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.

3,6-Bis-β-Dicarbonylsubstituted Carbazoles Bearing N-Spacers and Their Eu(III) Complexes as Immunofluorescent Labelling Agents

New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu3+ ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.

A Fluorescent Probe based on a Carbazole Derivative for Detecting Brilliant Blue in Food

Here a fluorescent probe based on a carbazole derivative(CNS)was developed to increase the detection range and reduce the detection limit of brilliant blue.Characteristics of CNS are studied.Due to the quenching ability of colorants,CNS shows an excellent current response to brilliant blue(from 1 to 10μM)with a detection limit of 2.7×10^(-8)mol/L(3σ/k)in the conditions of a 1:1 volume ratio of water to tetrahydrofuran.And the stability and reproducibility of CNS in the detection of actual samples indicate great potential for application.

Syntheses,Structures,Luminescence and Magnetic Properties of Three New Metal-organic Frameworks Based on Rigid Carbazole Ligand

Three new metal-organic frameworks [Cd(L)(obba)]·H)2O(1),[Co(L)(obba)]·MeCN(2) and [Cd_2(L)_2(ip)_2]·6H_2O·DMF(3)(H_2obba = 4,4?-oxybisbenzoic acid,H2 ip = m-phthalic acid) have been successfully synthesized based on the controllable self-assembly of 9-ethyl-3,6-diimidazolyl-carbazole(L),varied carboxylates and different metal ions under solvothermal conditions,which were characterized by single-crystal X-ray diffraction,elemental analysis,IR spectroscopy and thermogravimetry. Furthermore,luminescence and magnetic susceptibility of compound 2 are also investigated in detail. Single-crystal X-ray diffraction and topology analysis reveal that complexes 1~3 exhibit similar two-dimensional(2D) networks.

Cytotoxic and Anti-Tumour Promoting Activities of Carbazole Alkaloids from Malayan <i>Murraya koenigii</i>(L.) Spreng

Murraya koenigii (L.) (Rutaceae) is an indigenous medicinally important herb of Indian origin and now is widely distributed throughout southern Asia. The stem bark, leaves and roots of Malayan Murraya koenigii were selected for phytochemical investigation. Eight carbazole alkaloids was isolated and identified using spectroscopic methods including NMR, IR, UV, MS spectra data. Crude extract and isolated compounds from the roots of this plant were screened for cytotoxic activity and antitumor promoting activity. All crude extracts of the roots including the isolated compounds, mahanimbine, mahanine and murrayafoline-A exhibited significant cytotoxic activity against CEM-SS cell line with IC50 3mg/mL. Girinimbine inhibited EBV-activation in the antitumor promoting assay.

Purification of carbazole by solvent crystallization under two forced cooling modes

To identify the effect of solvents and anthracene on the purification of carbazole,the solvent crystallization of carbazole was investigated with xylene,chlorobenzene and tetrachloroethylene(TCE)as solvents under two forced circulation cooling(FCC)modes.The co-crystalline experimental data were obtained from runs carried out at different anthracene levels between 1%(mass)and 10%(mass).The results showed that a uniform flake carbazole crystal obtained when using xylene and chlorobenzene under the FCC-1 mode with gradual cooling rate.Nevertheless,fine flake crystals grown under shock cooling of FCC-2 mode.It is beneficial to improving the purity of carbazole with chlorobenzene as solvent under cooling mode of FCC-1.Anthracene could promote the growth of carbazole in solution,and it has a significant influence on the purification of carbazole.

SYNTHESIS AND PROPERTIES OF POLYACETYLENES CONTAINING CARBAZOLE AND AMINO ACID MOIETIES

Novel 9-proparylcarbazole monomers containing amino acid moieties,2-N(tert-butoxycarbonyl)-L-alanine- 9-proparylcarbazole ester(1),2-N-(tert-butoxycarbonyl)-L-O-cyclohexyl-L-glutamic acid-9-proparylcarbazole ester(2) and 2-N-(tert-butoxycarbonyl)-L-phenylalanine-9-proparylcarbazole ester(3) were synthesized and polymerized with (nbd)Rh^+[η~6-C_6H_5B^-(C_6H_5)_3]to give the corresponding polymers with number-average molecular weights ranging from 7050 to 10500 in 70%-86%yields.The polymers were completely...

Preparation and Characterization of Fullerene C_(60) and Phthalocyanine Co-grafted Poly(epoxy propyl carbazole)

The fullerene C60 and phthalocyanine co-grafted poly (epoxy propyl carbazole) (C60-CuPC-PEPC) was synthesized by Friedel-Crafts reaction. It was found that C60-CuPc-PEPC had good UV-Vis absorption property, whose active spectral range was expanded from UV to visible spectrum region, and exhibited better photoconductivity than CuPc-PEPC and PEPC. These improvements could be attributed to the interaction between C60, phthalocyanine and PEPC.

SYNTHESIS,CHARACTERIZATION AND PHOTOLUMINESCENT PROPERTIES OF NEW PLATINUM-CONTAINING POLY(FLUORENYLENEETHYNYLENE) ANCHORED WITH CARBAZOLE PENDANTS

A new luminescent and thermally stable platinum(Ⅱ) polyyne polymer trans-[-Pt(PBu_3)_2C=CArC=C-]_n(P1) containing the 2,7-fluorene chromophoric spacer substituted by pendant carbazolyl group via long alkyl bridges. The regiochemical structures of these compounds were studied by various spectroscopic analyses.We report the photophysical properties of this group 10 polymetallayne and a comparison was made to its binuclear model complex trans-[Pt(Ph)(PEt_3)_2C≡CArC≡CPt(Ph)(PEt_3)_2](M1) as well as to those ...

A novel carbazole-based fluorescent probe:3,6-Bis-[(N-ethylcarbazole-3-y1)-propene-1-keto]-N-ethylcarbazole

A novel carbazole-based compound 5,3,6-bis[(N-ethylcarbazole-3-yl)-propene-1-keto]-N-ethylcarbazole has been designed, synthesized and characterized.The absorption and fluorescence spectra in solvents of different polarities prove that the compound has a distinct intramolecular charge transfer character.Compound 5 can be used as a new class of fluorescent probe or biosensor due to its sensitivity to the local microenvironment such as solvent polarity.

Blue Electroluminescent Diodes Utilizing Blend of Poly (2,5-Dibutoxyphenylene) in Poly (N-Vinylcarbazole)

Blue emission from polymer blends composed of poly(2,5-dibutoxyphenyiene)(PPP)in a matrix polymer poly(N-vinylcarbazole)(PVK)is reported.The light-emitting layer can be fabricated by spin-coating of PPP-PVK blend solution without subsequent processing or heat treatment.A cell structure of glass substrate/indium-tin-oxide/PPP-PVK blend/aluminum is employed.Blue light emission with a peak position at 448nm occurs at a bias of about 8V.

Synthesis,Crystal Structure and Optical Prosperities of a Carboxylic Acid Functionalized Carbazole Derivative

A novel carbazole derivative 2-cyano-3-(9-ethyl-9H-carbazol-3-yl)-acrylic acid ethyl ester(L) was designed and synthesized through Vilsmeier and Knoevenagelreactions, which was characterized by FT-IR, ~1H NMR and13 C NMR spectra. The crystal of L crystallizes in the monoclinic system, space group P21/c with a = 10.8298(15), b = 13.4660(19), c = 15.4358(16) ?, β = 131.214(6)o, V = 1693.4(4) ?~3, Z = 4, Dc = 1.249 g/cm^3, Mr = 318.36, μ = 0.082 mm-1, F(000) = 672, completeness to theta was 99.9% and GOOF = 1.091.Rint = 0.0338, R(I >2σ(I)) = 0.0631, w R(I > 2σ(I)) = 0.1861, R(all data) = 0.1027 andw R(all data) = 0.2105. There were three types of weak intermolecular interactions(C(8)–H(8)···N(2), C(14)–H(14)···O(2) and C(20B)– H(20B)···π)among the adjacent molecules to construct a three-dimensional single crystal. The UV-Vis spectra, fluorescence emission and time-dependent density functional theory(TD-DFT) calculation of L were studied and the results revealedthe existence of intramolecular charge transfer(ICT) process of L molecule. The optical properties indicated that it can be used as a potential candidate in the application oforganic light emitting diodes(OLEDs).

Photorefractive Effect in Poly (N-Vinylcarbazole) Composite with Fullerene

The photorefractive effect was observed in poly(N-vinylcarbazole)composite films doped with electro-optic chromophore 2,5-dimetly-4(p-nitrophenylazo)anisole,plasticizer N-ethylcarbazole and different content fullerene C60.Their two-beam coupling experiment was performed by using a cw He-Ne laser at 632.8nm.The two-beam-coupling gain coefficient as higher as 140cm^(-1) was measured at poling dc electric field of 76V/μm and it was also found to be relied on the content of photosensitizer C60.

Synthesis and Photoelectrical Properties of D-A Type Carbazole-quinoline

The key issues concerning the design and synthesis of high fluorescent efficiency, good thermal stability of organic blue materials should be solved urgently in organic light emitting diodes. In this article, three D-A type blue emitters based on carbazole and phenylquinoline with flexible chains were prepared through Friedlander condensation reaction in relatively high yield. The photoelectric properties of all compounds were studied by UV-vis absorption, emission spectra and cyclic voltammograms. Density functional theory calculations(DFT) were performed to obtain a better understanding of the electronic structures. Interestingly, compound a3 with the highest fluorescence quantum yield of 0.53 can be applied into blue light emission materials on account of good thermal performance. Furthermore, a1～a3 with narrow band gap make them become potential candidates in the fields of OLED, solar cells and OFET.

Synthesis and Photophysical Properties of Fluorene or Carbazole-Based Alternating Copolymers Containing Si and Ethynylene Units in the Main Chain

Alternating copolymerization of 9,9-dihexyl-2,7-dibromofluorene, N-hexyl-2,7-dibromocarbazole (HCz) with diethynyldimethylsilane, diethynyldiphenylsilane, has been investigated using Sonogashira coupling reaction. Photophysical properties of the resulting copolymers were investigated with UV-Vis absorption and photoluminescence spectroscopy. All the copolymers in chloro-form solution showed absorption peaks at 270 - 280 nm with shoulder peaks at around 380 nm derived from π-π* transition or intra-molecular charge transfer through σ-π moiety, respectively. The chloroform solutions of the copolymers showed broad emission peaks at 415 - 425 nm. The emission wave lengths of the copolymers in the solid state (cast film) detected at 360 - 385 nm were remarkably blue-shifted in comparison with those in the chloroform solutions. Hydrosilylation reaction of the copolymers with 1,4-bis(dimethylsilyl)benzene yielded networked copolymers soluble in chloroform, indicating formation of branching polymers. The chloroform solutions of the HCz-based networked copolymers showed bimodal emission derived from new highly energy states in the σ-π conjugation.

Optical Properties of Fullerenated Poly(epoxy propyl carbazole)

The optical properties of the fullerenated poly(epoxy propyl carbazole) (PEPC) havebeen investigated. Compared with pure PEPC, fullerenated PEPC has the same structure inthe UV region of the absorption spectrum, and extends the active range to a longerwavelength. The apparent quenching of PEPC fluorescence was observed in thefullerenated polymer and it can be attributed to intramolecular excited state energytransfer.

Matrix-Mediated Color-Tunable Ultralong Organic Room Temperature Phosphorescence of 7H-Benzo[c]carbazole Derivatives

Building on the recent systematic research on 1Hbenzo[f]indole(Bd),an important advancement in constructing ultralong organic room temperature(UORTP)materials with a universal strategy via a readily obtained unit(7H-Benzo[c]carbazole,BCz)is proposed in this work.Pure powders of BCz and its derivatives merely exhibit blue fluorescence at ambient condition.However,when BCz and its derivatives are dispersed into polymer or powder matrixes,strong photo-activated green UORTP can be observed from their doped systems at room temperature.Moreover,the UORTP color can be tuned between green and yellow depending on the matrix.The ultralong phosphorescence originates from the generation of charge-separated states via radicals.The matrixes play a key role in both stabilizing charge-separated states and controlling UORTP color.More interestingly,when using polymethyl methacrylate as matrix,the doped films achieve stronger photo-activated ultralong phosphorescence underwater than in air at room temperature.Comparedwith Bd,BCz achieves better performance not only in ultralong phosphorescence properties but also in practical applications.This work gains a deeper insight into the mechanism of UORTP and paves a new approach to applying organic phosphorescent materials to underwater coating and imaging.

Carbazole-Based Donor-Acceptor Conjugated Microporous Polymers for Efficient Visible-Light-Driven Photocatalytic H_(2) Evolution

Conjugated microporous polymers (CMPs) featuring extended π-structures, large specific surface area and tailor-made functionalities are a class of promising organic photocatalysts for hydrogen evolution reaction (HER) from water. However, the photocatalytic activities of most CMPs are severely hindered by slow charge transfer rate and fast charge recombination process. Herein, we develop a strategy for the synthesis of donor-acceptor CMPs through nickel(0)-catalyzed Yamamoto cross-coupling of 3,6-dibromo-9-(4-bromophenyl)carbazole (CZ) with 5,5'-dibromo-2,2'-bipyridine (DBPy) for efficient HER from water. The PCZN-4 prepared with a 2 : 3 stoichiometric ratio of CZ to DBPy exhibited the highest photocatalytic hydrogen evolution rate of 7160 μmol·g^(–1)·h^(–1), which was nearly equal to 179 times and 143 times that of PCZN-1 (40 μmol·g^(–1)·h^(–1)) and PCZN-6 (50 μmol·g^(–1)·h^(–1)) obtained by Yamamoto homocoupling of CZ and DBPy, respectively. Compared to the homocoupling counterparts, the enhanced photocatalytic activity of PCZN-4 results from improved separation efficiency of charge carriers. Interestingly, the photocatalytic H2 evolution performance of PCZN-4 could be further improved up to 17080 μmol·g^(–1)·h^(–1) by adjusting pH of the aqueous solution. This work offers a novel approach for improving photocatalytic efficiency by tuning the chemical structures and surrounding microenvironment of the polymer backbone.

Carbazole and tetrahydro-carboline derivatives as dopamine D_(3) receptor antagonists with the multiple antipsychotic-like properties

Dopamine D_(3) receptor(D_(3)R)is implicated in multiple psychotic symptoms.Increasing the D_(3)R selectivity over dopamine D_2 receptor(D_2R)would facilitate the antipsychotic treatments.Herein,novel carbazole and tetrahydro-carboline derivatives were reported as D_(3)R selective ligands.Through a structure-based virtual screen,ZLG-25(D_(3)R K_i=685 nmol/L;D_2R K_i>10,000 nmol/L)was identified as a novel D_(3)R selective bitopic ligand with a carbazole scaffold.Scaffolds hopping led to the discovery of novel D_(3)R-selective analogs with tetrahydro-β-carboline or tetrahydro-γ-carboline core.Further functional studies showed that most derivatives acted as h D_(3)R-selective antagonists.Several lead compounds could dose-dependently inhibit the MK-801-induced hyperactivity.Additional investigation revealed that 23j and 36b could decrease the apomorphine-induced climbing without cataleptic reaction.Furthermore,36b demonstrated unusual antidepressant-like activity in the forced swimming tests and the tail suspension tests,and alleviated the MK-801-induced disruption of novel object recognition in mice.Additionally,preliminary studies confirmed the favorable PK/PD profiles,no weight gain and limited serum prolactin levels in mice.These results revealed that 36b provided potential opportunities to new antipsychotic drugs with the multiple antipsychotic-like properties.

Polyhalogenated carbazoles induce hepatic metabolic disorders in mice via alteration in gut microbiota

Polyhalogenated carbazoles(PHCZs)have been widely accepted as emerging pollutants,whereas their ecological and health risks remain uncertain.Herein,female and male Sprague-Dawley(SD)mice were treated with four typical PHCZs to investigate their negative consequences,along with alternations in gutmicrobiota to indicate underlyingmechanisms.In female mice,the relative liver weight ratio increased after four PHCZs exposure;2-bromocarbazole(2-BCZ)increased urine glucose level;3-bromocarbazole(3-BCZ)decreased the glucose and total cholesterol levels;3,6-dichlorocarbazole(3,6-DCCZ)decreased glucose level.The only disturbed biochemical index in male mice was the promoted alkaline phosphatase(ALP)level by 3,6-DCCZ.We also found that the differential blood biochemical indices were correlated with gut microbiota.3-BCZ and 3,6-DCCZ altered Bacteroidetes and Proteobacteria phyla in female and male mice,which were correlated with metabolic disorders.Our findings demonstrated the correlation between PHCZs induced potential hepatotoxicity andmetabolic disordersmay be due to their dioxin-like potentials and endocrine disrupting activities,and the gender differences might result from their estrogenic activities.Overall,data presented here can help to evaluate the ecological and health risks of PHCZs and reveal the underlying mechanisms.