Acenaphthenequinone Research Articles

Photo responsive dyads for fast recognition of cyanide and fluoride in aqueous media

Three new photo responsive molecular dyads have been synthesized by the reaction of 4-hydrazino-N-benzyl-1,8-naphthalimide with different diketone derivatives (benzil, acenaphthene quinone, pyrene-4,5-dione). Naph-diones have been observed to exhibit photo tautomerization plausibly due to proton transfer from the 4-amino-naphthalimide, –NH to the carbonyl, >CO moiety of the dione when photo-irradiated in a polar aprotic solvent (THF). The synthesized dyads also respond to protonation and de-protonation on change of pH of the medium and exhibited well defined multi-colour solvatochromism in different solvents. The synthesized derivatives have been determined to be highly sensitive towards critical anions (e.g., fluoride and cyanide ions). Observed photo tautomerization has been confirmed by DFT calculations and solvent induced spectral changes. The recognition of cyanide and fluoride in dilute solutions has been observed to be very fast and required less than 15 s response time. Mechanism of interaction has been confirmed through 1H NMR and UV-Vis spectra. Details of experiments conducted, energy calculations and spectral observations made for ionic recognition have been described.

Stereoselective synthesis of dispiroindano pyrrolidines by the [3 + 2] cycloaddition of thiazolo[3,2‐a]indole tethered dipolarophile with azomethine ylides

AbstractAzomethine ylides generated by the reaction of cyclic ketones, namely ninhydrin, acenaphthene quinone and 11H‐indeno[1,2‐b]‐quinoxalin‐11‐one, with (i) α‐amino acids (ii) primary/secondary amines, have been successfully utilized for one‐pot three‐component [3 + 2] cycloaddition reactions with a thiazolo[3,2‐a]indole containing dipolarophile (in‐turn generated by the reaction of thieno[2,3‐b]indole‐2,3‐dione and dimethyl acetylene dicarboxylate). Dispiro heterocycles were synthesized in excellent yields and with high stereo‐ and regioselectivity.

Simple and Strong Dative Attachment of α-Diimine Nickel (II) Catalysts on Supports for Ethylene Polymerization with Controlled Morphology

In this article, preparation of novel spherical MgCl2 supported α-diimine nickel (II) catalysts for ethylene polymerization in slurry phase is reported. α-Diimine ligands were synthesized by condensation reaction of 2, 6-disubstituted alkyls or aryls anilines and Ace naphthoquinone Which have hydroxyl functionality in their para-position. Hydroxyl functionalized α-diimine attached strongly on to the spherical MgCl2 support surface by dative bonding. No linker was needed to attach the complexes onto the support surface and the amount of loaded Nickel was controllable to improve morphology and especially bulk density of polymer powder. A significant reduction in catalysts activity has happened when homogeneous catalysts were supported onto silica but this reduction was decreased when they were supported onto thermally treated spherical MgCl2. As homogeneous bis(N,N′-(4-(3-hydroxyl-propyl)-2,6-di[(4-tert-butyl-phenyl)-phenyl) amino] Ace naphthoquinone Nickel dibromide(d) showed the highest activity among other evaluated homogeneous catalysts, its MgCl2 supported catalyst (d/S-MgCl2) has shown the highest activity among MgCl2 supported catalysts too. These MgCl2 supported catalysts were pre-polymerized in presence of ethylene monomer in the mild polymerization condition to yield a pre-polymerized catalyst with polymer/catalyst weight ratio equal to six. Ethylene polymerization was carried out to make spherical particles of polyethylene without reactor fouling by these pre-polymerized catalysts. Clearly, it is shown in SEM images that the spherical morphology of MgCl2 support is replicated in the produced polymer. The molecular weight and molecular weight distribution of produced polymer with MgCl2 supported catalysts were higher than those produced by homogeneous catalysts. α–Diimine nickel (II) complexes have hydroxy functionality where produce strong dative bonding onto spherical MgCl2. This bonding is strong enough that these catalysts are suitable for slurry polymerization of ethylene without reactor fouling due to catalyst leaching from support. The chemical structure of MgCl2 leads to high active supported catalysts. The molecular weight and polydispersity index of produced polymrers using these supported catalysts are higher than those produced by equivalent homogeneous catalysts and are controllable by selection of appropriate ligand for used α–diimine nickel (II) complex or hydrogen concentration in ethylene polymerization.

1,2‐Diketones as photoinitiators of both cationic and free‐radical photopolymerization under UV (392 nm) or Blue (455 nm) LEDs

ABSTRACTThe photoinitiation abilities of three 1,2‐diketones [i.e., acenaphthenequinone (ANPQ), aceanthrenequinone (AATQ), and 9,10‐phenanthrenequinone (PANQ)]‐based photoinitiating systems [PISs, with additives such as iodonium salt, N‐vinylcarbazole (NVK), tertiary amine, and phenacyl bromide (R‐Br)] for cationic photopolymerization and free‐radical photopolymerization under the irradiation of ultraviolet (UV; 392 nm) or blue (455 nm) light‐emitting diode (LED) bulb are investigated. All 1,2‐diketones studied exhibit ground state absorption that match with the emission spectra of UV (392 nm) or blue LED (455 nm) better than that of the well‐known blue‐light‐sensitive photoinitiator camphorquinone (CQ). In particular, AATQ/iodonium salt/NVK can show high photoinitiating ability (with epoxide conversion yield >70%) under the UV light irradiation due to the effect of NVK. In addition, 1,2‐diketone/iodonium salt (and optional NVK) systems are capable of initiating free‐radical photopolymerization of methacrylates, with conversions of 50–58%. Furthermore, some 1,2‐diketone/tertiary amine (and optional R‐Br) combinations are found to demonstrate high efficiency to initiate free‐radical photopolymerization, and 71% of methacrylate conversion can be achieved with PANQ/tertiary amine/R‐Br PIS. Some 1,2‐ketone‐based PISs can even exhibit higher efficiency than the CQ‐based systems. The photochemical mechanism of the radical generation from the 1,2‐diketone‐based PISs is investigated and found to be consistent with the related photopolymerization efficiency. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 792–802

Typical airborne quinones modulate oxidative stress and cytokine expression in lung epithelial A549 cells

ABSTRACTQuinones that exist in ambient particulate matter (PM) are hypothesized to be associated with adverse health effects through the generation of reactive oxygen species (ROS). However, the impacts of the quinones on the inflammatory processes have yet to be clearly understood. In this study, we examined the oxidative potentials and biological effects of typical airborne quinones in the human lung epithelial A549 cells. Significant change of redox status, loss of mitochondrial membrane potentials (△Ψ) and increase of superoxide dismutase (SOD) activity were induced by exposure to quinones. Some pro-inflammatory genes including interleukin-6 (IL-6), interleukin-8 (IL-8), tumor necrosis factor (TNF-α) and monocyte chemoattractant protein-1 (MCP-1); two aromatic hydrocarbon receptor-regulated genes, cytochromes P450 1A1 (Cyp1a1) and cytochromes P450 1B1 (Cyp1b1); and oxidative stress-related gene heme oxygenase-1 (HO-1) were up-regulated after quinones treatment. Among these quinones, 1,2-naphthoquinone (1,2-NQ) up-regulated expressions of IL-6, IL-8, TNF-α, Cyp1a1, and HO-1; 2-methoxy-1,4-naphthoquinone (MNQ) up-regulated MCP-1, Cyp1b1, Cyp1a1, and HO-1; 2-methylanthraquinone (MAQ) up-regulated IL-6, IL-8, TNF-α, MCP-1, Cyp1b1, and Cyp1a1; acenaphthenequinone (ACQ) up-regulated IL-8, TNF-α, MCP-1, Cyp1b1, and Cyp1a1. These results suggested that all these five quinones had a considerable pro-inflammatory potential by inducing oxidative stress and releasing different types of cytokines/chemokines.

Ligand "Brackets" for Ga-Ga Bond.

The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward acenaphthenequinone (AcQ), sulfur dioxide, and azobenzene was investigated. The reaction of 1 with AcQ in 1:1 molar ratio proceeds via two-electron reduction of AcQ to give (dpp-Bian)Ga(μ2-AcQ)Ga(dpp-Bian) (2), in which diolate [AcQ](2-) acts as "bracket" for the Ga-Ga bond. The interaction of 1 with AcQ in 1:2 molar ratio proceeds with an oxidation of the both dpp-Bian ligands as well as of the Ga-Ga bond to give (dpp-Bian)Ga(μ2-AcQ)2Ga(dpp-Bian) (3). At 330 K in toluene complex 2 decomposes to give compounds 3 and 1. The reaction of complex 2 with atmospheric oxygen results in oxidation of a Ga-Ga bond and affords (dpp-Bian)Ga(μ2-AcQ)(μ2-O)Ga(dpp-Bian) (4). The reaction of digallane 1 with SO2 produces, depending on the ratio (1:2 or 1:4), dithionites (dpp-Bian)Ga(μ2-O2S-SO2)Ga(dpp-Bian) (5) and (dpp-Bian)Ga(μ2-O2S-SO2)2Ga(dpp-Bian) (6). In compound 5 the Ga-Ga bond is preserved and supported by dithionite dianionic bracket. In compound 6 the gallium centers are bridged by two dithionite ligands. Both 5 and 6 consist of dpp-Bian radical anionic ligands. Four-electron reduction of azobenzene with 1 mol equiv of digallane 1 leads to complex (dpp-Bian)Ga(μ2-NPh)2Ga(dpp-Bian) (7). Paramagnetic compounds 2-7 were characterized by electron spin resonance spectroscopy, and their molecular structures were established by single-crystal X-ray analysis. Magnetic behavior of compounds 2, 5, and 6 was investigated by superconducting quantum interference device technique in the range of 2-295 K.

Effects of oxygenated polycyclic aromatic hydrocarbons on the early life stages of Japanese medaka.

Oxygenated polycyclic aromatic hydrocarbons (oxyPAHs) are directly discharged into the atmosphere with exhaust gas from diesel engine automobiles and industry and are also generated by photo-oxidation and/or microbial metabolism of parent polycyclic aromatic hydrocarbons (PAHs). They are widely distributed in environment, especially around urban areas. We evaluated the effects of exposure to oxyPAHs as acenaphthenequinone (ANQ), 7,12-benz(a)anthracenequinone (BAQ), 1,4-naphthoquinone (NAQ), and 9,10-phenanethrenequinone (PHQ) in Japanese medaka (Oryzias latipes) embryos. ANQ (>2720μg/L) caused caving in the yolk sac, and BAQ (>22.4μg/L) caused tanning of the oil droplet. Additionally, NAQ (>314μg/L) and PHQ (>734μg/L) stopped development of medaka embryos beginning 2days after the start of exposure. The hatched larvae from embryos exposed to ANQ, BAQ, NAQ, or PHQ at 518, 9.86, 36.5, or 80.7μg/L, respectively, exhibited incomplete development of the cephalic region, incomplete palate, unabsorbed and hypertrophied yolk sac, tubular heart, altered axial curvature, and poor swimming ability. These symptoms were similar to those observed in blue sac disease, which is caused by exposure to PAHs.

Efficient Host‐Guest Complexation of a Bisporphyrin Host with Electron Deficient Guests: Synthesis, Structure, and Photoinduced Electron Transfer

AbstractThe encapsulation of 1,8‐naphthalic anhydride (NAN), 9‐dicyanomethylenefluorene (9‐DCF), acenaphthenequinone (ANQ), and 4‐chloro‐7‐nitrobenzofurazan (NBD‐Cl) by diethylpyrrole‐bridged bisporphyrin (H4DEP) and its dizinc(II) analogue (Zn2DEP) are employed to investigate the structural and spectroscopic changes within the bisporphyrin cavity upon substrate binding. Synthesis and X‐ray structures of all four encapsulated host‐guest complexes (H4DEP⋅NAN, H4DEP⋅9‐DCF, Zn2DEP⋅ANQ, and Zn2DEP⋅NBD‐Cl) are reported here. The binding constant calculations show strong 1 : 1 binding between the hosts (H4DEP and Zn2DEP) and the guests (NAN/9‐DCF/ANQ/NBD‐Cl). 1H‐NMR spectra also support the retention of the host‐guest assemblies in solution. Negative and positive shifts of the reduction and oxidation potentials, respectively, indicate that it is difficult to reduce/oxidize the encapsulated complexes. The emission intensities of the bisporphyrins (H4DEP and Zn2DEP) are substantially quenched in all the complexes, owing to photoinduced electron transfer from the excited state of the bisporphyrins to guest molecules. All the experimental evidence is further substantiated by DFT calculations. Such an efficient electron transfer is only possible when the donor and the acceptor moieties are in close propinquity to each other, which eventually lowers the reorganization energy.

Addition of phenylacetylene to a magnesium complex of monoiminoacenaphtheneone (dpp-mian).

In the presence of formic acid, acenaphthenequinone (AQ) reacts with one molar equivalent of 2,6-diisopropylaniline in toluene to give monoiminoacenaphtheneone (3, dpp-mian) in good yield. Reduction of compound 3 with an excess of magnesium in thf results in green crystalline amido-alcoholate [(dpp-mian)Mg(thf)2]2 (4). Crystallization of complex 4 from toluene affords a blue tetramer [(dpp-mian)Mg(thf)]4 (5). Reactions of compounds 4 and 5 with phenylacetylene proceed with C-C bond formation between the alkyne and the dpp-mian ligand to give the monomeric alkynyl-magnesium derivative [(dpp-mian)(PhC=CH2)Mg(C≡CPh)2(thf)]2 (7). Hydrolysis of complex 5 gives metal-free dpp-mian(PhC=CH2)H (8). Reaction of 7 with acetylacetone yields [{dpp-mian(PhC=CH2)}Mg(acac)]2 (9). Compounds 3-5 and 7-9 have been characterized by IR and NMR spectroscopy; molecular structures of 3, 5, 7, 8 and 9 have been determined by single crystal X-ray analysis.

ChemInform Abstract: Synthesis of Novel Dispiro[acenaphthylene‐pyrrolidine‐pyrrolizine] Derivatives via a 1,3‐Dipolar Cycloaddition of Azomethine Ylide

Abstractgenerated in situ from acenaphthenequinone (IV) and sarcosine with 2‐arylidenepyrrolizinone derivatives (III)

Laser flash photolysis study on the quenching reaction of the excited triplet state of acenaphthenequinone by antioxidant vitamin C

The photo-induced reactions of acenaphthenequinone (ACQ) as well as ACQ and vitamin C (VC) in ACN–H2O (v/v, 4:1) mixed solvent have been investigated by means of laser flash photolysis technique. The reaction intermediates have been identified and the reaction mechanism has been analyzed. The self-quenching rate constant of 3ACQ* by ground state ACQ and the quenching rate constant of 3ACQ* by biological antioxidant VC have also been measured. The results indicate that there is a hydrogen transfer from VC to 3ACQ* during the laser photolysis. VC is an effective quencher to 3ACQ* and the quenching rate constant is 4.0 × 108 L mol−1 s−1.

Acenaphthenequinone induces cell cycle arrest and mitochondrial apoptosis via disruption of cellular microtubules

Acenaphthenequinone (AcQ) is a polycyclic aromatic hydrocarbon, present in diesel exhausts. In this report, mechanism(s) of cytotoxicity of AcQ in human lung epithelial cells (A549) and human peripheral blood mononuclear cells (PBMC) have been investigated. Treatment with AcQ resulted in the disruption of the microtubule network in A549 cells in time and concentration-dependent manners and caused cell cycle arrest in the G2/M phase and apoptosis, with an IC50 value of ∼35 and ∼14 μM for 24 h and 48 h respectively. AcQ induced apoptosis in PBMC cells (IC50 ≈ 15 μM, 24 h). We found up-regulation of cyclin B1 and down-regulation of cyclin D1 caused G2/M arrest in treated cells. Up-regulation of pro-apoptotic proteins like p53 and Bax, and down-regulation of anti-apoptotic protein Bcl-2 were observed in treated A549 cells. Loss of mitochondrial membrane potential and activation of caspase-3 as well as release of mitochondrial cytochrome c was also obtained. AcQ also inhibited the tubulin polymerization in cell free system (IC50 ≈ 10 μM). The stoichiometry of AcQ binding to purified tubulin was nearly 1 : 1 with a dissociation constant of 11.0 ± 0.8 μM at 25 °C. Interaction of AcQ with tubulin resulted in conformational changes, monitored by quenching of tryptophan fluorescence, tubulin–colchicine and tubulin–ANS binding and CD experiments.

Electron-vibron coupling in halogenated acenaphthenequinone upon O K-edge soft x-ray absorption

We present high resolution oxygen K near-edge x-ray absorption spectra of the acenaphthenequinone (ANQ) derivative 3,8-dibromo-5,6-dichloro-ANQ (Br(2)Cl(2)-ANQ). The spectral features exhibit an almost identical vibronic fine structure compared to that shown by ANQ. The unequal distances of the vibronic levels as derived from the least-squares fit analysis of the vibronic progressions allows us to determine the anharmonicity of the excited state potentials involved. We conclude that a single vibrational progression couples to the resonant excitation of O 1s core electrons preferentially. Comparison of the two ANQ derivatives gives a clear indication that the vibronic mode corresponds to a C=O stretching mode, rather than coupling to a C-H mode as suggested previously. These conclusions are supported by density functional theory calculations.

Electronic structure, non-linear properties and vibrational analysis of Acenaphthene and its carbonyl derivative Acenaphthenequinone by density functional theory

The non-linear optical properties of Acenaphthene (ANP) and its derivative Acenaphthenequinone (ANPQ) have been evaluated and compared using the Hartree Fock (HF) and density functional theory (DFT). According to the calculations, the β value of ANP is more than five times and ANPQ is almost five times than that of urea. The molecular HOMO, LUMO composition, their respective energy gaps, MESP contours/surfaces have also been drawn and compared to explain the activity of ANPQ over ANP. For a complete description of molecular dynamics, vibrational wavenumber calculation along with normal mode analysis have been carried out at the DFT level.

Synthesis and Characterization of Dialkyl-/diphenyltin( IV) Complexes Derived from Acenaphthenequinone Monooxime

Synthesis and Characterization of Dialkyl-/diphenyltin( IV) Complexes Derived from Acenaphthenequinone Monooxime

Ethylene polymerization by sterically and electronically modulated Ni(II) α‐diimine complexes

AbstractA series of highly active ethylene polymerization catalysts based on bidendate α‐diimine ligands coordinated to nickel are reported. The ligands are prepared via the condensation of bulky ortho‐substituted anilines bearing remote push–pull substituents with acenaphthenequinone, and the precatalysts are prepared via coordination of these ligands to (DME)NiBr2 (DME = 1,2‐dimethoxyethane) to form complexes having general formula [ZN = C(An)‐C(An) = NZ]NiBr2 [Z = (4‐NH2‐3,5‐C6H2R2)2CH(4‐C6H4Y); An, acenaphthene quinone; R, Me, Et, iPr; Y = H, NO2, OCH3]. When activated with methylaluminoxane (MAO) or common alkyl aluminiums such as ethyl aluminium sesquichloride (EAS) all catalysts polymerize ethylene with activities exceeding 107 g‐PE/ mol‐Ni h atm at 30 °C and atmospheric pressure. Among the cocatalysts used EAS records the best activity. Effects of remote substituents on ethylene polymerization activity are also investigated. The change in potential of metal center induced by remote substituents, as evidenced by cyclic voltammetric measurements, influences the polymerization activity. UV–visible spectroscopic data have specified the important role of cocatalyst in the stabilization of nickel‐based active species. A tentative interpretation based on the formation of active and dormant species has been discussed. The resulting polyethylene was characterized by high molecular weight and relatively broad molecular weight distribution, and their microstructure varied with the structure of catalyst and cocatalyst. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1066–1082, 2008

Activation of 5-Lipoxygenase and NF-κB in the Action of Acenaphthenequinone by Modulation of Oxidative Stress

Quinoid polycyclic aromatic hydrocarbons are potent redox-active compounds that undergo enzymatic and nonenzymatic redox cycling with their semiquinone radical. We previously reported that acenaphthenequinone (AcQ) can damage human lung epithelial A549 cells through the formation of reactive species (RS). However, the biochemical mechanisms by which RS-generating enzymes cause oxidative burst during AcQ exposure remain elusive. Here we examined the biochemical mechanism of AcQ-induced RS generation by using selective metabolic inhibitors in A549 cells. We found that AA861, a 5-lipoxygenase (5-LO)-specific inhibitor significantly decreases RS generation. This inhibition of RS seems to be 5-LO specific because other inhibitors did not suppress AcQ-induced RS generation by nicotinamide adenine nucleotide phosphate (reduced) oxidase and/or xanthine oxidase. In addition, the inhibition of 5-LO by AA861 markedly reduced AcQ-induced nuclear factor kappa B (NF-kappa B) activation. We further found the activation of 5-LO pathway by exposing cells to AcQ mediates the secretion of inflammatory leukotriene B4, which can be significantly suppressed by a potent RS scavenger, N-acetylcysteine. Thus, based on our findings, we propose that AcQ-induced damage is likely due to increased RS generation and NF-kappa B activity through 5-LO activation.

An Environmental Quinoid Polycyclic Aromatic Hydrocarbon, Acenaphthenequinone, Modulates Cyclooxygenase-2 Expression through Reactive Oxygen Species Generation and Nuclear Factor Kappa B Activation in A549 Cells

Diesel exhaust particles (DEPs) contain oxygen-containing polycyclic aromatic hydrocarbons (PAHs) called quinoid PAHs. Some quinoid PAHs generate free radicals as they undergo enzymatic and nonenzymatic redox cycling with their corresponding semiquinone radicals. Reactive oxygen species (ROS) produced by these reactions can cause severe oxidative stress connected with inflammatory processing. Although humans and animals are continuously exposed to these chemicals in the environment, little is known about which quinoid PAHs are active. In this study, we estimated the intracellular ROS production and nuclear factor kappa B (NF-kappaB) translocation in A549 cells exposed to isomers of quinoid PAHs having two to four rings. We found that both acenaphthenequinone (AcQ) and 9,10-phenanthrenequinone (PQ) enhanced ROS generation and that AcQ translocated NF-kappaB from the cytosol to the nucleus. However, PQ, which has been reported to induce apoptosis, did not influence NF-kappaB activation. In addition, AcQ induced cyclooxygenase-2 (COX-2) expression which is a key enzyme in the inflammatory processing involved in the activation of NF-kappaB. Upregulation of NF-kappaB and COX-2 expression by AcQ treatment was suppressed by the antioxidant N-acetylcysteine (NAC). These results provide that AcQ might play an important role in human lung inflammatory diseases as an air pollutant.

Anharmonicity of the core-excited state potential of an organic molecule from NEXAFS vibronic fine structure

We present a high-resolution C K- and O K-NEXAFS study for the large aromatic molecule acenaphthenequinone (ANQ) in the condensed phase. This is the largest molecule for which a distinct vibronic fine structure at the O K-edge has been resolved so far. The most prominent results are the appearance of only one predominant vibrational mode, a C–H stretching mode, in the O 1s NEXAFS spectra and the analysis of the anharmonicity of the excited state potential.

Polycyclic Aromatics from Veratrole and Ninhydrin and Acenaphthenequinone.

Treatment of 2,2-di(3,4-dimethoxyphenyl)indane-1,3-dione with concentrated sulfuric acid gives 2,3,6,7-tetramethoxydibenzo[a,c]fluoren-13-one while under the same conditions 2,2-di(3,4-dimethoxyphenyl)acenaphthenone produces 2,3,6,7-tetramethoxydibenzo[j,l]fluoranthene.