Heroin analysis

Methanol is a good universal solvent, but may result in the rapid hydrolysis of trace amounts of diamorphine to monoacetylmorphine and morphine itself. As such, where possible, it should be avoided for heroin analysis, in particular the analysis of trace samples of heroin. Chloroform is an ideal solvent, but will rapidly evaporate from the swab. With care, however, it can be used since there are not the hydrolysis problems associated with methanol. 

Of the solvents available, chloroform has been found to satisfy these criteria for heroin analysis. The samples should be dissolved at a concentration which is of the same order of magnitude as the standards against which they are to be compared. TLC of heroin samples is most frequently carried out on silica gel. Between 5 and 10 p,g of each component drug should be applied to the plate. The actual concentration of the solution prepared from a street drug sample will... 

First, if, for example, a powder is to be examined, then it should be freely soluble in the solvent chosen for injection into the chromatographic system. Secondly, the solvent should be fully miscible with the mobile phase. For these reasons, methanol is frequently chosen for heroin analysis, although the drug should not be left in this solvent for long periods because of the risk of hydrolysis of some of its components, e.g. monoacetylmorphine and diamorphine. 

Figure 11.12 GC analysis of (a) urine sample spiked with opiates 3 p.g/ml) and (b) blank urine sample. Peak identification is as follows 1, dihydrocodeine 2, codeine 3, ethylmor-phine 4, moipliine 5, heroin. Reprinted from Journal of Chromatography, A 771, T. Hyotylainen et al., Determination of morphine and its analogues in urine by on-line coupled reversed-phase liquied cliromatography-gas clrromatography with on-line derivatization, pp. 360-365, copyright 1997, with permission from Elsevier Science.

Sanchez-Carbonell X, Sens L Ten-year survival analysis of a cohort of heroin addicts in Catalonia the EMETYST project. Addiction 95 941—948, 2000 Schindler SD, Eder H, Ortner R, et al Neonatal outcome following buprenorphine maintenance during conception and throughout pregnancy. Addiction 98 103-... 

C03-0132. Police officers confiscate a packet of white powder that they believe contains heroin. Purification by a forensic chemist yields a 38.70-mg sample for combustion analysis. This sample gives 97.46 mg CO2 and 20.81 mg H2 O. A second sample is analyzed for its nitrogen content, which is 3.8%. Show by calculations whether these data are consistent with the formula for heroin, C21 H22 NO5. ... 

The analysis of codeine, morphine, 6-monoacetylmorphine (6-MAM, a metabohte of heroin), and cocaine is important for many toxicology labs to determine illicit drug use. When analyzing opiates in urine samples, frequently the matrix chosen for drug screening, the conjugated metabolites must be hydrolyzed however, this process can break down 6-MAM (Christophersen et al., 1987). These compounds can be derivatized to increase sensitivity, and both BCD and NPD are used for these assays. Derivatizations used include reaction with N-methyl-N-trimethylsilyltrifluoroacetamide followed by GC-FID (Lin et al., 1994) or with N,0-bis(trimethylsilyl)trifluoroacetamide (Christophersen et al., 1987 Lee and Lee, 1991), PFPA (Christophersen et al., 1987), or heptafluorobutyric anhydride (HFBA) followed by GC-ECD. All these methods show good sensitivity and selectivity. 

Lurie, I. S. (1996). The analysis of cations and anions in illicit heroin using capillary electrophoresis with indirect UV detection. J. Capillary Electrophor. 3, 237-242. 

Lurie, L, Hays, P., and Valentino, A. (2006). Analysis of carbohydrates in seized heroin using capillary electrophoresis. J. Forensic Sci. 51, 39—44. 

Liquid chromatography coupled with electrochemical detection this technique, in combination with a high-throughput liquid-absorption pre-concentrator (HTLAP) that sampled air and collected analytes from vapours or aerosols into a small volume of liquid absorbent, was used by Zaromb et al. [47] for the detection and analysis of cocaine and heroin in air. 

Forensic analysis of street drugs include that of cocaine together with excipients frequently encountered (579), amphetamines 080), and dyes found in heroin samples 081). An on-line photochemical derivitization of cannabinoids has been described 082). Other pharmaceutical agents studied in formation include nortriptyline in tablets. 083), glycyrrhizic acid from licorice extract 084, 585), pirimiphos methyl 086), digitalis glycosides 0S7), pilocarpine 088), and its antagonist atropine 009). 

Dams et al. [19] determined seven different opium alkaloids and derivatives in seized heroin using fast LC-MS analysis. Analytes were separated in 5 min on a monolithic silica column with a gradient elution system and an optimized flow of 5 mL/min. Detection was carried out using a sonic spray ion source [20] a modified ESI source were ionization is achieved using a nebulizer gas at sonic speed instead of applying an electrical field. 

The Raman spectra of heroin, morphine and codeine (Fig. 7.10) are highly characteristic because of the change in the bands due to the aromatic ring. The FT-IR spectra of these compounds are quite similar. Near-infrared Raman spectroscopy can provide a rapid method for characterising drugs with minimal sample preparation and analysis time. 

There are two types of analysis qualitative and quantitative. Qualitative analysis determines which chemical is present, while quantitative analysis determines the concentration of a chemical. Concentration means an amount of chemical per unit of sample, for example, 100 micrograms (pg) of morphine per liter (L) of blood (100 pg/L) or the amount of pure chemical per weight of material, such as 1 gram of heroin per 10 grams of white powder. 

Dijkgraaf M, van der Zanden B, de Borgie C, Blanken P, Van Ree J Van den Brink W (2005). Cost utility analysis of co-prescribed heroin compared with methadone maintenance treatment in heroin addicts in two randomized trials. British Medical Journal, 330, 1297... 

Similar analyses could be done for the movement of cocaine from Colombia to Europe, or the movement of heroin via the Balkan route, or any of a number of other trafficking patterns. The key limitation is the lack of standardised data. UNODC needs greater input from Member States to its individual seizures database, including detailed information on the nationalities of traffickers and the techniques employed. On this basis, important analysis of the world drug trafficking situation could be completed for the benefit of all. 

Liquid chromatography is two decades more mature than capillary electrophoresis. As trained electropherographers become more common, more separations will be handled by electrophoresis. For example, electrophoresis displaced liquid chromatography as the preferred method for forensic analysis of alkaloids in opium and heroin.51 The enabling technology for this application was dynamic coating of the capillary between runs to eliminate adsorption of analytes on the silica surface and decrease variations in migration times to less than 0.5%. 

The NARL inter laboratory study program is a proficiency testing scheme currently covering pesticide residues (in animal fats, soil, fruit and vegetables), pollution by petroleum products (in soil and water) and illicit drug analysis (heroin, cocaine, amphetamines and LSD). The objectives of the NARL studies are as follows ... 

N. K. Nair, V. Navaratnam, and V. Rajananda, Analysis of illicit heroin, I, an effective TLC system for separating eight opiates and five adulterants, J. Chromatogr., 366 363 1986). 

Rook EJ, Hillebrand MJX, Rosing H, van Ree J, Beijnen JH (2005) The quantitative analysis of heroin, methadone, and their metabolites and the simultaneous detection of cocaine, ace-tylcodeine and their metabolites in human plasma by high-performance liquid chromatography coupled with tandem mass spectrometry. J Chromatogr B 824 213-221... 

Schlesinger et al ( 3) reported that non-destructive neutron activation analysis (NAA) can be employed to compare drugs sold in illicit channels through the determination of their elemental compositions. This early work was amplified by Pro and Brunelle (4), combining atomic absorption analysis with NAA. Although the determination of elemental composition can be useful, this approach suffers from the fact that it may not be used when heroin has been packaged differently or adulterated with another... 

Lerner and Mills (JjO reported the presence of 0 -monoacetyl-morphine as a common constituent in heroin and suggested that the ratio of heroin to monoacetylmorphine would not change during adulteration. Others have dealt primarily with the identification of the adulterants present, either other drug substances or sugars (6,7). Grooms (j3) and Miller (9) have attempted to include the analysis of adulterants with the presence of monoacetylmorphine. In each of these cases, the resolution of the various components was insufficient to provide good quantitative data. 

Two procedures are presented for the analysis of these heroin impurities, one involving derivatization of the material followed by gas chromatographic analysis, and the other a direct gas chromatographic analysis. The derivatization method is the preferred procedure in that all components are well resolved on the chromatogram whereas 0 -monoacetylmorphine and acetylcodeine are not totally separated in the direct method. Also, the reproducibility of the former has been found to be superior. 

Transfer a portion of the exhibit equivalent to approximately 25 mg of heroin to a 1 ml glass-stoppered test tube. Add 0.2 ml of chloroform and 0.3 ml of N,0-Bis-(trimethylsilyl)-trifluoroacetand.de (BSTFA). Mix and heat at 75°C for ninety minutes giving the tube an occasional shake. Use 2-5 microliters of the solution for gas chromatographic analysis. 

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