Detection of Mitragynine in Mitragyna Speciosa (Kratom) Using Surface-Enhanced Raman Spectroscopy with Handheld Devices

A simple, quick, selective, sensitive, and effective field-friendly method capable of being used by nonexperts has been developed for detecting mitragynine in Mitragyna speciosa (kratom) using surface-enhanced Raman spectroscopy (SERS). Over 100 samples and blanks (known to be either positive or negative for the presence of mitragynine) were examined in duplicate using five identical handheld Raman spectrometers, which provided a data set of over 1,000 examinations. Based on the results of these analyses, the method yielded a true-positive rate of 99.3%, a true-negative rate of 97.9%, a false-positive rate of 2.1%, and a false-negative rate of 0.7%. The average minimum detectable concentration (C_m) of mitragynine that reproducibly yielded a match for one of the library spectra on all five instruments was determined to be 342 ng/mL (ppb). This C_m value is a conservative estimate considering that the extraction process was not fully optimized by this study, which was not necessary since the C_m value achieved was well below typical mitragynine concentrations in kratom (1.3–2.3%). The method is ideal (i) for prioritizing samples for additional testing using other more time-consuming laboratory-based techniques needed to detect and quantify mitragynine and (ii) for field use at international mail facility (IMF) satellite laboratories to help interdict kratom and prevent this dangerous product from reaching the U.S. supply chain.     

Chemical Imaging of Human Fingermark by X-ray Photoelectron Spectroscopy (XPS)

X-ray photoelectron spectroscopy (XPS) is a widely used technique to characterize the surface chemistry of materials. It plays a crucial role in accessing qualitative and quantitative information and in detecting the presence of chemical functional groups on the surface of any material. The forensic methods available to detect and identify elements and organic/inorganic compounds are often destructive, so evidence cannot be re-analyzed. However, XPS allows rapid analysis of samples without damaging them. Recently, an increasing number of forensic researchers have begun to study certain chemical information on fingermarks. In this study, the authors aimed to present the applicability and power of XPS imaging in fingermark analysis which can also provide specific information about the fingermark chemical composition. Herein, monochromated X-ray (Al Kα) spot size was fixed at 50 μm. XPS mapping resulted in the acquisition of spectra at each pixel, in an array of 41 × 30 pixels with a step size of 50 μm. Then, a simple discussion has been made about how the scanned surface spectrum and basic snapshot spectra are used to identify different components at a fingertip of a scanned surface area (~3 mm²). Hence, a fingermark pattern contaminated with caffeine, TiO₂, and Pb/PbO deposited on the silicon wafer can be chemically mapped and visualized by XPS using principal component analysis (PCA). Thus, the present study showed the possible applicability of XPS for the identification of illicit drugs of abuse, gunshot residue, and skin care products on latent fingermark by mimicking a crime scene evidence.     

Volatile Organic Compound Profiling from Postmortem Microbes using Gas Chromatography–Mass Spectrometry

Volatile organic compounds (VOCs) are by-products of cadaveric decomposition and are responsible for the odor associated with decomposing remains. The direct link between VOC production and individual postmortem microbes has not been well characterized experimentally. The purpose of this study was to profile VOCs released from three postmortem bacterial isolates (Bacillus subtilis, Ignatzschineria indica, I. ureiclastica) using solid-phase microextraction arrow (SPME Arrow) and gas chromatography–mass spectrometry (GC-MS). Species were inoculated in headspace vials on Standard Nutrient Agar and monitored over 5 days at 24°C. Each species exhibited a different VOC profile that included common decomposition VOCs. VOCs exhibited upward or downward temporal trends over time. Ignatzschineria indica produced a large amount of dimethyldisulfide. Other compounds of interest included alcohols, aldehydes, aromatics, and ketones. This provides foundational data to link decomposition odor with specific postmortem microbes to improve understanding of underlying mechanisms for decomposition VOC production.     

Evaluation of Suspected Counterfeit Pharmaceutical Tablets Declared to Contain Controlled Substances Using Handheld Raman Spectrometers

This study describes the performance of handheld Raman devices for determining whether suspect pharmaceutical tablets declared to contain controlled substances were consistent with authentic (CWA) or not consistent with authentic (NCWA) tablets using a simple, rapid, field-friendly method capable of being used by nonexperts. Twenty-five authentic products and 84 known NCWA tablets were examined using three “parent” devices for a total of 327 analyses. On average, the parent devices yielded a true pass rate of 100%, a true fail rate of 98.4%, a false pass rate of 1.6%, and a false fail rate of 0%. The methods/libraries were then transferred to 13 identical “daughter” devices, which were used to examine 10 suspect finished dosage forms in duplicate (six known NCWA tablets and four authentic tablets) for a total of 260 measurements. On average, the daughter devices had a true pass rate of 100%, a true fail rate of 95.5%, a false pass rate of 4.5%, and a false fail rate of 0.0%. These data demonstrate that the parent–daughter electronic transfer method was successful, which permits the ability to develop methods in the laboratory that can be seamlessly pushed out to field devices. The methods can then be used to (i) prioritize samples for additional testing using other more time-consuming laboratory-based techniques needed to detect and quantify active ingredients and (ii) help support the interdiction of dangerous tablets at ports of entry, thereby preventing them from reaching the supply chain.     

天然药物化学课程教学方法的探讨

随着当前对天然药物开发研究的不断深入,天然药物化学课程的重要性也越来越受到重视。而传统的天然药物化学教学方式多为教师讲授,学生被动地听、甚至靠死记硬背,学生的学习兴趣没有得到激发,效率不高,普遍反映枯燥难学。因而全面提高天然药物化学的学习水平和教学质量具有重要意义。为此,作者结合自己的教学经验谈一些感受。     

园林有害生物化学防治的冷思考

针对当前国内植物保护各领域,尤其是园林绿化植物保护在化学防治中存在的主要问题,理性地审视化学防治的功能定位和利弊,辨析一些模糊概念,从技术层面求得对农药使用规范化的认知和认同.     

Understanding Variations of Soil Mapping Units and Associated Data for Forensic Science

Soil samples have potential to be useful in forensic investigations, but their utility may be limited due to the inherent variability of soil properties, the wide array of analytical methods, and complexity of data analysis. This study examined the differentiation of similar soils based on both gross (texture, color, mineralogy) and explicit soil properties (elemental composition, cation exchange, Fe‐oxyhydroxides). Soils were collected from Fallbrook and adjacent map units from Riverside and San Diego Counties in California. Samples were characterized using multiple techniques, including chemical extracts, X‐ray diffraction (XRD), and Fourier transform infrared spectroscopy. Results were analyzed using multiple analytical approaches to compare counties and land uses. Some analyses (XRD, extractions) were better at distinguishing among samples than others (color, texture). Ratios of rare earth elements were particularly useful for distinguishing samples between counties. This potential to “fingerprint” soils illustrates the usefulness of a comprehensive soil database for criminal investigators.     

GC–MS studies on acylated derivatives of 3-methoxy-4-methyl- and 4-methoxy-3-methyl-phenethylamines: Regioisomers related to 3,4-MDMA

A series of side chain regioisomers of 3-methoxy-4-methyl- and 4-methoxy-4-methyl-phenethylamines have mass spectra essentially equivalent to the controlled drug substance 3,4-methylenedioxymethamphetamine (3,4-MDMA), all have molecular weight of 193 and major fragment ions in their electron ionization mass spectra at m/z 58 and 135/136. The acetyl, propionyl and trifluoroacetyl derivatives of the primary and secondary regioisomeric amines were prepared and evaluated in GC–MS studies. The mass spectra for these derivatives were significantly individualized and the resulting unique fragment ions allowed for specific side chain identification. The trifluoroacetyl derivatives provided more fragment ions for molecular individualization among these regioisomeric substances. These trifluoroacetyl derivatives showed excellent resolution on a non-polar stationary phase such as Rtx-1.     

Fatal bromethalin poisoning

Bromethalin is a neurotoxin found in some rodenticides. A delusional 21-year-old male presented to a hospital with altered mental status the day after ingesting a bromethalin-based rodenticide. He died 7 days after his self-reported exposure to c. 17 mg bromethalin (equivalent to 0.33 mg bromethalin/kg). His clinicopathologic course was characterized by altered mental status, obtundation, increased cerebrospinal fluid pressure, cerebral edema, death, and diffuse histologic vacuolization of the white matter in the central nervous system seen on microscopic examination at autopsy. The presence of a demethylated form of bromethalin in the patient's liver and brain was confirmed by gas chromatography with mass spectrometry. Clinical signs and lesions observed in this patient are similar to those seen in animals poisoned with bromethalin. This case illustrates the potential for bromethalin ingestion to result in fatal human poisoning.     

Bank security dye packs: synthesis, isolation, and characterization of chlorinated products of bleached 1-(methylamino)anthraquinone

Banknote evidence is often submitted after a suspect has attempted to disguise or remove red dye stain that has been released because of an anti-theft device that activates after banknotes have been unlawfully removed from bank premises. Three chlorinated compounds have been synthesized as forensic chemical standards to indicate bank security dye bleaching as a suspect's intentional method for masking a robbery involving dye pack release on banknotes. A novel, facile synthetic method to provide three chlorinated derivatives of 1-(methylamino)anthraquinone (MAAQ) is presented. The synthetic route involved Ultra Clorox bleach as the chlorine source, iron chloride as the catalyst, and MAAQ as the starting material and resulted in a three-component product mixture. Two mono-chlorinated isomers (2-chloro-1-(methylamino)anthraquinone and 4-chloro-1-(methylamino)anthraquinone) and one di-chlorinated compound (2,4-dichloro-1-(methylamino)anthraquinone) of the MAAQ parent molecule were detected by gas chromatography mass spectrometry (GC-MS), and subsequently isolated by liquid chromatography (LC) with postcolumn fraction collection. Although GC-MS is sensitive enough to detect all of the chlorinated products, it is not definitive enough to identify the structural isomers. Liquid-state nuclear magnetic resonance (NMR) spectroscopy was utilized to elucidate structurally the ortho- and para-mono-chlorinated isomers once enough material was properly isolated. A reaction mechanism involving iron is proposed to explain the presence of chlorinated MAAQ species on stolen banknotes after attempted bleaching.