Substitution reactions in the acenaphthene analog of quino[7,8-h]quinoline and an unusual synthesis of the corresponding acenaphthylenes by tele-elimination.

The possibility of functionalization of dipyrido[3,2-e:2',3'-h]acenaphthene containing a quino[7,8-h]quinoline fragment and being a highly basic diazine analog of 1,8-bis(dimethylamino)naphthalene ("proton sponge") has been studied for the first time. In addition to the pronounced tendency of the title compound to form associates with an intramolecular hydrogen bond of the NHN type (new examples with the participation of pyridine rings, including self-associates are shown) and its inertness to amination reactions of the pyridine rings, the naphthalene core at positions 5(8) and the CH2CH2 bridge (dehydrogenation) undergo chemical modifications under mild conditions, giving the corresponding acenaphthylenes. The latter can also be obtained in an unusual way by tele-elimination from 5,8-dibromodipyridoacenaphthene by reaction with neutral or anionic bases.

Comparative Bioaccumulation of PAH and BTEX in Malapterurus electricus (Siluriformes: Malapteruridae) and its Enteric Parasite, Electrotaenia malopteruri Sampled from Lekki Lagoon, Lagos, Nigeria / Bioacumulação comparativa de HAP e BTEX em Malapterurus electricus (Siluriformes: Malapteruridae) e seu parasita entérico, Electrotaenia malopteruri, coletado na lagoa Lekki, Lagos, Nigéria

Abstract Contamination of Lekki lagoon by petrogenic chemicals such as polycyclic aromatic hydrocarbons (PAH) and benzene, toluene, ethylbenzene, and xylene (BTEX) has been widely reported. The study was aimed at investigating the bioaccumulation of PAH and BTEX in Malapterurus electricus collected from Lekki lagoon in Lagos, Nigeria. BTEX was analyzed in the intestine, water, and sediment samples using 8260B Agilent 7890B gas chromatograph coupled to a mass spectrometer (GC-MS). While PAHs were tested in the same media using a gas chromatograph coupled to a flame ionization detector (GC-FID). Histopathological analysis of the fish intestine was conducted using haematoxylin and eosin (H&E) stains. Parasite intensity, antioxidant enzymes, and lipid peroxidation activities were investigated in the fish. The parasitic infection detected in Malapterurus electricus was Electrotaenia malopteruri. The parasite showed weak and no depurative capacities for BTEX and PAH respectively. The decrease in superoxide dismutase (SOD), catalase (CAT), and reduced glutathione (GSH) in conjunction with an increase in Malondialdehyde (MDA) characterized relatively higher susceptibility among the male fish. Varieties of tissue injuries increased with the standard length of the fish groups. Results suggest that lengthier and uninfected M. electricus were more susceptible to PAH in Lekki lagoon than the shorter and infected ones. The study demonstrated a promising tendency of the enteric parasite, E. malopteruri to depurate chlorobenzene, ethylbenzene, o-xylene, m+p-xylene, and 1,4-dichlorobenzene from the intestine of its host fish, M. electricus, while PAHs were poorly mediated by the parasite.

Resumo A contaminação da lagoa Lekki por produtos químicos petrogênicos, como hidrocarbonetos aromáticos policíclicos (HAP) e benzeno, tolueno, etilbenzeno e xileno (BTEX), foi amplamente relatada. O estudo teve como objetivo investigar a bioacumulação de HAP e BTEX em Malapterurus electricus, coletados na lagoa Lekki, em Lagos, Nigéria. O BTEX foi analisado no intestino, na água e nas amostras de sedimento usando o cromatógrafo de gás Agilent 7890B 8260B acoplado a um espectrômetro de massa (GC-MS). Já os HAP foram testados no mesmo meio utilizando cromatógrafo gasoso acoplado a detector de ionização de chama (GC-FID). A análise histopatológica do intestino do peixe foi conduzida usando colorações de hematoxilina e eosina (H&E). Intensidade de parasitas, enzimas antioxidantes e atividades de peroxidação lipídica foram investigadas nos peixes. A infecção parasitária detectada em Malapterurus electricus foi Electrotaenia malopteruri. O parasita mostrou fraca e nenhuma capacidade depurativa para BTEX e HAP, respectivamente. A diminuição da superóxido dismutase (SOD), catalase (CAT) e glutationa reduzida (GSH), em conjunto com o aumento do Malondialdeído (MDA), caracterizou a suscetibilidade relativamente maior entre os peixes machos. Variedades de lesões nos tecidos aumentaram com o comprimento padrão dos grupos de peixes. Os resultados sugerem que os M. electricus maiores e não infectados foram mais suscetíveis aos HAP na lagoa Lekki do que os menores e infectados. O estudo demonstrou uma tendência promissora do parasita entérico E. malopteruri de depurar clorobenzeno, etilbenzeno, o-xileno, m + p-xileno e 1,4-diclorobenzeno do intestino de seu peixe hospedeiro, M. electricus, enquanto os HAP foram mal mediados pelo parasita.

The Synthesis and Antitumor Activity of 1,8-Naphthalimide Derivatives Linked 1,2,3-Triazole.

In this study, acenaphthylene was used as the raw material, and a series of novel 1,8-naphthalimide-1,2,3-triazole derivatives was obtained through oxidation, acylation, alkylation, and click reactions, and subsequently, their anti-tumor activities were tested. After screening, we found that Compound 5e showed good activity against H1975 lung cancer cells, with the half maximal inhibitory concentration (IC50) reaching 16.56 µM.

Migration of creosote components from timbers treated with creosote and processed using Best Management Practices.

While creosote components have very low water solubility, concerns have been raised about potential environmental effects and stimulated research to minimize migration. Best management practices have been developed but there are few data quantifying their effects. The effects of post-treatment steaming on migration of polycyclic aromatic hydrocarbons (PAHs) from horizontally oriented creosote treated southern pine decking subjected to simulated rainfall were examined. Twelve of the 16 PAHs examined were detected in runoff during the rainfall exposure but at concentrations well below those predicted by water solubility. PAH levels declined with increasing rainfall time, although the differences were sometimes slight. Steaming for 1 h had minimal effect on PAH levels in runoff while 3 h of steaming produced more noticeable reductions ranging from ~20 to 80% for naphthalene, acenaphthylene, and acenaphthene. Longer post-treatment steaming times reduced initial losses of creosote components from treated wood.

Alternated biodegradation of naphthalene (NAP), acenaphthylene (ACY) and acenaphthene (ACE) in an aerobic granular sludge reactor (GSBR).

The paper presents quantitative changes of selected 2- and 3-ring PAHs after process phases of GSBR reactor. The studies have been carried out for 264 cycles of GSBR reactor, during which concentration of naphthalene was increased in the range of 3.00-710.00 µg/L, acenaphthylene 1.00-160.00 µg/L, acenaphthene 3.00-440.00 µg/L. GSBR operating cycle consisted of filling (30 min), mixing (90 min), aeration (540 min), sedimentation (10 min), decanting (30 min) and downtime (20 min) phases. Activated sludge dry mass concentration was 4.00 kg/m3. Conducted studies showed that in GSBR reactor naphthalene was degraded with the highest intensity. Results of the statistical analysis confirmed that naphthalene concentrations were statistically significantly different (α = 0.05) after each individual GSBR process phase, while in case of acenaphthene and acenaphthylene, the differences were observed only between mixing and aeration phases. Additionally, equations estimating concentrations of PAHs in treated wastewater were developed. Selected activated sludge technological parameters (sludge volume index, sludge and hydraulic retention time) and concentration of PAHs were used for equations. The R2 coefficients of equations were above 0.99, which indicates a good adjustment of estimation to observed values.

Azaacenes Bearing Five-Membered Rings.

We report the synthesis of processible (dihydro)pyracyclene- and acenaphthylene-substituted azaacenes using condensation reactions in solution. The targets are characterized via cyclic voltammetry, X-ray crystallography, UV/Vis, fluorescence spectroscopy and DFT/NICS calculations. Formal hydrogenation of the annulated five-membered ring surprisingly alters emission in the solid-state as a consequence of modulation of aromaticity and HOMO-LUMO overlap. Five highly fluorescent, crystalline azaacenes were investigated as emitters in organic light-emitting diodes, and their performance with respect to luminance and efficiency was compared to that of structurally related azaacenes.

Comparative Bioaccumulation of PAH and BTEX in Malapterurus electricus (Siluriformes: Malapteruridae) and its Enteric Parasite, Electrotaenia malopteruri Sampled from Lekki Lagoon, Lagos, Nigeria

Abstract Contamination of Lekki lagoon by petrogenic chemicals such as polycyclic aromatic hydrocarbons (PAH) and benzene, toluene, ethylbenzene, and xylene (BTEX) has been widely reported. The study was aimed at investigating the bioaccumulation of PAH and BTEX in Malapterurus electricus collected from Lekki lagoon in Lagos, Nigeria. BTEX was analyzed in the intestine, water, and sediment samples using 8260B Agilent 7890B gas chromatograph coupled to a mass spectrometer (GC-MS). While PAHs were tested in the same media using a gas chromatograph coupled to a flame ionization detector (GC-FID). Histopathological analysis of the fish intestine was conducted using haematoxylin and eosin (H&E) stains. Parasite intensity, antioxidant enzymes, and lipid peroxidation activities were investigated in the fish. The parasitic infection detected in Malapterurus electricus was Electrotaenia malopteruri. The parasite showed weak and no depurative capacities for BTEX and PAH respectively. The decrease in superoxide dismutase (SOD), catalase (CAT), and reduced glutathione (GSH) in conjunction with an increase in Malondialdehyde (MDA) characterized relatively higher susceptibility among the male fish. Varieties of tissue injuries increased with the standard length of the fish groups. Results suggest that lengthier and uninfected M. electricus were more susceptible to PAH in Lekki lagoon than the shorter and infected ones. The study demonstrated a promising tendency of the enteric parasite, E. malopteruri to depurate chlorobenzene, ethylbenzene, o-xylene, m+p-xylene, and 1,4-dichlorobenzene from the intestine of its host fish, M. electricus, while PAHs were poorly mediated by the parasite.

Resumo A contaminação da lagoa Lekki por produtos químicos petrogênicos, como hidrocarbonetos aromáticos policíclicos (HAP) e benzeno, tolueno, etilbenzeno e xileno (BTEX), foi amplamente relatada. O estudo teve como objetivo investigar a bioacumulação de HAP e BTEX em Malapterurus electricus, coletados na lagoa Lekki, em Lagos, Nigéria. O BTEX foi analisado no intestino, na água e nas amostras de sedimento usando o cromatógrafo de gás Agilent 7890B 8260B acoplado a um espectrômetro de massa (GC-MS). Já os HAP foram testados no mesmo meio utilizando cromatógrafo gasoso acoplado a detector de ionização de chama (GC-FID). A análise histopatológica do intestino do peixe foi conduzida usando colorações de hematoxilina e eosina (H&E). Intensidade de parasitas, enzimas antioxidantes e atividades de peroxidação lipídica foram investigadas nos peixes. A infecção parasitária detectada em Malapterurus electricus foi Electrotaenia malopteruri. O parasita mostrou fraca e nenhuma capacidade depurativa para BTEX e HAP, respectivamente. A diminuição da superóxido dismutase (SOD), catalase (CAT) e glutationa reduzida (GSH), em conjunto com o aumento do Malondialdeído (MDA), caracterizou a suscetibilidade relativamente maior entre os peixes machos. Variedades de lesões nos tecidos aumentaram com o comprimento padrão dos grupos de peixes. Os resultados sugerem que os M. electricus maiores e não infectados foram mais suscetíveis aos HAP na lagoa Lekki do que os menores e infectados. O estudo demonstrou uma tendência promissora do parasita entérico E. malopteruri de depurar clorobenzeno, etilbenzeno, o-xileno, m + p-xileno e 1,4-diclorobenzeno do intestino de seu peixe hospedeiro, M. electricus, enquanto os HAP foram mal mediados pelo parasita.

Crystal structures of two substituted thia-zolidine derivatives.

In the first of the compounds reported herein, namely 6'-ferrocenyl-6a'-nitro-6',6a',6b',7',9',11a'-hexa-hydro-2H-spiro-[ace-naphthyl-ene-1,11'-chromeno[3',4':3,4]pyrrolo-[1,2-c]thia-zol]-2-one, [Fe(C5H5)(C29H21N2O4S)], (I), the thia-zolidine ring adopts a twist conformation on the methine N-C atoms. In the second compound, viz. 6'-(4-methoxy-phen-yl)-6a'-nitro-6',6a',6b',7',9',11a'-hexa-hydro-2H-spiro-[ace-naphthyl-ene-1,11'-chromeno[3',4':3,4]pyrrolo-[1,2-c]thia-zol]-2-one, [Fe(C5H5)(C26H19N2O5S)], (II), the thia-zolidine ring adopts an envelope conformation with a methine C atom as the flap. In both compounds, the pyrrolidine ring adopts a twist conformation on the thia-zolidine and tetra-hydro-pyran C atoms. The mean planes of the thia-zolidine and pyrrolidine rings subtend angles of 67.30 (1) and 62.95 (7)° in (I) and (II), respectively, while the mean plane of the pyrrolidine ring makes dihedral angles of 76.53 (1) and 87.74 (7)° with the ace-naphthyl-ene ring system in (I) and (II), respectively. In both compounds, an intra-molecular C-H⋯O hydrogen bond forms an S(7) ring motif. In the crystal of (I), mol-ecules are linked via two different C-H⋯O hydrogen bonds, forming chains along [001] and [100]. In (II), they are linked through C-H⋯O hydrogen bonds, forming dimers with an R 2 (2)(10) ring motif while C-H⋯π inter-actions link the mol-ecules in a head-to-tail fashion, forming chains along the a-axis direction.

Crystal structure of 5''-benzyl-idene-1'-methyl-4'-phenyl-tri-spiro-[ace-naphthyl-ene-1,2'-pyrrolidine-3',1''-cyclo-hexane-3'',2'''-[1,3]dioxane]-2,6''-dione.

In the title compound, C36H31NO4, two spiro links connect the methyl-substituted pyrrolidine ring to the ace-naphthyl-ene and cyclo-hexa-none rings. The cyclo-hexa-none ring is further connected to the dioxalane ring by a third spiro junction. The five-membered ring of the ace-naphthylen-1-one ring system adopts a flattened envelope conformation with the ketonic C atom as flap, whereas the dioxalane and pyrrolidine rings each have a twist conformation. The cyclo-hexa-none ring assumes a boat conformation. Three intra-molecular C-H⋯O hydrogen bonds involving both ketonic O atoms as acceptors are present. In the crystal, C-H⋯O hydrogen bonds connect centrosymmetrically related mol-ecule into chains parallel to the b axis, forming rings of R 2 (2)(10)and R 2 (2)(8) graph-set motifs.

Crystal structure of 5''-(4-chloro-benzyl-idene)-4'-(4-chloro-phen-yl)-1'-methyltri-spiro[acenapthylene-1,2'-pyrrolidine-3',1''-cyclo-hexane-3'',2'''-[1,3]dioxane]-2(1H),6''-dione.

In the title compound, C36H29Cl2NO4, two spiro links connect the methyl-substituted pyrrolidine ring to the ace-naphthyl-ene and cyclo-hexa-none rings. The cyclo-hexa-none ring is further connected to the dioxalane ring by a third spiro junction. The five-membered ring of the ace-naphthylen-1-one ring system adopts a flattened envelope conformation, with the ketonic C atom as the flap, whereas the dioxalane and pyrrolidine rings each have a twist conformation. The cyclo-hexenone ring assumes a boat conformation. An intra-molecular C-H⋯O hydrogen-bond inter-action is present. In the crystal, mol-ecules are linked by non-classical C-H⋯O hydrogen bonds, forming chains extending parallel to the a axis.

Mechanism and thermal rate constant for the gas-phase ozonolysis of acenaphthylene in the atmosphere.

Due to its prevalent presence, it is critical to clarify the atmospheric fate of acenaphthylene (Ary). In this paper, the reaction mechanism of the gas-phase ozonolysis of Ary was investigated by using quantum chemistry methods. Possible reaction pathways were discussed, and the theoretical results were compared with the available experimental data. The rate constants of the crucial elementary reactions were determined by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The main products include secondary ozonide, naphthalene-1,8-dicarbaldehyde, 1,8-naphthalic anhydride, oxaacenaphthylene-2-one, 1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and α-hydroxyhydroperoxide. The reaction of the unsaturated cyclo-pentafused ring with O3 is the dominant pathway. The overall rate constant of the O3 addition reaction is 5.31×10(-16)cm(3)molecule(-1)s(-1) at 298 K and 1 atm. The atmospheric lifetime of Ary determined by O3 is about 0.75 h. This work provides a comprehensive investigation of the ozonolysis of Ary and should help to understand its atmospheric fate.

Crystal structure of (2E)-N-methyl-2-(2-oxo-1,2-di-hydroacenaphthylen-1-ylidene)hydrazinecarbo-thioamide.

In the title compound, C14H11N3OS, the ace-naphthyl-ene ring system and hydrazinecarbo-thio-amide unit (=N-NH-C=S-NH-) are essentially coplanar [with maximum deviations from their mean planes of -0.009 (2) and 0.033 (2) Å, respectively], and make a dihedral angle of 1.59 (9)°. The mol-ecular conformation is stabilized by two weak intra-molecular hydrogen bonds (N-H⋯O and N-H⋯N), which generate S(6) and S(5) ring motifs. In the crystal, mol-ecules are linked by N-H⋯S hydrogen bonds, forming chains along [010]. The chains are linked via pairs of C-H⋯O hydrogen bonds, enclosing R (2) 2(10) ring motifs, and C-H⋯π inter-actions, forming a three-dimensional framework. The absolute structure of the title compound was determined by resonant scattering.

Optimizing separation conditions of 19 polycyclic aromatic hydrocarbons by cyclodextrin-modified capillary electrophoresis and applications to edible oils.

For the first time, the separation of 19 polycyclic aromatic hydrocarbons (PAHs) listed as priority pollutants in environmental and food samples by the United States Environmental Protection Agency (US-EPA) and the European Food Safety Authority was developed in cyclodextrin (CD)-modified capillary zone electrophoresis with laser-induced fluorescence detection (excitation wavelength: 325 nm). The use of a dual CD system, involving a mixture of one neutral CD and one anionic CD, enabled to reach unique selectivity. As solutes were separated based on their differential partitioning between the two CDs, the CD relative concentrations were investigated to optimize selectivity. Separation of 19 PAHs with enhanced resolutions as compared with previous studies on the 16 US-EPA PAHs and efficiencies superior to 1.5 × 10(5) were achieved in 15 min using 10mM sulfobutyl ether-ß-CD and 20mM methyl-ß-CD. The use of an internal standard (umbelliferone) with appropriate electrolyte and sample compositions, rinse sequences and sample vial material resulted in a significant improvement in method repeatability. Typical RSD variations for 6 successive experiments were between 0.8% and 1.7% for peak migration times and between 1.2% and 4.9% for normalized corrected peak areas. LOQs in the low µg/L range were obtained. For the first time in capillary electrophoresis, applications to real vegetable oil extracts were successfully carried out using the separation method developed here.

Capabilities and limitations of dispersive liquid-liquid microextraction with solidification of floating organic drop for the extraction of organic pollutants from water samples.

Dispersive liquid-liquid microextraction with solidification of floating organic drop (DLLME-SFO) is one of the most interesting sample preparation techniques developed in recent years. Although several applications have been reported, the potentiality and limitations of this simple and rapid extraction technique have not been made sufficiently explicit. In this work, the extraction efficiency of DLLME-SFO for pollutants from different chemical families was determined. Studied compounds include: 10 polycyclic aromatic hydrocarbons, 5 pesticides (chlorophenoxy herbicides and DDT), 8 phenols and 6 sulfonamides, thus, covering a large range of polarity and hydrophobicity (LogKow 0-7, overall). After optimization of extraction conditions using 1-dodecanol as extractant, the procedure was applied for extraction of each family from 10-mL spiked water samples, only adjusting sample pH as required. Absolute recoveries for pollutants with LogKow 3-7 were >70% and recovery values within this group (18 compounds) were independent of structure or hydrophobicity; the precision of recovery was very acceptable (RSD<12%) and linear behavior was observed in the studied concentration range (r(2)>0.995). Extraction recoveries for pollutants with LogKow 1.46-2.8 were in the range 13-62%, directly depending on individual LogKow values; however, good linearity (r(2)>0.993) and precision (RSD<6.5%) were also demonstrated for these polar solutes, despite recovery level. DLLME-SFO with 1-dodecanol completely failed for extraction of compounds with LogKow≤1 (sulfa drugs), other more polar extraction solvents (ionic liquids) should be explored for highly hydrophilic pollutants.

Effect of 16 pure hydrocarbons on the stabilization and lysis of fish (mudskipper: Boleophthalmus dussumieri) erythrocytes.

The in vitro effects of polycyclic aromatic hydrocarbons (PAHs) on erythrocyte membrane stability of the mudskipper (i.e., Boleophthalmus dussumieri) were tested by using field concentrations, acute and chronic potency divisor concentrations. This was achieved by studying their lytic or antilytic effects on fish erythrocytes in critical hypotonic saline media. The interaction of PAHs acute potency divisor concentrations with mudskipper erythrocyte causes dramatic changes in the structure of the membrane. A significant difference (p<0.05) was found between the control and treatment groups of mudskipper erythrocyte exposed to acute potency divisor concentrations. No significant difference (p>0.05) was observed between the control and the treatment groups of mudskipper erythrocyte exposed to field concentrations. The results showed that chronic potency divisor concentrations of PAHs protect mudskipper erythrocyte against osmotic hemolysis. Our results could be extended to the use of Erythrocyte Osmotic Fragility (EOF) test as a biochemical marker of membrane toxicity in marine pollution biomonitoring. However, results showed that membrane stability is not an appropriate biomarker for PAHs pollution after short exposure duration.

Topochemical control of the photodimerization of aromatic compounds by γ-cyclodextrin thioethers in aqueous solution.

The formation of soluble 1:2 complexes within hydrophilic γ-cyclodextrin (γ-CD) thioethers allows to perform photodimerizations of aromatic guests under controlled, homogenous reaction conditions. The quantum yields for unsubstituted anthracene, acenaphthylene, and coumarin complexed in these γ-CD thioethers were found to be up to 10 times higher than in the non-complexed state. The configuration of the photoproduct reflected the configuration of the dimeric inclusion complex of the guest. Anti-parallel orientation of acenaphthylene within the CD cavity led to the exclusive formation of the anti photo-dimer in quantitative yield. Parallel orientation of coumarin within the complex of a CD thioether led to the formation of the syn head-to-head dimer. The degree of complexation of coumarin could be increased by employing the salting out effect.

Using SPMDs to monitor the seawater concentrations of PAHs and PCBs in marine protected areas (Western Mediterranean).

Aqueous concentrations of individual polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in coastal sites of two marine protected areas (MPAs), that is, Asinara and the La Maddalena Archipelago, in Sardinia (Western Mediterranean Sea). The use of semi-permeable membrane devices (SPMDs) enabled the detection of dissolved PAHs and PCBs, even in very low concentrations of (pgL(-1)), in seawater. The results reveal significant differences between the two sampling areas relative to the concentration of the individual PAHs, which provide information concerning the pollution sources affecting relatively pristine environments. The PCBs were generally observed at levels below the detection limits of the utilised method.