Energy‐resolved mass spectrometry for differentiation of the fluorine substitution position on the phenyl ring of fluoromethcathinones

A reliable method for structural analysis is crucial for the forensic investigation of new psychoactive substances (NPSs). Towards this end, mass spectrometry is one of the most efficient and facile methods for the identification of NPSs. However, the differentiation among 2‐, 3‐, and 4‐fluoromethcathinones (o‐, m‐, and p‐FMCs), which are ring‐fluorinated positional isomers part of the major class of NPSs referred to as synthetic cathinones, remains a challenge. This is mostly due to their similar retention properties and nearly identical full scan mass spectra, which hinder their identification. In this study, we describe a novel and practical method for differentiating the fluorine substitution position on the phenyl ring of FMCs, based on energy‐resolved mass spectrometry (ERMS) using an electron ionization‐triple quadrupole mass spectrometer. ERMS measurements showed that the three FMC positional isomers exhibited differences in relative abundances of both the fluorophenyl cation (m/z 95) and the fluorobenzoyl cation (m/z 123). The logarithmic plots of the abundance ratio of these two cations (m/z 95 to m/z 123) as a function of the collision energy (CE) followed the order of o‐FMC < p‐FMC < m‐FMC at each CE, which allowed the three isomers to be unambiguously and reliably differentiated. The theoretical dissociation energy calculations confirmed the relationship obtained by ERMS analyses, and additional ERMS measurements of methylmethcathinone positional isomers showed that the differences in abundance among the FMCs were attributed to the differences in their collision‐induced dissociation reactivities arising from the halogen‐induced resonance effects on the phenyl ring. Moreover, the method for differentiation described herein was successfully applied to the actual samples containing seized drugs. We expect that the described methodology will also contribute significantly to the reliable and accurate structural identification of NPSs in the fields of therapeutic, clinical, and forensic toxicology.     

Synthesis of isoquinoline derivatives using ROM-RCM of cyclobutene-yne

Isoquinoline derivatives were synthesized from cyclobutenylmethylamine derivatives having an alkyne moiety in a tether using a second-generation ruthenium carbene complex under ethylene gas in good yields.     

Mixing behavior of fluorinated and hydrogenated gemini surfactants at the air-water interface

Mixing behavior of hydrogenated and fluorinated cationic gemini surfactants was studied at the air-water interface by Brewster angle microscopy and pi-A isotherm curves. In the bulk, these two molecules did not mix and showed phase separation. At the air-water interface, if a monolayer was formed by separate deposition of the two solutions, they formed separate domains, and the compression occurred in two steps: first the domains with hydrogenated gemini surfactant were compressed until they showed collapse; then the domains with fluorinated gemini surfactant were compressed. If the two solutions were mixed before the deposition, they remained mixed upon compression; on the other hand, separate domains under separate deposition were shown to mix if the subphase was heated.     

Measurements of the bimolecular rate constants for S + O2 → SO + O and CS2 + O2 → CS + SO2 at high temperatures

The bimolecular reactions in the title were measured behind shock waves by monitoring the O-atom production in COS? O₂? Ar and CS₂? O₂? Ar mixtures over the temperature range between 1400 and 2200 K. A value of the rate constant for S + O₂ → SO + O was evaluated to be (3.8 ± 0.7) × 10¹² cm³ mol^?1 s^?1 between 1900 and 2200 K. This was connected with the data at lower temperatures to give an expression k₂ = 10^10.85 T^0.52 cm³ mol^?1 s^?1 between 250 and 2200 K. An expression of the rate constant for CS₂ + O₂ → CS + SO₂ was obtained to be k₂₁ = 10^12.0 exp(?32 kcal mol^?1/RT) cm³ mol^?1 s^?1 with an error factor of 2 between 1500 and 2100 K.     

Hidden symmetry in chains of biological coupled oscillators

We experimentally investigated spatiotemporal patterns in chains of coupled biological oscillators with boundaries and found hidden symmetric patterns that are not straightforwardly derived from explicit geometrical symmetry of the systems. We propose a model of coupled oscillators in chains with a hidden oscillator interconnecting its boundaries. The model can explain all observed patterns including the hidden symmetric ones, while other models such as discrete analogs of Neumann boundary conditions in continuous systems cannot.     

Reductive dehalogenation of aliphatic vic-dihalides with metallic samarium in a methanolic medium

In the title reaction, eight vic-dibromides and three vinylene dibromides gave the corresponding debromination products (alkenes and alkynes) at room temperature under neutral condition and an argon atmosphere. 2,3-Dibromosuccinic acid derivatives gave overreduction products or an unusual coupling dimer.     

8-Methylguanosine: a powerful Z-DNA stabilizer

Various modified guanine derivatives were synthesized and introduced into G(4) of d(CGCGCG)(2) to evaluate their capacity to stabilize Z-form DNA. It was found that the incorporation of 8-methylguanosine (m(8)rG) in oligonucleotides stabilizes the Z form more dramatically than does the incorporation of 8-methyl-2'-deoxyguanosine (m(8)G). This enhancement is ascribed to a reduction in the entropic penalty, which arises from the introduction of hydrophilic groups in solvent-exposed regions. The incorporation of m(8)rG into DNA sequences markedly stabilizes the Z form even in the absence of NaCl. The Z-DNA stabilizer allows oligonucleotides with a wide range of sequences to be converted to the Z form. It could be a powerful tool for examining the molecular basis of many types of Z-form-specific reactions at the molecular level under physiological salt conditions.