Three-dimensional Holographic Vector of Atomic Interaction Field(3D-HoVAIF) for the QSPR/QSAR of Polychlorinated Naphthalenes

Three-dimensional holographic vector of atomic interaction field（3D-HoVAIF） is used to describe the chemical structures of polychlorinated naphthalenes（PCNs）.After variable screening by stepwise multiple regression（SMR） technique,the liner relationships between gas-chromatographic relative retention time（RRT）,298 K supercooled liquid pressures（logPL）,n-octanol/air partition coefficient（logKOA）,n-octanol/water partition coefficient（logKOW）,aqueous solubilities（logSW）,relative in vitro potency values（-logEROD） of PCNs and 3D-HoVAIF descriptors have been established by partial least-square（PLS） regression.The result shows that the 3D-HoVAIF descriptors can be well used to express the quantitative structure-property（activity） relationships of PCNs.Predictive capability of the models has also been demonstrated by leave-one-out cross-validation.Moreover,the predicted values have been presented for those PCNs which are lack of experimentally physico-chemical properties and biological activity by the optimum models.

Alkyl Naphthalenes and Phenanthrenes:Molecular Markers for Tracing Filling Pathways of Light Oil and Condensate Reservoirs

Condensates and light oils are generally characterized by high maturity, low concentration of sterane and terpane biomarkers and low content of non-hydrocarbon fraction. As a result, some commonly-used sterane, terpane and carbazole migration parameters in conventional oil reservoirs may have a certain limitation in condensate and light oil reservoirs for their poor signal-noise ratios in the gas chromatography-mass spectrometry （GC-MS）. Naphthalene, phenanthrene and their methylated substituents, however, are present in significant concentrations in condensates and light oils. Taking the Fushan depression （in the Beibuwan Basin, Northern South China Sea） as an example, this paper attempts for the first time to use polycyclic aromatic hydrocarbon （PAH）-related parameters to trace migration directions and filling pathways for condensate and light oil reservoirs. The result shows that TMNr （i.e. 1, 3, 7-TMN/（1, 3, 7-TMN ＋ 1, 2, 5-TMN）, TMN： trimethylnaphthalene））, MPI-1 （i.e. 1.5×（2-MP ＋ 3-MP）/（P ＋ 1-MP ＋ 9-MP）, P： phenanthrene MP： methyiphenanthrene）, MN/DMN （∑methylnaphthalene/∑dimethylnaphthalene, %） and MN/TMN （∑nethylnaphthalene/∑trimethylna- phthalene, %） can be used to trace the filling pathways of condensate and light oil reservoirs. These parameters, together with geological consideration and other bulk oil properties （e.g. the gas to oil ratio and density）, suggest that the condensates and light oils in the Huachang oil and gas field are mainly sourced from the Bailian sag that is located to the northeast of the Huachang uplift in the Fushan depression.

MEDV-13 for QSRR of 62 Polychlorinated Naphthalenes

A molecular electronegativity distance vector based on 13 atomic types (MEDV-13) is used to describe the structures of 62 polychlorinated naphthalene (PCN) congeners and related to the gas chromatographic relative retention indices (RIs) of PCNs. Using multiple linear regression, a 4-variable quantitative structure-retention relationship (QSRR) with the correlation coefficient of estimations (r) being 0.9912 and the root mean square error of estimations (RMSEE) being 31.4 and the correlation coefficient of predictions (q) and the root mean square error of predictions (RMSEP) in the leave-one-out procedure are 0.9898 and 33.76, respectively.

Iodocyclization of Diallyl-Dihydroxy Naphthalenes Using <i>N</i>-Iodosuccinimide vs Molecular Iodine in Aqueous Micelle

A number of doubly-fused [1,2] naphthodifurans have been synthesized from the corresponding diallyl-dihydroxy naphthalene precursors involving N-iodosuccinimide in acetonitrile and also by molecular iodine in aqueous micelle using CTAB as surfactant. The electrophilic cyclization occurs regioselectively by a 5-exo-trig mode of cyclization.

Electrode material promoted dehydrogenative homo-/cross-coupling of weakly activated naphthalenes

Herein,we reported an electrochemical dehydrogenative homo-/cross-coupling of weakly activated naphthalene in the exogenous transition metal-and oxidants-free manner.Benefiting from the microscopic interaction between the reactants and the carbon plate anode,the electropolymerization of aromatic rings was suppressed.And a series of binaphthyl and naphthalene-aryl privileged scaffolds were obtained in 28%–90%yields by homo-or cross-coupling.This C(sp2)-H activation strategy featured atom and step economy as well as the ready scalability.

Palladium-Catalyzed Asymmetric Domino Heck/Carbocyclization/Suzuki Reaction:A Dearomatization of Nonactivated Naphthalenes

Herein,we report a novel palladium(Pd)-catalyzed asymmetric domino Heck/carbocyclization/Suzuki reaction of N-(2-bromoaryl)-2-naphthylacrylamides.The reaction involves a novel and enantioselective dearomative 1,2-insertion of the naphthalene group,thus providing a unique dearomatization strategy of nonactivated naphthalenes.A new phosphoramidite ligand L12,which displayed excellent reactivity and enantioselectivity in the reaction,has been developed.

MeOTf-catalyzed formal[4+2]annulations of styrene oxides with alkynes leading to polysubstituted naphthalenes through sequential electrophilic cyclization/ring expansion

Me OTf-catalyzed formal[4+2]annulation of styrene oxides with alkynes to afford polysubstituted naphthalenes has been realized,which undergoes sequential electrophilic cyclization/ring expansion.A range of substrates were tolerated in the formation of naphthalene derivatives with high regioselectivity in satisfactory yields.The reaction could also be carried out on gram scale.

Polychlorinated Naphthalenes (PCNs) in Surface Sediments of the Yangtze and Yellow River Estuaries,China

The concentrations and congener profiles of poly- chlorinated naphthalenes （PCNs） in surface sediment samples collected from the Yangtze and Yellow River Estuaries were inves- tigated. PCN congeners （from MoCNs to OCN） were determined by isotope dilution/high-resolution gas chromatography/high- resolution mass spectrometry （HRGC-HRMS）. The total concen- trations of PCNs were 34.3-303.0 pg/g （dry weight, dw） in the Yangtze Estuary samples and 6.2-408.0 pg/g （dw） in the Yellow River Estuary samples, which were lower compared with that in other sediments reported by previous studies. In addition, the re- markably different homologue or congener profiles of PCNs have been obtained in this study. Samples dominated with MoCNs to TrCNs might be attributed to atmospheric deposition and global fractionation, while in other samples taken from the surrounding industrial areas the enrichment of higher chlorinated homologues suggested that the industrial and human activities should be the main potential sources.

Synthesis of Substituted Naphthalenes by 1,4-Palladium Migration Involved Annulatlon w,th Internal Alkynes

The palladium catalyzed annulation of 1-bromo-2-vinylbenzene derivatives with internal alkynes was realized for the efficient synthesis of substituted naphthalenes. A controllable aryl to vinylic 1,4-palladium migration process is the key for success.

Rheological and physicomechanical properties of rod milling sand-based cemented paste backfill modified by sulfonated naphthalene formaldehyde condensate

Rod milling sand(RMS)—a coarse sand aggregate—was recycled for cemented paste backfill(CPB)for the underground mined area at the Jinchuan nickel deposit,named rod milling sand-based cemented paste backfill(RCPB).The adverse effects of coarse particles on the transportation of CPB slurry through pipelines to underground stopes resulting in weakening of the stability of the backfill system are well known.Therefore,sulfonated naphthalene formaldehyde(SNF)condensate was used for the performance improvement of RCPB.The synergistic effect of solid content(SC),lime-to-sand ratio,and SNF dosage on the rheological and physicomechanical properties,including slump,yield stress,bleeding rate,uniaxial compressive strength(UCS),as well as mechanism analysis of RCPB,have been explored.The results indicate that the effect of SNF on RCPB performance is related to the SNF dosage,lime-to-sand ratio,and SC.The slump of fresh RCPB with 0.1wt%-0.5wt%SNF increased by 2.6%-26.2%,whereas the yield stress reduced by 4.1%-50.3%,indicating better workability and improved cohesiveness of the mix.The bleeding rate of fresh RCPB decreased first and then rose with the increase of SNF dosage,and the peak decrease was 67.67%.UCS of RCPB first increased and then decreased with the increase of SNF dosage.At the optimal SNF addition ratio of 0.3wt%,the UCS of RCPB curing for 7,14 and,28 d ages increased by 31.5%,28.4%,and 29.5%,respectively.The beneficial effects of SNF in enhancing the early UCS of RCPB have been corroborated.However,the later UCS increases at a slower rate.The research findings may guide the design and preparation of RCPB with adequate performance for practical applications.

Chelators to assist the high dispersion of Ni_(2)P particles over mesoporous silica nanospheres for hydrogenating reaction

NizP supported catalysts exhibit high catalytic activities in hydrogenation reaction,of which the particle sizes of Ni_(2)P active phases are the key influential factor.This research focus on the effect of chelators on the size of Ni_(2)P particles over wrinkle silica nanoparticles(WSNs)by introducing chelating agents EDTA and NTA during impregnation process.The characterization results show that chelators modified cata-lysts possess smaller size of Ni_(2)P particles than the unmodified Ni_(2)P catalysts.Among all the synthesized catalysts,the EDTA modified Ni_(2)PE(1.5)/WSNs catalyst possesses smallest average particle size of Ni_(2)P,only 2.6 nm.Moreover,the Ni_(2)P catalysts with the assistance of EDTA exhibits better catalytic activity than that of NTA under high reaction temperature,which can be ascribed to the strong bonding between EDTA and Ni.And the EDTA modified Ni_(2)PE(1.5)/WSNs catalyst shows highest hydrogenation ability,almost reaching 100%decalin selectivity.

Photoactive Naphthalene Diimide Functionalized Titanium-Oxo Clusters with High Photoelectrochemical Responses

Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two cyclic TOCs are reported,namely,[Ti_(6)(μ_(3)-O)_(2)(Oi-Pr)_(8))(LA)_(2)]·i-PrOH(S1)and[Ti_(6)(μ_(3)-O)2(Oi-Pr)_(8))(LV)_(2)]·i-PrOH(S2),which are functionalized by photoactive naphthalene diimide(NDI)chromophores.Their molecular structures and photophysical and photochemical properties were systematically studied.As shown by ultraviolet-visible(UV-vis)spectra and photocurrent study results,the band gap and the photocurrent response of S1 and S2 were derived from NDI ligands which extend the absorption edge of S1 and S2 approaching 500 nm and afford high photocurrent densities of 2.12μA/cm^(2)and 1.95μA/cm^(2)for S1 and S2,respectively,demonstrating the significance of the photoactive ligand in modulating photoresponse of TOCs.This work is expected to enrich the structural library of photoactive TOCs and provide insights into understanding the structure-property relationships of sensitized clusters.

Computational Study for the Aromatic Nucleophilic Substitution Reaction on 1-Dimethylamino-2,4-bis(trifluoroacetyl)-naphthalene with Amines

Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.

Treatment of naphthalene derivatives with iron-carbon micro-electrolysis

The degradation of five naphthalene derivatives in the simulated wastewater was investigated using the iron-carbon micro-electrolysis method.The optimal initial pH of solution and adsorption of iron-carbon and removal efficiency of the total organic carbon(TOC)were investigated.The results show that the removal efficiency of the naphthalene derivatives can reach 48.9%?92.6% and the removal efficiency of TOC is 42.8%?78.0% for the simulated wastewater with 200 mg/L naphthalene derivatives at optimal pH of 2.0?2.5 after 120 min treatment.The degradation of five naphthalene derivatives with the micro-electrolysis shows the apparent first-order kinetics and the order of removal efficiency of the naphthalene derivatives is sodium 2-naphthalenesulfonate,2-naphthol,2,7-dihydroxynaphthalene,1-naphthamine,1-naphthol-8-sulfonic acid in turn.It is illustrated that the substituents of the naphthalene ring can affect the removal efficiency of naphthalene due to their electron-withdrawing or electron-donating ability.

Effects of temperature and surfactants on naphthalene and phenanthrene sorption by soil

Adsorption experiments were carried out to investigate the sorption behaviors of naphthalene and phenanthrene in six different soils and to determine the effects of temperature, linear alkylbenzene sulfonate （LAS） and cetylrimethyl ammonium bromide （CTAB） on sorption. The results show that for a given sorbent phenanthrene exhibited greater nonlinear and stronger sorption than naphthalene. There was a strong negative correlation for the Koc values with organic carbon content （foc）. The increase of temperature was not favorable to sorption. Sorption decreased along with the increasing aqueous LAS concentration from 0 to 1000 mg/L. At low CTAB concentration （〈 100 mg/L）, the adsorption increased as CTAB hemimicelles formed on the soil surface. At high concentration, CTAB decreased the adsorption by occupying active hydrophobic adsorption sites and solubilization of naphthalene and phenanthrene.

Effect of Competitive Adsorption between Sodium Tripolyphosphate and Naphthalene Superplasticizer on Fluidity of Cement Paste

The adsorption amount, ξ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer （FDN） and STPP. The experimental results showed that the presence of STPP could significantly improve the fluidity of cement paste and reduce the fluidity loss with FDN. There existed a competitive adsorption between STPP and FDN. STPP and calcium ions formed complexes; they preferentially adsorbed onto surface of cement particles and preempt adsorption points of FDN; and it reduced adsorption amount of FDN. In the absence of STPP, saturation adsorption amount of FDN was 5.93 mg/g; but when the dosage of STPP was 0.1%, it reduced to 4.3 mg/g （about 72.5%）. The adsorption amount of FDN was reduced by STPP, but ξ-potential of cement particles enhanced and fluidity of cement paste increased because of strong negative charge effect of the complexes. Adsorption of the complexes would delay Ca^2＋ into liquid and inhibit formation of active adsorption points. Then, content of FDN in liquid increased with the addition of STPP and ξ-potential of cement particles became stable. In this way, fluidity loss of cement paste reduced.

Catalytic performance of Cu-and Zr-modified beta zeolite catalysts in the methylation of 2-methylnaphthalene

2,6-Dimethylnaphthalene(2,6-DMN) is a commercially important chemical for the production of polyethylenenaphthalate and polybutylene naphthalate. However, its complex synthesis procedure and high production cost significantly reduce the use of 2,6-DMN. In this study, the synthesis of 2,6-DMN was investigated with methylation of 2-methylnaphthalene(2-MN) over metal-loaded beta zeolite catalysts including beta zeolite, Cu-impregnated beta zeolite and Zr-impregnated beta zeolite. The experiments were performed in a fixed-bed reactor at atmospheric pressure under a nitrogen atmosphere. The reactor was operated at a temperature range of 400–500 °C and varying weight hourly space velocity between 1 and 3 h^(-1).The results demonstrated that 2,6-DMN can be synthesized by methylation of 2-MN over beta type zeolite catalysts.Besides 2,6-DMN, the product stream also contained other DMN isomers such as 2,7-DMN, 1,3-DMN, 1,2-DMN and 2,3-DMN. The activity and selectivity of beta zeolite catalyst were remarkably enhanced by Zr impregnation, whereas Cu modification of beta zeolite catalyst had an insignificant effect on its selectivity. The highest conversion of 2-MN reached81%, the highest ratio of 2,6-DMN/2,7-DMN reached 2.6 and the highest selectivity of 2,6-DMN was found to be 20% by using Zr-modified beta zeolite catalyst.

Selective catalytic hydrogenation of naphthalene to tetralin over a NiMo/Al2O3 catalyst

The selective catalytic hydrogenation of naphthalene to high-value tetralin was systematically investigated.A series of Al2O3 catalysts containing different active metals(Co,Mo,Ni,W)were prepared by incipient wetness impregnation.The effects of different active metals forms(oxidation,reduction,sulfuration)and reaction conditions on naphthalene hydrogenation were investigated and the catalysts were characterized by XRD,XPS,BET,NH3-TPD and SEM.Especially,Ni-Mo/Al2O3 was first used in this reactive system.The results show that the oxidative4%Ni O-20%MoO3/Al2O3 is the best catalyst for the preparation of tetralin.The conversion of naphthalene and the selectivity of tetralin can reach 95.62%and 99.75%respectively at 200℃,8 h and 6 MPa.Compared with reduced and sulfureted 4%Ni O-20%MoO3/Al2O3 catalysts,oxidative 4%Ni O-20%MoO3/Al2O3 has a well dispersed and uniform monolayer of the active metals,larger pore volume and size,and larger total acidity.NiO-MoO3/Al2O3 has a synergistic effect between NiO activity and MoO3 selectivity.

Effect of combining the metals of group VI supported on H-ZSM-5 zeolite as catalysts for non-oxidative conversion of natural gas to petrochemicals

The most prestigious catalyst applied in natural gas （methane） non-oxidative conversion to petrochemicals is 6%Mo/H-ZSM-5. Chromium, molybdenum and tungsten are the group VI metals. Hence, in this work, 6%Mo/H-ZSM-5 was correlated with 3%Cr＋3%Mo/H-ZSM-5 and 3%W＋3%Mo/H-ZSM-5 as catalysts to examine their promoting or inhibiting effects on the various reactions taking place during methane conversion. The catalytic activities of these catalysts were tested in a continuous flow fixed bed reactor at 700℃ and a GHSV of 1500 ml·g^-1·h^-1 Characterization of the catalysts using XRD, TGA and TPD were investigated. XRD and NH3-TPD showed greater interaction between the W-phase and the Bronsted acid sites in the channels of the zeolite than between Cr-phase and the acid sites in the zeolite.

Two new glycosides from the genus of Cassia

Two new glycosides were isolated and characterized by spectral analysis from the seeds of Cassia obtusifolia and the leaves of Cassia angustifolia. The structure was elucidated as 1-hydroxyl-2-acetyl-3,8-dimethoxynaphthalene-6-O-β-D-apiofuranosyl- （1→2）-β-D-glucopyranoside and 2-acetyl-3-methyl-8-methoxyl-1,4-naphthoquinone-6-O-β-D-glucopyranoside.