Rapid comparison of diacetylmorphine on banknotes by tandem mass spectrometry

A procedure is described for the determination of the distribution of the contamination of banknotes with controlled drugs using tandem mass spectrometry. The method is illustrated using diacetylmorphine, which is the major active component of heroin. A series of banknotes is introduced into the mass spectrometer and the intensities of two product ions (m/z 328 and 268) derived from the precursor protonated molecule (m/z 370) are recorded. A banknote is considered contaminated if it shows a significant peak for both product ions, and if the ratio of intensities of these two peaks falls within accepted limits. The distribution of diacetylmorphine on sterling banknotes taken from general circulation within the UK can be modelled by an arcsin (square root) transformation of the data or by a log transformation of the data with a higher proportion of contamination. The two models were found to be in close agreement, predicting an upper limit (at 99.9% confidence) of contamination on banknotes from general circulation between 9 and 10%. The percentage contamination in a case study was calculated and compared to the background distribution using the two models proposed. This comparison revealed that the contamination present in the case study was inconsistent with that present on banknotes in general circulation.     

An accurate and nondestructive GC method for determination of cocaine on US paper currency

The presence of cocaine on US paper currency has been known for a long time. Banknotes become contaminated during the exchange, storage, and abuse of cocaine. The analysis of cocaine on various denominations of US banknotes in the general circulation can provide law enforcement circles and forensic epidemiologists objective and timely information on epidemiology of illicit drug use and on how to differentiate money contaminated in the general circulation from banknotes used in drug transaction. A simple, nondestructive, and accurate capillary gas chromatographic method has been developed for the determination of cocaine on various denominations of US banknotes in this study. The method comprises a fast ultrasonic extraction using water as a solvent followed by a SPE cleanup process with a C(18) cartridge and capillary GC separation, identification, and quantification. This nondestructive analytical method has been successfully applied to determine the cocaine contamination in US paper currency of all denominations. Standard calibration curve was linear over the concentration range from the LOQ (2.00 ng/mL) to 100 microg/mL and the RSD less than 2.0%. Cocaine was detected in 67% of the circulated banknotes collected in Southeastern Massachusetts in amounts ranging from approximately 2 ng to 49.4 microg per note. On average, $5, 10, 20, and 50 denominations contain higher amounts of cocaine than $1 and 100 denominations of US banknotes.     

Analytical methods to determine cocaine contamination of banknotes from around the world

The presence of cocaine in a significant number of UK pounds (Xxxx), Euros (€) and North American banknotes ($) in general circulation requires appropriate tools to do determinations. This article discusses the-state-of-the-art in the analysis of cocaine on banknotes. We summarize the usual extraction methods of currency samples and compare them, especially with respect to avoiding sample damage. We critically discuss analytical methods, namely gas chromatography (GC) and liquid chromatography (LC), capillary electrophoresis (CE), immunoassay, thermal desorption tandem mass spectrometry (TD-MS²) and ion-mobility spectrometry (IMS). We also review cocaine levels on banknotes around the world and their possible relationship with drug consumption.     

Evaluation of monolithic and sub 2 microm particle packed columns for the rapid screening for illicit drugs--application to the determination of drug contamination on Irish euro banknotes

A study comparing recently available 100 x 3 mm id, 200 x 3 mm id monolithic reversed-phase columns with a 50 x 2.1 mm id, 1.8 microm particle packed reversed-phase columns was carried out to determine the most efficient approach (using traditional van Deemter analysis and a modern kinetic plot approach) for the rapid screening of samples for 16 illicit drugs and associated metabolites. A plot of column backpressure versus plate number (N) showed a significant advantage of using the monolithic phases, with the 20 cm monolithic column exhibiting a maximum 15,000 plates at a column backpressure of approximately 70 bar, compared to approximately 7000 plates at 150 bar for the 5 cm 1.8 microm particle packed column. Optimum linear velocities were found to be 0.40 mm s(-1), 0.52 mm s(-1) and 0.98 mm s(-1) for the three above columns, respectively. The 20 cm monolithic column was subsequently applied to the separation and determination of illicit drug contamination on Irish euro banknotes, using methanol extraction followed by LC-MS/MS. Method performance data showed that the new LC-MS/MS method was significantly more sensitive than previous GC-MS/MS based methods for this application, with detection limits in the pg note(-1) region, based upon a 20 microL standard injection. All of the notes examined tested positive for trace quantities of cocaine, with benzoylecgonine detected on 12 of the 45 notes sampled. Traces of heroin were also detected on three of the 45 notes.     

微束X射线荧光光谱分析技术在一种黑色纸张物证检验中的应用研究

对7种真假纸币样本和2003年～2008年的32宗诈骗案件中共计225件被染黑的真假纸币物证,采用微束X射线荧光光谱仪(micro-XRF)分析其二维元素分布.结果表明:纸币元素分布特征都具有特定性,相同面额相同年版的纸币元素分布特征相同,相同面额不同年版的纸币元素分布特征有差异;真假纸币元素分布特征存在显著差异;被染黑的纸币元素分布特征与原纸币相同;因而可根据被染黑真假纸币的元素分布特征,鉴定其真伪并判断纸币种类.微束XRF分析在实际案件中黑色纸张物证的检验准确率为100%.因此,微束XRF技术能有效检验被染料染黑的真假纸币,具有灵敏度高,分析过程中不破坏样品,结果准确的特点,在该类物证的检验中具有较高的应用价值.     

Field-amplified sample stacking capillary electrophoresis with electrochemiluminescence applied to the determination of illicit drugs on banknotes

Capillary electrophoresis (CE) with Ru(bpy)3(2+) electrochemiluminescence (ECL) detection system was established to the determination of contamination of banknotes with controlled drugs and a high efficiency on-column field-amplified sample stacking (FASS) technique was also optimized to increase the ECL intensity. The method was illustrated using heroin and cocaine, which are two typical and popular illicit drugs. Highest sample stacking was obtained when 0.01 mM acetic acid was chosen for sample dissolution with electrokinetical injection for 6 s at 17 kV. Under the optimized conditions: ECL detection at 1.2 V, separation voltage 10.0 kV, 20 mM phosphate-acetate (pH 7.2) as running buffer, 5 mM Ru(bpy)3(2+) with 50 mM phosphate-acetate (pH 7.2) in the detection cell, the standard curves were linear in the range of 7.50x10(-8) to 1.00x10(-5) M for heroin and 2.50x10(-7) to 1.00x10(-4) M for cocaine and detection limits of 50 nM for heroin and 60 nM for cocaine were achieved (S/N = 3), respectively. Relative standard derivations of the ECL intensity and the migration time were 3.50 and 0.51% for heroin and 4.44 and 0.12% for cocaine, respectively. The developed method was successfully applied to the determination of heroin and cocaine on illicit drug contaminated banknotes without any damage of the paper currency. A baseline resolution for heroin and cocaine was achieved within 6 min.     

Determination of cationic surfactants in pharmaceuticals based on competitive aggregation in ternary amphiphile mixtures

Since the introduction of the euro as the common currency in most of the countries of the European Union, the production of counterfeit banknotes has increased steadily. The European Central Bank has distributed information on a systematic procedure to distinguish genuine notes from counterfeits based on the look, feel and tilt of the notes. Counterfeits, however, have remained difficult to detect. In order to improve such detection, a procedure based on the analysis of several areas of euro notes using microscope ATR-infrared spectroscopy is proposed. This procedure is fast, robust and non-destructive and it can be applied in situ. The present study is focused on the denomination most frequently falsified, the 50€ note, but 100€ notes were also analysed. The inter- and intra-bank reproducibility of the original notes was also evaluated. Results indicate that characteristics of the spectra depend mainly on the area of the note studied and, furthermore, these characteristics do not change with the nominal value of the notes. Counterfeit banknotes were also analysed and were clearly distinguished from authentic notes in all cases. Unlike genuine notes, the spectra of fakes are the same in all areas of the note analysed.     

Effect of UV irradiation on detection of cocaine hydrochloride and crack vapors by IMIS and API-MS methods

Detection of drug vapors and volatile products of their decomposition is an important, and sometimes the only way to determine the presence of illegal drug traces at the surface of mail items, documents, hands and banknotes. This paper gives the results of experimental studies on the effect of UV irradiation on the sensitivity of a vapor phase detection of cocaine of different origin by a technology of ion mobility increment spectrometry (IMIS). It is shown that the influence of UV irradiation on the surface of cocaine hydrochloride and crack increases the amplitude of IMIS signals by about eight times. We analyzed ions emerged by photolysis of tested cocaine samples using mass-spectrometry with atmospheric pressure ionization (API-MS). The assumption is made about structural formula of volatile products of photolysis of crack and cocaine hydrochloride. By the results of API-MS and IMIS studies on photolysis of cocaine samples it is assumed that compound C₁₀H₁₅NO₃ with a molecular weight of 197 amu and ecgonidine methyl ester with a molecular weight of 181 amu are responsible for the increase of an amplitude of IMIS signals upon UV irradiation of samples of crack and cocaine hydrochloride.     

Validated, non-destructive and environmentally friendly determination of cocaine in euro bank notes

A non-destructive, fast and environmentally friendly procedure has been developed for cocaine determination in euro bank notes. Cocaine was extracted with 15 ml methanol by vortex agitation during 5 min. The extract was evaporated and reconstituted in 0.5 ml methanol. GC-MS-MS analysis was performed using as precursor ion m/z 182.2, with an excitation energy voltage of 1.60 eV, being the product ions measured m/z 150.2 and 82.0. A limit of detection of 0.15 ng per note and a repeatability of 6%, established from the relative standard deviation, of a 1 ng ml(-1) level, were achieved. Recoveries of 101+/-2 and 98+/-3% were obtained for samples spiked with 100 and 10 microg respectively. Results show that all the euro bank notes measured (16 samples) were contaminated with cocaine in the range between 1.25 and 889 microg. Two different contamination levels, high level (150-889 microg) and low one (1.25-77 microg) were found and it could be related with the direct or indirect contact with the drug.     

Determination of cocaine and methadone in urine samples by thin-film solid-phase microextraction and direct analysis in real time (DART) coupled with tandem mass spectrometry

The use of thin-film solid-phase microextraction (SPME) as the sampling preparation step before direct analysis in real time (DART) was evaluated for the determination of two prohibited doping substances, cocaine and methadone, in urine samples. Results showed that thin-film SPME improves the detectability of these compounds: signal-to-blank ratios of 5 (cocaine) and 13 (methadone) were obtained in the analysis of 0.5 ng/ml in human urine. Thin-film SPME also provides efficient sample cleanup, avoiding contamination of the ion source by salt residues from the urine samples. Extraction time was established in 10 min, thus providing relatively short analysis time and high throughput when combined with a 96-well shaker and coupled with DART technique.

Critical assessment of ionization patterns and applications of ambient desorption/ionization mass spectrometry using FAPA–MS

Ambient desorption/ionization mass spectrometry (MS) has gained growing interest during the last decade due to its high analytical performance and yet simplicity. Here, one of the recently developed ambient desorption/ionization MS sources, the flowing atmospheric‐pressure afterglow (FAPA) source, was investigated in detail regarding background ions and typical ionization patterns in the positive as well as the negative ion mode for a variety of compound classes, comprising alkanes, alcohols, aldehydes, ketones, carboxylic acids, organic peroxides and alkaloids. A broad range of signals for adducts and losses was found, besides the usually emphasized detection of quasimolecular ions, i.e. [M + H]⁺ and [M ? H]^? in the positive and the negative mode, respectively. It was found that FAPA–MS is best suited for polar analytes containing nitrogen and/or oxygen functionalities, e.g. carboxylic acids, with low molecular weights and relatively high vapor pressures. In addition, the source was used in proof‐of‐principle studies, illustrating the capabilities and limitations of the technique: Firstly, traces of cocaine were detected and unambiguously identified on euro banknotes using FAPA ionization in combination with tandem MS, suggesting a correlation between cocaine abundance and age of the banknote. Secondly, FAPA–MS was used for the identification of acidic marker compounds in organic aerosol samples, indicating yet‐undiscovered matrix and sample surface effects of ionization pathways in the afterglow region. Copyright © 2016 John Wiley & Sons, Ltd.     

Discrimination of almonds (Prunus dulcis) geographical origin by minerals and fatty acids profiling

Twenty-one almond samples from three different geographical origins (Sicily, Spain and California) were investigated by determining minerals and fatty acids compositions. Data were used to discriminate by chemometry almond origin by linear discriminant analysis. With respect to previous PCA profiling studies, this work provides a simpler analytical protocol for the identification of almonds geographical origin. Classification by using mineral contents data only was correct in 77% of the samples, while, by using fatty acid profiles, the percentages of samples correctly classified reached 82%. The coupling of mineral contents and fatty acid profiles lead to an increased efficiency of the classification with 87% of samples correctly classified.     

Genotyping using single nucleotide polymorphism, fluorescence spectroscopy and pattern recognition

This paper describes a method for genetic screening using single nucleotide polymorphism. Fluorescence spectra with an excitation frequency of 488 nm are recorded over a range of 550 to 660 nm of fragments of human DNA together with two fluorescent probe dyes attached to specific primers, one for each type of allele and a background dye, prepared using the Taqman reaction. The fluorescence spectra are monitored and principal components analysis used to separate spectra into three groups, which are visually identified as allele 1 (wild type), allele 2 (mutant) and mixed allele by comparison to reference samples. Malahanobis distance using 4 principal components are used to correctly classify samples into groups.     

Improved detectability with a polymer-based trapping device in rapid HPLC analysis for ultra-low levels of bisphenol A (BPA) in environmental samples.

A new high-performance liquid chromatography (HPLC) method has been developed to detect ultra-low concentrations of bisphenol-A (BPA) (below 1 ng/L (ppt)) using column switching electrochemical detection (ECD). The results were superior to those obtained from manual pretreatment procedure with membrane stationary phase. BPA is inherently ubiquitous in the environment, including tools and solvents used for its analysis; to obtain meaningful results, therefore, the concentration of the overall BPA contamination must be below the detection limit for BPA using the analytical system. Therefore, purified water for preparing the standard BPA solution must be filtered with a hydrophobic membrane to suppress BPA background levels of contamination. In addition, we investigated methods for effectively preserving environmental water containing BPA. The addition of a small amount of ethylenediaminetetraacetic acid (EDTA) provided good recovery even after overnight storage. By employing these precautionary measures and procedures to reduce BPA contamination from the analytical procedure, we could accurately determine l(-10) ppt of BPA in environmental water samples using a column switching HPLC system.     

Screening of microdialysates taken before and after induced liver damage; on-line solid phase extraction-electrospray ionization-mass spectrometry

A novel method is described to follow known and unknown compounds in biological processes using microdialysis sampling and mass spectrometric detection. By implementation of internal standard, desalting/enrichment for the sample work-up, and multivariate data analysis, this methodology is a basis for future applications in early diagnosis of diseases and organ damage, as a complement to the routinely used clinical methods for biological samples. The present study includes screening without specific target analytes, of samples collected by microdialysis from liver of anaesthetized rats before and after local damage to this organ. Sample series were classified by principal component analysis, and the stimulation was identified in the chemical patterns produced by the presented analytical tool.     

Application of instrumental neutron activation analysis to study ceramic fragments from Damascus Castle site,Syria

Summary Thirty-three archaeological ceramic fragment samples from Damascus Castle archaeological site, Damascus city, Syria, were analyzed using instrumental neutron activation analysis (INAA). 36 elements were determined. These elemental concentrations have been processed using two multivariate statistical methods, cluster and factor analysis in order to determine similarities and correlation between the various samples. Factor analysis confirms that 84.8% of the ceramics samples classified by cluster analysis are correctly classified by cluster analysis. The results provided persuasive evidence that Castle pottery used at least four different clay sources. Moreover, by means of systematic local analysis it will be clear whether these sources are local or not.     

Differentiation of two main ammunition brands in Chile by Regularized Discriminant Analysis (RDA) of metals in gunshot residues

Conventionally, chemical patterns of gunshot residues (GSR) can be used for identification of a suspect involved in criminal fire arm incidents. Furthermore, metals composition in GSR is well related with the ammunition brand. In Chile the two main ammunition brands used are FAMAE and CBC. Metals, such as Pb, Ba, Sb, Cu, Zn and Ca are common elements detected in both brands. This work describes the application of both conventional and chemometric analysis of data (Regularized Discriminant Analysis, RDA) for differentiation of ammunition brands according to the metal patterns of GSR collected from shooter individuals. Real samples of GSR were collected from hands (dorsal region) of both shooters and non-shooters. Metals were analyzed using the techniques Atomic Absorption Spectrometry (AAS) and Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-OES). By means of conventional plotting techniques for differentiation, such as binary and ternary plots, differences between the two brands are observed although without quantitative certainty. For the first time, applying chemometric analysis, such as regularized discriminant analysis (RDA), the investigated ammunition brands can be classified and differentiated correctly with 100% certainty.     

MALDI-ToF mass spectrometry–multivariate data analysis as a tool for classification of reactivation and non-culturable states of bacteria

Some bacterial life states are only difficult to describe and to detect because they are on the border of active metabolism. A prominent example is the so-called viable but non-culturable state, which is mainly characterized by the inability of bacteria to grow on synthetic media. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-ToF/MS) in combination with multivariate data analysis represents a powerful tool for mass-spectrometric pattern recognition of biological samples. This method is already used for differentiation of bacterial strains. In this study we present a rapid readout method based on MALDI-ToF/MS in combination with principal component analysis to classify the bacterial non-culturable state using Enterococcus faecalis as a model organism. By applying this technique to samples of different physiological states, distinct clusters were calculated and all mass spectra were classified correctly into groups of similar type concerning their physiological state.     

Combining visible and near-infrared spectroscopy with chemometrics to trace muscles from an autochthonous breed of pig produced in Uruguay: a feasibility study

Visible (Vis) and near-infrared reflectance (NIR) spectroscopy combined with chemometrics was explored as a tool to trace muscles from autochthonous and crossbreed pigs from Uruguay. Muscles were sourced from two breeds, namely, the Pampa-Rocha (PR) and the Pampa-Rocha x Duroc (PRxD) crossbreed. Minced muscles were scanned in the Vis and NIR regions (400–2,500 nm) in a monochromator instrument in reflectance. Principal component analysis (PCA), discriminant partial least square regression (DPLS), linear discriminant analysis (LDA) based on PCA scores and soft independent modelling of class analogy (SIMCA) were used to identify the origin of the muscles based on Vis and NIR data. Full cross validation was used as validation method when classification models were developed. DPLS correctly classified 87% of PR and 78% of PRxD muscle samples. LDA calibration models correctly classified 87 and 67% of muscles as PR and PRxD, respectively. SIMCA correctly classified 100% of PR muscles. The results demonstrated the usefulness of Vis and NIR spectra combined with chemometrics as rapid method for authentication and identification of muscles according to the breed of pig.     

表面解吸常压化学电离质谱法直接测定火锅底料中的痕量可卡因

采用表面解吸常压化学电离(SDAPCI)质谱法, 在无需样品预处理情况下, 直接测定了火锅底料中可卡因的含量. 采用取样针取样, 单次取样量在纳升级, 单个样品测定时间少于0.5 min, 回收率为92.9%～106.6%; 相对标准偏差(RSD)为4.7%～11.6%; 可卡因的检出限可达1.5×10-12 g/mL. 该方法适用于批量火锅底料等食品类样品的快速半定量检测.