Field-portable detection of fentanyl and its analogs: A review

The need to detect fentanyl and its analogs in the field is an important capability to help prevent unintentional exposure or overdose on these substances, which may result in death. Many portable methods historically used in the field by first responders and other field users to detect and identify other chemical substances, such as hazardous materials, have been applied to the detection and identification of these synthetic opioids. This paper describes field portable spectroscopic methods used for the detection and identification of fentanyl and its analogs. The methods described are automated colorimetric tests including lateral flow assays; vibrational spectroscopy (mid-infrared and Raman); gas chromatography–mass spectrometry; ion mobility spectrometry, and high-pressure mass spectrometry. In each case the background and key details of these technologies are outlined, followed by a discussion of the application of the technology in the field. Attention is paid to the analysis of complex mixtures and limits of detection, including the required spectral databases and algorithms used to interrogate these types of samples. There is also an emphasis on providing actionable information to the (likely) non-scientist operators of these instruments in the field.     

Model verification for population detection of counterfeits

The quality of counterfeit items has increased dramatically, with modern global manufacturing being able to duplicate the materials, construction, and visual features of items. Detection of fraudulent coinage can parallel authentication of food, beverages, and manufactured goods by studying product-inherent features. Counterfeit detection is performed by comparing an Example group with a Questioned group. A model is developed for both groups using standard tests on individual pieces. Coin weight is used here as an illustration. The model should also follow the natural science of the system. In this case, the manufacturing process variation is known and steady, and the underlying distribution is known or can be determined from authentic pieces. The proposed detection method uses testing of many individual pieces, then using reverse-quality-engineering methods to identify possible sources. This strategy looks at the variation between individual pieces to determine the process capability of a machine, assembly line, or plant to create product consistency for a manufacturer. Fraudulent items may be manufactured within specification, but demonstrate a manufacturing process capability different than that of the authentic manufacturer. In this report, we examine the model previously reported and use reconstruction techniques to re-create the evidence set to validate the model, increase model accuracy, and confirm the conclusion previously reached, showing that the Questioned set is likely over 37% non-conforming by weight. In this case, the decision outcome of the analysis was improved by using additional methods not included in the modeling software package originally used.     

Intentional overdose of glargine insulin: Determination of the parent compound in postmortem blood by LC-HRMS

Insulin glargine is a long-acting insulin analog that is converted after enzymatic cleavage of the arginine pair of the β-chain into its main metabolite M1 (21^A-Gly-insulin), which is responsible for the hypoglycemic activity. In all the overdose cases described in the literature, only M1 concentrations have been reported, whereas insulin glargine was always absent or below the limit of quantitation. In this study, we present a case of suicide of a young nurse by injection of insulin glargine in which the parent molecule was found at a toxic concentration in blood. The determination and the discrimination of insulin glargine from human insulin and other synthetic analogs in the blood specimen were performed by liquid chromatography coupled to high-resolution mass spectrometry (Waters XEVO G2-XS QToF) and extraction after precipitation in the presence of bovine insulin (internal standard), with a mixture of acetonitrile/methanol +1% formic acid followed by purification on solid phase extraction cartridges C18. Glargine insulin tested highly positive in the blood with a concentration of 1.06 mg/L. Due to the difficulty in obtaining a M1 pure standard, the metabolite could not be dosed. This unique presence of the parent molecule, reported for the first time, can be explained by inter-individual variability in the rate of conversion to metabolite. Intravenous injection versus subcutaneous injection can also explain the presence of insulin glargine. Finally, the dose injected may have been so high that saturation of the proteolytic enzymes responsible for conversion to M1 should have occurred.     

Can latent fingerprint disclose the sex of the donor? A preliminary test study using GC–MS analysis of latent fingerprints

While fingerprints are a highly used means of identification, not every fingerprint left behind on a potential crime scene can be used for identification purposes. In some cases, the fingerprint may be smudged, partially preserved or overlapping with other prints hence distorting the ridge pattern and may therefore be not appropriate for identification. Further, fingermark residue yields a very low abundance of genetic material for DNA analysis. In such cases, the fingermark may be used to retrieve basic donor information such as sex. The focus of this paper was to assess the possibility of differentiating between the sexes of the donor of latent fingermarks. Analytical method was GC–MS analysis of the chemical compounds of latent fingermarks using 22 male and 22 female donors. Results showed 44 identified compounds. Two alcohols, octadecanol C₁₈ and eicosanol C₂₀, were found to show a difference that was statistically significant between male and female donors. There is also some evidence for the possibility of distinguishing sex of the fingermark donor based on the distribution of branched chain fatty acids, as free compounds or esterified in wax esters.     

Delayed elimination in humans after ingestion of colchicine: Two fatal cases of colchicine poisoning

Colchicine has been widely used in the treatment of acute gout over the years, but it has a narrow therapeutic index, and overdose can be life threatening. A method using ultra-high-performance liquid chromatography–tandem mass spectrometry system was applied in two fatal cases of colchicine poisoning in this study to the determination of colchicine in blood. In case 1, a 19-year-old man suffered from depression and ingested 160 colchicine tablets (each 0.5 mg). The concentration of colchicine in his blood samples showed a fluctuating trend and kept above the therapeutic steady-state concentration for 5 days. In case 2, a 70-year-old female patient with a history of gout and chronic colchicine intake ingested five times the usual dose of colchicine (5 mg) and died after 12 days of medical care, with 5 ng/mL of colchicine in her blood sample. Our findings suggest that the delayed elimination and accumulation in humans after colchicine overdose could keep the concentration of colchicine maintaining above the therapeutic steady-state concentration for many days before dying, probably along with a fluctuating trend.     

Research on detection techniques for pattern modifications of playing cards used in illegal gambling operations

We investigated pattern-modified marked cards used in fraudulent gambling cases in Korea. These cards are printed with modifications to some of the repeated marks on the back, revealing the hand on the front and enabling fraudsters to deceive their victims. We proposed a method for identifying the modified part by first enhancing the card's color difference using an image processing technique and then calculating the similarity between the repeated basic patterns with a Siamese network. This method is fast and convenient, as it can determine the deformation with only 1 or 2 cards and can be implemented in mobile applications, allowing law enforcement officers to investigate quickly. The proposed method serves as a useful tool to aid document examiners in making judgments, as it does not require expensive equipment and effectively visualizes the alterations.     

Rapid enantiomeric analysis of zopiclone in serum by supercritical fluid chromatography–tandem mass spectrometry

Zopiclone (ZOP) is a hypnotic drug prescribed to treat insomnia. Due to the chiral nature of ZOP, the psychologically active S-form and inactive R-form need to be determined enantiomerically in a forensic drug analysis. In the present study, a supercritical fluid chromatography (SFC) method was designed with a faster analysis ability than that of previously reported techniques. The SFC–tandem mass spectrometry (SFC–MS/MS) method was optimized using a column with a chiral polysaccharide stationary phase (Trefoil CEL2). ZOP was extracted from pooled human serum using solid-phase extraction (Oasis HLB) and analyzed. The developed SFC–MS/MS method achieved the baseline separation of S-ZOP and R-ZOP within 2 min. The fit-for-purpose method validation indicated that the optimized solid-phase extraction achieved near complete recovery and approximately 70% of the matrix effect. Both the retention time and peak area showed sufficient precision. The lower and upper limits of quantification (LOQ) were 5.7 × 10⁻² ng/mL and 25 ng/mL for R-ZOP, and 5.2 × 10⁻² ng/mL and 25 ng/mL for S-ZOP. The calibration line was linear in the range from lower LOQ to upper LOQ. The stability test indicated that ZOP in serum stored in a refrigerator (4°C) degraded and about 55% remained in 31 days. The quick analysis of the SFC–MS/MS method makes it a valid option for the enantiomeric analysis of ZOP.     

Palynology and mycology as biological evidence in a homicide case

Criminal cases are studied from several disciplines to link a suspect with a criminal act. In this case, a man was reported missing in a coastal area in Buenos Aires Province, Argentina. The victim's relatives pointed to a possible suspect, and the local police carried out the investigation. We contributed to this research by applying palynological and mycological techniques. Palynomorphs and fungal spores offer valuable trace evidence, as they can be easily transferred between objects and crime scenes due to their minute size and persist on them for a long time. The victim was found 25 days later, lying on sandy soil, which partially covered the body, 35 km from where the suspect was arrested. Comparative samples were collected from the crime scene and the suspect's home and belongings (clothes, footwear, and seized vehicle). The palynological associations obtained from the crime scene and the defendant's belongings were dominated by diatoms and acritarchs (Acantomorphitae), all elements of marine origin, and a high CFU number of Bipolaris cynodontis, which allowed the defendant's clothing to be related to the place of corpse discovery. Soil from the defendant's home had an entirely continental composition, and the fungal biota was characteristic of prairie areas which were different from those of the crime scene.     

Shedder status—An analysis over time and assessment of various contributing factors

The shedder status of a person is an important consideration when evaluating probabilities of DNA transfer during activity-level assessments. As an extension of our previously published study, the shedder statuses of 38 individuals were reassessed 1 year later. The study found that shedder status may change over time for some individuals and was associated with one's gender, number of items touched, and mobile phone usage. In 29% of touch events, no DNA allele was detected and in 99% of touch events, the amount of DNA deposited was <2 ng. The study also found that in 0.6% of touch events, the participant could be excluded as a contributor of the observed DNA profile, with another person being included. Additionally, our investigations suggest that the current three-category system for shedder status classification may require further refinement to better represent the individuals' shedder status in a population.