Fused Indacene Dimers.

Polycyclic hydrocarbons consisting of two or more directly fused antiaromatic subunits are rare due to their high reactivity. However, it is important to understand how the interactions between the antiaromatic subunits influence the electronic properties of the fused structure. Herein, we present the synthesis of two fused indacene dimer isomers: s-indaceno[2,1-a]-s-indacene (s-ID) and as-indaceno[3,2-b]-as-indacene (as-ID), containing two fused antiaromatic s-indacene or as-indacene units, respectively. Their structures were confirmed by X-ray crystallographic analysis. 1 H NMR/ESR measurements and DFT calculations revealed that both s-ID and as-ID have an open-shell singlet ground state. However, while localized antiaromaticity was observed in s-ID, as-ID showed weak global aromaticity. Moreover, as-ID exhibited a larger diradical character and a smaller singlet-triplet gap than s-ID. All the differences can be attributed to their distinct quinoidal substructures.

Azulene-Fused Acenes.

Non-alternant non-benzenoid π-conjugated polycyclic hydrocarbons (PHs) are expected to exhibit very different electronic properties from the all-benzenoid PHs. Herein, we report the synthesis and physical properties of three azulene-fused acene molecules (1, 2 and 3), which are isoelectronic to the pentacene, hexacene and heptacene, respectively. X-ray crystallographic analysis, NMR spectra, and theoretical calculations reveal a localised aromatic backbone comprising all the six- and five-membered rings while the seven-membered ring remains non-aromatic. They display properties of both azulene and acenes and are much more stable than the respective acenes. The dications of 1, 2 and 3 were formed by chemical oxidation. Notably, 32+ exhibited an open-shell diradical character (y0 =30.2 %) as confirmed by variable-temperature NMR and ESR measurements, which can be explained by recovery of aromaticity of an 2,6-anthraquinodimethane unit annulated with two aromatic tropylium rings.

Solution-Phase Synthesis and Isolation of An Aza-Triangulene and Its Cation in Crystalline Form.

Synthesis of triangulene and its derivatives is challenging due to their intrinsic high spin nature. Herein, we report solution-phase synthesis and isolation of a nitrogen-doped triangulene (i.e., aza-triangulene) (NT) and its cation (NT+ ) in single-crystal form. Notably, the cation NT+ can be regarded as an isoelectronic structure of the corresponding all-carbon triangulene. Both NT and NT+ show reasonable stability due to kinetic blocking by bulky and electron-withdrawing aryl substituents, and intramolecular donor-acceptor interaction. Bond length analysis, magnetic measurements and theoretical calculations reveal that the neutral NT has a doublet ground state with a zwitterionic character, while the cation NT+ exhibits a triplet ground state with a singlet-triplet energy gap of +0.84 kcal mol-1 . This study provides a rational strategy to access high-spin systems by heteroatom doping of pure π-conjugated polycyclic hydrocarbons.

Rational integration of porous organic polymer and multiwall carbon nanotube for the microextraction of polycyclic aromatic hydrocarbons.

By integration of benzene-constructed porous organic polymer (KBF) and multiwalled carbon nanotube (MWCNT), a MWCNT-KBF hybrid material was constructed through in situ knitting benzene with formaldehyde dimethyl acetal in the presence of MWCNTs to form a network. MWCNT-KBF was then adopted as a novel solid-phase microextraction (SPME) fiber coating. Coupled to gas chromatography-flame ionization detection, the MWCNT-KBF-assisted SPME method showed large enhancement factors (483-2066), low limits of detection (0.04-0.12 µg L-1), good linearity (0.13-50 µg L-1), and acceptable reproducibility (4.2-10.2%) for the determination of polycyclic aromatic hydrocarbons (PAHs). The method recoveries of seven PAHs were in the range 80.1-116.3%, with relative standard deviations (RSDs) ranging from 3.5 to 11.9%. The SPME method was successfully applied to the determination of PAHs in river, pond, rain, and waste water, providing a good alternative for monitoring trace level of PAHs in environmental water. Graphical abstract Schematic representation of the rational integration of porous organic polymer (KBF) and multiwalled carbon nanotube (MWCNT) to form a MWCNT-KBF hybrid material through in situ knitting benzene with formaldehyde dimethyl acetal at the presence of MWCNT.

Diazuleno-s-indacene Diradicaloids: Syntheses, Properties, and Local (anti)Aromaticity Shift from Neutral to Dicationic State.

Non-alternant, non-benzenoid π-conjugated polycyclic hydrocarbons (PHs) are expected to exhibit very different electronic properties from all-benzenoid PHs. Reported herein are the syntheses and physical properties of four derivatives of two azulene-fused s-indacene isomers, the diazuleno[2,1-a:2',1'-g]-s-indacene (DAI-1) and diazuleno[2,1-a:1',2'-h]-s-indacene (DAI-2). The backbone of both isomers contains 28π electrons and is a 7-5-5-6-5-5-7 fused ring system. X-ray crystallographic analysis, NMR spectra, and theoretical calculations (ACID, NICS) reveal a structure with two aromatic azulene units fused with a central anti-aromatic s-indacene moiety. All compounds exhibit open-shell diradical character and are magnetically active, but the derivatives of DAI-2 show larger radical character than the respective ones of DAI-1. Their dications were isolated in crystalline form and all experimental and theoretical analyses disclose a shift of local (anti)aromaticity along the backbone, with two aromatic tropylium rings at the termini.

Embryonic exposure to benzo[a]pyrene causes age-dependent behavioral alterations and long-term metabolic dysfunction in zebrafish.

Polycyclic aromatic hydrocarbons (PAH) are products of incomplete combustion which are ubiquitous pollutants and constituents of harmful mixtures such as tobacco smoke, petroleum and creosote. Animal studies have shown that these compounds exert developmental toxicity in multiple organ systems, including the nervous system. The relative persistence of or recovery from these effects across the lifespan remain poorly characterized. These studies tested for persistence of neurobehavioral effects in AB* zebrafish exposed 5-120 h post-fertilization to a typical PAH, benzo[a]pyrene (BAP). Study 1 evaluated the neurobehavioral effects of a wide concentration range of BAP (0.02-10 µM) exposures from 5 to 120 hpf during larval (6 days) and adult (6 months) stages of development, while study 2 evaluated neurobehavioral effects of BAP (0.3-3 µM) from 5 to 120 hpf across four stages of development: larval (6 days), adolescence (2.5 months), adulthood (8 months) and late adulthood (14 months). Embryonic BAP exposure caused minimal effects on larval motility, but did cause neurobehavioral changes at later points in life. Embryonic BAP exposure led to nonmonotonic effects on adolescent activity (0.3 µM hyperactive, Study 2), which attenuated with age, as well as startle responses (0.2 µM enhanced, Study 1) at 6 months of age. Similar startle changes were also detected in Study 2 (1.0 µM), though it was observed that the phenotype shifted from reduced pretap activity to enhanced posttap activity from 8 to 14 months of age. Changes in the avoidance (0.02-10 µM, Study 1) and approach (reduced, 0.3 µM, Study 2) of aversive/social cues were also detected, with the latter attenuating from 8 to 14 months of age. Fish from study 2 were maintained into aging (18 months) and evaluated for overall and tissue-specific oxygen consumption to determine whether metabolic processes in the brain and other target organs show altered function in late life based on embryonic PAH toxicity. BAP reduced whole animal oxygen consumption, and overall reductions in total basal, mitochondrial basal, and mitochondrial maximum respiration in target organs, including the brain, liver and heart. The present data show that embryonic BAP exposure can lead to neurobehavioral impairment across the life-span, but that these long-term risks differentially emerge or attenuate as development progresses.

Characterization of Benzo[a]naphtho[2,3-f]pentalene: Interrelation between Open-shell and Antiaromatic Characters Governed by Mode of the Quinoidal Subunit and Molecular Symmetry.

The singlet open-shell character and antiaromaticity are intriguing features in π-conjugated carbocycles. These two exhibit similar chemical and physical properties. However, they rarely coexist in the same molecule. Understanding the interrelation between the open-shell and antiaromatic characteristics in the same molecule is crucial to control the electronic properties. Herein we describe the synthesis and characterization of a new member of diareno[a,f]pentalene, benzo[a]naphtho[2,3-f]pentalene 6. Unlike its isomer 5 with a closed-shell ground state, 6 exhibits an appreciable open-shell character and a moderate antiaromatic feature. The behaviors of the open-shell index (y0 ) against the difference of the proton chemical signal (Δδ(H1 )) between pentalenide dianions/neutral pentalenes for our reported pentalenes 1, 4, 5, and 6 give a thought-provoking conclusion about the interrelation between open-shell and antiaromatic characteristics in this series. The mode of the incorporated quinoidal moiety and the formal molecular symmetry are critical to balance these two characteristics.

The head-to-head photodimer of indeno-indene.

Irradiation of 1-(1-benzo-cyclo-butenyl-idene)benzo-cyclo-butene gives indeno-indene and its head-to-head photodimer nona-cyclo-[9.7.7.72,10.01,11.02,10.03,8.012,17.019,24.026,31]dotriaconta-3,5,7,12,14,16,19,21,23,26,28,30-dodeca-ene, C32H24. The mol-ecule is built from four essentially planar indane units attached to an elongated cyclo-butane ring. In the crystal, C-H⋯π inter-actions connect mol-ecules into layers parallel to the bc plane.

Cuantificación de hidrocarburos policíclicos aromáticos urinarios en policías de tránsito del área metropolitana de Bogotá / Quantifying polycyclic aromatichydrocarbons in urine samples taken from traffic police working in Bogota's metropolitan area

Objetivos Cuantificar niveles urinarios de 1-hidroxipireno (1-OHP) y 3-hidroxibenzo [a] pireno (3-BAP) metabolitos de hidrocarburos policíclicos aromáticos (HAP) de interés toxicológico y relacionar su detección con el grado de exposición a material particulado de tamaño menor a 10 micras (PM10) u otros factores, en una población de Policías de Tránsito ocupacionalmente expuestos en el área metropolitana de Bogotá D.C. Métodos Se realizó un estudio de corte transversal en 524 Policías de Tránsito de los cuales 413 desarrollaban funciones operativas y 111 administrativas. Se tomaron muestras de orina de todos los individuos incluidos, para la determinación de metabolitos de HAP mediante cromatografía de gases con detección de masas. Se analizó la presencia de factores asociados con la detección de los metabolitos como tabaquismo, consumo de alimentos asados, lugar de residencia y exposición a PM10. Como medida de asociación se calcularon Odds Ratio (OR). Resultados Se encontraron niveles de 1-OHP y 3-BAP superiores en los individuos expuestos con OR significativos para detección de los metabolitos de 6,3 (IC 95% (3,6-11,1)) y 15,6 (IC 95% (6,2-39)), respectivamente. Se hallaron OR significativos para detección de metabolitos de HAP y exposición a PM10, tabaquismo y consumo de alimentos asados. Discusión Existe una asociación importante y significativa entre la exposición laboral a contaminación ambiental y la detección de metabolitos de HAP de importancia toxicológica en muestras de orina. Factores tales como tabaquismo, consumo de alimentos asados recientemente y exposición a PM10 también se encontraron asociados positivamente con la detección de dichos metabolitos pero en menor proporción.(AU)

Objective Quantifying polycyclic aromatic hydrocarbon levels in urine samples taken from a population of traffic police working in the metropolitan area of Bogotá who were occupationally exposed to 1-hydroxypyrene (1-OHP) and 3-hydroxy-benzo [a] pyrene (3-BaP) metabolites from polycyclic aromatic hydrocarbons (PAH) having toxicological interest, related to their detection, and a degree of exposure to particulate material having a size less than 10 micrometres (PM10) and/or other factors. Methods A cross-sectional study was made of 524 traffic police, 413 of whom were engaged in operational and 111 in administrative functions. Urine samples were taken from all the individuals included in the study for determining PAH metabolites by gas chromatography/mass spectrometry (GC/MS). The presence of factors associated with the detection of metabolites was analysed, such as smoking, consuming roasted/grilled food, place of residence and exposure to PM10. The odds ratio (OR) was calculated as a measure of association. Results Higher 1-OHP and 3-BaP levels were found in exposed individuals, having a significant OR for detecting 6.3 ((3.6-11.1) 95 % CI) and 15.6 ((6.2-39) 95 % CI) metabolites, respectively. Significant OR were found for detecting PAH metabolites and exposure to PM10, smoking and consuming roasted/grilled food. Discussion There was an important and significant association between work-related exposure to environmental contamination and detecting toxicologically important PAH metabolites in urine samples. Factors such as smoking, consuming freshly grilled/roasted food and exposure to PM10 were also found to be positively associated with detecting such metabolites, but to a lesser extent.(AU)