In this work, a new microextraction method termed ionic liquid based dispersive liquid-liquid microextraction （IL-DLLME） was demonstrated for the extraction of 2-methylaniline, 4-chloroaniline, 1-naphthylamine and 4...In this work, a new microextraction method termed ionic liquid based dispersive liquid-liquid microextraction （IL-DLLME） was demonstrated for the extraction of 2-methylaniline, 4-chloroaniline, 1-naphthylamine and 4-aminobiphenyl in aqueous matrices. After extraction the ionic liquid （IL） phase was injected directly into the high performance liquid chromatography （HPLC） system for determination. Some parameters that might affect the extraction efficiency were optimized. Under the optimum conditions, good linear relationship, sensitivity and reproducibility were obtained. The limits of detection （LOD, S/N = 3） for the four analytes were in the range of 0.45-2.6 μg L^-1. The relative standard deviations （R.S.D., n = 6） were in the range of 6.2-9.8%. This method was applied for the analysis of the real water samples. The recoveries ranged from 93.4 to 106.4%. The main advantages of the method are high speed, high recovery, good repeatability and volatile organic solvent-free.展开更多
In current paper, a quantitative structure-activity relationship （QSAR） study was performed for the prediction of acute toxicity of aromatic amines. A set of 56 compounds was randomly divided into a training set of ...In current paper, a quantitative structure-activity relationship （QSAR） study was performed for the prediction of acute toxicity of aromatic amines. A set of 56 compounds was randomly divided into a training set of 46 compounds and a test set of 10 compounds. The electronic and topological descriptors computed by the Scigress package and Dragon software were used as predictor variables. Multiple linear regression （MLR） and support vector machine （SVM） were utilized to build the linear and nonlinear QSAR models, respectively. The obtained models with five descriptors show strong predictive ability. The linear model fits the training set with R2 = 0.71, with higher SVM values of R2 = 0.77. The validation results obtained from the test set indicate that the SVM model is comparable or superior to that obtained by MLR, both in terms of prediction ability and robustness.展开更多
Meat products are an important part in our daily diet,providing valuable nutrients for the human body.However,heating processes cause the meat to become more appetizing with changes in texture,appearance,flavor,and ch...Meat products are an important part in our daily diet,providing valuable nutrients for the human body.However,heating processes cause the meat to become more appetizing with changes in texture,appearance,flavor,and chemical properties by the altering of protein structure and other ingredients.As one kind of cooking-induced contaminants,heterocyclic aromatic amines(HAAs)are widely present in protein aceous food products with strong carcinogenic and mutagenic properties.In order to promote the safety of traditional meat products,this review focused on the formation,metabolism,biological monitoring and inhibitory mechanism of HAA.An overview of the formation pathways,hazards,and control methods of HAAs during food processing in recent years was studied,aiming to provide some valuable information for exploring effective methods to inhibit the production of associated hazards during food processing.Systematic selection of different types of flavonoids to explore their effects on the formation of HAAs in an actual barbecue system can provide theoretical reference for effectively controlling the formation of HAAs and reducing their harm to human health.展开更多
A facile synthesis of N-methyl-N-aryl carbamates from aromatic amines and dimethyl carbonate (DMC) has been achieved with high yields in the presence of potassium carbonate (K2CO3)and tetrabutylammonium bromide (Bu4NB...A facile synthesis of N-methyl-N-aryl carbamates from aromatic amines and dimethyl carbonate (DMC) has been achieved with high yields in the presence of potassium carbonate (K2CO3)and tetrabutylammonium bromide (Bu4NBr) under solvent-free conditions.展开更多
A novel on-line solid-phase microextraction–high-performance liquid chromatography（SPME–HPLC）system was developed for the determination of heterocyclic aromatic amines（HAAs） in food samples. A poly（vinylphenylb...A novel on-line solid-phase microextraction–high-performance liquid chromatography（SPME–HPLC）system was developed for the determination of heterocyclic aromatic amines（HAAs） in food samples. A poly（vinylphenylboronic acid-co-ethylene glycol dimethacrylate） polymer monolith was prepared for on-line efficient extraction and large-volume injection was used to increase the sensitivity of detection.The polymermonolith, based on a ternary porogen, was prepared by in situ polymerization of vinylphenylboronic acid（VPBA） and ethylene glycol dimethacrylate（EGDMA） in a fused-silica capillary column. It showed good permeability, high extraction capacity, and high selectivity. The column-tocolumn reproducibility was satisfactory, and the enrichment factors for HAAs were 3746–7414.Conditions influencing the on-line extraction efficiency, including p H of sample solutions, flow rate of extraction and desorption, and desorption volume, were investigated. The proposed method had low limit of detection（0.10–0.15 ng/L） and good linearity. Trace HAAs in roast beef and lamb samples were determined, and the amounts of 2-amino-3-methylimidazo[4,5-f]quinoline, 2-amino-3,4-dimethylimidazo[4,5-f]quinoline, 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline, 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline, and 2-amino-3,4,7,8-tetramethyl-3H-imidazo[4,5-f]quinoxaline in these samples were 0.235–2.08 ng/g. The recoveries for the five HAAs ranged from74.3% to 119%, and the relative standard deviation（RSDs） were less than 8.2%. The results showed that the proposed on-line method was highly sensitive for monitoring HAAs in different food samples.展开更多
Five marinades were developed using natural antioxidants. Based on a consumer test of the appearance, three marinades were chosen for further investigation: an oregano, an acerola and a Dijon marinade, the Dijon marin...Five marinades were developed using natural antioxidants. Based on a consumer test of the appearance, three marinades were chosen for further investigation: an oregano, an acerola and a Dijon marinade, the Dijon marinade containing acerola, sumac and oregano. A barbecue and a sumac marinade were not included in the further study. In a home use test, consumers barbecued pork chops with the three marinades. Most of the consumers preferred the oregano and the Dijon marinade, while the acerola marinade was less liked. After controlled cooking using both direct and indirect heat to a core temperature of 65°C and 80°C, the content of the heterocyclic aromatic amines (HCA) PhiP, MeIQx, DiMeIQx, Harman and Norharman was analysed. All of the marinades reduced the content of MeIQx and DiMeIQx, although only with indirect heat, while PhiP was reduced using both grilling methods. Surprisingly, in particular the content of Harman—and to a lesser extent Norhaman—was very high in the Dijon-marinated chops. The results demonstrated that it was possible to develop well-liked marinades that can reduce the formation of selected HCAs.展开更多
Primary aromatic amines （PAAs） are substances with toxicity and suspected human carcinogenicity. A facile method for highly sensitive detection of PAAs using surface-enhanced Raman spectroscopy （SERS） is reported....Primary aromatic amines （PAAs） are substances with toxicity and suspected human carcinogenicity. A facile method for highly sensitive detection of PAAs using surface-enhanced Raman spectroscopy （SERS） is reported. The immobilization of Au nanoparticles （AuNPs） on the glycidyl methacrylate-ethylene dimethacrylate （GMA-EDMA） materials makes the suhstrate a closely packed but not aggregated Au NP arrays which provides a prominent SERS enhancement. Four PAAs with different substituent groups, namely, p-toluidine, p-nitroaniline, benzidine and 4,4-methylene-bis-（2-chloroaniline） have been successfully identified and quantified. High sensitivity and good linear relationship between SERS signals and concentrations of PAAs are obtained for all four PAAs.展开更多
Allyldialkyltelluronium bromides were treated with aromatic amines in 1,2-dichloroethane,readily giving allyl aryl amines in excel- lent yields.This method provides a convenient one-pot reaction for the synthesis of a...Allyldialkyltelluronium bromides were treated with aromatic amines in 1,2-dichloroethane,readily giving allyl aryl amines in excel- lent yields.This method provides a convenient one-pot reaction for the synthesis of allylic amines.展开更多
The curing reaction and reaction mechanism of epoxy resin E-44, for which aromatic amine modified dicyandiamide was used as a curing reagent, were investigated by means of differential scanning calorimetry （DSC）. Th...The curing reaction and reaction mechanism of epoxy resin E-44, for which aromatic amine modified dicyandiamide was used as a curing reagent, were investigated by means of differential scanning calorimetry （DSC）. The results showed that the modified dicyandiamide had better curing characteristic than unmodified dicyandiamide for epoxy resin E-44, and the curing reaction could be carried out at moderate temperature. Apparent activation energy of the curing reaction was decreased appreciably from 123.829 kJ/mol to 61.550-64.405 kJ/mol, and reaction order was decreased from 0.941 to 0.896-0.900. Curing reaction mechanism also was discussed.展开更多
The oxidative coupling of primary aromatic amines was investigated. Ce（SO4）2 can mediate the oxidative coupling of primary aromatic amines in water to dimers, trimers and/or tetramers, which depended on the substitu...The oxidative coupling of primary aromatic amines was investigated. Ce（SO4）2 can mediate the oxidative coupling of primary aromatic amines in water to dimers, trimers and/or tetramers, which depended on the substituents of primary aromatic amines. When 2,6-dimethylaniline or 2,6-diethylaniline was used as substrate, dimer, and tetramer were formed as major products. When 2,6-diisopropylaniline or 2,6-dihaloanilines was used as substrate, dimer, and trimer were formed. The mechanistic aspect was also investigated.展开更多
Sometimes chemistry doesn’t just make new molecules-it overturns old assumptions.For 140 years,drugmakers have accepted that transforming aromatic amines-a very important reaction for building drug molecules-means li...Sometimes chemistry doesn’t just make new molecules-it overturns old assumptions.For 140 years,drugmakers have accepted that transforming aromatic amines-a very important reaction for building drug molecules-means living with explosive risks.The danger was considered unavoidable,the tradeoff permanent-until a team in Hangzhou proved otherwise.展开更多
Aromatic amines are crucial in pharmaceuticals,but their synthesis is challenging due to unfavorable reaction equilibria and the use of costly,environmentally unfriendly methods.This study presents a membrane extracti...Aromatic amines are crucial in pharmaceuticals,but their synthesis is challenging due to unfavorable reaction equilibria and the use of costly,environmentally unfriendly methods.This study presents a membrane extraction(ME)process for in situ product removal(ISPR)of aromatic amines.Using a supported liquid membrane(SLM),α-methylbenzylamine(MBA)and 1-methyl-3-phenylpropylamine(MPPA)were separated from isopropyl amine(IPA).Conductor-like Screening Model for Real Solvents(COSMO-RS)was employed to screen over 200 organic mixtures,identifying twelve mixtures based on trioctylphosphine oxide(TOPO),lidocaine,and menthol as solvent candidates,due to their hydrophobicity.These mixtures were analysed for critical solvent properties including density,viscosity,hydrophobicity,and H-bonding interactions.ME tests showed TOPO-thymol had the highest solvent residual and selectivity.Moreover,TOPO-thymol demonstrated solute fluxes of 9.0±3.0 g/(m^(2)h)for MBA,16.5±5.4 g/(m^(2)h)for MPPA,and 0.7±0.3 g/(m^(2)h)for IPA,with selectivity values of 12.4±0.8 for MBA/IPA and 22.8±1.4 for MPPA/IPA.Compared to undecane,which had lower selectivity values of 6.9±0.8 for MBA/IPA and 10.1±1.3 for MPPA/IPA,TOPO-thymol showed superior selectivity,indicating its promise as an extractant for ME applications.展开更多
A simple and efficient protocol for the electrophilic thiocyanation of indoles and aromatic amines with thiourea/NCS/NH4SCN system has been developed. The major features of the present procedure are the mild condition...A simple and efficient protocol for the electrophilic thiocyanation of indoles and aromatic amines with thiourea/NCS/NH4SCN system has been developed. The major features of the present procedure are the mild conditions, good yields, short reaction times, and the use of inexpensive and readily available organocatalyst. Moreover, N-chlorosueeinimide （NCS） was found to be indispensable, and thiourea could greatly promote the reaction.展开更多
An asymmetric allylic amination of Morita-Baylis-Hillman acetates with simple aromatic amines catalyzed by planarly chiral ligand/palladium-catalyst was developed in good yield with excellent a-regioselectivity （a/γ...An asymmetric allylic amination of Morita-Baylis-Hillman acetates with simple aromatic amines catalyzed by planarly chiral ligand/palladium-catalyst was developed in good yield with excellent a-regioselectivity （a/γ up to 30 ： 1） and moderate enantioselectivity （up to 70% ee）.展开更多
Contamination by the heterocyclic aromatic amines(HAAs)norharman and harman is one of the risks in vegetable oil production,so oil producers strive to decrease their content in the end products.In this study,the effec...Contamination by the heterocyclic aromatic amines(HAAs)norharman and harman is one of the risks in vegetable oil production,so oil producers strive to decrease their content in the end products.In this study,the effects of production conditions—specifically,two pretreatment methods(roasting and microwaving),four extraction methods(two pressing and two solvent extraction)and adsorption refining(four absorbents)—of five oils(flaxseed,peanut,rapeseed,sesame,and sunflower seed)were evaluated.The results showed that microwaving as a pretreatment produced significantly fewer HAAs than roasting(P<0.05).After two pretreatments,the HAA content of oils was ranked from high to low as follows:sunflower oil,sesame oil,flaxseed oil,rapeseed oil,and peanut oil.Solvent-extracted oils(9.16–316.73μg/kg)had fewer HAAs than pressed oils(26.61–633.93μg/kg).Using adsorbents reduced HAAs in oils from the initial 21.77–484.22 to 0.31–41.58μg/kg,and the removal rate reached 99.28%.This study provides critical HAA reduction strategies for application in the oil production process to obtain safe final products.展开更多
A simple copper-promoted one-pot Sandmeyer trifluoromethylation of aromatic amines with Langlois＇ reagent has been demonstrated. The reaction is performed in mild reaction conditions under an air atmosphere with good...A simple copper-promoted one-pot Sandmeyer trifluoromethylation of aromatic amines with Langlois＇ reagent has been demonstrated. The reaction is performed in mild reaction conditions under an air atmosphere with good substrate scope and functional group compatibility. It provides an alternative and straightforward synthetic approach to access a variety of trifluoromethylated arenes.展开更多
Pure organic luminogens with efficient room temperature phosphorescence（RTP） and remarkable mechanochromism are highly desired in view of their fundamental significance and technical applications. Herein, four twist...Pure organic luminogens with efficient room temperature phosphorescence（RTP） and remarkable mechanochromism are highly desired in view of their fundamental significance and technical applications. Herein, four twisted pure organic luminogens based on benzophenone and aromatic amines were synthesized and their photophysical properties were thoroughly investigated. They exhibit crystallization-induced phosphorescence（CIP）, giving bright fluorescence and phosphorescence dual emission in crystals. Upon grinding, they become amorphous and emit predominantly red-shifted fluorescence, demonstrating remarkable mechanochromism. Furthermore, three of them even demonstrate greatly enhanced emission upon grinding, which is rarely observed in twisted D-A structured luminogens.展开更多
Aldehydes,heterocyclic aromatic amines(HAAs)and terpenes were sparsely studied for their sex-hormone disrupting effect in children and adolescents,although people are widely exposed.This study aimed to investigate the...Aldehydes,heterocyclic aromatic amines(HAAs)and terpenes were sparsely studied for their sex-hormone disrupting effect in children and adolescents,although people are widely exposed.This study aimed to investigate the individual and mixture effect of aldehydes,HAAs and terpenes on sex hormones among children and adolescents and explore the effect modification of Vitamin D(VD).Six aldehydes,three HAAs and three terpenes were collected from the National Health and Nutrition Examination Survey 2013-2014,which sampled representative U.S.population.Five sex hormone indicators[testosterone(TT),estradiol(E2),sex hormone binding globulin(SHBG),free androgen index(FAI)and ratio of TT to E2(TT/E2)]were measured.Multiple linear regression and Bayesian kernel machine regression were used to explore the individual-and joint-exposure to these chemicals with each sex hormone,respectively.We primarily found some chemicals were positively associated with SHBG and negatively associated with TT,E2,and FAI among male adolescents.In addition,when stratified by pubertal status,we mainly found certain chemicals were negatively associated with TT,E2,FAI and TT/E2 in pubertal male and prepubertal female.Joint exposure to HAAs were associated with significant decrease in TT and FAI in male adolescent.These associations present age-,sex-and development-dependent patterns.VD modified these associations with significant results more pronounced in VD≥75 nmol/L group.Our study provided novel findings for the hormonal effect of aldehydes,HAAs and terpenes in children and adolescents,and is also significant for potential avenues for public health action and intervention.展开更多
Aromatic amines(AAs)are widely used in manufacturing industries,where their oxidation plays a crucial role in direct applications and the synthesis of nitrogen-containing compounds.Understanding their reactivity is a ...Aromatic amines(AAs)are widely used in manufacturing industries,where their oxidation plays a crucial role in direct applications and the synthesis of nitrogen-containing compounds.Understanding their reactivity is a prerequisite for their use in various fields.Given their chemical diversity and significance,the behavior of AAs on surfaces is of considerable interest for potential applications.Herein,we combined scanning tunneling microscopy(STM)and X-ray photoelectron spectroscopy(XPS)to explore the reactivity of AAs on silver(Ag)and gold(Au)surfaces using a gas-mediated reaction strategy.Our results revealed that oxidative dehydrogenation was readily achieved after O2-mediated treatment on Ag surfaces,leading to the formation of organometallic nanopores,while AAs remained unperturbed on Au(111),indicating a substrate-dependent behavior.Density functional theory(DFT)calculations corroborate the experimental observations,by simulated core-level shifts and microscopy images,and demonstrate how the choice of substrate dictates the thermodynamics of the overall reactions.These findings emphasize the importance of substrate selection in modulating the surface chemistry of AAs,paving the way for more efficient catalytic processes and material design.展开更多
基金the National Natural Science Foundation of China(Nos.20375035,20527005,20775070)by Zhejiang Provincial Natural Science Foundation of China(Nos.Z404105,Y507252).
文摘In this work, a new microextraction method termed ionic liquid based dispersive liquid-liquid microextraction （IL-DLLME） was demonstrated for the extraction of 2-methylaniline, 4-chloroaniline, 1-naphthylamine and 4-aminobiphenyl in aqueous matrices. After extraction the ionic liquid （IL） phase was injected directly into the high performance liquid chromatography （HPLC） system for determination. Some parameters that might affect the extraction efficiency were optimized. Under the optimum conditions, good linear relationship, sensitivity and reproducibility were obtained. The limits of detection （LOD, S/N = 3） for the four analytes were in the range of 0.45-2.6 μg L^-1. The relative standard deviations （R.S.D., n = 6） were in the range of 6.2-9.8%. This method was applied for the analysis of the real water samples. The recoveries ranged from 93.4 to 106.4%. The main advantages of the method are high speed, high recovery, good repeatability and volatile organic solvent-free.
基金Supported by the Ministry of Environmental Protection of China(No.2011467037)
文摘In current paper, a quantitative structure-activity relationship （QSAR） study was performed for the prediction of acute toxicity of aromatic amines. A set of 56 compounds was randomly divided into a training set of 46 compounds and a test set of 10 compounds. The electronic and topological descriptors computed by the Scigress package and Dragon software were used as predictor variables. Multiple linear regression （MLR） and support vector machine （SVM） were utilized to build the linear and nonlinear QSAR models, respectively. The obtained models with five descriptors show strong predictive ability. The linear model fits the training set with R2 = 0.71, with higher SVM values of R2 = 0.77. The validation results obtained from the test set indicate that the SVM model is comparable or superior to that obtained by MLR, both in terms of prediction ability and robustness.
基金supported by National Postdoctoral Program(2020M682073)the National Natural Science Foundation of China(NSFC,32061160477)+1 种基金The National Natural Science Foundation of China(32272315,32072209)the Natural Science Foundation of Guangdong Province(2022A1515010694).
文摘Meat products are an important part in our daily diet,providing valuable nutrients for the human body.However,heating processes cause the meat to become more appetizing with changes in texture,appearance,flavor,and chemical properties by the altering of protein structure and other ingredients.As one kind of cooking-induced contaminants,heterocyclic aromatic amines(HAAs)are widely present in protein aceous food products with strong carcinogenic and mutagenic properties.In order to promote the safety of traditional meat products,this review focused on the formation,metabolism,biological monitoring and inhibitory mechanism of HAA.An overview of the formation pathways,hazards,and control methods of HAAs during food processing in recent years was studied,aiming to provide some valuable information for exploring effective methods to inhibit the production of associated hazards during food processing.Systematic selection of different types of flavonoids to explore their effects on the formation of HAAs in an actual barbecue system can provide theoretical reference for effectively controlling the formation of HAAs and reducing their harm to human health.
文摘A facile synthesis of N-methyl-N-aryl carbamates from aromatic amines and dimethyl carbonate (DMC) has been achieved with high yields in the presence of potassium carbonate (K2CO3)and tetrabutylammonium bromide (Bu4NBr) under solvent-free conditions.
基金supported by the National Natural Science Foundation of China(Nos.21127008,21375155)the Specialized Research Fund for the Doctoral Program of Higher Education(No.20120171110001)the Guangdong Provincial Natural Science Foundation of China(No.2015A030311020)
文摘A novel on-line solid-phase microextraction–high-performance liquid chromatography（SPME–HPLC）system was developed for the determination of heterocyclic aromatic amines（HAAs） in food samples. A poly（vinylphenylboronic acid-co-ethylene glycol dimethacrylate） polymer monolith was prepared for on-line efficient extraction and large-volume injection was used to increase the sensitivity of detection.The polymermonolith, based on a ternary porogen, was prepared by in situ polymerization of vinylphenylboronic acid（VPBA） and ethylene glycol dimethacrylate（EGDMA） in a fused-silica capillary column. It showed good permeability, high extraction capacity, and high selectivity. The column-tocolumn reproducibility was satisfactory, and the enrichment factors for HAAs were 3746–7414.Conditions influencing the on-line extraction efficiency, including p H of sample solutions, flow rate of extraction and desorption, and desorption volume, were investigated. The proposed method had low limit of detection（0.10–0.15 ng/L） and good linearity. Trace HAAs in roast beef and lamb samples were determined, and the amounts of 2-amino-3-methylimidazo[4,5-f]quinoline, 2-amino-3,4-dimethylimidazo[4,5-f]quinoline, 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline, 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline, and 2-amino-3,4,7,8-tetramethyl-3H-imidazo[4,5-f]quinoxaline in these samples were 0.235–2.08 ng/g. The recoveries for the five HAAs ranged from74.3% to 119%, and the relative standard deviation（RSDs） were less than 8.2%. The results showed that the proposed on-line method was highly sensitive for monitoring HAAs in different food samples.
文摘Five marinades were developed using natural antioxidants. Based on a consumer test of the appearance, three marinades were chosen for further investigation: an oregano, an acerola and a Dijon marinade, the Dijon marinade containing acerola, sumac and oregano. A barbecue and a sumac marinade were not included in the further study. In a home use test, consumers barbecued pork chops with the three marinades. Most of the consumers preferred the oregano and the Dijon marinade, while the acerola marinade was less liked. After controlled cooking using both direct and indirect heat to a core temperature of 65°C and 80°C, the content of the heterocyclic aromatic amines (HCA) PhiP, MeIQx, DiMeIQx, Harman and Norharman was analysed. All of the marinades reduced the content of MeIQx and DiMeIQx, although only with indirect heat, while PhiP was reduced using both grilling methods. Surprisingly, in particular the content of Harman—and to a lesser extent Norhaman—was very high in the Dijon-marinated chops. The results demonstrated that it was possible to develop well-liked marinades that can reduce the formation of selected HCAs.
基金supported by the National Natural Science Foundation of China (No. 21205041)the Fundamental Research Funds for the Central Universities (No. 222201314039)+2 种基金General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China (No. 2014IK077)Shanghai Inspection & Inspection and Quarantine Bureau (No. HK012-2015)a grant of Laboratory team construction program for universities in Shanghai
文摘Primary aromatic amines （PAAs） are substances with toxicity and suspected human carcinogenicity. A facile method for highly sensitive detection of PAAs using surface-enhanced Raman spectroscopy （SERS） is reported. The immobilization of Au nanoparticles （AuNPs） on the glycidyl methacrylate-ethylene dimethacrylate （GMA-EDMA） materials makes the suhstrate a closely packed but not aggregated Au NP arrays which provides a prominent SERS enhancement. Four PAAs with different substituent groups, namely, p-toluidine, p-nitroaniline, benzidine and 4,4-methylene-bis-（2-chloroaniline） have been successfully identified and quantified. High sensitivity and good linear relationship between SERS signals and concentrations of PAAs are obtained for all four PAAs.
文摘Allyldialkyltelluronium bromides were treated with aromatic amines in 1,2-dichloroethane,readily giving allyl aryl amines in excel- lent yields.This method provides a convenient one-pot reaction for the synthesis of allylic amines.
基金Supported by the National High Technology Research and Development Program of China (863 Program) (2003AA305920)
文摘The curing reaction and reaction mechanism of epoxy resin E-44, for which aromatic amine modified dicyandiamide was used as a curing reagent, were investigated by means of differential scanning calorimetry （DSC）. The results showed that the modified dicyandiamide had better curing characteristic than unmodified dicyandiamide for epoxy resin E-44, and the curing reaction could be carried out at moderate temperature. Apparent activation energy of the curing reaction was decreased appreciably from 123.829 kJ/mol to 61.550-64.405 kJ/mol, and reaction order was decreased from 0.941 to 0.896-0.900. Curing reaction mechanism also was discussed.
基金Supported by the National Natural Science Foundation of China(No.20572058)
文摘The oxidative coupling of primary aromatic amines was investigated. Ce（SO4）2 can mediate the oxidative coupling of primary aromatic amines in water to dimers, trimers and/or tetramers, which depended on the substituents of primary aromatic amines. When 2,6-dimethylaniline or 2,6-diethylaniline was used as substrate, dimer, and tetramer were formed as major products. When 2,6-diisopropylaniline or 2,6-dihaloanilines was used as substrate, dimer, and trimer were formed. The mechanistic aspect was also investigated.
文摘Sometimes chemistry doesn’t just make new molecules-it overturns old assumptions.For 140 years,drugmakers have accepted that transforming aromatic amines-a very important reaction for building drug molecules-means living with explosive risks.The danger was considered unavoidable,the tradeoff permanent-until a team in Hangzhou proved otherwise.
基金the support provided by the Flemish Strategic Basic Research Program under the Catalisti clusterFlanders Innovation & Entrepreneurship, through the EASiCHEM project (contracts HBC.2018.0484 and K200522 N)+1 种基金partially conducted within the framework of the CICECO-Aveiro Institute of Materials project (UIDB/50011/ 2020, UIDP/50011/2020, and LA/P/0006/2020)funding from national sources through FCT/MEC (PIDDAC)
文摘Aromatic amines are crucial in pharmaceuticals,but their synthesis is challenging due to unfavorable reaction equilibria and the use of costly,environmentally unfriendly methods.This study presents a membrane extraction(ME)process for in situ product removal(ISPR)of aromatic amines.Using a supported liquid membrane(SLM),α-methylbenzylamine(MBA)and 1-methyl-3-phenylpropylamine(MPPA)were separated from isopropyl amine(IPA).Conductor-like Screening Model for Real Solvents(COSMO-RS)was employed to screen over 200 organic mixtures,identifying twelve mixtures based on trioctylphosphine oxide(TOPO),lidocaine,and menthol as solvent candidates,due to their hydrophobicity.These mixtures were analysed for critical solvent properties including density,viscosity,hydrophobicity,and H-bonding interactions.ME tests showed TOPO-thymol had the highest solvent residual and selectivity.Moreover,TOPO-thymol demonstrated solute fluxes of 9.0±3.0 g/(m^(2)h)for MBA,16.5±5.4 g/(m^(2)h)for MPPA,and 0.7±0.3 g/(m^(2)h)for IPA,with selectivity values of 12.4±0.8 for MBA/IPA and 22.8±1.4 for MPPA/IPA.Compared to undecane,which had lower selectivity values of 6.9±0.8 for MBA/IPA and 10.1±1.3 for MPPA/IPA,TOPO-thymol showed superior selectivity,indicating its promise as an extractant for ME applications.
基金This project was financially supported by the National Natural Science Foundation of China （No. 21302014）.
文摘A simple and efficient protocol for the electrophilic thiocyanation of indoles and aromatic amines with thiourea/NCS/NH4SCN system has been developed. The major features of the present procedure are the mild conditions, good yields, short reaction times, and the use of inexpensive and readily available organocatalyst. Moreover, N-chlorosueeinimide （NCS） was found to be indispensable, and thiourea could greatly promote the reaction.
文摘An asymmetric allylic amination of Morita-Baylis-Hillman acetates with simple aromatic amines catalyzed by planarly chiral ligand/palladium-catalyst was developed in good yield with excellent a-regioselectivity （a/γ up to 30 ： 1） and moderate enantioselectivity （up to 70% ee）.
基金This work was funded in part by the earmarked fund for China Agriculture Research system of MOF and MARA(No.CARS-14)the Central Government-Guided Local S&T Development Fund Project of Henan(No.Z20221343038)the Key Research and Development Project of Henan Province(No.221111520400),China.
文摘Contamination by the heterocyclic aromatic amines(HAAs)norharman and harman is one of the risks in vegetable oil production,so oil producers strive to decrease their content in the end products.In this study,the effects of production conditions—specifically,two pretreatment methods(roasting and microwaving),four extraction methods(two pressing and two solvent extraction)and adsorption refining(four absorbents)—of five oils(flaxseed,peanut,rapeseed,sesame,and sunflower seed)were evaluated.The results showed that microwaving as a pretreatment produced significantly fewer HAAs than roasting(P<0.05).After two pretreatments,the HAA content of oils was ranked from high to low as follows:sunflower oil,sesame oil,flaxseed oil,rapeseed oil,and peanut oil.Solvent-extracted oils(9.16–316.73μg/kg)had fewer HAAs than pressed oils(26.61–633.93μg/kg).Using adsorbents reduced HAAs in oils from the initial 21.77–484.22 to 0.31–41.58μg/kg,and the removal rate reached 99.28%.This study provides critical HAA reduction strategies for application in the oil production process to obtain safe final products.
基金We acknowledge the financial support for this work from the National Natural Science Foundation of China （Nos. 21502070 and 21562041） and the Fundamental Research Funds for the Central Universities （No. JUSRP51626B）.
文摘A simple copper-promoted one-pot Sandmeyer trifluoromethylation of aromatic amines with Langlois＇ reagent has been demonstrated. The reaction is performed in mild reaction conditions under an air atmosphere with good substrate scope and functional group compatibility. It provides an alternative and straightforward synthetic approach to access a variety of trifluoromethylated arenes.
基金financially supported by the National Natural Science Foundation of China (No. 51473092)
文摘Pure organic luminogens with efficient room temperature phosphorescence（RTP） and remarkable mechanochromism are highly desired in view of their fundamental significance and technical applications. Herein, four twisted pure organic luminogens based on benzophenone and aromatic amines were synthesized and their photophysical properties were thoroughly investigated. They exhibit crystallization-induced phosphorescence（CIP）, giving bright fluorescence and phosphorescence dual emission in crystals. Upon grinding, they become amorphous and emit predominantly red-shifted fluorescence, demonstrating remarkable mechanochromism. Furthermore, three of them even demonstrate greatly enhanced emission upon grinding, which is rarely observed in twisted D-A structured luminogens.
基金funded by Open Project of Hebei Key Laboratory of Environment and Human Health(202301,202303)Beihang University&Capital Medical University Advanced Innovation Center for Big Data-Based Precision Medicine Plan(BHME-201901)+2 种基金China Postdoctoral Science Foundation(2023M7303172023T160066)Fundamental Research Funds for the Central Universities(3332023042).
文摘Aldehydes,heterocyclic aromatic amines(HAAs)and terpenes were sparsely studied for their sex-hormone disrupting effect in children and adolescents,although people are widely exposed.This study aimed to investigate the individual and mixture effect of aldehydes,HAAs and terpenes on sex hormones among children and adolescents and explore the effect modification of Vitamin D(VD).Six aldehydes,three HAAs and three terpenes were collected from the National Health and Nutrition Examination Survey 2013-2014,which sampled representative U.S.population.Five sex hormone indicators[testosterone(TT),estradiol(E2),sex hormone binding globulin(SHBG),free androgen index(FAI)and ratio of TT to E2(TT/E2)]were measured.Multiple linear regression and Bayesian kernel machine regression were used to explore the individual-and joint-exposure to these chemicals with each sex hormone,respectively.We primarily found some chemicals were positively associated with SHBG and negatively associated with TT,E2,and FAI among male adolescents.In addition,when stratified by pubertal status,we mainly found certain chemicals were negatively associated with TT,E2,FAI and TT/E2 in pubertal male and prepubertal female.Joint exposure to HAAs were associated with significant decrease in TT and FAI in male adolescent.These associations present age-,sex-and development-dependent patterns.VD modified these associations with significant results more pronounced in VD≥75 nmol/L group.Our study provided novel findings for the hormonal effect of aldehydes,HAAs and terpenes in children and adolescents,and is also significant for potential avenues for public health action and intervention.
基金This research was made possible as a result of a generous grant from the National Natural Science Foundation of China(grant nos.U24A20496 and 22402139)the Natural Science Foundation of Jiangsu Province,China(grant no.BK20240765)the German Research Foundation via the Excellence Cluster e-conversion.
文摘Aromatic amines(AAs)are widely used in manufacturing industries,where their oxidation plays a crucial role in direct applications and the synthesis of nitrogen-containing compounds.Understanding their reactivity is a prerequisite for their use in various fields.Given their chemical diversity and significance,the behavior of AAs on surfaces is of considerable interest for potential applications.Herein,we combined scanning tunneling microscopy(STM)and X-ray photoelectron spectroscopy(XPS)to explore the reactivity of AAs on silver(Ag)and gold(Au)surfaces using a gas-mediated reaction strategy.Our results revealed that oxidative dehydrogenation was readily achieved after O2-mediated treatment on Ag surfaces,leading to the formation of organometallic nanopores,while AAs remained unperturbed on Au(111),indicating a substrate-dependent behavior.Density functional theory(DFT)calculations corroborate the experimental observations,by simulated core-level shifts and microscopy images,and demonstrate how the choice of substrate dictates the thermodynamics of the overall reactions.These findings emphasize the importance of substrate selection in modulating the surface chemistry of AAs,paving the way for more efficient catalytic processes and material design.
