Raman spectroscopy for forensic examination of ß-ketophenethylamine "legal highs": reference and seized samples of cathinone derivatives.

Raman spectra of a representative range of ß-ketophenethylamine (ß-KP), the rapidly growing family of cathinone-related "legal high" recreational drugs, have been recorded. These spectra showed characteristic changes that were associated with the pattern of substitution on the aromatic rings, for example, the compounds carrying substituents at the 4- position could be distinguished from 3,4-methylenedioxy "ecstasy" derivatives. They also showed small but detectable changes with differences in substitution on the ethylamine substituent. These features allowed the ß-KPs present in seized casework samples to be identified. The seized samples typically contained only small amounts of bulking agents, which meant that the band intensities of these components within averaged data were very small. In contrast, grid sampling normally gave at least some spectra which had a higher than average proportion of the bulking agent(s), which allowed them to also be identified. This study therefore demonstrates that Raman spectroscopy can be used both to provide a rapid, non-destructive technique for identification of this class of drugs in seized samples and to detect minor constituents, giving a composition profile which can be used for drugs intelligence work.

Screening tablets for DOB using surface-enhanced Raman spectroscopy.

2,5,-Dimethoxy-4-bromoamphetamine (DOB) is of particular interest among the various "ecstasy" variants because there is an unusually long delay between consumption and effect, which dramatically increases the danger of accidental overdose in users. Screening for DOB in tablets is problematic because it is pharmacologically active at 0.2-3 mg, which is c. 50 times less than 3,4-methylenedioxy-N-methylamphetamine (MDMA) and makes it more difficult to detect in seized tablets using conventional spot tests. The normal Raman spectra of seized DOB tablets are dominated by the bands of the excipient with no evidence of the drug component. Here we report the first use of on-tablet surface-enhanced Raman spectroscopy (SERS) to enhance the signal from a low concentration drug. Raman studies (785-nm excitation) were carried on series of model DOB/lactose tablets (total mass c. 400 mg) containing between 1 mg and 15 microg of DOB and on seized DOB tablets. To generate surface-enhanced spectra, 5 microL of centrifuged silver colloid was dispensed onto the upper surface of the tablets, followed by 5 microL of 1.0 mol/dm(3) NaCl. The probe laser was directed onto the treated area and spectra accumulated for c. 20 sec (10 sec x 2). It was found that the enhancement of the DOB component in the model tablets containing 1 mg DOB/tablet and in the seized tablets tested was so large that their spectra were completely dominated by the vibrational bands of DOB with little or no contribution from the unenhanced lactose excipient. Indeed, the most intense DOB band was visible even in tablets containing just 15 microg of the drug. On-tablet surface-enhanced Raman spectroscopy is a simple method to distinguish between low dose DOB tablets and those with no active constituent. The fact that unique spectra are obtained allows identification of the drug while the lack of sample preparation and short signal accumulation times mean that the entire test can be carried out in <1 min.

Forensic analysis of architectural finishes using fourier transform infrared and Raman spectroscopy, part I: the resin bases.

The ability of Raman spectroscopy and Fourier transform infrared (FT-IR) microscopy to discriminate between resins used for the manufacture of architectural finishes was examined in a study of 39 samples taken from a commercial resin library. Both Raman and FT-IR were able to discriminate between different types of resin and both split the samples into several groups (six for FT-IR, six for Raman), each of which gave similar, but not identical, spectra. In addition, three resins gave unique Raman spectra (four in FT-IR). However, approximately half the library comprised samples that were sufficiently similar that they fell into a single large group, whether classified using FT-IR or Raman, although the remaining samples fell into much smaller groups. Further sub-division of the FT-IR groups was not possible because the experimental uncertainty was of similar magnitude to the within-group variation. In contrast, Raman spectroscopy was able to further discriminate between resins that fell within the same groups because the differences in the relative band intensities of the resins, although small, were larger than the experimental uncertainty.

Forensic analysis of architectural finishes using fourier transform infrared and Raman spectroscopy, part II: white paint.

White household paints are commonly encountered as evidence in the forensic laboratory but they often cannot be readily distinguished by color alone so Fourier transform infrared (FT-IR) microscopy is used since it can sometimes discriminate between paints prepared with different organic resins. Here we report the first comparative study of FT-IR and Raman spectroscopy for forensic analysis of white paint. Both techniques allowed the 51 white paint samples in the study to be classified by inspection as either belonging to distinct groups or as unique samples. FT-IR gave five groups and four unique samples; Raman gave seven groups and six unique samples. The basis for this discrimination was the type of resin and/or inorganic pigments/extenders present. Although this allowed approximately half of the white paints to be distinguished by inspection, the other half were all based on a similar resin and did not contain the distinctive modifiers/pigments and extenders that allowed the other samples to be identified. The experimental uncertainty in the relative band intensities measured using FT-IR was similar to the variation within this large group, so no further discrimination was possible. However, the variation in the Raman spectra was larger than the uncertainty, which allowed the large group to be divided into three subgroups and four distinct spectra, based on relative band intensities. The combination of increased discrimination and higher sample throughput means that the Raman method is superior to FT-IR for samples of this type.

Rapid forensic analysis and identification of ''lilac'' architectural finishes using Raman spectroscopy.

The potential of Raman spectroscopy to discriminate between architectural finishes (household paint) has been investigated using a test set of 51 ''lilac'' paints and three different excitation wavelengths. The spectra obtained with visible excitation typically displayed a series of intense Raman bands on a featureless fluorescence background but the spectra of all the paints studied had essentially identical bands. With 785 nm excitation, although the same bands that dominated the 514 nm spectra were still observed, other bands with comparable intensity also appeared. The two strongest scattering constituents were identified as a dioxazine dye, Violet 23 and beta-Cu(phthalocyanine). A scatter plot of the intensities of marker bands for these constituents (normalized to the strong rutile bands that were always present) showed that, despite the fact that the sample set spanned a wide range of rutile : dioxazine dye : phthalo- cyanine ratios, many of the samples had very similar ratios and could not be discriminated. However, all the samples (even those with similar relative proportions of the main constituents) could be discriminated on the basis of their minor constituents, either by manually measuring band intensities or through the creation and searching of spectral libraries.

Tracking the distribution of "ecstasy" tablets by Raman composition profiling: a large scale feasibility study.

Here we report the results of the largest study yet carried out on composition profiling of seized "ecstasy" tablets by Raman spectroscopy. Approximately 1500 tablets from different seizures in N. Ireland were analysed and even though practically all the tablets contained MDMA as active constituent, there were very significant differences in their Raman spectra, which were due to variations in both the nature and concentration of the excipients used and/or the degree of hydration of the MDMA. The ratios of the peak heights of the prominent drug bands at 810 cm(-1) and 716 cm(-1) (which vary with hydration state of the drug), and the drug band at 810 cm(-1) against the largest clearly discernible excipient band in the spectrum were measured for all the samples. It was found that there was sufficient variation in composition in the general sample population to make any matches between batches of tablets taken from different seizures significant, rather than the result of random chance. Despite the large number of different batches of tablets examined in this study, only two examples of indistinguishable sets of tablets were found and in only one of these had the two batches of tablets been seized at different times. Finally, the fact that there are many examples of batches of tablets (particularly in different batches taken from single seizures) in which the differences between each set are sufficiently small that they appear to arise only from random variations within a standard manufacturing method implies that, with more extensive data, it may be possible to recognize the "signature" of tablets prepared by major manufacturers.