Insight into the experiment and extraction mechanism for separating carbazole from anthracene oil with quaternary ammonium-based deep eutectic solvents

Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar.

Interlayer Energy Transfer from Naphthalene to Anthracene Chromophores Organized in Langmuir-Blodgett Films

Interlayer energy transfer between 2, 3-naphtho-10-hexadecylaza-15-crown-5 (NC16) and N-[1-(9-methoxyanthryl)]decylaza-15-crown-5 (A10C) within multilayer Langmuir-Blodgett films has been studied by steady-state fluorescence spectra. The donor and acceptor could be separated precisely by inserting stearic acid (SA) spacers. The efficiency of the energy transfer increases with the decrease in the donor-acceptor distance by a quadratic manner, suggesting the donor excitations are delocalized in the layer.

Isolation and purification of carbazole contained in anthracene slag by extraction combined with medium pressure liquid chromatography

Ultrasonic-assisted extraction(UAE)combined with medium pressure liquid chromatography(MPLC)was designed for carbazole separation from anthracene slag(AS).The effects of liquid/solid ratio,temperature,and extraction times on carbazole separation were investigated.When using CC14 and ethyl acetate as extraction solvents and combining with MPLC,carbazole recovery and purity are 75.1%and 95.4%,respectively.The mechanism for carbazole separation were presumed by examining intermolecular interactions such as N-H…π,π-π,and C-Cl…πinteractions.These results demonstrate that UAE/MPLC has a considerable potential as a green and promising strategy for separating and purifying carbazole and other chemicals from AS.

Fluorescence Quenching of Anthracene by N,N-Diethylaniline and Phenothiazine in Triton X-100/n-C_(10)H_(21) OH/H_2O Microemulsion

The photo-induced electron transfer reactions of anthracene with N,N -diethylaniline(DEA) and phenothiazine(PTZ) occur in the membrane phase of a Triton X-100/ n -C 10 H 21 OH(1-decanol)/H 2O microemulsion. DEA and PTZ exist in the membrane phase of the microemulsion. Anthracene exists in the oil continuous phase of the W/O microemulsion and in the oil core and membrane phase of the O/W microemulsion.

Establishment and evaluation of a mouse model of skin squamous cell carcinoma induced by 7, 12-dimethyl-benzodiazepine [a] anthracene at high dose

Objective: To establish a mouse model of skin squamous cell carcinoma induced by high dose 7, 12-dimethyl-benzodiazepine [a] anthracene, and to provide experimental basis for the prevention and treatment of skin squamous cell carcinoma. Methods: 36 BALB/c mice were randomly divided into 3 groups, respectively is: the high dose group (group A), low dose group (group B), and blank control group (group c), recorded in the process of building body weight in mice, and skin changes back, local skin tissue for building after HE staining of PCNA immunohistochemical staining, and the expression of PCNA positive staining level as reflected in mice skin squamous cell carcinoma of the malignant indicators, using the Image Pro Plus calculation PCNA staining of integral optical density (IOD) and positive area, and the results were statistically analyzed. Results: at 12 weeks, there were statistically significant differences in tumor number and tumor volume between group A and group B (P<0.05), and the tumor bearing rate was up to 83.3% and 66.7%, and the incidence of SCC was up to 75% and 33.3%. Immunohistochemical analysis showed statistical differences in IOD and positive area of mice in groups A, B and C (P<0.01). Conclusion: compared with the mouse model of skin squamous cell carcinoma established by the traditional two-stage protocol, this model has the characteristics of shorter experimental period, higher tumor formation rate and easier operation, providing a reliable experimental basis for the study of skin squamous cell carcinoma.

ELECTRON TRANSFER AND PHOTOCHEMICAL VALENCE ISOMERIZATION IN ANTHRACENE AND NORBORNADIENE SYSTEMS

To harvest the sun light and to promote the amount of energy stored,a new binary compound which links a sensitizer(electron donor), anthracene,and substrate(electron acceptor),norbornadiene,in a non- conjugated manner without increase in molecular weight was synthesized.The inter-and intramolecular photosensitized isomerization and the mechanism were studied.

EPR Study of the Thermal Decomposition of Transannular Peroxide of Anthracene

Thermal decomposition of transannular peroxide of anthracene (POA) (or 9,10-epidioxido anthracene) was studied by means of electron paramagnetic resonance spectroscopy (EPR) in the solid as well as in the liquid phases. Decomposition process proceeds via cleavage of the O-O bridge of the POA molecule, generating thus an alcoxy intermediate radical. Its concentration increases to a certain equilibrium stage during the time scale of the experiment. EPR spectra in the solid state were of the singlet type at the temperatures over 350 K, a doublet like anisotropic spectra were measured at the room temperature, both having g-value 2.0033. EPR spectrum from POA decomposed in benzene indicates four protons with higher (2aH = 0.305 mT, 2aH = 0.335 mT) and four protons with a lower (2aH = 0.075 mT, 2aH = 0.105 mT) splitting constants, corresponding well the radical expected after cleavage of O-O bridge.

Pilot Test of Preparing 2-Alkylanthraquinone Using Alkylation-Oxidation Technology

To expedite the development of industrial technology for producing 2-alkylanthraquinone,a novel pilot test of alkylation-oxidation technology was conducted.The process mainly included anthracene alkylation,separation of anthracene and 2-alkylanthracene,oxidation of 2-alkylanthracene,and product purification.Optimal alkylation conditions yielded a 91.1%conversion of anthracene and a 71.73%selectivity for 2-alkylanthracene.To address the separation problem of anthracene and 2-alkylanthracene,solvent-assisted distillation technology was developed,resulting in a 98.9%purity of 2-alkylanthracene and a 91.82%separation yield.When the molar ratio of H2O_(2) to 2-alkylanthracene was 7:1,a 98.96%conversion of 2-alkylanthracene and a 99.94%selectivity for 2-alkylanthraquinone were achieved.A novel composition of 2-alkylanthraquinone,including 2-tert-butylanthraquinone,2-tert-amylanthraquinone,and 2-hexylanthraquinone,was developed.This composition could be effectively separated and purified through a combination of crystallization and washing processes.The elemental composition of the product met the existing standards,and its hydrogenation performance closely matched that of commercially available 2-tert-amylanthraquinone products.

Degradation of anthracene, pyrene and benzo[a]-anthracene in aqueous solution by chlorine dioxide

Polycyclic aromatic hydrocarbons (PAHs) constitute an important group of micropollutants, which are known to be mutagenic, carcinogenic and/or co-carcinogenic and relatively persistent in the environment. The effects of chlorine dioxide (ClO2) on the degradation of anthracene (ANTH), pyrene (PYR) and benzo[a]anthracene (BaA) in aqueous solution were investigated using high performance liquid chromatography (HPLC). In preliminary experiments, it was observed that ClO2 could remove these three PAHs effectively within a short time. Several factors including reaction time, the concentration of ClO2 and pH of the reaction mixture influencing the degradation ratio of PAHs have been studied by batch experiments. The results showed that the degradation ratio of PAHs was affected by reaction time and the concentration of ClO2 instead of pH. The degradation ratio of ANTH, PYR and BaA could reach their maximum as approximately 99.0%, 67.5% and 89.5%, respectively, under the condition as follows: reaction time 30, 60 and 120 min, the concentration of ClO2 0.1, 0.4 and 0.5 mmol·L-1, and pH 7.2. ANTH was selected as the representative to study the reaction mechanism with ClO2. The oxidation products formed in the reaction of ANTH with ClO2 were tentatively identified by gas chromatography-mass spectrometry (GC-MS), and the results showed that the main product was 9, 10-anthraquinone, which could be biodegraded more easily and quickly than ANTH. Through analyzing the reaction properties of ANTH and ClO2, the possible pathway for the ANTH-ClO2 reaction was proposed based on the theory of single electron transfer (SET).

Thermal and Optoelectronic Properties of Anthracene and Dibenz[a,c]Anthracene

The basic characteristics of anthracene（AN） and dibenz[a,c]anthracene（D[a,c]A） derivatives, important semiconductors, were systematically studied. Differential scanning calorimetry（DSC） shows that D[a,c]A has the reversibility of solid and liquid phases. Thermalgravimetric analysis（TGA） shows that D[a,c]A exhibits higher Td（decomposition temperature）, which indicates D[a,c]A, as active layers, should be more suitable to being made into stable devices. D[a,c]A shows blue-shifted UV-Vis absorption and emission despite increased conjugation compared to anthracene due to different symmetries. Both the compounds are planar and show weak blue fluorescence in the tetrahydrofuran（THF） solution and higher fluorescence in the solid-state, due to different energy levels in solution and solid-state, explained via Jablonski diagram.

A new asymmetric anthracene derivative with high mobility

An asymmetric anthracene derivative(4-HDPA) was designed and synthesized. With the optimization of proper scenario of fabrication process, top-contact thin film devices based on 4-HDPA exhibit mobility as high as 3.59 cm^2 V^(–1) s^(–1), while its singlecrystal devices exhibit mobility as high as 5.12 cm^2 V^(–1) s^(–1), which is higher than the symmetrical counterpart of 4-HDPA in both single-crystal and thin film devices.

Enhanced enzymatic removal of anthracene by the mangrove soil-derived fungus,Aspergillus sydowii BPOI

The present study investigated the efficiency of Aspergillus sydowii strain bpol(GenBank Accession Number:MK373021)in the removal of anthracene(100 mg/L).Optimal degradation efficiency(98.7%)was observed at neutral pH,temperature(30℃),biomass weight(2 g)and salinity(0.2%w/v)within 72 h.The enzyme analyses revealed 131%,107%,and 89%induction in laccase,lignin peroxidase,and manganese peroxidase respectively during anthracene degradation.Furthermore,the degradation efficiency(99.8%)and enzyme induction were significantly enhanced with the addition of 100 mg/L of citric acid and glucose to the culture.At varying anthracene concentrations(100-500 mg/L),the degradation rate constants(K1)peaked with increasing concentration of anthracene while the half-life(t1/2)decreases with increase in anthracene concentration.Goodness of fit(R2=0.976 and 0.982)was observed when the experimental data were subjected to Langmuir and Temkin models respectively which affirmed the monolayer and heterogeneous nature exhibited by A.sydwoii cells during degradation.Four distinct metabolites;anthracene-1,8,9(2H,8aH,9aH)-trione,2,4adihydronaphthalene-1,5-dione,l,3,3a,7a-tetrahydro-2-benzofuran-4,7-dione and 2-hydroxybenzoic acid was obtained through Gas Chromatography-Mass spectrometry(GC-MS).A.sydowii exhibited promising potentials in the removal of PAHs.

SiO2-coated pure anatase TiO2 catalysts for enhanced photo-oxidation of naphthalene and anthracene

Our current efforts reveal the preparation of SiO2@TiO2 nanocomposites having different thicknesses of silica shell and the relationship to photocatalytic activity （PCA） for the photo-oxidation of naph-thalene and anthracene. The presence of SiO2 coating over TiO2 surface was demonstrated by FT-IR analysis, with peaks corresponding to Si-O-Si （1081 cm 1） and Si-O-Ti （950 cm-1） bonds observed. High-resolution transmission electron microscopy analysis confirmed the presence of SiO2 in the as- prepared nanocomposites and the amount of Si, Ti, and O was determined by energy dispersive X-ray spectroscopy analysis. Increasing the Si02 shell thickness increases the surface area of the nanocompos- ites （69-235 m2/g）, which enhances naphthalene/anthracene adsorption. However, the observed PCA trend presents an inverse correlation to the adsorption studies, where the as-prepared samples possess- ing the highest surface areas exhibited the least PCA, while catalysts having lower surface areas （among silica coated samples） displayed the highest PCA in the degradation of naphthalene and anthracene to CO2. Despite complete degradation of naphthalene and anthracene, incomplete mineralization occurred, ascribed to the formation of various intermediates, identified by GC-MS analysis.

Preparation and spectral characteristics of anthracene/tetracene mixed crystals

A series of tetracene-doped anthracene crystals with different doping concentrations(the highest mo-lar ratio 100:1) are grown from solution.Crystal structures and optical characteristics of the above mixed crystals are investigated at room temperature.By changing the doping concentrations,the fluorescence can be adjusted from blue-green to green and even to yellow-green.The emission spectra of anthracene/tetracene(An/Te) mixed crystals reveal the sensitized fluorescence of tetracene and the partial quenching of anthracene emission.The data of transient photoluminescence(PL) decays illus-trate that in An/Te mixed crystals,the decay of anthracene becomes faster,while the PL lifetime of tet-racene is longer than that of the tetracene single crystals.All above experimental results suggest that there is excitation energy transfer from anthracene to tetracene in the mixed crystals.

Nonlinear two-photon absorption properties induced by femtosecond laser with the films of two novel anthracene derivatives

Two novel anthracene derivatives containing 4-vinylpyridine （FPEA） and 2-vinylpyridine （TPEA） poly（methyl methacrylate） films are prepared on quartz glass substrates. Their nonlinear absorption properties are investigated by using a 120-fs, 800-nm Ti：sapphire femtosecond pulsed laser operating at a 1-kHz repetition rate. The unique nonlinear absorption properties of these new compounds are observed by utilizing a Z-scan system. These two-photon absorption （TPA） properties are proven by the two-photon fluorescence excited at 800 nm. The FPEA and TPEA films have nonlinear TPA coefficients of 0.164 and 0.148 cm/GW and the TPA cross sections of 3.345 × 10^-48 and 3.081 × 10^-48 cm4 ·s/photon, respectively. The influence of the chemical structures on the nonlinear TPA properties of the compounds is also discussed. The highly nonlinear TPA activities of the films implied that the new anthracene derivatives are suitable materials with promising applications in super-high-density three-dimensional data storage and nano- or microstructure fabrication.

Microporous Hypercross-linked Conjugated Quinonoid Chromophores of Anthracene: Novel Polymers for CO_2 Adsorption

Microporous hypercross-linked conjugated quinonoid chromophores represent a novel class of amorphous polymers, synthesized by the reaction of anthracene with dimethoxy methane in the presence of FeCl3 catalyst. Their N2 adsorption isotherms confirm their microporous nature. Diffuse reflectance UV-Visible（DRS UV-Vis） spectroscopy confirms their matrix built with the conjugated quinonoids by their broad light absorption characteristics extending from 1000 nm to 200 nm with the absorbance maximum close to 400 nm. The catalyst cross-linked anthracene with ―CH2― bridges and subsequently dehydrogenating them to form quinonoids. Their Fourier transform infrared（FTIR） spectra showed their characteristic quinonoid vibrations between 1600 and 1700 cm-1. The synthesis of polymers was carried out at 30, 40, 50, 60, 70 and 80 ℃, but the quinonoid content of the polymer obtained at 80 ℃ was higher than that of the others. Their scanning electron microscopy（SEM） images showed microspheres of 1 to 5 μm size built with tiny particles. Their surfaces were not smooth. The polymer synthesized at 80 ℃ showed 5.1 wt% CO2 sorption at 25 ℃ and 0.1 MPa, but when it was recross-linked, the CO2 sorption increased to 8 wt%. Hence, hypercross-linked conjugated quinonoid chromophores of anthracene are good for sorption of CO2.

Synthesis and properties of novel blue-emitting materials:anthracene-based derivatives

Two kinds of novel blue-emitting materials, anthracene-based derivatives, are synthesized by the Suzuki cou- pling reaction. It is worth noting that the maximum emission wavelengths of the two materials are 441 and 444 nm in tetrahydrofuran and 456 and 454 nm in film states, which are the typical blue fluorescence and the fluorescence quantum yields of them are 0.87 and 1.12 by using 9,10-diphenylanthracene （Фf = 0.90） as a calibration standard. The full width at half maximum of them are 56, 55 nm in solution, respectively, pre- senting good color purity. Both of them display superior thermal properties and electrochemical properties. Scanning electronic microscope results show that the films of two compounds are continuous, compact, and smooth after 100℃ for 3 h. These data indicate their potential to be prepared for high efficiency and long operation lifetime organic light-emitting diodes devices.

Fused multifunctionalized bridge aromatic hydrocarbons from in situ-generated arynes and anthracene derivatives

This study presents a facile strategy for the formation of highly substituted butterfly 1,4-adducts/9,10-adducts via the Diels-Alder reaction of benzyne intermediates.The method achieves very good to excellent yields of the respective anthracene derivative s under mild conditions.This practical protocol is compatible with a variety of sensitive functional groups and provides access to difunctionalized bridge 1,4-adducts/9,10-adducts.

Overcoming the limitations of anthracene alkylation using SZ-DeAl-DFNS acid catalyst

In situ formation of composite micro-mesoporous dendritic fibrous nano-silica(DFNS) and Al-DFNS was prepared using a cetylpyridinium bromide(CPB) template synthetic system. Dealumination is induced by impregnation of zirconium with flux followed by a sulfuric acid treatment. This procedure results in a series of highly uniform nano-spheres, which exhibit stronger acid property than that of Al-MCM-41. In the selective alkylation of anthracene with tert–amyl alcohol, SO_(4)^(2-)modified Zr-contained dealuminated Al-DFNS(SZ-De Al-DFNS) shows great catalytic activity and higher conversion(60.8%). The DFNS samples were characterized with XRD, SEM, TEM, NH_(3)-TPD and other techniques. The results reveal that DFNSs consist of center-radial micro-mesopores and that the acid contribution of SZ-De Al-DFNS is much broader,as compared with amorphous aluminosilicate.

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol （SOA） formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer （SMPS） during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer （VUV-ATOFMS）. Gas chromatograph/mass spectrometer （GC/MS） analyses of oxidation products of anthracene were carried out for assigning the time-of-flight （TOF） mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.