Fifteen novel carbazole alkaloids,euchrestifolines A-O(1-15),were obtained from Murraya euchrestifolia.Their structures were elucidated by spectroscopic analysis,Mosher's ester,calculated ECD,and transition metal ...Fifteen novel carbazole alkaloids,euchrestifolines A-O(1-15),were obtained from Murraya euchrestifolia.Their structures were elucidated by spectroscopic analysis,Mosher's ester,calculated ECD,and transition metal complex ECD methods.Notably,euchrestifolines A-C(1-3)are the first naturally occurring pyrrolidone carbazoles to be identified,while euchrestifolines D-F(4-6)represent rare carbazole alkaloids containing a phenylpropanyl moiety;euchrestifoline G(7)features a unique benzopyranocarbazole skeleton.More importantly,these compounds exhibited significant anti-ferroptotic activity,along with inhibitory effects of nitric oxide(NO)production and notable cytotoxicity.This study marks the first disclosure of carbazole's inhibitory effects against ferroptosis,and the EC_(50) values of some carbazoles ranging from 0.04 to 1 μM,substantially lower than the positive control,ferrostatin-1.In sum,this research not only enhances our understanding of carbazole alkaloids but also opens new avenues for the discovery of ferroptosis-related leading compounds.展开更多
Bottom sediments of the North American Great Lakes are characterized by a high loading(over 3,000 tonnes)of polyhalogenated carbazoles(PHCZs).The origin of this environmental contaminant loading is unclear.Here,we fir...Bottom sediments of the North American Great Lakes are characterized by a high loading(over 3,000 tonnes)of polyhalogenated carbazoles(PHCZs).The origin of this environmental contaminant loading is unclear.Here,we first examined PHCZs levels and profiles in sediment,lotus,and fish fromthe Ya-Er Lake(China)that has been under the influence of an obsolete chlor-alkali facility for forty years and discovered substantial PHCZs contamination.Among the PHCZs determined,3,6-dichlorocarbazole(36-CCZ)and 3-chlorocarbazole(3-CCZ)were the most frequently detected.Sediments frombackfilled land exhibited ∑_(11)PHCZs at median concentration of 973 ng/g(dry weight),suggesting the chlor-alkali industry as an important source.Even after 20 years of dredging treatment,the concentration of ∑_(11)PHCZs in the sediment of the oxidation ponds(median=41.1 ng/g)remained substantially higher than in other areas globally.Furthermore,the concentration of ∑_(11)PHCZs was found to be higher in surface sediments(median)at 66.7 ng/g if compared to middle(14.1 ng/g)and lower layers(18.2 ng/g),indicating the potential availability of PHCZs from surface sediments to aquatic plants and animals.Notably,this study detected PHCZs in both fish(26.3 ng/g lipid weight)and lotus(14.5 ng/g dry weight),with significant enrichment of 3-monobromocarbazole(3-BCZ)observed in both lotus root systems(bio-soil accumulation factor,BSAF_(root)=5.04)and fish muscle(BSAF_(fish)=3.04).展开更多
In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especia...In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.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
Hydrogen-bonded organic frameworks(HOFs)are a promising candidate for optical sensing,but the lack of effective design strategies poses significant challenges to the construction of HOFs for organic acid sensing.In th...Hydrogen-bonded organic frameworks(HOFs)are a promising candidate for optical sensing,but the lack of effective design strategies poses significant challenges to the construction of HOFs for organic acid sensing.In this work,the first HOF for organic acid sensing is reported by constructing a multiplepyridine carbazole-based dense HOF,namely HOF-FJU-206,from a tripyridine-carbazole molecular 3,6-bis(pyridin-4-yl)-9-(4-(pyridin-4-yl)phenyl)-9H-carbazole(CPPY)with carbazole center for luminescence,pyridyl sites for its responsive of hydrogen proton,and narrow channels in the dense framework for the diffusion of hydrogen protons.HOF-FJU-206 exhibits differential responsively fluorescence sensing and recovery properties to formic,acetic,and propionic acids with different molecular sizes and p Kavalue(acid dissociation constant).The dissociation degree of various acids can be determined by analyzing the slope of changes in both peak wavelength and intensity of in-situ fluorescence,which easily enables the dual-corrective recognition of different acids.The varying degree of protonation at pyridine sites is proved to be the reason for differential sensing of various acids,as demonstrated by1H NMR spectra,X-ray photoelectron spectroscopy(XPS)characterization,and modeling studies.展开更多
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
Carbazole-core multi-branched chromophores 9-ethyl- 3, 6-bis （ 2- { 4- [ 5- （4-tert-butyl-phenyl） - [ 1, 3, 4 ] oxadiazol-2-yl ] - phenyl }-vinyl） -carbazole（3） and 9-ethyl-3-（ 2- {4-[ 5-（4-tert-butyl- phenyl...Carbazole-core multi-branched chromophores 9-ethyl- 3, 6-bis （ 2- { 4- [ 5- （4-tert-butyl-phenyl） - [ 1, 3, 4 ] oxadiazol-2-yl ] - phenyl }-vinyl） -carbazole（3） and 9-ethyl-3-（ 2- {4-[ 5-（4-tert-butyl- phenyl） -[ 1, 3, 4 ] oxadiazol-2-yl ] -phenyl }-vinyl ） -carbazole （ 2 ） are synthesized through Wittig reaction and characterized by nuclear magnetic resonance（NMR）and infrared（IR）. The two- photon absorption properties of chromophores are investigated. These chromophores exhibit large two-photon absorption crosssections and strong blue two-photon excited fluorescence. The cooperative enhancement of two-photon absorption（TPA） in the multi-branched structures is observed. This enhancement is partly attributed to the electronic coupling between the branches. The electronic push-pull structures in the arm and their cooperative effects help the extended charge transfer for TPA.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
Pharmaceutical research has focused on the discovery and development of anticancer drugs. Clinical application of chemotherapy drugs is limited due to their severe side effects. In this regard, new naturally occurring...Pharmaceutical research has focused on the discovery and development of anticancer drugs. Clinical application of chemotherapy drugs is limited due to their severe side effects. In this regard, new naturally occurring anticancer drugs have gained increasing attention because of their potential effectiveness and safety. Fruits and vegetables are promising sources of anticancer remedy. Clausena(family Rutaceae) is a genus of flowering plants and includes several kinds of edible fruits and vegetables. Phytochemical and pharmacological studies show that carbazole alkaloids and coumarins from Clausena plants exhibit anticancer activity. This review summarizes research progresses made in the anticancer properties of plants belonging to Clausena; in particular, compounds with direct cytotoxicity, cell cycle arrest, apoptosis induction, and immune potentiation effects are discussed. This review reveals the potential use of plants from Clausena in preventing and treating cancer and provides a basis for development of relevant therapeutic agents.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
Kailu Basin in which the Western Lujiapu Depression is located is a typical continental rift basin.Biomarker parameters of the oils indicate that depositional facies and environments vary between the Bao 1 and Bao 14 ...Kailu Basin in which the Western Lujiapu Depression is located is a typical continental rift basin.Biomarker parameters of the oils indicate that depositional facies and environments vary between the Bao 1 and Bao 14 fault blocks with a higher saline environment in the Bao 1 fault block, but such difference has no significant impact on carbazole abundance and distribution.Maturity and migration distance are the main controls on carbazole abundance and distribution in the Western Lujiapu Depression.The commonly used migration indices,such as ratios of nitrogen shield isomers to nitrogen exposed isomers（1-/4-methylcarbazole ratio,1,8-/2,4-dimethylcarbazole（DMC） ratio and half-shield/exposed-DMC ratio）,absolute concentrations of alkylated carbazoles and BC ratio（=benzo [a]carbazole/（benzo[a]carbazole＋benzo[c]carbazole）） increase at the low mature range and decrease at a higher mature range with increasing maturity.At relatively low maturity stage（Rc〈0.77%）, maturation has reversal effects with migration on the ratios of nitrogen shield isomers to nitrogen exposed isomers,which may cover migration influence and makes these parameters fail to indicate migration effects.Valid migration indicators at this maturity stage are concentrations of alkylated carbazoles and BC ratios,which can provide ideal tools for migration direction assessment even within short migration distance.Maturity effects should be taken into account when carbazole compounds are applied to indicate migration direction,and at different maturity stages,these commonly used parameters have different validity in tracing migration direction.Coupled with our previous study in the Eastern Lujiapu Depression,a conceptual model of the variation of nitrogen migration indices can be established for terrestrial rifted basins,that is,strong fractionation lateral migration model through sandy beds,weak fractionation vertical migration model along faults,and maturity impacts on migration assessment.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
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
In this paper, we report a novel approach to the heteroaryl-condensed nuclei of natural furo[3,2- a]carbazole alkaloids. Our synthetic studies use N-phthaloyl tryptophan methyl ester as starting material and zinc ion ...In this paper, we report a novel approach to the heteroaryl-condensed nuclei of natural furo[3,2- a]carbazole alkaloids. Our synthetic studies use N-phthaloyl tryptophan methyl ester as starting material and zinc ion mediated transamination reaction as the key step. This work also implicated a novel strategy to assemble other [a]-fused carbazoles.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
Indolocarbazole derivatives have been reported to be promising organic semicon- ductor candidates and electroluminescent （EL） materials. One novel indolocarbazole derivative, 2,8-acetyl-5,11-dihexyl-6,12-（di-p-toly...Indolocarbazole derivatives have been reported to be promising organic semicon- ductor candidates and electroluminescent （EL） materials. One novel indolocarbazole derivative, 2,8-acetyl-5,11-dihexyl-6,12-（di-p-tolyl）-5,11-indolo[3,2-b]carbazole （YK4）, has been synthesized, and its crystal structure has also been carefully studied. YK4 is triclinic, space groups Pi with a = 9.409（5）, b = 13.974（5）, c = 15.488（5） A, α = 90.281（5）, β = 105.456（5）, Z= 93.728（5）°, M,. = 688.94, V= 1958.1（14） A3, Z = 2, Dc.= 1.168 g/cm-3,μ = 0.070 mm-1, F（000） = 740, Rint = 0.0475, R （I〉 20（/）） = 0.1146, wR （I〉 20（/）） = 0.2186, R（all data） = 0.2192 and wR （all data） = 0.2701. Like other indolo[3, 2-b]carbazole derivatives which were introduced in the 5- and 11-positions, the intermolecular short contacts are localized between the pendant groups and acetyl groups of the neighboring indolocarbazole molecules. The molecule of YK4 possesses poor face-to-face π-π stacking between two adjacent molecules in the crystal. The calculated bond lengths and bond angles of YK4 also proved the result of crystallography.展开更多
Two new functional polyacetylenes bearing carbazole group as pendant, poly { 3-[（4-ethynylstyryl）-N-butyl] carbazole } （P1 ） and poly{3-14-（prop-2-ynyloxy）phenyl-N-butyl]carbazole}（P2）, were prepared using [Rb...Two new functional polyacetylenes bearing carbazole group as pendant, poly { 3-[（4-ethynylstyryl）-N-butyl] carbazole } （P1 ） and poly{3-14-（prop-2-ynyloxy）phenyl-N-butyl]carbazole}（P2）, were prepared using [Rb（nbd）Cl]2-Et3N as catalyst. The polymers were soluble in common organic solvents such as CHCl3 and THF. Their structures and properties were characterized and evaluated with FTIR, lit NMR, UV, TGA, GPC, and CV, respectively. The results show that the polymers possess high thermal stability and well hole-injection property.展开更多
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 se...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.展开更多
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 ...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.展开更多
基金the National Natural Science Foundation of China(NSFC)for their financial support through grant numbers 81973199,82173949,U23A20514,81773864,and 81473106the funding provided by the Key Research and Development Project of Shandong Province(2021CXGC010507).
文摘Fifteen novel carbazole alkaloids,euchrestifolines A-O(1-15),were obtained from Murraya euchrestifolia.Their structures were elucidated by spectroscopic analysis,Mosher's ester,calculated ECD,and transition metal complex ECD methods.Notably,euchrestifolines A-C(1-3)are the first naturally occurring pyrrolidone carbazoles to be identified,while euchrestifolines D-F(4-6)represent rare carbazole alkaloids containing a phenylpropanyl moiety;euchrestifoline G(7)features a unique benzopyranocarbazole skeleton.More importantly,these compounds exhibited significant anti-ferroptotic activity,along with inhibitory effects of nitric oxide(NO)production and notable cytotoxicity.This study marks the first disclosure of carbazole's inhibitory effects against ferroptosis,and the EC_(50) values of some carbazoles ranging from 0.04 to 1 μM,substantially lower than the positive control,ferrostatin-1.In sum,this research not only enhances our understanding of carbazole alkaloids but also opens new avenues for the discovery of ferroptosis-related leading compounds.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0750400)the National Natural Science Foundation of China(Nos.22076201,21936007 and 22376204).
文摘Bottom sediments of the North American Great Lakes are characterized by a high loading(over 3,000 tonnes)of polyhalogenated carbazoles(PHCZs).The origin of this environmental contaminant loading is unclear.Here,we first examined PHCZs levels and profiles in sediment,lotus,and fish fromthe Ya-Er Lake(China)that has been under the influence of an obsolete chlor-alkali facility for forty years and discovered substantial PHCZs contamination.Among the PHCZs determined,3,6-dichlorocarbazole(36-CCZ)and 3-chlorocarbazole(3-CCZ)were the most frequently detected.Sediments frombackfilled land exhibited ∑_(11)PHCZs at median concentration of 973 ng/g(dry weight),suggesting the chlor-alkali industry as an important source.Even after 20 years of dredging treatment,the concentration of ∑_(11)PHCZs in the sediment of the oxidation ponds(median=41.1 ng/g)remained substantially higher than in other areas globally.Furthermore,the concentration of ∑_(11)PHCZs was found to be higher in surface sediments(median)at 66.7 ng/g if compared to middle(14.1 ng/g)and lower layers(18.2 ng/g),indicating the potential availability of PHCZs from surface sediments to aquatic plants and animals.Notably,this study detected PHCZs in both fish(26.3 ng/g lipid weight)and lotus(14.5 ng/g dry weight),with significant enrichment of 3-monobromocarbazole(3-BCZ)observed in both lotus root systems(bio-soil accumulation factor,BSAF_(root)=5.04)and fish muscle(BSAF_(fish)=3.04).
文摘In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.
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 Natural Science Foundation of China(Nos.22271046,21971038,21975044)the Fujian Provincial Department of Science and Technology(No.2019L3004)the Foundation of National Key Laboratory of Human Factors Engineering(No.HFNKL2023W04)。
文摘Hydrogen-bonded organic frameworks(HOFs)are a promising candidate for optical sensing,but the lack of effective design strategies poses significant challenges to the construction of HOFs for organic acid sensing.In this work,the first HOF for organic acid sensing is reported by constructing a multiplepyridine carbazole-based dense HOF,namely HOF-FJU-206,from a tripyridine-carbazole molecular 3,6-bis(pyridin-4-yl)-9-(4-(pyridin-4-yl)phenyl)-9H-carbazole(CPPY)with carbazole center for luminescence,pyridyl sites for its responsive of hydrogen proton,and narrow channels in the dense framework for the diffusion of hydrogen protons.HOF-FJU-206 exhibits differential responsively fluorescence sensing and recovery properties to formic,acetic,and propionic acids with different molecular sizes and p Kavalue(acid dissociation constant).The dissociation degree of various acids can be determined by analyzing the slope of changes in both peak wavelength and intensity of in-situ fluorescence,which easily enables the dual-corrective recognition of different acids.The varying degree of protonation at pyridine sites is proved to be the reason for differential sensing of various acids,as demonstrated by1H NMR spectra,X-ray photoelectron spectroscopy(XPS)characterization,and modeling studies.
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The National Natural Science Foundation of China(No.60678042)the Natural Science Foundation of Jiangsu Province(No.BK2006553)the Pre-Research Project of the National Natural Science Foundation supported by Southeast University(No.9207041399)
文摘Carbazole-core multi-branched chromophores 9-ethyl- 3, 6-bis （ 2- { 4- [ 5- （4-tert-butyl-phenyl） - [ 1, 3, 4 ] oxadiazol-2-yl ] - phenyl }-vinyl） -carbazole（3） and 9-ethyl-3-（ 2- {4-[ 5-（4-tert-butyl- phenyl） -[ 1, 3, 4 ] oxadiazol-2-yl ] -phenyl }-vinyl ） -carbazole （ 2 ） are synthesized through Wittig reaction and characterized by nuclear magnetic resonance（NMR）and infrared（IR）. The two- photon absorption properties of chromophores are investigated. These chromophores exhibit large two-photon absorption crosssections and strong blue two-photon excited fluorescence. The cooperative enhancement of two-photon absorption（TPA） in the multi-branched structures is observed. This enhancement is partly attributed to the electronic coupling between the branches. The electronic push-pull structures in the arm and their cooperative effects help the extended charge transfer for TPA.
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 the Macao Science and Technology Development Fund(No.120/2013/A3)the Research Fund of University of Macao(Nos.MYRG2015-00153-ICMS-QRCM and MYRG2017-00109-ICMS)
文摘Pharmaceutical research has focused on the discovery and development of anticancer drugs. Clinical application of chemotherapy drugs is limited due to their severe side effects. In this regard, new naturally occurring anticancer drugs have gained increasing attention because of their potential effectiveness and safety. Fruits and vegetables are promising sources of anticancer remedy. Clausena(family Rutaceae) is a genus of flowering plants and includes several kinds of edible fruits and vegetables. Phytochemical and pharmacological studies show that carbazole alkaloids and coumarins from Clausena plants exhibit anticancer activity. This review summarizes research progresses made in the anticancer properties of plants belonging to Clausena; in particular, compounds with direct cytotoxicity, cell cycle arrest, apoptosis induction, and immune potentiation effects are discussed. This review reveals the potential use of plants from Clausena in preventing and treating cancer and provides a basis for development of relevant therapeutic agents.
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Supported by Program for Changjiang Scholars and Innovative Research Team in University(IRT0864) for financial support of this work.
文摘Kailu Basin in which the Western Lujiapu Depression is located is a typical continental rift basin.Biomarker parameters of the oils indicate that depositional facies and environments vary between the Bao 1 and Bao 14 fault blocks with a higher saline environment in the Bao 1 fault block, but such difference has no significant impact on carbazole abundance and distribution.Maturity and migration distance are the main controls on carbazole abundance and distribution in the Western Lujiapu Depression.The commonly used migration indices,such as ratios of nitrogen shield isomers to nitrogen exposed isomers（1-/4-methylcarbazole ratio,1,8-/2,4-dimethylcarbazole（DMC） ratio and half-shield/exposed-DMC ratio）,absolute concentrations of alkylated carbazoles and BC ratio（=benzo [a]carbazole/（benzo[a]carbazole＋benzo[c]carbazole）） increase at the low mature range and decrease at a higher mature range with increasing maturity.At relatively low maturity stage（Rc〈0.77%）, maturation has reversal effects with migration on the ratios of nitrogen shield isomers to nitrogen exposed isomers,which may cover migration influence and makes these parameters fail to indicate migration effects.Valid migration indicators at this maturity stage are concentrations of alkylated carbazoles and BC ratios,which can provide ideal tools for migration direction assessment even within short migration distance.Maturity effects should be taken into account when carbazole compounds are applied to indicate migration direction,and at different maturity stages,these commonly used parameters have different validity in tracing migration direction.Coupled with our previous study in the Eastern Lujiapu Depression,a conceptual model of the variation of nitrogen migration indices can be established for terrestrial rifted basins,that is,strong fractionation lateral migration model through sandy beds,weak fractionation vertical migration model along faults,and maturity impacts on migration assessment.
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 NSFC (No.21102026)Qiankehe [2011] 3002West Light Foundation of the Chinese Academy of Sciences
文摘In this paper, we report a novel approach to the heteroaryl-condensed nuclei of natural furo[3,2- a]carbazole alkaloids. Our synthetic studies use N-phthaloyl tryptophan methyl ester as starting material and zinc ion mediated transamination reaction as the key step. This work also implicated a novel strategy to assemble other [a]-fused carbazoles.
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Natural Science Foundation of Anhui Province(06070343)National Natural Science Foundation of China(21101001)
文摘Indolocarbazole derivatives have been reported to be promising organic semicon- ductor candidates and electroluminescent （EL） materials. One novel indolocarbazole derivative, 2,8-acetyl-5,11-dihexyl-6,12-（di-p-tolyl）-5,11-indolo[3,2-b]carbazole （YK4）, has been synthesized, and its crystal structure has also been carefully studied. YK4 is triclinic, space groups Pi with a = 9.409（5）, b = 13.974（5）, c = 15.488（5） A, α = 90.281（5）, β = 105.456（5）, Z= 93.728（5）°, M,. = 688.94, V= 1958.1（14） A3, Z = 2, Dc.= 1.168 g/cm-3,μ = 0.070 mm-1, F（000） = 740, Rint = 0.0475, R （I〉 20（/）） = 0.1146, wR （I〉 20（/）） = 0.2186, R（all data） = 0.2192 and wR （all data） = 0.2701. Like other indolo[3, 2-b]carbazole derivatives which were introduced in the 5- and 11-positions, the intermolecular short contacts are localized between the pendant groups and acetyl groups of the neighboring indolocarbazole molecules. The molecule of YK4 possesses poor face-to-face π-π stacking between two adjacent molecules in the crystal. The calculated bond lengths and bond angles of YK4 also proved the result of crystallography.
基金supported by the National Natural Science Fund of China(No.21071002/B0111)the Natural Science Fund of Anhui Province(No.11040606M33)
文摘Two new functional polyacetylenes bearing carbazole group as pendant, poly { 3-[（4-ethynylstyryl）-N-butyl] carbazole } （P1 ） and poly{3-14-（prop-2-ynyloxy）phenyl-N-butyl]carbazole}（P2）, were prepared using [Rb（nbd）Cl]2-Et3N as catalyst. The polymers were soluble in common organic solvents such as CHCl3 and THF. Their structures and properties were characterized and evaluated with FTIR, lit NMR, UV, TGA, GPC, and CV, respectively. The results show that the polymers possess high thermal stability and well hole-injection property.
文摘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.
基金supported by the National Natural Science Foundation of China(21776192,22038008)。
文摘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.
