (TLC). The hair samples were decontaminated by washing with isopropanol, deionized water, and isopropanol, dried at room temperature, and cut into small pieces. Samples of the latter (30 mg ) were digested by incubation in a mixture of methanol–trifluoroacetic acid (9:1) for 18 h at 45 °C and sonicated to improve the extraction process. The methanolic phase was evaporated to dryness under a stream of nitrogen at 50 °C. The sample was derivatized by addition of N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA) and 1% trimethyliodosilane (TMIS) at 70 °C for 20 min, with sonication. Derivatized samples (1 L) were injected into a gas chromatograph–mass spectrometer (GC–MS) system fitted with a capillary column; the Finnigan MS was operated in SIM mode. Naltrexone was used as internal standard (IS). The masses of the ions selected for morphine and naltrexone were 429 and 557, respectively. The limit of quantitation was set at 0.03 ng mg^–1 hair. By using the above procedure we detected morphine in all the samples examined, in the concentration range 0.26–10.31 ng mg^–1 hair.     

海洛因的X射线衍射谱

本文给出海洛因和鸦片的实测Ｘ射线衍射谱;并且列出海洛因的每一个衍射峰参数。海洛因属于正交晶系;原胞基矢是：ａ＝８．００３,ｂ＝１４．３７３,ｃ＝１６．０９２×１０－１０ｍ。对比纯净的海洛因和蔗糖的标准谱,我们检查出主要的掺杂物是糖。     

HPLC separation of opium alkaloids on porous and non-porous stationary phases

Summary A new reversed-phase (RP) HPLC method has been developed and validated for the separation of the main opium alkaloids morphine, codeine, thebaine, papaverine and noscapine on a non-porous (micropellicular) stationary phase. On this phase quantification of the compounds by internal standardization with brucine was achieved extremely rapidly, in ca 1.5 min, only. Thus, the analysis time for the opium alkaloids was approximately one tenth of that on porous stationary phases. Different opium samples were investigated using non-porous and porous packings. The correlation between the results was excellent. Presented at Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 1–3, 1999     

Spectrofluorimetric Determination of Opium Alkaloids by Mixed Anhydride Reagent

Abstract

The spectrofluorimetric determination of five major opium alkaloids by malonic acid-acetic anhydride reagent is reported. The fluorescence characteristics of various alkaloidal systems and the effect of different parameters like temperature, time of heating and diluent on the fluorescence intensity are described. The interference of various foreign substances has also been checked.     

Rapid and sensitive determination of morphine in street opium samples by thermal desorption gas chromatography using a microfurnace pyrolyzer

Thermal desorption of the alkaloids in opium samples at 300 degrees C using a vertical microfurnace pyrolyzer was followed by their on-line gas chromatographic (GC) analysis on a large-bore glass capillary column. This method permitted rapid and sensitive determination of the content of the main alkaloid, morphine, in the small (ca. 100 microg) opium samples with a relative standard deviation within 4% for 5 runs. The observed morphine contents of about 12 to 15 w/w% in the given opium samples were in fairly good agreement with those estimated by a conventional GC-MS method.     

Determination of the five major opium alkaloids by reversed-phase high-performance liquid chromatography on a base-deactivated stationary phase

Summary A reversed phase HPLC method for the separation of the five major alkaloids fromPapaver somniferum L., morphine, codeine, thebaine, papaverine and noscapine, has been developed and validated. By use of a basedeactivated silica-based stationary phase excellent peak shape was achieved for each substance. The five alkaloids were quantified by internal standardization within 20 min and with good precision. The method is applicable to opium and to poppy straw.     

Capillary electrophoresis time-of-flight mass spectrometry of an opium powder

Summary Intensive work has been invested in recent years to evaluate the performance of capillary electrophoresis (CE) in forensic analysis. Tremendous progress has also been achieved in interfacing CE to sensitive and specific detection systems such as the mass spectrometer (MS). We have recently developed an electrospray time-of-flight mass spectrometer (ESI-TOFMS) for use as a detector for fast and efficient liquid phase separations. In the present paper we investigated ESI-TOFMS for the analysis of an opium powder. Both continuous infusion and CE were studied for direct sample introduction into the TOFMS and mixture separation, respectively. CEMS analysis of the opium was performed in a citrate buffer, using aqueous or mixed aqueous/organic eluents. Low fmol detection was achieved.     

The rapid quantitative analysis of codeine phosphate drug substance by reversed-phase high-performance liquid chromatography

Summary A rapid procedure for the evaluation of codeine phosphate drug substance derived from poppy straw or opium concentrate is described. The gradient HPLC procedure employs a pH 2.5 phosphate buffer, methanol and acetonitrile mobile phase at 40°C and a Bondapak C-18 column. Eight opium alkaloids, including the four major alkaloids, are separated from each other. The paper describes details of the assay procedure and presents data documenting the linearity, specificity, precision, and sensitivity of the method.