N-cyanomethyl-N-methyl-1-(3',4'-methylenedioxyphenyl)-2-propylamine: an MDMA manufacturing by-product

This paper describes the structural elucidation of a compound produced during the synthesis of 3,4-methylenedioxymethylamphetamine (MDMA) via the reductive amination of 3,4-methylenedioxyphenyl-2-propanone (3,4-MDP-2-P) with methylamine and sodium cyanoborohydride. The compound was isolated from MDMA by column chromatography, proton and carbon nuclear magnetic resonance spectroscopy, LC/mass spectrometry, and total synthesis were used to identify the compound as N-cyanomethyl-N-methyl-1-(3',4'-methylenedioxyphenyl)-2-propylamine. This compound has been identified as a potential synthetic route marker for the reductive amination of 3,4-MDP-2-P with methylamine and sodium cyanoborohydride and as such it should prove valuable to forensic scientists engaged in profiling illicit drugs. Profiling MDMA can provide useful information to law enforcement agencies relating to synthetic route, precursor chemicals and reagents employed and may be used for comparative analyses of different drug seizures. This paper also describes the structural elucidation of the analogous methylamphetamine synthetic route marker compound, N-cyanomethyl-N-methyl-1-phenyl-2-propylamine, produced during the reductive amination of phenyl-2-propanone using methylamine and sodium cyanoborohydride.     

Isolation and Identification of Three By‐products Found in Methylamphetamine Synthesized by the Emde Route

This article describes the isolation and structural elucidation of three compounds produced during the synthesis of methylamphetamine by the so‐called “Emde” procedure. The “Emde” procedure involves the preparation of the intermediate chloropseudoephedrine or chloroephedrine from ephedrine or pseudoephedrine, respectively. The intermediates are then reduced to methylamphetamine with hydrogen under pressure in the presence of a catalyst. The by‐product compounds were isolated from methylamphetamine by column chromatography and liquid chromatography (LC). Proton nuclear magnetic resonance spectroscopy (¹H NMR), carbon nuclear magnetic resonance spectroscopy (¹³C NMR), and nanospray quadrupole‐time of flight‐mass spectrometry (Q‐TOF‐MS) were used to identify them as two stereoisomers of the compound N, N′‐dimethyl‐3,4‐diphenylhexane‐2,5‐diamine and N‐methyl‐1‐{4‐[2‐(methylamino)propyl]phenyl}‐1‐phenylpropan‐2‐amine.     

Blunt Craniofacial Trauma as a Manifestation of Excited Delirium Caused by New Psychoactive Substances

The body of a 19‐year‐old male was found apparently concealed underneath bushes with recent head and facial trauma, and multiple superficial abrasions. Subsequently, it was discovered that the decedent had been running into objects and buildings following the ingestion the evening before of what was thought to be lysergic acid diethylamide (LSD). Blood staining of a nearby wall close to where the body was lying was in keeping with the described behavior. Toxicology revealed 3,4‐methylenedioxymethamphetamine (Ecstasy), in addition to two only recently available drugs 2‐(4‐bromo‐2,5‐dimethoxyphenyl)‐N‐[(2‐methoxyphenyl)methyl]ethanamine, (25B‐NBOMe), and 1‐(3,4‐methylenedioxyphenyl)‐2‐(1‐pyrrolidinyl)‐1‐butanone, (MDPBP). At autopsy, the skull was fractured with cerebral swelling, contusions, and subarachnoid hemorrhage. Death was due to blunt cranial trauma against a background of mixed drug toxicity. The case demonstrates a rare cause of death in a drug‐induced acute delirium, as well as highlighting two new designer street drugs that may result in significant aberrant behavior.     

Identification of 2‐(ethylamino)‐1‐(4‐methylphenyl)‐1‐pentanone (4‐MEAP), a New “Legal High” Sold by an Internet Vendor as 4‐Methyl Pentedrone

Online vendors are offering a new legal high, 4‐methylpentedrone (4‐MPD). Information for potential users provided by internet vendors of 4‐MPD includes incorrect structures and nonexistent CAS numbers. A sample of 4‐MPD was obtained and analyzed using GC‐MS, NMR, and LC‐EIS. The fragmentation data from the GC‐MS and LC‐EIS produced an M‐1 ion that suggested the molecular mass was 219 amu, rather than 205 amu as calculated for 4‐methylpentedrone. The difference in molecular mass corresponded to the addition of a methyl group. Based on the mass and fragmentation pattern, two standards were synthesized, 2‐(ethylamino)‐1‐(4‐methylphenyl)‐1‐pentanone and 1‐(4‐methylphenyl)‐2‐(propylamino)‐1‐butanone. The synthesis involved bromination of the appropriate ketone followed by the reaction with ethylamine or propylamine. Based on the NMR data and unique fragmentation patterns produced by these molecules, the sample was identified as 2‐(ethylamino)‐1‐(4‐methylphenyl)‐1‐pentanone, not 4‐methylpentedrone.     

A quantitative method for simultaneous determination of 5-methoxy-N,N-diisopropyltryptamine and its metabolites in urine using liquid chromatography-electrospray ionization-tandem mass spectrometry

5-Methoxy-N,N-diisopropyltryptamine (5-MeO-DIPT) is a designer hallucinogen derived from tryptamine and is reportedly abused and involved in criminal activities. For the detection of 5-MeO-DIPT use, a liquid chromatography-tandem mass spectrometric method for 5-MeO-DIPT and its metabolites, 5-hydroxy-N,N-diisopropyltryptamine (5-OH-DIPT) and 5-methoxy-N,N-isopropyltryptamine (5-MeO-IPT) was developed and validated in rat urine. The urine samples were pretreated by protein precipitation with acetonitrile and introduced into a BDS HYPERSIL C(18) column (50 × 2.0 mm, 5 μm) for chromatographic separation. Mobile phases consisted of methanol, water, and 1% formic acid, and gradient elution was used at a flow rate of 0.2 mL/min. For the MS detection, multiple-reaction monitoring analysis was adopted. The linear range was 0.01-10 μg/mL, and the lower limit of quantification was 10 ng/mL for all analytes. The intra- and interday accuracies and precisions met the criteria (<15%). The developed method was successfully applied to the drug-treated rat urine.     

Experimental Study on the Postmortem Redistribution of the Substituted Phenethylamine, 25B‐NBOMe

2‐(4‐Bromo‐2,5‐dimethoxyphenyl)‐N‐(2‐methoxybenzyl)ethanamine (25B‐NBOMe) is a substituted phenethylamine, which has become highly prevalent worldwide since 2014. Recently, in an autopsy case involving fatal 25B‐NBOMe intoxication, we found the postmortem increase of 25B‐NBOMe concentration in the cardiac blood approximately 2 days after death. The aim of this study was to investigate the distribution of 25B‐NBOMe and reproduce the postmortem redistribution using a rat model. Sprague‐Dawley rats were killed 30 min after intraperitoneal injection of 25B‐NBOMe (0.5 mg/kg) and left for 0, 3, 6, 9, 15, or 24 h (six rats at each time point). Postmortem 25B‐NBOMe concentrations in the cardiac blood increased by more than 10‐fold at 6‐h postmortem. 25B‐NBOMe accumulated primarily in the lung. Moreover, this postmortem redistribution occurred even in rats that had died 1 week following the 25B‐NBOMe administration. These findings indicate that attention should be paid to sample collection and data interpretation in the toxicological analysis of 25B‐NBOMe.     

Perceptions of Remote and Walk‐In Service Delivery in Family Law Cases

In recent years, the number of litigants representing themselves without legal counsel has increased across the United States. Courts have responded by creating programs and services to help litigants represent themselves. Self‐help centers nationwide use different models to deliver legal advice and information to unrepresented litigants. Some offer court‐based, walk‐in self‐help centers. Others provide services remotely via phone, web, email, video conferencing, and live chat. In Maryland, self‐help center services are offered at walk‐in centers and remotely by phone and live chat. This article examines litigants' perceptions of in‐person and remote delivery of legal advice and information on family law matters. Results revealed that all three service delivery methods have high satisfaction rates, but chat users were less likely to feel as though they knew what to do next. They were also less optimistic about their case than were phone or in‐person users.     

Development of impulsivity and risk‐seeking: Implications for the dimensionality and stability of self‐control*

In Gottfredson and Hirschi's self‐control theory, introduced in 1990, they contend that self‐control is a unidimensional construct that develops early in childhood and remains stable throughout the life span. According to findings reported in recent research, however, these arguments are now being challenged, with scholars pointing to ways in which self‐control may be multidimensional in nature and may change beyond the period of alleged stabilization. In this study, we draw on Steinberg's dual systems model, introduced in 2008, to consider this issue further. We examine that model's two key elements of low self‐control—risk‐seeking and impulsivity—to determine whether they are empirically distinguishable from one another and have differing developmental trajectories from childhood to early adulthood. We also consider the consequences of changes in risk‐seeking and impulsivity for within‐individual changes in crime. We examine these issues with data from the National Longitudinal Survey of Youth 1979 (NLSY79) for individuals from 10 to 30 years old. The results of our analyses show support for a multidimensional and dynamic conception of self‐control—from age 10 to age 30, risk‐seeking and impulsivity are empirically distinct and develop in divergent ways that are consistent with the dual systems model. Changes in risk‐seeking and impulsivity also affect changes in crime, but their effects vary with age and changes in the other element. We discuss these findings and their implications for self‐control and the development of life‐course criminology.     

Delirium Due to Intoxication from the Novel Synthetic Tryptamine 5‐MeO‐DALT

Synthetic tryptamines have gained popularity for their hallucinogenic properties, unscheduled status, and availability from “head shops” and through the internet. Here, we present a case of synthetic tryptamine‐induced delirium secondary to 5‐MeO‐DALT ingestion in a previously healthy young male. 5‐MeO‐DALT led to the hospitalization of our patient after ingestion of a standard dose, presenting with extreme agitation, tachycardia, diaphoresis, and combativeness leading to physical restraint and intravenous sedation. A search of PubMed, Ovid, and Google Scholar for keywords of “5‐MeO‐DALT,” “5‐methoxy‐N,N‐diallyltryptamine,” or “Lucy‐N‐Nate” found no case reports or clinical articles in the literature. Rapid emergence and commercialization of this novel synthetic tryptamine 5‐MeO‐DALT points to the importance of health care and forensic professionals keeping abreast of the latest drugs of abuse and their clinical features. The authors hope this report leads the way in disseminating the potential risks associated with unscheduled and unregulated substances, synthetic tryptamines such as 5‐MeO‐DALT in particular.     

The Class Characteristic Mark of the H&M Mul‐T‐Lock Picking Tool in Toolmarks Examination

Mul‐T‐Lock is a high security lock cylinder distinguished by the use of a telescoping “pin‐in‐pin”—tumbler design. Picking the Mul‐T‐Lock cylinder with a traditional picking tool is highly complicated because it can get stuck between the inner and outer pins. The H&M Mul‐T‐Lock picking tool was designed to overcome this problem and facilitate the picking of the “pin‐in‐pin” cylinder. The purpose of this research is to determine whether H&M Mul‐T‐Lock picking tool leaves class characteristic mark and whether it can be distinguished from traditional picking tools marks and from regular key marks. It also describes and determines the class characteristic mark left on telescopic pins, its origin, recurrence, and its benefit to the toolmarks examiner. When receiving a Mul‐T‐Lock from a crime scene, a toolmarks examiner can quickly determine whether or not it was picked by an H&M Mul‐T‐Lock picking tool by noticing the class characteristic mark which this typical tool leaves.     

SELF‐CONTROL AND VICTIMIZATION: A META‐ANALYSIS

A consequential development in victimization theory and research was the idea that individuals with low self‐control self‐select into the various risky behaviors that may ultimately result in their victimization. To establish the empirical status of the self‐control–victimization link, we subjected this body of work to a meta‐analysis. Our multilevel analyses of 311 effect size estimates drawn from 66 studies (42 independent data sets) indicate that self‐control is a modest yet consistent predictor of victimization. The results also show that the effect of self‐control is significantly stronger when predicting noncontact forms of victimization (e.g., online victimization) and is significantly reduced in studies that control directly for the risky behaviors that are assumed to mediate the self‐control–victimization link. We also note that the studies assessing self‐control and victimization are not representative of victimization research as a whole, with intimate partner violence (IPV), violence against women, and child abuse being severely underrepresented. We conclude that future research should continue to examine the causal processes linking self‐control to victimization, how self‐control shapes victims’ coping responses to their experience, and whether self‐control matters in contexts where individuals may have limited autonomy over the behavioral routines that put them at risk for victimization.     

TOWARD THE DIFFERENTIATION OF HIGH‐CONFLICT FAMILIES: AN ANALYSIS OF SOCIAL SCIENCE RESEARCH AND CANADIAN CASE LAW

Social science research and the courts have begun to recognize the special challenges posed by “high‐conflict” separations for children and the justice system. The use of “high conflict” terminology by social science researchers and the courts has increased dramatically over the past decade. This is an important development, but the term is often used vaguely and to characterize very different types of cases. An analysis of Canadian case law reveals that some judges are starting to differentiate between various degrees and types of high conflict. Often this judicial differentiation is implicit and occurs without full articulation of the factors that are taken into account in applying different remedies. There is a need for the development of more refined, explicit analytical concepts for the identification and differentiation of various types of high conflict cases. Empirically driven social science research can assist mental health professionals, lawyers and the courts in better understanding these cases and providing the most appropriate interventions. As a tentative scheme for differentiating cases, we propose distinguishing between high conflict cases where there is: (1) poor communication; (2) domestic violence; and (3) alienation. Further, there must be a differentiation between cases where one parent is a primary instigator for the conflict or abuse, and those where both parents bear significant responsibility.     

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.     

Latent Fingerprint Development on Thermal Paper Using Traditional Ninhydrin and 1,2‐indanedione

Thermal paper poses a significant challenge to latent print development as it tends to change color when traditional fingerprint development formulations are applied to it. In this study, the optimal components of ninhydrin, 1,2‐indanedione, 1,8‐diazafluoren‐9‐one (DFO), and 5‐methylthioninhydrin (5‐MTN) for yielding clear fingerprints on thermal paper were determined by systematically adjusting the relative amounts of the reagents, polar solvents, and the nonpolar diluent petroleum ether, followed by validation on text‐printed thermal paper. Specifically, 3.0% ethyl acetate as the polar solvent in petroleum ether was found to be the optimal combination; the optimal dilution ratios of ninhydrin, DFO, and 5‐MTN original solutions with petroleum ether were 1 to 2, 11, and 7, respectively. The optimal concentration of 1,2‐indanedione in petroleum ether was 0.125 g/L, with a string of 0.5% ethyl acetate in petroleum ether.     

Detection of trace drugs of abuse in baby formula using solid‐phase microextraction direct analysis in real‐time mass spectrometry (SPME‐DART‐MS)

The intentional or unintentional adulteration of baby formula with drugs of abuse is one of the many increasingly complex samples forensic chemists may have to analyze. This sample type presents a challenge because of a complex matrix that can mask the detection of trace drug residues. To enable screening of baby formula for trace levels of drugs, the use of solid‐phase microextraction (SPME) coupled with direct analysis in real‐time mass spectrometry (DART‐MS) was investigated. A suite of five drugs was used as adulterants and spiked into baby formula. Samples were then extracted using SPME fibers which were analyzed by DART‐MS. Development of a proof‐of‐concept method was completed by investigating the effects of the DART gas stream temperature and the linear speed of the sample holder. Optimal values of 350°C and 0.2 mm/s were found. Once the method was established, representative responses and sensitivities for the five drugs were measured and found to be in the range of single ng/mL to hundreds ng/mL. Additional studies found that the presence of the baby formula matrix increased analyte signal (relative to methanolic solutions) by greater than 200%. Comparison of the SPME‐DART‐MS method to a traditional DART‐MS method for trace drug detection found at least a factor of 13 improvement in signal for the drugs investigated. This work demonstrates that SPME‐DART‐MS is a viable technique for the screening of complex matrices, such as baby formula, for trace drug residues and that development of a comprehensive method is warranted.     

Bacterial Degradation of Risperidone and Paliperidone in Decomposing Blood

The stability of two benzisoxazole antipsychotics was determined in vitro in decomposing porcine blood inoculated with bacteria, utilizing a high‐performance liquid chromatography with ultraviolet and fluorescence detection method for drug quantitation. Stability experiments for risperidone and paliperidone were conducted at 7, 20 and 37°C for 4 days using sterile and bacterially inoculated porcine blood. The drugs were stable in sterile blood at each temperature and in inoculated blood at 7°C, but degraded significantly in inoculated blood at 20 and 37°C. Complete loss occurred within 2 days when incubated at 37°C. The benzisoxazole‐cleaved degradation products for both drugs were identified as 2‐hydroxybenzoyl‐risperidone and 2‐hydroxybenzoyl‐paliperidone utilizing liquid chromatography quadrupole‐time‐of‐flight mass spectrometry and accurate mass measurements. The degradation products have been found in postmortem case studies, including one case where risperidone and paliperidone were not detected, indicating complete conversion can occur in situ.     

The Accuracy and Applicability of 3D Modeling and Printing Blunt Force Cranial Injuries

The purpose of this study was to determine the factors affecting the accuracy of 3D models and 3D prints of cranial blunt force trauma, to evaluate the applicability and limitations of modeling such injuries. Three types of cranial blunt force lesions were documented (hinge, depressed, and comminuted) using three forms of surface scanning (laser, structured light scanner, and photogrammetry) at two different quality settings (standard and high). 3D printed models of the lesions were produced using two different materials (a gypsum‐like composite powder called VisiJet^® PXL and an acrylic engineered composite plastic called VisiJet^® M3 in crystal colour). The results of these analyzes indicate the prints in this study exhibit some statistically significant differences from the actual bone lesions, but details of the lesions can be reproduced to within 2 mm accuracy.     

Identification of furosemide in hair in a post‐mortem case by UHPLC‐MS/MS with guidance on interpretation

Testing for drugs in hair raises several difficulties. Among them is the interpretation of the final concentration(s). In a post‐mortem case, analyses revealed the presence of furosemide (12 ng/mL) in femoral blood, although it was not part of the victim's treatment. The prosecutor requested our laboratory to undertake an additional analysis in hair to obtain information about the use of furosemide. A specific method was therefore developed and validated to identify and quantify furosemide in hair by UHPLC‐MS/MS. After decontamination of 30 mg of hair, incubation in acidic condition, extraction with ethyl acetate, the samples were analyzed by UHPLC‐MS/MS. Furosemide was found in the victim's hair at 225 pg/mg. However, it was not possible to interpret this concentration due to the absence of data in the literature. Therefore, the authors performed a controlled study in two parts. In order to establish the basis of interpretation, several volunteers were tested (four after a single 20 mg administration and twenty‐four under daily treatment). The first part indicated that a single dose is not detectable in hair using our method. The second part demonstrated concentrations ranging from 5 to 1110 pg/mg with no correlation between dosage and hair concentrations. The decedent's hair result was interpreted as repeated exposures. In the case of furosemide analysis, hair can provide information about its presence but cannot give information about dosage or frequency of use.     

EXPERTISE AND DECISION‐MAKING IN THE LINKING OF CAR CRIME SERIES

The aim of the present study was to investigate whether experienced car crime investigators have special expertise in the linking of car crime and what characterises effective decision‐making in this context. Groups of experienced car crime investigators, experienced other investigators, novice participants, and naive participants attempted to link 10 series of three car crimes while thinking aloud. The results showed that experience had an effect on actual and self‐assessed linking accuracy but not on processing speed. Linking accuracy was also related to the use of a limited subset of case characteristics. Characteristics used in successful linking were included in a multidimensional scaling analysis which showed that these characteristics could be used to link the cases together also automatically. The implications of the findings for car crime investigation and for the creation of automated decision‐support systems were discussed.