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 carb...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 Eu<sup>3+</sup> 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.展开更多
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...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.展开更多
Polyhalogenated carbazoles(PHCZs)are recently raising much attention due to their toxicity and ubiquitous environmental distribution.However,little knowledge is known about their ambient occurrences and the potential ...Polyhalogenated carbazoles(PHCZs)are recently raising much attention due to their toxicity and ubiquitous environmental distribution.However,little knowledge is known about their ambient occurrences and the potential source.In this study,we developed an analytical method based on GC-MS/MS to simultaneously determine 11 PHCZs in PM_(2.5) from urban Beijing,China.The optimized method provided low method limit of quantifications(MLOQs,1.45–7.39 fg/m^(3))and satisfied recoveries(73.4%–109.5%).This method was applied to analyze the PHCZs in the outdoor PM_(2.5)(n=46)and fly ash(n=6)collected from 3 kinds of surrounding incinerator plants(steel plant,medical waste incinerator and domestic waste incinerator).The levels of Σ_(11)PHCZs in PM_(2.5) ranged from 0.117 to 5.54 pg/m^(3)(median 1.18 pg/m^(3)).3-chloro-9H-carbazole(3-CCZ),3-bromo-9H-carbazole(3-BCZ),and 3,6-dichloro-9Hcarbazole(36-CCZ)were the dominant compounds,accounting for 93%.3-CCZ and 3-BCZ were significantly higher in winter due to the high PM_(2.5) concentration,while 36-CCZ was higher in spring,which may be related to the resuspending of surface soil.Furthermore,the levels of11PHCZs in fly ash ranged from 338 to 6101 pg/g.3-CCZ,3-BCZ and 36-CCZ accounted for 86.0%.The congener profiles of PHCZs between fly ash and PM_(2.5) were highly similar,indicating that combustion process could be an important source of ambient PHCZs.To the best of our knowledge,this is the first research providing the occurrences of PHCZs in outdoor PM_(2.5).展开更多
The synthesis of carbazoles based on the electrochemical Pd-catalyzed intramolecular C-H amination of 2-amidobiaryls through oxidative cross coupling has been achieved under mild reaction conditions.The reaction can b...The synthesis of carbazoles based on the electrochemical Pd-catalyzed intramolecular C-H amination of 2-amidobiaryls through oxidative cross coupling has been achieved under mild reaction conditions.The reaction can be carried out in undivided cell without the addition of external chemical oxidant.Besides good functional group compatibility,the desired carbazoles can be scaled up and modified easily.Compared with previous methods,this protocol affords a simple and sustainable avenue for the construction of car-bazoles.展开更多
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 che...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.展开更多
Albeit their high efficiencies, the operational stability of the organic light emitting diodes(OLEDs) based on thermally activated delayed fluorescence(TADF) emitters is still far from satisfaction, and few strategies...Albeit their high efficiencies, the operational stability of the organic light emitting diodes(OLEDs) based on thermally activated delayed fluorescence(TADF) emitters is still far from satisfaction, and few strategies have been proposed to improve their stability. Here, we show that by modifying the carbazole unit, one of the most commonly used donors in TADF emitters, with peripheral groups, both the device efficiency and operational stability can be greatly improved. Awell-known TADF molecule—4,5-di(9H-carbazol-9-yl)phthalonitrile(2CzPN) was chosen as the prototype and modified by introducing peripheral tert-butyl and phenyl groups to the 3,6-positions of the carbazole(named 2tBuCzPN and 2PhCzPN, respectively). The introduced groups not only improve the compounds' electrochemical stabilities referred to the cyclic voltammetry multi-sweep results, but also promote their photoluminescence quantum yields. Furthermore, reduced singlet-triplet energy gaps are observed, leading to the shortened exciton lifetimes which are benefit to suppress the exciton annihilations. Besides, the steric hindrance of introduced phenyl groups can partly restrain the concentration quenching of the TADF emitter. Consequently, OLEDs based on 2tBuCzPN and 2PhCzPN achieved improved maximum external quantum efficiencies(EQEs) of 17.0% and 14.0%, respectively(compared to 8.5% for 2CzPN). Meanwhile, 2PhCzPN based OLED showed reduced roll-off characteristics and a longer lifetime of 7.8 times higher than that of 2CzPN, testifying the effectiveness of subtle modification of the unstable moieties in simultaneous enhancement of efficiency and stability of OLEDs based on TADF emitters.展开更多
A convenient and highly efficient method is described for the synthesis of N-methoxycarbazole derivatives,including those with sterically demanding,benzannulated,or strongly electron-donating or-withdrawing substituen...A convenient and highly efficient method is described for the synthesis of N-methoxycarbazole derivatives,including those with sterically demanding,benzannulated,or strongly electron-donating or-withdrawing substituents.Various N-methoxycarbazole derivatives were directly prepared in good-to-moderate yields by the Pd_(2)(dba)_(3)CHCl_(3)/9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene-catalyzed reactions of the corresponding dibromobiphenyl compounds and methoxyamine.Based on this methodology,the first total synthesis of 3,3′-[oxybis(methylene)]bis(9-methoxy-9H-carbazole),an antimicrobial dimeric carbazole alkaloid previously isolated from the stem bark of Murraya koenigii,was achieved in 18% yield over seven steps from 1,2-dibromobenzene.展开更多
The integration of multiscale and multicomponent of molecules and nanoparticles into thin films for applications requires the abilities of controlled their processing and assembly,which has been an great challenge bec...The integration of multiscale and multicomponent of molecules and nanoparticles into thin films for applications requires the abilities of controlled their processing and assembly,which has been an great challenge because of the difficulty in manipulating the various materials such as small molecules,complexes,polymers,and inorganic nanomaterials through synergetic combinations of chemical or physical fabrications.Eletropolymerization is of great significance to fabricate polymeric film materials straight on the conductive substrates with tunable morphologies and thicknesses.However,unlimited electrochemical reactions(polymerization)have been usually leading to disadvantageous in ill-defined structure and highly doped state.Thanks to finding of exceptional electrochemical reaction(oligomerization)of N-alkylcarbazole,electrochemical layer by layer assembly has emerged as a promising strategy for a wide library of applications.The capability of this strategy can manipulate various molecules and nanoparticles into the scale and component controllable thin films.Unlike other electropolymerizable precursors such as aniline and thiophene,the resulting di-N-alkylcarbazole is transparent in the visible light region and thus does not impair the intrinsic properties of the components in the film.This account highlights of the typical findings in investigating both single-and multi-components thin films as a forum for discussing new opportunities in exploiting novel designs and applications of optical thin films.展开更多
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 abili...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.展开更多
A SPE/GC-MS method for separation and determination of carbazoles in crude oil was developed.Alumina and silicic acid solid-phase extraction(SPE) columns were used to separate resin from crude oil and neutral nitrogen...A SPE/GC-MS method for separation and determination of carbazoles in crude oil was developed.Alumina and silicic acid solid-phase extraction(SPE) columns were used to separate resin from crude oil and neutral nitrogen compounds from nitrogen riched resin.Carbazole and its alkylation series were quantitatively analysed by use of deuterate carbazole as an internal standard and the 9-benzocarbazole as an recovery rate standard.The modified method was very suitable for batch processing in organic geochemistry owing to its low cost,time saving,environmental friendliness.展开更多
The direction of oil charges within a field in the Niger Delta, Nigeria was determined by the sum of differences ranking method of carbazole concentrations after ascertaining other possible geological constraints on t...The direction of oil charges within a field in the Niger Delta, Nigeria was determined by the sum of differences ranking method of carbazole concentrations after ascertaining other possible geological constraints on their compositional variations. The principle is that the smaller the sum, the closer the well to the source kitchen. The approach makes use of carbazoles' interaction with the matrix, which leads to a reduction in their concentration with increasing distance from the source kitchen, allowing prediction of the charging direction. A wide range of compositional variations was observed for C1(806.72–2152.90 lg/g) and C2(767–2469.72 lg/g) carbazoles within the field. Based on these results, we inferred a filling pathway orientation from west to east. This suggests that the source kitchen—the most promising region for oil exploration—is located in the western part of the oil field.展开更多
The results obtained in this paper indicate that carbazole-type compounds have high thermal stability and also show stability in oxidation and bio-degradation. This kind of compounds still has a high concentration and...The results obtained in this paper indicate that carbazole-type compounds have high thermal stability and also show stability in oxidation and bio-degradation. This kind of compounds still has a high concentration and complete distribution in the analyzed dry asphalt samples, showing that they are particularly useful in studying petroleum migration of paleo-pool. During the basin's first-stage of oil-gas pool formation in the Silurian in Tazhong and Tabei areas of Tarim Basin (at the end of Silurian period) and the second-stage in the Awati area (in Permian), the petroleum experienced a long-distance migration. During the formation of the Silurian paleo-pools in Tazhong Uplift at the end of Silurian, the petroleum mainly came from the lower and middle Cambrian source rocks in the Manjiaer sag. The petroleum migrated towards the southwest-south entering the Silurian reservoir beds in Tazhong first. Then, it further migrated within Silurian from northwest to southeast along the highs of the Structural Belts to the region of the Silurian pinchout boundary in Tazhong. In Tabei Uplift, during the first-stage of pool formation, the petroleum was also from the lower and middle Cambrian source rocks in the Manjiaer sag. It migrated northwest entering the Silurian reservoir beds in the Tabei Uplift firstly, and then the migration continued in the same direction within the Silurian reservoirs and finally the petroleum was trapped in higher positions. During the second-stage pool formation in the Silurian beds in the areas around Awati sag, the petroleum mainly came from the lower-middle Cambrian source rocks in the Awati sag. The petroleum migrated from the generation center to Silurian reservoirs in all directions around the sag through major paths, and the petroleum was finally trapped in higher locations.展开更多
Hydrogenation of carbazole and N-ethylcarbazole over Raney-Ni catalyst were realized in the temperature range of 393-503 K. 4[H] adduct dominated the hydrogenation products and the formation of 2[H] adduct was the rat...Hydrogenation of carbazole and N-ethylcarbazole over Raney-Ni catalyst were realized in the temperature range of 393-503 K. 4[H] adduct dominated the hydrogenation products and the formation of 2[H] adduct was the rate-limiting step during the period, in which the conversion of carbazole was less than 40%. The hydrogenation process followed pseudo-first-order kinetics and the hydrogenation activation energies of carbazole and N-ethylcarbazole were 90 kJ/mol and 115 kJ/mol, respectively. The reaction starting position as well as the pathway of the hydrogenation of (N-ethyl)carbazole were investigated by comparing the kinetic characteristics of hydrogen uptake of carbazole and N- ethylcarbazole. The results showed that the reaction was a stepwise hydrogenation process and the first H_2 was added to the C1 = C10 double bond in the hydrogenation.展开更多
A novel carbazole functionalized β-diketone, methyl 6-(9-ethylcarbazole-3-yl)-oxoacetyl-2-pyridinecarboxylate (MEP), and its corresponding binary Eu(III) complexes Eu(MEP)y2H2O and ternary complex Eu(MEP)aP...A novel carbazole functionalized β-diketone, methyl 6-(9-ethylcarbazole-3-yl)-oxoacetyl-2-pyridinecarboxylate (MEP), and its corresponding binary Eu(III) complexes Eu(MEP)y2H2O and ternary complex Eu(MEP)aPhen with 1,10-Phenanthroline (Phen) were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ^1H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis (TG-DTA). The investigation of fluorescence properties of the complexes Eu(MEP)3·2H2O and Eu(MEP)3Phen showed that the Eu(III) ion could be sensitized efficiently by the ligand to some extent, in partitular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the n-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.展开更多
Herein, we report the design and synthesis of three new D-A type metal-free carbazole based dyes(S1-3)as effective co-sensitizers for dye-sensitized solar cell(DSSC) sensitized with Ru(Ⅱ) complex(NCSU-10).In ...Herein, we report the design and synthesis of three new D-A type metal-free carbazole based dyes(S1-3)as effective co-sensitizers for dye-sensitized solar cell(DSSC) sensitized with Ru(Ⅱ) complex(NCSU-10).In this new design, the electron rich carbazole unit was attached to three different electron withdrawing/anchoring species, viz. 4-amino benzoic acid, sulfanilic acid and barbituric acid. The dyes were characterized by spectral, photophysical and electrochemical analysis. Their optical and electrochemical parameters along with molecular geometries, optimized from DFT have been employed to apprehend the effect of the structures of these co-sensitizers on the photovoltaic performances. Further, S1-3 dyes were co-sensitized along with a well-known NCSU-10 dye in order to broaden the spectral response of the co-sensitized devices and hence improve the efficiency. The photovoltaic performance studies indicated that, the device fabricated using S1 dye as co-sensitizer with 0.2 mM of NCSU-10 exhibited improved PCE of 9.55% with JSC of 22.85 mA cm-2, VOC of 0.672 V and FF of 62.2%, whereas the DSSC fabricated with dye NCSU-10(0.2 mM) alone displayed PCE of 8.25% with JSC of 20.41 mA cm-2, VOC of 0.667 V and FF of 60.6%. Furthermore, electronic excitations simulated using time-dependent DFT, were in good agreement with the experimentally obtained results of the co-sensitizers, indicating that the exchange-correlation function and basis set utilized for predicting the spectra of the co-sensitizers are quite appropriate for the calculations. In conclusion, the results showed the potential of simple organic co-sensitizers in the development of efficient DSSCs.展开更多
The unconformity surface at the bottom of the Paleogene is one of the most important migration pathways in the Sikeshu Sag of the Junggar Basin,which consists of three layers:upper coarse clastic rock,lower weatherin...The unconformity surface at the bottom of the Paleogene is one of the most important migration pathways in the Sikeshu Sag of the Junggar Basin,which consists of three layers:upper coarse clastic rock,lower weathering crust and leached zone.The upper coarse clastic rock is characterized by higher density and lower SDT and gamma-ray logging parameters,while the lower weathering crust displays opposite features.The transport coefficient of the unconformity surface is controlled by its position in respect to the basal sandstone; it is higher in the ramp region but lower in the adjacent uplifted and sag areas.The content of saturated hydrocarbons increases with the decrease of the content of nonhydrocarbons and asphaltenes.The content of benzo[c] carbazole decreases as the content of benzo[a]carbazole and [alkyl carbazole]/[alkyl + benzo carbazole] increases.This suggests that the unconformity surface is an efficient medium for the transportation of hydrocarbons.展开更多
Amorphous 2,4,6-trissubstituted pyridines containing three peripheral carbazole or two triphenylamine and one carbazole moieties, respectively, have been synthesized and characterized. The properties of the compounds ...Amorphous 2,4,6-trissubstituted pyridines containing three peripheral carbazole or two triphenylamine and one carbazole moieties, respectively, have been synthesized and characterized. The properties of the compounds are investigated by UV-vis absorption, photoluminescence spectroscopy, thermal analysis as well as cyclic voltammetry. The results show that the compounds have high thermal stability, emit blue light. Also, the compounds possess the HOMO and LUMO energy levels comparable to those of NPB. The effects of different substituents on the electronic properties of the materials have been discussed.展开更多
A novel organic chromophore 4, 4'-bis(9-carbazyl-trans-styryl)-biphenyl (BCSBP) has been synthesized and characterized by IHNMR and elemental analysis. Three-photon absorption(3PA) induced upconvention fluoresc...A novel organic chromophore 4, 4'-bis(9-carbazyl-trans-styryl)-biphenyl (BCSBP) has been synthesized and characterized by IHNMR and elemental analysis. Three-photon absorption(3PA) induced upconvention fluorescence was observed and large 3PA cross section as high as 10^-74 cm^6 s^2 was obtained for nanosecond laser pulses at 1064 nm from optical limiting measurements.展开更多
The title compound, 2,10-di-tert-butylindolo[3,2,1-jk]carbazole (C26H27N, Mr=353.49), has been synthesized by palladium-catalyzed intramolecular arylation and characterized by 1H NMR, 13C NMR and X-ray crystal struc...The title compound, 2,10-di-tert-butylindolo[3,2,1-jk]carbazole (C26H27N, Mr=353.49), has been synthesized by palladium-catalyzed intramolecular arylation and characterized by 1H NMR, 13C NMR and X-ray crystal structure determination. The crystal crystallizes in the monoclinic system, space group P21/c with a=13.6409(5), b=11.6706(4), c=13.1678(5), β=100.6180(10)°, V=2060.39(13)3 , Z=4, Dc=1.140 mg/m3 , μ=0.065mm-1 , F(000)=760, the final R=0.0456 and wR=0.1209 for 3012 observed reflections (I 〉 2σ(I)).展开更多
A novel thiosemicarbazide derivative, (E)-1-(9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl) methylene)-thiosemicarbazide (CMT), was synthesized and structurally characterized by IR, 1H-NMR, EI-MS and single...A novel thiosemicarbazide derivative, (E)-1-(9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl) methylene)-thiosemicarbazide (CMT), was synthesized and structurally characterized by IR, 1H-NMR, EI-MS and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.769(5), b = 8.279(5), c = 17.166(5) , β = 114.391(5)°, V = 1911.6(14) 3, Z = 4, F(000) = 784, Dc = 1.287 g/m3, Mr = 370.47, μ = 0.190 mm-1, the final R = 0.0390 and wR = 0.1358 for 1446 observed reflections with Ⅰ 〉 2σ(Ⅰ). The UV-vis absorption spectra of CMT were explained based on quantum chemical calculations, using time dependent density functional theory (TD-DFT) at the B3LYP/6-31G (d) level.展开更多
文摘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 Eu<sup>3+</sup> 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.
基金supported by Joint Innovation Fund for Regional Development of National Natural Science Foundation of China(No.U20A20134)Leading Talent of Technological Innovation of Ten-Thousands Talents Program of Zhejiang Province(No.2020R52012).
文摘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.
基金supported by the National Key Research and Development Program of China(Nos.2018YFA0901104 and 2019YFE0111100)the National Natural Science Foundation of China(No.91743206)the Special Project of Eco-Environmental Technology for Peak Carbon Dioxide Emissions and Carbon Neutrality(No.RCEES-TDZ-2021-23).
文摘Polyhalogenated carbazoles(PHCZs)are recently raising much attention due to their toxicity and ubiquitous environmental distribution.However,little knowledge is known about their ambient occurrences and the potential source.In this study,we developed an analytical method based on GC-MS/MS to simultaneously determine 11 PHCZs in PM_(2.5) from urban Beijing,China.The optimized method provided low method limit of quantifications(MLOQs,1.45–7.39 fg/m^(3))and satisfied recoveries(73.4%–109.5%).This method was applied to analyze the PHCZs in the outdoor PM_(2.5)(n=46)and fly ash(n=6)collected from 3 kinds of surrounding incinerator plants(steel plant,medical waste incinerator and domestic waste incinerator).The levels of Σ_(11)PHCZs in PM_(2.5) ranged from 0.117 to 5.54 pg/m^(3)(median 1.18 pg/m^(3)).3-chloro-9H-carbazole(3-CCZ),3-bromo-9H-carbazole(3-BCZ),and 3,6-dichloro-9Hcarbazole(36-CCZ)were the dominant compounds,accounting for 93%.3-CCZ and 3-BCZ were significantly higher in winter due to the high PM_(2.5) concentration,while 36-CCZ was higher in spring,which may be related to the resuspending of surface soil.Furthermore,the levels of11PHCZs in fly ash ranged from 338 to 6101 pg/g.3-CCZ,3-BCZ and 36-CCZ accounted for 86.0%.The congener profiles of PHCZs between fly ash and PM_(2.5) were highly similar,indicating that combustion process could be an important source of ambient PHCZs.To the best of our knowledge,this is the first research providing the occurrences of PHCZs in outdoor PM_(2.5).
基金This work was supported by the National Natural Science Foundation of China(No.21520102003)the Hubei Province Natural Science Foundation of China(No.2017CFA010).The Program of Introducing Talents of Discipline to Universities of China(111 Program)is also appreciated.
文摘The synthesis of carbazoles based on the electrochemical Pd-catalyzed intramolecular C-H amination of 2-amidobiaryls through oxidative cross coupling has been achieved under mild reaction conditions.The reaction can be carried out in undivided cell without the addition of external chemical oxidant.Besides good functional group compatibility,the desired carbazoles can be scaled up and modified easily.Compared with previous methods,this protocol affords a simple and sustainable avenue for the construction of car-bazoles.
基金financially supported by Shanxi Province Natural Science Foundation of China(20210302123167)NSFC-Shanxi joint fund for coal-based low carbon(U1610223)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2021SX-TD006).
文摘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.
基金supported by the National Key Research and Development Program of China (2017YFA0204501)the National Science Fund of China (51525304, 61890942, U1601651)
文摘Albeit their high efficiencies, the operational stability of the organic light emitting diodes(OLEDs) based on thermally activated delayed fluorescence(TADF) emitters is still far from satisfaction, and few strategies have been proposed to improve their stability. Here, we show that by modifying the carbazole unit, one of the most commonly used donors in TADF emitters, with peripheral groups, both the device efficiency and operational stability can be greatly improved. Awell-known TADF molecule—4,5-di(9H-carbazol-9-yl)phthalonitrile(2CzPN) was chosen as the prototype and modified by introducing peripheral tert-butyl and phenyl groups to the 3,6-positions of the carbazole(named 2tBuCzPN and 2PhCzPN, respectively). The introduced groups not only improve the compounds' electrochemical stabilities referred to the cyclic voltammetry multi-sweep results, but also promote their photoluminescence quantum yields. Furthermore, reduced singlet-triplet energy gaps are observed, leading to the shortened exciton lifetimes which are benefit to suppress the exciton annihilations. Besides, the steric hindrance of introduced phenyl groups can partly restrain the concentration quenching of the TADF emitter. Consequently, OLEDs based on 2tBuCzPN and 2PhCzPN achieved improved maximum external quantum efficiencies(EQEs) of 17.0% and 14.0%, respectively(compared to 8.5% for 2CzPN). Meanwhile, 2PhCzPN based OLED showed reduced roll-off characteristics and a longer lifetime of 7.8 times higher than that of 2CzPN, testifying the effectiveness of subtle modification of the unstable moieties in simultaneous enhancement of efficiency and stability of OLEDs based on TADF emitters.
基金supported by the Natural Science Foundation of Tianjin,China(No.15JCYBJC20100).
文摘A convenient and highly efficient method is described for the synthesis of N-methoxycarbazole derivatives,including those with sterically demanding,benzannulated,or strongly electron-donating or-withdrawing substituents.Various N-methoxycarbazole derivatives were directly prepared in good-to-moderate yields by the Pd_(2)(dba)_(3)CHCl_(3)/9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene-catalyzed reactions of the corresponding dibromobiphenyl compounds and methoxyamine.Based on this methodology,the first total synthesis of 3,3′-[oxybis(methylene)]bis(9-methoxy-9H-carbazole),an antimicrobial dimeric carbazole alkaloid previously isolated from the stem bark of Murraya koenigii,was achieved in 18% yield over seven steps from 1,2-dibromobenzene.
基金supported by the National Natural Science Foundation of China (Nos. 21374115, 51573181, and 21504088)the Hundred Talents Program, CAS, China
文摘The integration of multiscale and multicomponent of molecules and nanoparticles into thin films for applications requires the abilities of controlled their processing and assembly,which has been an great challenge because of the difficulty in manipulating the various materials such as small molecules,complexes,polymers,and inorganic nanomaterials through synergetic combinations of chemical or physical fabrications.Eletropolymerization is of great significance to fabricate polymeric film materials straight on the conductive substrates with tunable morphologies and thicknesses.However,unlimited electrochemical reactions(polymerization)have been usually leading to disadvantageous in ill-defined structure and highly doped state.Thanks to finding of exceptional electrochemical reaction(oligomerization)of N-alkylcarbazole,electrochemical layer by layer assembly has emerged as a promising strategy for a wide library of applications.The capability of this strategy can manipulate various molecules and nanoparticles into the scale and component controllable thin films.Unlike other electropolymerizable precursors such as aniline and thiophene,the resulting di-N-alkylcarbazole is transparent in the visible light region and thus does not impair the intrinsic properties of the components in the film.This account highlights of the typical findings in investigating both single-and multi-components thin films as a forum for discussing new opportunities in exploiting novel designs and applications of optical thin films.
基金Funded by the Open Subject from Jiangsu Marine Resources Development Research Institute (JSIMR202117)the Training Programs of Innovation and Entrepreneurship for College Students in Jiangsu Ocean University。
文摘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.
文摘A SPE/GC-MS method for separation and determination of carbazoles in crude oil was developed.Alumina and silicic acid solid-phase extraction(SPE) columns were used to separate resin from crude oil and neutral nitrogen compounds from nitrogen riched resin.Carbazole and its alkylation series were quantitatively analysed by use of deuterate carbazole as an internal standard and the 9-benzocarbazole as an recovery rate standard.The modified method was very suitable for batch processing in organic geochemistry owing to its low cost,time saving,environmental friendliness.
文摘The direction of oil charges within a field in the Niger Delta, Nigeria was determined by the sum of differences ranking method of carbazole concentrations after ascertaining other possible geological constraints on their compositional variations. The principle is that the smaller the sum, the closer the well to the source kitchen. The approach makes use of carbazoles' interaction with the matrix, which leads to a reduction in their concentration with increasing distance from the source kitchen, allowing prediction of the charging direction. A wide range of compositional variations was observed for C1(806.72–2152.90 lg/g) and C2(767–2469.72 lg/g) carbazoles within the field. Based on these results, we inferred a filling pathway orientation from west to east. This suggests that the source kitchen—the most promising region for oil exploration—is located in the western part of the oil field.
文摘The results obtained in this paper indicate that carbazole-type compounds have high thermal stability and also show stability in oxidation and bio-degradation. This kind of compounds still has a high concentration and complete distribution in the analyzed dry asphalt samples, showing that they are particularly useful in studying petroleum migration of paleo-pool. During the basin's first-stage of oil-gas pool formation in the Silurian in Tazhong and Tabei areas of Tarim Basin (at the end of Silurian period) and the second-stage in the Awati area (in Permian), the petroleum experienced a long-distance migration. During the formation of the Silurian paleo-pools in Tazhong Uplift at the end of Silurian, the petroleum mainly came from the lower and middle Cambrian source rocks in the Manjiaer sag. The petroleum migrated towards the southwest-south entering the Silurian reservoir beds in Tazhong first. Then, it further migrated within Silurian from northwest to southeast along the highs of the Structural Belts to the region of the Silurian pinchout boundary in Tazhong. In Tabei Uplift, during the first-stage of pool formation, the petroleum was also from the lower and middle Cambrian source rocks in the Manjiaer sag. It migrated northwest entering the Silurian reservoir beds in the Tabei Uplift firstly, and then the migration continued in the same direction within the Silurian reservoirs and finally the petroleum was trapped in higher positions. During the second-stage pool formation in the Silurian beds in the areas around Awati sag, the petroleum mainly came from the lower-middle Cambrian source rocks in the Awati sag. The petroleum migrated from the generation center to Silurian reservoirs in all directions around the sag through major paths, and the petroleum was finally trapped in higher locations.
基金supported by the National Natural Science Foundation of China(U1162127,U1462201,21076189,21476202 and 21276231)
文摘Hydrogenation of carbazole and N-ethylcarbazole over Raney-Ni catalyst were realized in the temperature range of 393-503 K. 4[H] adduct dominated the hydrogenation products and the formation of 2[H] adduct was the rate-limiting step during the period, in which the conversion of carbazole was less than 40%. The hydrogenation process followed pseudo-first-order kinetics and the hydrogenation activation energies of carbazole and N-ethylcarbazole were 90 kJ/mol and 115 kJ/mol, respectively. The reaction starting position as well as the pathway of the hydrogenation of (N-ethyl)carbazole were investigated by comparing the kinetic characteristics of hydrogen uptake of carbazole and N- ethylcarbazole. The results showed that the reaction was a stepwise hydrogenation process and the first H_2 was added to the C1 = C10 double bond in the hydrogenation.
基金supported by China Postdoctoral Science Foundation (20080431027)the Postdoctoral Science Foundation of Central South University (50573019)
文摘A novel carbazole functionalized β-diketone, methyl 6-(9-ethylcarbazole-3-yl)-oxoacetyl-2-pyridinecarboxylate (MEP), and its corresponding binary Eu(III) complexes Eu(MEP)y2H2O and ternary complex Eu(MEP)aPhen with 1,10-Phenanthroline (Phen) were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ^1H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis (TG-DTA). The investigation of fluorescence properties of the complexes Eu(MEP)3·2H2O and Eu(MEP)3Phen showed that the Eu(III) ion could be sensitized efficiently by the ligand to some extent, in partitular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the n-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.
基金Department of Textile Engineering, Chemistry and Science at North Carolina State University for the financial support
文摘Herein, we report the design and synthesis of three new D-A type metal-free carbazole based dyes(S1-3)as effective co-sensitizers for dye-sensitized solar cell(DSSC) sensitized with Ru(Ⅱ) complex(NCSU-10).In this new design, the electron rich carbazole unit was attached to three different electron withdrawing/anchoring species, viz. 4-amino benzoic acid, sulfanilic acid and barbituric acid. The dyes were characterized by spectral, photophysical and electrochemical analysis. Their optical and electrochemical parameters along with molecular geometries, optimized from DFT have been employed to apprehend the effect of the structures of these co-sensitizers on the photovoltaic performances. Further, S1-3 dyes were co-sensitized along with a well-known NCSU-10 dye in order to broaden the spectral response of the co-sensitized devices and hence improve the efficiency. The photovoltaic performance studies indicated that, the device fabricated using S1 dye as co-sensitizer with 0.2 mM of NCSU-10 exhibited improved PCE of 9.55% with JSC of 22.85 mA cm-2, VOC of 0.672 V and FF of 62.2%, whereas the DSSC fabricated with dye NCSU-10(0.2 mM) alone displayed PCE of 8.25% with JSC of 20.41 mA cm-2, VOC of 0.667 V and FF of 60.6%. Furthermore, electronic excitations simulated using time-dependent DFT, were in good agreement with the experimentally obtained results of the co-sensitizers, indicating that the exchange-correlation function and basis set utilized for predicting the spectra of the co-sensitizers are quite appropriate for the calculations. In conclusion, the results showed the potential of simple organic co-sensitizers in the development of efficient DSSCs.
基金fnancially supported by the National Key Project of Science and Technology for Development of Large-size Oil&Gas Fields and Coal-bed Gas(Grant No.2008ZX05003-002)by the State Key Laboratory of Petroleum Resources and Prospecting(No.prp2009-02)The study is a contribution to IGCP#592 Project
文摘The unconformity surface at the bottom of the Paleogene is one of the most important migration pathways in the Sikeshu Sag of the Junggar Basin,which consists of three layers:upper coarse clastic rock,lower weathering crust and leached zone.The upper coarse clastic rock is characterized by higher density and lower SDT and gamma-ray logging parameters,while the lower weathering crust displays opposite features.The transport coefficient of the unconformity surface is controlled by its position in respect to the basal sandstone; it is higher in the ramp region but lower in the adjacent uplifted and sag areas.The content of saturated hydrocarbons increases with the decrease of the content of nonhydrocarbons and asphaltenes.The content of benzo[c] carbazole decreases as the content of benzo[a]carbazole and [alkyl carbazole]/[alkyl + benzo carbazole] increases.This suggests that the unconformity surface is an efficient medium for the transportation of hydrocarbons.
文摘Amorphous 2,4,6-trissubstituted pyridines containing three peripheral carbazole or two triphenylamine and one carbazole moieties, respectively, have been synthesized and characterized. The properties of the compounds are investigated by UV-vis absorption, photoluminescence spectroscopy, thermal analysis as well as cyclic voltammetry. The results show that the compounds have high thermal stability, emit blue light. Also, the compounds possess the HOMO and LUMO energy levels comparable to those of NPB. The effects of different substituents on the electronic properties of the materials have been discussed.
基金This work was supported by the National Natural Science Foundation of China(No:50025309,and No:90201016).
文摘A novel organic chromophore 4, 4'-bis(9-carbazyl-trans-styryl)-biphenyl (BCSBP) has been synthesized and characterized by IHNMR and elemental analysis. Three-photon absorption(3PA) induced upconvention fluorescence was observed and large 3PA cross section as high as 10^-74 cm^6 s^2 was obtained for nanosecond laser pulses at 1064 nm from optical limiting measurements.
基金supported by the Natural Science Foundation of Shanghai (No.09ZR1409400)Shanghai Committee of Science and Technology (No.10520710100)the Sino-French Institute of ECNU
文摘The title compound, 2,10-di-tert-butylindolo[3,2,1-jk]carbazole (C26H27N, Mr=353.49), has been synthesized by palladium-catalyzed intramolecular arylation and characterized by 1H NMR, 13C NMR and X-ray crystal structure determination. The crystal crystallizes in the monoclinic system, space group P21/c with a=13.6409(5), b=11.6706(4), c=13.1678(5), β=100.6180(10)°, V=2060.39(13)3 , Z=4, Dc=1.140 mg/m3 , μ=0.065mm-1 , F(000)=760, the final R=0.0456 and wR=0.1209 for 3012 observed reflections (I 〉 2σ(I)).
基金supported by the National Natural Science Foundation of China (51142011)Natural Science Foundation of Anhui Province (1208085MB22)Education Department of Anhui Province (KJ2010A030)
文摘A novel thiosemicarbazide derivative, (E)-1-(9-(2-(2-methoxyethoxy)ethyl)-9H-carbazol-3-yl) methylene)-thiosemicarbazide (CMT), was synthesized and structurally characterized by IR, 1H-NMR, EI-MS and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.769(5), b = 8.279(5), c = 17.166(5) , β = 114.391(5)°, V = 1911.6(14) 3, Z = 4, F(000) = 784, Dc = 1.287 g/m3, Mr = 370.47, μ = 0.190 mm-1, the final R = 0.0390 and wR = 0.1358 for 1446 observed reflections with Ⅰ 〉 2σ(Ⅰ). The UV-vis absorption spectra of CMT were explained based on quantum chemical calculations, using time dependent density functional theory (TD-DFT) at the B3LYP/6-31G (d) level.