Isomeric Compounds Research Articles

The Safety of Glucosodiene on an In-Vitro Biopsy Cell Line Model.

This manuscript explores the safety and potential efficacy of glucosodiene, an isomeric alkaline glucose compound, as a therapeutic agent for cancer treatment. The study focuses on conducting safety tests using BJ1 cells (Normal Skin Fibroblasts) and evaluates the cytotoxic effects of glucosodiene on these cells. The results indicate that glucosodiene, at a concentration of 100 ppm, does not exhibit toxicity or impair normal cellular functions. These findings suggest that the compound may selectively target tumor cells without affecting healthy cells. However, further research is needed to understand the mechanisms of action and confirm its efficacy.

The Safety of Glucosodiene on an In-Vitro Biopsy Cell Line Model.

This manuscript explores the safety and potential efficacy of glucosodiene, an isomeric alkaline glucose compound, as a therapeutic agent for cancer treatment. The study focuses on conducting safety tests using BJ1 cells (Normal Skin Fibroblasts) and evaluates the cytotoxic effects of glucosodiene on these cells. The results indicate that glucosodiene, at a concentration of 100 ppm, does not exhibit toxicity or impair normal cellular functions. These findings suggest that the compound may selectively target tumor cells without affecting healthy cells. However, further research is needed to understand the mechanisms of action and confirm its efficacy.

Regulating the Coordination Environment by Using Isomeric Ligands: Enhancing the Energy and Sensitivity of Energetic Coordination Compounds.

Transforming the energy storage structure is an effective approach to achieve a balance between the detonation performance and the sensitivity of energetic compounds, with a goal of high energy and low sensitivity. Building upon previous work, this study employed an isomeric compound 1H-pyrazole-3-carbohydrazide (3-PZCA) as a ligand and creatively designed the energetic coordination compound (ECC) Ag(3-HPZCA)2(ClO4)3 (ECC-1). It is a novel material with a dual structure of ionic salts and coordination compounds, which represents the first report of such a structure in Ag(I)-based ECCs. With its unique structures, ECC-1 exhibits a larger [ClO4-] content, a higher oxygen balance constant (OB = 0%), and superior mechanical sensitivity (IS = 13 J and FS = 40 N). Theoretical calculations indicate that ECC-1 has a higher detonation performance compared to previous work. Furthermore, the explosive experiment testing results demonstrate that it can be ignited by lower-threshold lasers and possesses excellent initiation capability and explosive power, making it suitable not only as a primary explosive but also as a secondary explosive.

Imaging and Structural Characterization of Phosphatidylcholine Isomers from Rat Brain Tissue Using Sequential Collision-Induced Dissociation/Electron-Induced Dissociation.

The chemical complexity of biological tissues creates challenges in the analysis of lipids via imaging mass spectrometry. The presence of isobaric and isomeric compounds introduces chemical noise that makes it difficult to unambiguously identify and accurately map the spatial distributions of these compounds. Electron-induced dissociation (EID) has previously been shown to profile phosphatidylcholine (PCs) sn-isomers directly from rat brain tissue in matrix-assisted laser desorption/ionization (MALDI) imaging mass spectrometry. However, the acquisition of true pixel-by-pixel images, as opposed to regional profiling measurements, using EID is difficult due to low fragmentation efficiency and precursor ion signal dilution into multiple fragment ion channels, resulting in low sensitivity. In this work, we have developed a sequential collision-induced dissociation (CID)/EID method to visualize the distribution of sn-isomers in MALDI imaging mass spectrometry experiments. Briefly, CID is performed on sodium-adducted PCs, which results in facile loss of the phosphocholine headgroup. This ion is then subjected to an EID analysis. Since the lipid headgroup is removed prior to EID, a major fragmentation pathway common to EID ion activation is eliminated, resulting in a more sensitive analysis. This sequential CID/EID workflow generates sn-specific fragment ions allowing for the assignment of the sn-positions. Carbon-carbon double-bond (C═C) positions are also localized along the fatty acyl tails by the presence of a 2 Da shift pattern in the fragment ions arising from carbon-carbon bond cleavages. Moreover, the integration of the CID/EID method into MALDI imaging mass spectrometry enables the mapping of the absolute and relative distribution of sn-isomers at every pixel. The localized relative abundances of sn-isomers vary throughout brain substructures and likely reflect different biological functions and metabolism.

Proton tautomerism and stereoisomerism in isomeric 4-(metoxyphenyl)amino-1,3-thiazol-2(5H)-one derivatives: Synthesis, crystal structure and spectroscopic studies

In this article, we have reported the most recent results of our systematic studies of phenyl-ring substituent effect on proton tautomerism and stereoisomerism in 4-phenylamino-1,3-thiazol-2(5H)-one derivatives. The work concerns the synthesis, analysis of 1H and 13C NMR and FT-IR spectra, and X-ray crystal studies of three isomeric compounds, i.e. 5-dimethylaminomethylidene-4-(o-,m-,p-methoxyphenyl)amino-1,3-thiazol-2(5H)-ones. All three isomers were found to solely exist in the amino tautomeric form, both in the DMSO solution and the solid phase. In the molecules of all the title compounds, the o-,m-,p-methoxyphenylamine residue has synperiplanar disposition with respect to the thiazolone system, while the 5-dimethylaminomethylidene residue adopts the Z-configuration. DFT calculations correctly predict that the synperiplanar arrangement is favored in all investigated materials

A new alkaloid from Pancratium maritimum - Structure elucidation using computer-assisted structure elucidation (CASE) and evaluation of cytotoxicity and anti-SARS-CoV-2 activity

Pancratium maritimum L. (or ‘sea daffodil’) is one of the most studied plant species in the Amaryllidaceae family. Recently, due to the advancement of new probabilistic methods and spectroscopic techniques, the potential for phytochemical investigations on isomeric compounds has significantly improved. In this study, application of these techniques in combination with conventional phytochemical analysis led to the isolation and identification of a new alkaloid named 2β,10bα-dihydroxy-9-O-demethylhomolycorine from P. maritimum, together with 17 known ones. Assessment of anti-SARS-CoV-2 activity and cytotoxicity on a Vero E6 cell line for all compounds revealed four compounds with weak anti-SARS-CoV-2 potency at non-cytotoxic concentrations, namely of 9-O-demethylhomolycorine (EC50 = 44 µM), galanthamine (EC50 = 70 µM), 1-O-acetyl-norpluviine (EC50 = 80 µM) and 1-O-acetyl-10-O-methylpseudolycorine (EC50 = 47 µM). On the other hand, cytotoxicity was observed for 2β,10bα-dihydroxy-9-O-demethylhomolycorine (CC50 = 13.28 µM), haemanthamine (CC50 = 0.76 µM), 6α- and 6β-haemanthidine (CC50 = 5.43 µM), 11-hydroxyvittatine (CC50 = 10.57 µM) and pseudolycorine (CC50 = 3.41 µM).

Evaluation of natural resveratrol multimers as marine antifoulants

In the current study we investigate the antifouling potential of three polyphenolic resveratrol multimers (–)-hopeaphenol, vaticanol B and vatalbinoside A, isolated from two species of Anisoptera found in the Papua New Guinean rainforest. The compounds were evaluated against the growth and settlement of eight marine microfoulers and against the settlement and metamorphosis of Amphibalanus improvisus barnacle cyprids. The two isomeric compounds (–)-hopeaphenol and vaticanol B displayed a high inhibitory potential against the cyprid larvae metamorphosis at 2.8 and 1.1 μM. (–)-Hopeaphenol was also shown to be a strong inhibitor of both microalgal and bacterial adhesion at submicromolar concentrations with low toxicity. Resveratrol displayed a lower antifouling activity compared to the multimers and had higher off target toxicity against MCR-5 fibroblasts. This study illustrates the potential of natural products as a valuable source for the discovery of novel antifouling leads with low toxicity.

Tweaking the conjugation effects on a pair of new triazene compounds by targeted deprotonation: a spectroscopic and theoretical overview.

Triazene compounds (-NNN(H)-) exhibit versatility in biological, physical, and chemical applications. In their anionic form (-NNN-)(-), they can act as coordinating sites for metals, forming metallic complexes. In this study, two new isomeric triazene compounds with meta- and para-substituents in their neutral and anionic forms were investigated. A combination of detailed experimental spectroscopic characterization and computational chemistry analyses were employed. The new compounds, 1-(2-benzamide)-3-(3-nitrophenyl) triazene (m-TZN) and 1-(2-benzamide)-3-(4-nitrophenyl) triazene (p-TZN), were compared to 1,3-diphenyltriazene (dph-TZN) to understand the effects of functionalization and targeted triazene deprotonation. The anionic forms are stable, and our investigation suggests that these new compounds are suitable tridentate ligands that can act as chelating agents for metallic cations in stable complexes, similar to those found in vitamin B12. The absorption, vibrational, and electronic properties of the newly synthesized triazene compounds were extensively characterized using FT-IR/FT-Raman and UV-Vis spectroscopy. Their distinct molecular properties, intramolecular hydrogen bond effects, stability, and electronic transitions were investigated using the ORCA software. These analyses involved DFT and TD-DFT calculations at the ωB97X-D3/Def2-TZVP level of theory with THF CPCM implicit solvation to determine the molecular topology and electronic structure. The advanced STEOM-DLPNO-CCSD method for excited states was employed, enabling an in-depth analysis of ground and excited-state chemistry, accounting for precise electronic correlation and solvation effects. Explicit THF solvation was tested on the full TD-DFT ωB97X-D3/Def2-TZVP level and using ONIOM on the STEOM calculation. Reactivity was studied using Fukui functions, and action as chelating agents was investigated using GFN-xTB2 and DFT.

Homochiral Metallacycle Used as a Stationary Phase for Capillary Gas Chromatographic Separation of Chiral and Achiral Compounds.

Metallacycles are a novel class of supramolecular materials with circular structures, internal cavities, and abundant host-guest chemical properties that have exhibited good application prospects in many fields. However, to the best of our knowledge, no research on the use of metallacycles as stationary phases for gas chromatographic (GC) separations has been published yet. In this work, we report for the first time the use of a homochiral metallacycle, [ZnCl2L]2, as a stationary phase for GC separations. [ZnCl2L]2 was synthesized by reaction of (S)-(1-isonicotinoylpyrrolidin-2-yl)methyl-isonicotinate (L) with ZnCl2 via coordination-driven self-assembly. The [ZnCl2L]2-coated column displayed an excellent separation performance not only of organic isomers but also of racemic compounds. Sixteen racemates (including alcohols, esters, amino acid derivatives, ethers, organic acids, and epoxides) and 21 isomeric compounds (including positional, structural, and cis/trans-isomers) were well separated on the [ZnCl2L]2-coated column. Impressively, some racemates were resolved with high resolution values (Rs), including 1,2-butanediol diacetate (Rs = 25.86), ethyl 3-hydroxybutyrate (Rs = 20.97), 1,3-butanediol diacetate (Rs = 18.09), and threonine derivative (Rs = 18.61). Compared with the commercial β-DEX 120 column for separation of the tested racemates, the [ZnCl2L]2-coated column exhibited good enantioseparation complementarity, enabling separation of some racemates that could not be separated, or were not well resolved, by the β-DEX 120 column. In addition, many organic mixtures, such as n-alkanes, alkylbenzenes, n-alcohols, and a Grob test mixture, were also well separated on the [ZnCl2L]2-coated column. The column also has good reproducibility and thermal stability on separation. This work not only reveals the great potential of metallacycles for GC separations but also opens up a new application of metallacycles in separation science.

Triphenylamine (TPA)‐Functionalized Structural Isomeric Polythiophenes as Dopant Free Hole‐Transporting Materials for Tin Perovskite Solar Cells

AbstractA new series of triphenylamine (TPA)‐functionalized isomeric polythiophenes are developed as hole transporting materials (HTM) for inverted tin‐based perovskite solar cells (TPSCs). Bithiophene (BT) is first functionalized with two TPA (electron donor; D) at 3 and 5 positions to give two structural isomeric compounds (3BT2D and 5BT2D). The functionalized BT2Ds are then coupled with 3,3′‐bis(tetradecylthio)‐2,2′‐bithiophene (SBT‐14)/3,3′‐ditetradecyl‐2,2′‐bithiophene (BT‐14) to produce structural isomeric polythiophenes (1‐4), which are compared to conventional poly[N,N″‐bis(4‐butylphenyl)‐N,N″‐bis(phenyl)‐benzidine] (poly‐TPD) as HTMs for TPSCs. With the appropriate alignment of energy levels with regard to the perovskite layer, the TPA‐functionalized polymers‐based TPSCs exhibit enhanced operational stability and efficiency. Moreover, the long thiotetradecyl chain in SBT‐14 with intramolecular S(alkyl)∙∙∙S(thio) interactions restricts the molecular rotation and has a strong impact on the molecular solubility and wettability of the film during device fabrication. Among all the polymers studied, TPSCs fabricated with 3‐SBT‐BT2D polymer exhibit the highest hole mobility as well as the slowest charge recombination and achieve the highest power conversion efficiency of 8.6%, with great long‐term stability for the performance retaining ≈90% of its initial values for shelf storage over 4000 h, which is the best efficiency for non‐PEDOT:PSS‐based TPSCs ever reported.

Three Isomeric Tetraphenylethylene-pyridine Compounds: Synthesis, Crystal Structures, and Photophysical Properties.

Many aggregation-induced emission (AIE) molecules based on tetraphenylethylene (TPE) structure have been synthesized, but a clear understanding of the photophysical difference between different isomeric pyridyl-based tetraphenylethylene molecules remains elusive. Herein, we designed a series of isomeric tetraphenylethylene-pyridines (o-Py-TPE, m-Py-TPE, p-Py-TPE) to investigate the influence of the position of N atoms in the pyridine subunit on the photophysical property of the whole molecule by detailed DFT calculations and single crystal structures analysis. All compounds show typical AIE properties, and notably, the meta pyridyl isomer (m-Py-TPE) shows the highest solid photoluminescence quantum yield (PLQY) up to 64.56%. Further investigation and DFT calculations indicate that the center C=C bond dihedral angles of the TPE subunit in the solid state of these compounds, which are affected by C-H···π interaction, play a vital role in their emission and PLQY properties. This work provides underlying principles for the design of pyridyl-based TPE molecules with high photoluminescent performance in the future.

Effects of the change of isomers on room-temperature phosphorescence, thermally activated delayed fluorescence, and long persistent luminescence of organic hole-transporting materials with the selective potential for the application in electronic devices and optical sensors of oxygen

Competition of room-temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) was investigated on the example of four newly synthesised organic isomeric compounds containing two electron-donating triphenylamine moieties and single electron-accepting dibenzothiophene-2-yl(phenyl)methanone unit by numerous theoretical and experimental approaches. The different emission origin (RTP or TADF) of the isomeric compounds was caused by the different energy gaps between the lowest singlet and triplet states locally exited and charge transfer in nature. Very different external quantum efficiencies ranging from 2.8 to 13.9% were observed for green phosphorescent organic light-emitting diodes fabricated using the isomeric compounds as the hosts. Such device efficiency differences were related to the different hole mobility values. The hole mobilities of ca. 1 × 10−3 cm2V−1s−1 were observed at an electric field of 6.4 × 105 V/cm for the derivatives having triphenylamine moieties at C-2, C-4, and at C-3, C-5 positions of the central benzene ring. Considerably lower hole mobilities of ca. 1 × 10−5 cm2 V−1 s−1 were recorded at the same electric field for the compounds with triphenylamine groups at C-2, C-3, and at C-2, C-6 positions. Depending to the great extent on RTP and TADF processes, different efficiencies of long persistent luminescence (LPL) of the exciplex-forming solid-state mixtures of the isomers and bis[2-(diphenylphosphine)phenyl] ether oxide (DPEPO) were detected. The compound with triphenylamine groups at C-3, and C-5 positions as RTP emitter and its molecular mixture with DPEPO as LPL emitter the active layers of optical sensors of oxygen were prepared. They showed the Stern–Volmer constant of 4.55 × 10−4 ppm in the range of oxygen concentrations up to 10000 ppm.

Analysis of Volatile Esters and Alkanoic Acids by an Atmospheric Pressure Corona Discharge Ionization Collision-Induced Dissociation Mass Spectrometry in Positive-Ion Mode: Ionization, Fragmentation Patterns, and Discrimination between Isomeric Compounds.

The ionization and fragmentation patterns of 24 compounds with elemental composition of CmH2mO2, including isomeric esters and alkanoic acids, were investigated by atmospheric pressure corona discharge ionization collision-induced dissociation (CID) mass spectrometry in the positive-ion mode. All compounds were ionized as protonated molecules and NH4+ adducts. In addition, fragment ions were observed in mass spectra of esters other than methyl esters, which are owing to the dissociation of the alkyl group in the alcohol side from the protonated molecules. In CID spectra, protonated alkanoic acids/methyl esters split off H2O/CH3OH and CO or the alkyl group in the acid side, depending on the carbon chain length. Protonated esters (other than methyl esters) mainly fragmented the alkyl group in the alcohol side. These general rules on ionization and fragmentation patterns can provide relevant information on the discrimination of isomers.

The Effect of Acyl Chain Position on the 2D Monolayer Formation of Monoacyl-sn-Glycerol at the Air/Water Interface: Quantum Chemical Modeling

This paper deals with the results of quantum chemical modeling of the monoacyl-sn-glycerol 2D cluster formation at the air/water interface using a semi-empirical PM3 method. The impact of the 2 or 3 positions of the acyl substituent on the thermodynamics of the monolayer formation is assessed for surfactants with an acyl substituent CnH2n+1COO chain length of n = 6–17 carbon atoms. The calculation shows a significant change in the spontaneous clusterization threshold for isomeric compounds, which differs only in the position of the acyl substituent with respect to the glycerol backbone. This change is almost equal to substituent shortening by approximately two methylene fragments. At the same time, the geometric parameters of the unit cell for resulting monolayers are not affected so drastically. The 2D films in question possess an oblique or orthorhombic unit cell with parameters for 2 and 3-monoacyl-sn-glycerol monolayers, as follows: a = 4.91 Å and 4.82 Å and b = 5.00 Å and 4.92 Å, with hydrocarbon chains tilted at t = 23.0° and 23.5°. The calculated results are in accordance with existing experimental data obtained using grazing incidence X-ray diffraction measurements and the π-A isotherm technique.

Metabolites of progesterone in pregnancy: Associations with perinatal anxiety

BackgroundAnxiety disorders are the most common psychiatric disorder during the perinatal period and one of the major risk factors for postpartum depression, yet we know little about biological factors in the etiology of perinatal anxiety. A growing literature points to neuroactive steroid (NAS) dysregulation in perinatal mental illness, but directionality has not been clearly demonstrated, results are not consistent, and no studies have investigated NAS in a population with pure anxiety without comorbid depression. We aimed to add to the limited literature by examining the association between anxiety without comorbid depression and metabolic pathways of NAS longitudinally across the peripartum. MethodsWe measured anxiety symptoms by psychological scales and NAS levels using Gas Chromatography-Mass Spectrometry (GC-MS) at the second and third trimester (T2 and T3) and week 6 postpartum (W6) in n = 36 women with anxiety and n = 38 healthy controls. The anxiety group was determined by a data-driven approach, and cross-sectional and longitudinal statistical methods were used to examine the relationship between the study population and NAS. ResultsWe found that anxiety had a significant moderating effect on the relationship between progesterone and allopregnanolone, with no such effect for the relationships between progesterone and the intermediate (5α-DHP) or isomeric (isoallopregnanolone) compounds in this pathway, and no effects on the corresponding pathway converting progesterone to pregnanolone and epipregnanolone. We also found a less precipitous decline in the ratio of allopregnanolone to progesterone between T3 and W6 in the anxiety group compared to the non-anxiety group. A genotype analysis of a single-nucleotide polymorphism in the AKR1C2 gene demonstrated that the relationship of allopregnanolone to the intermediate metabolite, 5α-DHP, differed by genotype. ConclusionOur exploratory findings indicate that, for pregnant people with anxiety, metabolism is shunted more aggressively toward the endpoint of the progesterone to allopregnanolone metabolic pathway than it is for those without anxiety.

Comparison of Compound Identification Tools Using Data Dependent and Data Independent High-Resolution Mass Spectrometry Spectra.

Liquid chromatography combined with high-resolution mass spectrometry (LC-HRMS) is a frequently applied technique for suspect screening (SS) and non-target screening (NTS) in metabolomics and environmental toxicology. However, correctly identifying compounds based on SS or NTS approaches remains challenging, especially when using data-independent acquisition (DIA). This study assessed the performance of four HRMS-spectra identification tools to annotate in-house generated data-dependent acquisition (DDA) and DIA HRMS spectra of 32 pesticides, veterinary drugs, and their metabolites. The identification tools were challenged with a diversity of compounds, including isomeric compounds. The identification power was evaluated in solvent standards and spiked feed extract. In DDA spectra, the mass spectral library mzCloud provided the highest success rate, with 84% and 88% of the compounds correctly identified in the top three in solvent standard and spiked feed extract, respectively. The in silico tools MSfinder, CFM-ID, and Chemdistiller also performed well in DDA data, with identification success rates above 75% for both solvent standard and spiked feed extract. MSfinder provided the highest identification success rates using DIA spectra with 72% and 75% (solvent standard and spiked feed extract, respectively), and CFM-ID performed almost similarly in solvent standard and slightly less in spiked feed extract (72% and 63%). The identification success rates for Chemdistiller (66% and 38%) and mzCloud (66% and 31%) were lower, especially in spiked feed extract. The difference in success rates between DDA and DIA is most likely caused by the higher complexity of the DIA spectra, making direct spectral matching more complex. However, this study demonstrates that DIA spectra can be used for compound annotation in certain software tools, although the success rate is lower than for DDA spectra.

Biomass-based activated carbons produced by chemical activation with H3PO4 as catalysts for the transformation of α-pinene to high-added chemicals.

In the era of ecology and careful care for the environment, it becomes important to use renewable raw materials of plant origin, which are often more easily available and cheaper. One of the important and rapidly developing directions of research are works related to the use of waste plant biomass; an example of this trend is the production of activated carbons from food industry waste. One of the examples of the application of derived from biomass activated carbons can be using them as catalysts for the isomerization of terpene compounds. Carbons based on waste biomass are characterized by the minimal amount of waste formation during their manufacture, and their use in the isomerization reaction allows to obtain high conversion of organic raw material and high selectivities of transformation to the desired products, making these carbons environmentally friendly substitutes for the catalysts used usually in this process. In this work, obtained carbonaceous catalysts were tested in the process of isomerization of α-pinene to high value chemicals (mainly camphene and limonene). Under the most favorable conditions (activated carbon from sunflower husks content in reaction mixture 5 wt%, temperature 180°C, and reaction time 100min), α-pinene was completely converted (conversion 100mol%) with high selectivity towards camphene (54mol%). To prepare activated carbons, biomass precursors (orange peels, sunflower husks, spent coffee grounds) were activated with 85% H3PO4 through the chemical activation. The obtained materials were characterized by such methods as sorption N2 at - 196°C, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and X-ray fluorescence (XRF) to determine the relationship between their textural-chemical properties and catalysts activity in isomerization process. The synthesized materials were characterized by a specific surface area in the range of 930-1764 m2, total pore volume in the range of 0.551-1.02 cm3/g, and total acid-site concentrations in the range of 1.47-2.33mmol/g. These results showed that textural parameters of the obtained activated carbons have the important role in the isomerization of α-pinene.

N, N-Dimethylpentylone (Dipentylone)-A New Synthetic Cathinone Identified in a Postmortem Forensic Toxicology Case Series.

Synthetic cathinones emerged on the novel psychoactive substance (NPS) drug market as alternatives to controlled stimulants and entactogens such as methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA). The majority of synthetic cathinones can be subclassified into two groups: beta-keto amphetamines (i.e., NPS with the suffix "drone") and beta-keto methylenedioxyamphetamines (i.e., NPS with the suffix "lone"). Although a significant number of beta-keto amphetamines have been identified, beta-keto methylenedioxyamphetamines have dominated the NPS market, including notable drugs like methylone, butylone, N-ethyl pentylone (ephylone), eutylone, and now N, N-dimethylpentylone. N, N-Dimethylpentylone, also known as dipentylone or bk-DMBDP, emerged into the illicit drug supply within two months of the international control of eutylone (September 2021). A novel standard addition method was developed and validated for N, N-dimethylpentylone, pentylone, and eutylone, and 18 postmortem cases were quantitated using the method described in this manuscript. The resulting blood concentration range for N, N-dimethylpentylone in this case series was 3.3 to 970 ng/mL (median: 145 ng/mL, mean: 277 ± 283 ng/mL). Pentylone, a metabolite of N, N-dimethylpentylone, was detected in all cases (range: 1.3-420 ng/mL, median: 31 ng/mL, and mean: 88 ± 127 ng/mL). Due to the rise in identifications of N, N-dimethylpentylone in postmortem investigations as well as the potential misidentification of N, N-dimethylpentylone as N-ethyl pentylone, samples testing positive for pentylone should be additionally confirmed for the presence of N, N-dimethylpentylone. Based on prior trends of new synthetic cathinones, it can be theorized that N, N-dimethylpentylone may predominate the U.S. synthetic stimulant market for the next one to two years, however; given the emergence of additional closely related isomeric compounds, it is important to utilize methodology capable of differentiating N, N-dimethylpentylone from its isomers (N-isopropylbutylone, N-ethyl pentylone, N-ethyl N-methyl butylone, hexylone, N-propylbutylone, diethylone, and tertylone).

Formation and Tandem Mass Spectrometry of Doubly Charged Lipid-Metal Ion Complexes.

Phospholipids are major components of most eukaryotic cell membranes. Changes in metabolic states are often accompanied by phospholipid structure variations. The structural changes of phospholipids are the hallmark of disease states, or specific lipid structures have been associated with distinct organisms. Prime examples are microorganisms that synthesize phospholipids with, for example, different branched chain fatty acids. Assignment and relative quantitation of structural isomers of phospholipids that arise from attachment of different fatty acids to the glycerophospholipid backbone are difficult with routine tandem mass spectrometry or with liquid chromatography without authentic standards. In this work, we report on the observation that all investigated phospholipid classes form doubly charged lipid-metal ion complexes during electrospray ionization (ESI) and show that these complexes can be used to assign lipid classes and fatty acid moieties, distinguish isomers of branched chain fatty acids, and relatively quantify these isomers in positive-ion mode. Use of water free methanol and addition of divalent metal salts (100 mol %) to ESI spray solutions afford highly abundant doubly charged lipid-metal ion complexes (up to 70 times of protonated compounds). Higher-energy collisional dissociation and collision-induced dissociation of doubly charged complexes yield a diverse set of lipid class-dependent fragment ions. In common for all lipid classes is the liberation of fatty acid-metal adducts that yield fragment ions from the fatty acid hydrocarbon chain upon activation. This ability is used to pinpoint sites of branching in saturated fatty acids and is showcased for free fatty acids as well as glycerophospholipids. The analytical utility of doubly charged phospholipid-metal ion complexes is demonstrated by distinguishing fatty acid branching-site isomers in phospholipid mixtures and relatively quantifying the corresponding isomeric compounds.

The Topology of Molecules with Twelve Fused Phenyl Rings ([12]Circulenes): Rings, Infinitenes, and Möbius Infinitenes.

Following the recent preparation of infinitene (J. Am. Chem. Soc. 2022, 144, 862-871), a computational (ωB97XD/6-311G(d)) exploration of 42 isomeric compounds with 12 fused phenyl rings identified structures with linking number of zero (ring, saddle, and ribbon shapes), two (infinitene-like shape), and one (Möbius infinitene shape) is reported. An infinitene isomer composed of two [5]helicene fragments connected to two stacked phenyl rings and a Möbius infinitene isomer are identified that are more stable than the known infinitene. The energies of the structures are examined by assessing their macrocyclization (strain) energies, π-stacking, and possible aromaticity. Examples of fused phenyl molecules with linking numbers of 3, 4, 5, and 6 are shown, indicating the potential topological range that these molecules can possess.