Naphthalene System Research Articles

Toxic effects of polycyclic aromatic hydrocarbons on the two-sludge system: Combined functional gene, resistance gene and microbial community assessment

Polycyclic aromatic hydrocarbons (PAHs) were a class of persistent organic matter, and contained PAHs wastewater was discharged into wastewater treatment plants (WWTPs) finally, which could greatly affect their operational efficiency. The toxic effects of PAHs on the two-sludge system were assessed from functional genes, resistance genes, and microbial community. Three types of PAHs including Naphthalene (NAP), Anthracene (ANT), and Phenanthrene (PHE) were individually introduced into three separate two-sludge systems. Results showed that three types of PAHs did not adversely affect on nitrification performance, but exhibited a significant toxic effect on denitrification and phosphorus (PO43--P) removal. The effluent NH4+-N was almost 0 mg/L in all three systems, the highest total nitrogen (TN) removal rate was achieved at 90.88% in the PHE system, whereas the lowest rate was 72.46% in the ANT system. Concurrently, the PO43--P removal rate decreased from 93.10% to 51.22% in the ANT system. Functional genes, such as NORB and NIRS, and resistance genes such as PAH-RHD GNF/R and NAH-F/NH-R, were enriched in the PHE and NAP system, contributing to improved pollutant removal. However, the NIRK and PAH-RHD GPF/R were more abundant in the ANT system, resulting in varied pollutant removal capabilities. The composition of the microbial community was also influenced by PAH exposure with some specific functional bacteria being identified across the different systems. Among the PAHs tested, ANT was found to exert the highest toxicity towards the two-sludge system, surpassing the toxic effects of NAP and PHE. This study highlights the importance of considering PAH toxicity in the context of WWTPs operations and the potential need for tailored strategies to mitigate their impact on biological processes.

Study on novel biphenyl chalcone scaffolds: A dual spectroscopic approach for efficient sensing of hydrazine with low concentration

Hydrazine and its derivatives, as harmful substances, seriously risk the health of humans and the environment. On the basis of the admirable luminescent properties and low biological harmfulness of the biphenyl moiety, a biphenyl moiety can be combined with a naphthalene ring via the chalcone scaffold easily traced by a nucleophilic group. Therefore, biphenyl chalcones (BPCs) decorated with various naphthalene systems as fluorescent sensors for hydrazine are synthesised by Claisen-Schmidt condensation. The present work describes the comparative studies of two different protocols for the synthesis of three different BPCs. The structures of all novel BPCs were investigated by FT-IR, NMR, and HRMS spectroscopy. These BPCs show a red shift with a fluorescent peak and an enhancement in intensity with increasing solvent polarity from hexane to methanol. Methanol shows strong fluorescence emission; therefore, methanol is used as the solvent in hydrazine sensing experiments. The BPCs display fluorescent variation from yellow to blue fluorescence after binding with hydrazine. These BPCs sensors are able to identify hydrazine in a fast response rate and 5 min response time. The screening study of hydrazine in various soil samples by prepared BPCs is highly efficient. A study of the pH dependence of these probes shows excellent sensitivity in the pH range of 5 to 10.

Effect of Chemical Activation on Surface Properties of Poly(tetrafluoroethylene-co-hexafluoropropylene) Film.

Due to their low surface energy, poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films must be treated by chemical or physical activation methods before using. Among these activation strategies, using sodium naphthalene solution is a popular one. However, the effect of this strategy's chemical activation conditions on the surface properties of the FEP film is rarely discussed. In this study, FEP films were chemically activated by the sodium naphthalene solution with adjusting concentration, solvent, and activation time. With increasing concentration and activation time, many granular substances appeared on the surface of the FEP film. When tetrahydrofuran was used as a solvent, the color of the film gradually turned brown; when 1,3-dimethyl-2-imidazolidinone was chosen as the solvent, the color change was not very significant. The contact angle was significantly reduced from 112° before activation to 26° after activation, and the surface energy was greatly enhanced from 34 mN m-1 before activation to 66 mN m-1 after activation. In addition, compared with the FEP samples treated by Ar plasma, the sodium naphthalene system showed a stronger activation ability. Activated FEP films that suffered from the Ar plasma treatment could still maintain a higher energy surface than that of the pristine FEP.

X-ray Structure Determination of Naphthalen-2-yl 1-(Benzamido(diethoxyphosphoryl)methyl)-1H-1,2,3-triazole-4-carboxylate

We have previously published on a new triazolic phosphonic α-amino ester in position 4 on the triazole ring of a naphthalene ester. The aim of the present paper was to describe its crystallographic study by XRD. The crystal structure of naphthalen-2-yl 1-(benzamido(diethoxyphosphoryl)methyl)-1H-1,2,3-triazole-4-carboxylate was determined by single-crystal X-ray diffraction. This compound crystallizes in the monoclinic system, space group P21/c. The naphthalene system is almost planar and makes dihedral angles of 67.1(2)° and 63.9(2)° with the triazole ring and the phenyl cycle, respectively. The phosphorus atom is surrounded by three oxygen atoms and one carbon atom building a distorted tetrahedron. It is also noted, that one of the two ethyl groups is disordered. In the crystal, the molecules are connected through C-H…O and N-H…O hydrogen bonds to build dimers that are linked together by C-H…O hydrogen bonds, in addition to C-H…π interactions. The presence of an intramolecular hydrogen bond contributes to the stability of the molecular conformation by completing the S(5) cycle.

Comparison of naphthalene removal performance using H2O2, sodium percarbonate and calcium peroxide oxidants activated by ferrous ions and degradation mechanism

The presence of polycyclic aromatic hydrocarbons (PAHs) in groundwater is making a great threat to human health in the world which has received an increasing environmental concern. Among various Fenton oxidation processes, 97.6%, 92.1% and 89.4% naphthalene (NaP) removals were observed using hydrogen peroxide (H2O2), sodium percarbonate (SPC) and calcium peroxide (CP) as oxidants activated by Fe(II) in ultrapure water tests, respectively. While, the inhibitory effect on NaP degradation caused by the weak alkaline solution pH and the presence of HCO3− in actual groundwater could be compensated by doubling dosages of oxidants and Fe(II) to different extent. 98.0%, 49.8% and 11.5% of NaP were degraded by using H2O2, SPC and CP, respectively, strongly suggesting the best H2O2 performance among them. It was observed that 83.3% and 9.6% inhibition on NaP degradation in H2O2/Fe(II)/NaP system occurred in the presence of isopropyl alcohol and chloroform, confirming that both hydroxyl radical (HO) and superoxide anion radical (▪) contributed to NaP degradation in Fenton process and HO was the prominent radical. The presence of HO was further demonstrated by electro-spin resonance spectrometer analysis. The identification of transformation products of NaP revealed that hydroxylation and ring rupture were the main NaP degradation pathways.

Competition between Inter and Intramolecular Tetrel Bonds: Theoretical Studies Complemented by CSD Survey.

Crystal structures document the ability of a TF3 group (T=Si, Ge, Sn, Pb) situated on a naphthalene system to engage in an intramolecular tetrel bond (TB) with an amino group on the adjoining ring. Ab initio calculations evaluate the strength of this bond and evaluate whether it can influence the ability of the T atom to engage in a second, intermolecular TB with another nucleophile. A very strong CN- anionic base can approach the T either along the extension of a T-C or T-F bond and form a strong TB with an interaction energy approaching 100 kcal/mol, although this bond is weakened a bit by the presence of the internal T⋅⋅⋅N bond. The much less potent NCH base engages in a correspondingly longer and weaker TB, less than 10 kcal/mol. Such an intermolecular TB is weakened by the presence of the internal TB, to the point that it only occurs for the two heavier tetrel atoms Sn and Pb.

Synthesis of 9,10-bis(trifluoromethyl)benzobarrelenes through reaction of hexafluorobut-2-yne and substituted naphthalenes

The cycloadducts 9,10-bis(trifluoromethyl)benzobarrelenes were prepared by the reaction of hexafluorobut-2-yne (HFB) with 1- and, 2- substituted naphthalenes in moderate to high yields. In most cases the reaction proceeds with the formation of two isomeric products derived from cycloaddition of HFB to different aromatic rings of the naphthalene system. The individual isomers were isolated by column chromatography and fully characterized. The basic hydrolysis of ester derivatives of the various 9,10-bis(trifluoromethyl)benzobarrelenes provided the corresponding acids.

Crystal structure and Hirshfeld surface analysis and energy frameworks of 1-(2,4-di-methyl-phen-yl)-4-(4-meth-oxy-phen-yl)naphthalene.

In the title compound, C25H22O, the two rings of the naphthalene system are inclined to each other by 3.06 (15)°. The mean plane of the naphthalene ring system makes a dihedral angle of 65.24 (12)° with the di-methyl-phenyl ring and 55.82 (12)° with the meth-oxy-phenyl ring. The di-methyl-phenyl ring is inclined to the meth-oxy-phenyl ring by 59.28 (14)°. In the crystal, adjacent mol-ecules are linked via C-H⋯π inter-actions, forming chains along [100]. Using Hirshfeld surface and two-dimensional fingerprint plots, the presence of short inter-molecular inter-actions in the crystal structure were analysed. The inter-molecular inter-action energies were also calculated and their distribution over the crystal structure was visualized graphically using energy frameworks.

Mono BN-substituted analogues of naphthalene: a theoretical analysis of the effect of BN position on stability, aromaticity and frontier orbital energies

An insight into the electronic structure changes driven by CC → BN substitution in a naphthalene system has been given by quantum chemical calculations.

Alkyne Benzannulation Reactions for the Synthesis of Novel Aromatic Architectures.

Aromatic compounds and polymers are integrated into organic field effect transistors, light-emitting diodes, photovoltaic devices, and redox-flow batteries. These compounds and materials feature increasingly complex designs, and substituents influence energy levels, bandgaps, solution conformation, and crystal packing, all of which impact performance. However, many polycyclic aromatic hydrocarbons of interest are difficult to prepare because their substitution patterns lie outside the scope of current synthetic methods, as strategies for functionalizing benzene are often unselective when applied to naphthalene or larger systems. For example, cross-coupling and nucleophilic aromatic substitution reactions rely on prefunctionalized arenes, and even directed metalation methods most often modify positions near Lewis basic sites. Similarly, electrophilic aromatic substitutions access single regioisomers under substrate control. Cycloadditions provide a convergent route to densely functionalized aromatic compounds that compliment the above methods. After surveying cycloaddition reactions that might be used to modify the conjugated backbone of poly(phenylene ethynylene)s, we discovered that the Asao-Yamamoto benzannulation reaction is notably efficient. Although this reaction had been reported a decade earlier, its scope and usefulness for synthesizing complex aromatic systems had been under-recognized. This benzannulation reaction combines substituted 2-(phenylethynyl)benzaldehydes and substituted alkynes to form 2,3-substituted naphthalenes. The reaction tolerates a variety of sterically congested alkynes, making it well-suited for accessing poly- and oligo(ortho-arylene)s and contorted hexabenzocoronenes. In many cases in which asymmetric benzaldehyde and alkyne cycloaddition partners are used, the reaction is regiospecific based on the electronic character of the alkyne substrate. Recognizing these desirable features, we broadened the substrate scope to include silyl- and halogen-substituted alkynes. Through a combined experimental and computational approach, we have elucidated mechanistic insight and key principles that govern the regioselectivity outcome of the benzannulation of structurally diverse alkynes. We have applied these methods to prepare sterically hindered, shape-persistent aromatic systems, heterocyclic aromatic compounds, functionalized 2-aryne precursors, polyheterohalogenated naphthalenes, ortho-arylene foldamers, and graphene nanoribbons. As a result of these new synthetic avenues, aromatic structures with interesting properties were uncovered such as ambipolar charge transport in field effect transistors based on our graphene nanoribbons, conformational aspects of ortho-arylene architectures resulting from intramolecular π-stacking, and modulation of frontier molecular orbitals via protonation of heteroatom containing aromatic systems. Given the availability of many substituted 2-(phenylethynyl)benzaldehydes and the regioselectivity of the benzannulation reaction, naphthalenes can be prepared with control of the substitution pattern at seven of the eight substitutable positions. Researchers in a range of fields are likely to benefit directly from newly accessible molecular and polymeric systems derived from polyfunctionalized naphthalenes.

Understanding the effects of electronic polarization and delocalization on charge-transport levels in oligoacene systems.

Electronic polarization and charge delocalization are important aspects that affect the charge-transport levels in organic materials. Here, using a quantum mechanical/embedded-charge (QM/EC) approach based on a combination of the long-range corrected ωB97X-D exchange-correlation functional (QM) and charge model 5 (CM5) point-charge model (EC), we evaluate the vertical detachment energies and polarization energies of various sizes of crystalline and amorphous anionic oligoacene clusters. Our results indicate that QM/EC calculations yield vertical detachment energies and polarization energies that compare well with the experimental values obtained from ultraviolet photoemission spectroscopy measurements. In order to understand the effect of charge delocalization on the transport levels, we considered crystalline naphthalene systems with QM regions including one or five-molecules. The results for these systems show that the delocalization and polarization effects are additive; therefore, allowing for electron delocalization by increasing the size of the QM region leads to the additional stabilization of the transport levels.

Phase diagrams of nonadecane–decalin and nonadecane–naphthalene systems

Phase equilibria in nonadecane–decalin and nonadecane–naphthalene systems are studied. Curves of the liquidus and eutectic temperatures of these systems are calculated using the Schroder–Le Chatelier equation and the strictly regular solutions model (RSM). The calculated values and the experimental data are compared.

Thiophene-based bent-shaped luminescent liquid crystals: synthesis and characterisation

ABSTRACTFive new bent-shaped compounds based on the 2,5-disubstituted thiophene central core were successfully synthesised. The lengths of the rigid centres as well as the degree of conjugation were varied by coupling benzene, naphthalene and biphenyl systems to the thiophene through Sonogashira cross-coupling. The thermal, mesomorphic and optical properties of these variants were determined. Compounds 5a,b and 8a displayed liquid-crystalline smectic and nematic mesophases. Strong blue fluorescence was observed for the final compounds.

Electrooptical Absorption Measurements (EOAM) Testify Existence of two Conformers of Prodan and Laurdan with Different Dipole Moments in Equilibrium Ground and Franck-Condon Excited State.

The results from the electrooptical absorption measurements (EOAM) on the equilibrium ground and excited Franck-Condon state dipole moments of Prodan and Laurdan in 1,4-dioxane are presented. As follows from experiments Prodan and Laurdan in the equilibrium ground and excited Franck-Condon state have two conformers with considerably different dipole moments. The electrical dipole moments and the transition dipole moment, obtained from the short-wavelength region of the absorption spectrum are parallel. The electrical dipole moments measured at the long-wavelength spectral region are parallel to each other but not parallel to the transition dipole moment m a. The angle θ between the transition dipole moment m a and the dipole moment in the equilibrium ground state μ g of the long-wavelength conformer is about 30(0) for both probes. Obtained results evidence that donor-acceptor pairs of the short-wavelength and long-wavelength conformers are not located on the same axis. Two low-energy conformers of Prodan have been found by density functional theory (DFT) calculations, differing in the orientation of the carbonyl group towards the naphthalene system.

Impact of metal-alkoxide functionalized linkers on H2 binding: A density functional study

The effect of metal-alkoxide functionalization of different organic linkers on the H2 binding is investigated employing DFT approach. While analyzing the H2 binding interaction of magnesium-alkoxide modified benzene, naphthalene, anthracene and pyrene linkers, we find their comparable affinity toward H2 molecules. Six-member alkoxide ring containing naphthalene and pyrene systems interact with the H2 molecules in a comparatively better way than their five-member analogues. AIM, NBO and LMO-EDA analyses have been performed to comprehend the bonding nature between Mg center and the H2 molecules. Polarization along with the charge transfer interactions play significant role in stabilizing the systems.

The Excitation Spectra of Naphthalene Dimers: Frenkel and Charge‐transfer Excitons

AbstractVertical electronic excitation energies have been calculated at the second‐order approximate coupled‐cluster (CC2) level for a series of dimeric naphthalene systems. The calculated excitation energies are compared with values obtained for a single naphthalene molecule and provide information about the coupling between the naphthalene moieties in the dimers. The calculations show that the coupling between the naphthalenes depends on the distance and the energy of the exciton. At long distances and high energies the excitons on the two naphthalenes are strongly coupled, whereas the excitation energies of the few lowest states are almost unaffected by the presence of the neighboring molecules. We have also analyzed the composition of the dimeric states that consist of the individual monomer states, to investigate the charge‐transfer (CT) and the Frenkel character of the excitons. Our results indicate that the CT exciton exists at short distances, and that its population drops as the distance between the two naphthalene increases.

Photophysical Studies on Covalently-linked Naphthalene and TEMPO Free Radical Systems: Observation of a Charge Transfer State in the Ground State.

A series of molecules containing a naphthalene chromophore and a stable free radical 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) covalently linked by a spacer group of different lengths have been synthesized. In n-hexane solution, their photophysical behavior was studied and compared with a system of freely moving naphthalene and the free radical TEMPO. The linked molecules showed strong quenching of the singlet and triplet states of the naphthalene moiety, compared to when naphthalene and TEMPO were not linked. The quenching efficiency decreased with increasing the length of the spacer group. In addition, new electronic absorption and emission bands, along with the usual bands of the individual moieties, were also seen. These news bands have been attributed to the formation of electron donor-acceptor charge-transfer complexes in the ground state, arising from the interaction between the two moieties in close proximity. The photophysical dynamics of the linked molecules has been rationalized by assuming the existence of two types of population of the linked molecules: folded and extended. The ground state complex formation is proposed to occur only in the folded conformation of the linked molecules. To our knowledge, this is possibly the first example of a ground state charge-transfer complex formation involving a TEMPO free radical and naphthalene.

An enhanced “first freezing point” method for solid–liquid–gas equilibrium measurements in binary systems

This work presents an enhanced method for solid–liquid–gas (SLG) phase equilibrium measurements in binary systems. The method is mainly based on the observation of the first freezing point. It consists of the formation of first solids from fluid phase(s) by means of slow temperature decreases. In this work, additionally to the observation of the appearance of first solids, SLG equilibrium measurements were confirmed through a pressure change when the solids were formed while temperature was still decreasing at constant volume. A data acquisition system was built to allow registration of both temperature and pressure in the static-view cell in real time.The three-phase SLG equilibria for the well-studied carbon dioxide+naphthalene system were determined in order to validate our methodology. SLG equilibria were also measured for the binary systems constituted by carbon dioxide+hexadecanoic acid, octacosane, triacontane, or dotriacontane. The experiments were performed at pressures up to 39MPa and temperatures below the melting point of the pure solute. The reported uncertainties in temperature and pressure are ±0.02K and ±0.02MPa.

Synthesis of an isotopically labeled naphthalene derivative that supports a long-lived nuclear singlet state.

The synthesis of an octa-alkoxy substituted isotopically labeled naphthalene derivative, shown to have excellent properties in singlet NMR experiments, is described. This highly substituted naphthalene system, which incorporates an adjacent 13C spin pair, is readily accessed from a commercially available 13C2-labeled building block via sequential thermal alkynyl- and arylcyclobutenone rearrangements. The synthetic route incorporates a simple desymmetrization approach leading to a small difference in the chemical shifts of the 13C spin pair, a design constraint crucial for accessing nuclear singlet order.

Crystal structure of 1-nitro-4-(tri-methyl-silylethyn-yl)naphthalene.

In the title compound, C15H15NO2Si, the dihedral angle between the nitro group and the mean plane of the naphthalene system is 22.04 (11)°. In the crystal, π–π inter­actions generate supra­molecular chains propagating along the a-axis direction; the centroid-to-centroid distances range from 3.5590 (12) to 3.8535 (12) Å.