Electrochemically modified Corey-Fuchs reaction for the synthesis of arylalkynes. the case of 2-(2,2-dibromovinyl)naphthalene

The electrochemical reduction of 2-(2,2-dibromovinyl)naphthalene in a DMF solution (Pt cathode) yields selectively 2-ethynylnaphthalene or 2-(bromoethynyl)naphthalene in high yields, depending on the electrolysis conditions. In particular, by simply changing the working potential and the supporting electrolyte, the reaction can be directed towards the synthesis of the terminal alkyne (Et4NBF4) or the bromoalkyne (NaClO4). This study allowed to establish that 2-(bromoethynyl)naphthalene can be converted into 2-ethynylnaphthalene by cathodic reduction

Biodegradation of aromatic compounds by high latitude phytoplankton

"It was the purpose of the work undertaken to bring into pure culture representative diatoms from the Cook Inlet and the ice-edge in the Bering Sea and to examine their capacity for the oxidation of aromatic compounds using naphthalene as a model substrate. Three diatoms from the Cook Inlet (Kasitsna Bay) were shown to metabolize naphthalene at 6 or 12°C to 1-naphthol and other unidentified ethyl acetate and water-soluble products. Likewise, three diatoms isolated from samples collected at the ice-edge in the Bering Sea also formed small amounts of 1-naphthol from naphthalene when incubated in the light at 0 or 10°C. We have not been able to rigorously prove that any algal cell, be it a blue-green alga, a green alga, or a diatom can metabolize (1-¹⁴C) naphthalene far enough to produce ¹⁴CO₂. However, if we assume a stoichiometery of one 1-naphthol in the algae equivalent to one CO₂ in bacteria, then for mesophilic algae, the rate of 1-naphthol production is roughly estimated as 10% of the in situ marine potential, and perhaps higher if only the photic zone is considered. We have as yet, no corresponding values for rate of 1-naphthol formation from naphthalene by cold-adapted or psychrophilic diatom cultures, however, it seems reasonable to suggest that algal aromatic transformations may also be a significant fraction of bacterial activity in cold environments. In addition to studies on the oxidation of naphthalene we have also examined the sensitivity of the Bering Sea psychrophilic diatoms to crude oil samples from Cook Inlet and Prudhoe Bay. The results with pure cultures indicate that the toxicity of crude oil was enhanced in psychrophilic diatoms growing at O°C or 10°C as compared to previous studies with mesophilic forms. There are several important consequences of the results for Alaskan OCS oil and gas development. It is now clear that pure cultures of diatoms isolated from either the lower Cook Inlet or from the ice-edge in the Bering Sea can oxidize aromatic compounds such as naphthalene. Whether the metabolites persist through the food chain and will be more or less toxic than naphthalene itself is not known. The results with naphthalene also imply that the photic zone can be an important sink for aromatic hydrocarbon transformations. There are certainly differences among microalgae in the capacity to oxidize naphthalene. It seems prudent, therefore, to insure, via monitoring, that accidental introduction of aromatic compounds in Alaskan waters does not cause a selective or enrichment effect on existing phytoplankton populations. A second area of environmental concern is the suggestion of an enhanced crude oil toxicity in slower growing psychrophilic diatoms as compared to their mesophilic cousins. Crude oil spills near or under the sea ice may severely impact primary productivity, and thereby higher tropic level.Final report RD/MPF24-Effects-675April 30, 1982Marine Scienc

Novel (Heteromolecular) π-Complexes of Aromatic Cation Radicals. Isolation and Structural Characterization

Extensive (electron) delocalization in the novel heteromolecular π-complex of the hindered naphthalene cation radical (OMN+•) with naphthalene (NAP) accompanies the pronounced charge-transfer absorption band at ∼1100 nm in the near-IR. X-ray crystallography establishes the viability of the unusual “club sandwich” structure despite the repulsive electrostatic forces inherent to the dicationic unit

Phylogenetic Identification of Petroleum-Degrading Bacteria in Alaska Willow Soils

• Certain plant species may promote growth and activity of pollutant- degrading microbes in the rhizosphere. • Naphthalene is an aromatic component of petroleum fuels, which are common soil contaminants in Alaska. • Willows are known to produce and release salicylate, an intermediate in the naphthalene degradation pathway that induces the expression of microbial naphthalene degradation genes. • A previous pot study (McFarlin et al. in prep) tested the ability of Salix alaxensis (Alaskan willow) to rhizo-remediate diesel-contaminated soil. • Willow growth treatments significantly decreased the concentration of diesel range organics in soil and increased the number of cultured diesel-degrading bacteria in comparison to unplanted controls. • The effects of willow on the identity and diversity of diesel-degrading bacteria in this pot study are unknown

Protein-mediated dethreading of a biotin-functionalised pseudorotaxane

In this article, we describe the synthesis of new biotin-functionalised naphthalene derivatives 3 and 4 and their complexation behaviour with avidin and neutravidin using a range of analytical techniques. We have shown using 2-(4prime or minute-hydroxyazobenzene)benzoic acid displacement and ITC experiments{,} that compounds 3 and 4 have the propensity to form reasonably high-affinity bioconjugates with avidin and neutravidin. We have also demonstrated using 1H NMR{,} UV-vis and fluorescence spectroscopy that the naphthalene moiety of 3 and 4 facilitates the formation of pseudorotaxane-like structures with 1 in water. We have then investigated the ability of avidin and neutravidin to modulate the complexation between 1 and 3 or 4. UV-vis and fluorescence spectroscopy has shown that in both cases the addition of the protein disrupts complexation between the naphthalene moieties of 3 and 4 with 1

The effect of heavy tars (toluene and naphthalene) on the electrochemical performance of an anode-supported SOFC running on bio-syngas

The effect of heavy tar compounds on the performance of a Ni-YSZ anode supported solid oxide fuel cell was investigated. Both toluene and naphthalene were chosen as model compounds and tested separately with a simulated bio-syngas. Notably, the effect of naphthalene is almost negligible with pure H2 feed to the SOFC, whereas a severe degradation is observed when using a bio-syngas with an H2:CO = 1. The tar compound showed to have a remarkable effect on the inhibition of the WGS shift-reaction, possibly also on the CO direct electro-oxidation at the three-phase-boundary. An interaction through adsorption of naphthalene on nickel catalytic and electrocatalytic active sites is a plausible explanation for observed degradation and strong performance loss. Different sites seem to be involved for H2 and CO electro-oxidation and also with regard to catalytic water gas shift reaction. Finally, heavy tars (C>=10) must be regarded as a poison more than a fuel for SOFC applications, contrarily to lighter compounds such benzene or toluene that can directly reformed within the anode electrode. The presence of naphthalene strongly increases the risk of anode re-oxidation in a syngas stream as CO conversion to H2 is inhibited and also CH4 conversion is blocked

Elemental analysis of chamber organic aerosol using an Aerodyne high-resolution aerosol mass spectrometer

The elemental composition of laboratory chamber secondary organic aerosol (SOA) from glyoxal uptake, α-pinene ozonolysis, isoprene photooxidation, single-ring aromatic photooxidation, and naphthalene photooxidation is evaluated using Aerodyne high-resolution time-of-flight mass spectrometer data. SOA O/C ratios range from 1.13 for glyoxal uptake experiments to 0.30–0.43 for α-pinene ozonolysis. The elemental composition of α-pinene and naphthalene SOA is also confirmed by offline mass spectrometry. The fraction of organic signal at m/z 44 is generally a good measure of SOA oxygenation for α-pinene/O3, isoprene/high-NO_x, and naphthalene SOA systems. The agreement between measured and estimated O/C ratios tends to get closer as the fraction of organic signal at m/z 44 increases. This is in contrast to the glyoxal uptake system, in which m/z 44 substantially underpredicts O/C. Although chamber SOA has generally been considered less oxygenated than ambient SOA, single-ring aromatic- and naphthalene-derived SOA can reach O/C ratios upward of 0.7, well within the range of ambient PMF component OOA, though still not as high as some ambient measurements. The spectra of aromatic and isoprene-high-NO_x SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component

Benchmarking the SPARC software program for estimating solubilities of naphthalene and anthracene in organic solvents

The SPARC software program was benchmarked for calculating the solubilities of two representative polyaromatic hydrocarbons (PAHs), naphthalene and anthracene, in a range of organic solvents at various temperatures. Although SPARC was able to reasonably approximate the solubilities of naphthalene in some organic solvents, gross errors were obtained for other solvents. For anthracene, poor prediction performance was observed in all solvents considered. Overall, the results suggest that SPARC is currently not suitable for accurately predicting the solubilities of representative PAHs relevant for the petroleum sector in various organic solvents