A nickel-catalyzed C(sp^(2))–H alkynylation of unprotected α-substituted benzylamines is achieved by utilizing a transient directing group. The combination of a TDG with a nickel catalyst significantly improves the ...A nickel-catalyzed C(sp^(2))–H alkynylation of unprotected α-substituted benzylamines is achieved by utilizing a transient directing group. The combination of a TDG with a nickel catalyst significantly improves the reaction step and atom economy. It has been investigated that the 2,4,6-trimethylpyridine ligand was critical to achieve the optimized reactivity. This protocol provides a straightforward route for synthesizing the alkynylated free benzylamines, featuring good substrate compatibility and monoselectivity.展开更多
The biphasic solvent is a promising solution to reduce regeneration energy consumption in CO_(2) capture.However,most current biphasic solvents suffer from high viscosity and poor desorption of the rich phase.To the i...The biphasic solvent is a promising solution to reduce regeneration energy consumption in CO_(2) capture.However,most current biphasic solvents suffer from high viscosity and poor desorption of the rich phase.To the issues,a novel pentamethyldiethylenetriamine(PMDETA)-2-amino-2-methyl-1-propanol(AMP)/diethylenetriamine(DETA)-sulfolane biphasic solvent was developed.The mechanism of AMP affecting CO_(2) recycling capacity was analyzed.By adjusting the ratio of AMP and DETA,the absorption and desorption performance were balanced,and the recycling capacity and renewable energy consumption of the absorbent were improved.For the P_(2.4)A_(0.8)D_(0.8)S_(2) biphasic solvent,the CO_(2) loading of the rich phase was 5.87 mol/L,and the proportion of the rich phase volume ratio was 35%,which surpasses most reported biphasic solvents.The viscosity of the absorbent significantly decreased from 527.00 mPa·s to 92.26 mPa·s,attributed to the beneficial effect of AMP.Thermodynamic analysis showed that the biphasic solvent produced a lower regeneration energy consumption of 1.70 GJ/t CO_(2),which was 57%lower than that of monoethanolamine(MEA).Overall,the PMDETA-AMP/DETA-sulfolane biphasic solvent exhibited cycle capacity,which provided new insights for the designing of biphasic solvent.展开更多
An electronic circular dichroism(ECD)-based chiroptical sensing method has been developed forβ-andγ-chiral primary amines via a C-H activation reaction.With the addition of Pd(OAc)_(2),the flexible remote chiral pri...An electronic circular dichroism(ECD)-based chiroptical sensing method has been developed forβ-andγ-chiral primary amines via a C-H activation reaction.With the addition of Pd(OAc)_(2),the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex,producing an intense ECD response.The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed,together with theoretical verification using timedependent density functional theory(TDDFT).Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity.This work introduces an alternative perspective of C-H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.展开更多
N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imi...N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imine reductase from Streptomyces albidoflavus(SaIRED)for the reductive amination of biobased furans.A simple,fast and interference-resistant high-throughput screening(HTS)method was developed,based on the coloration reaction of carbonyl compounds with 2,4-dinitrophenylhydrazine.The reductive amination activity of IREDs can be directly indicated by a colorimetric assay.With the reductive amination of furfural with allylamine as the model reaction,SaIRED with the activity of 4.8 U mg^(-1) was subjected to three rounds of protein engineering and screening by this HTS method,affording a high-activity tri-variant I127V/D241A/A242T(named M3,20.2 U mg^(-1)).The variant M3 showed broad substrate scope,and enabled efficient reductive amination of biobased furans with a variety of amines including small aliphatic amines and sterically hindered amines,giving the target FAs in yields up to>99%.In addition,other variants were identified for preparative-scale synthesis of commercially interesting amines such as N-2-(methylsulfonyl)ethyl-FA by the screen method,with isolated yields up to 87%and turnover numbers up to 9700 for enzyme.Gram-scale synthesis of N-allyl-FA,a valuable building block and potential polymer monomer,was implemented at 0.25 mol L^(-1) substrate loading by a whole-cell catalyst incorporating variant M3,with 4.7 g L^(-1) h^(-1) space-time yield and 91%isolated yield.展开更多
The collecting power of tertiary amines（DRN,DEN and DPN） on kaolinite follows the order of DENDPNDRN.After reacting with DRN,DEN and DPN,the surface potentials of kaolinite increase remarkably,and the recruitments c...The collecting power of tertiary amines（DRN,DEN and DPN） on kaolinite follows the order of DENDPNDRN.After reacting with DRN,DEN and DPN,the surface potentials of kaolinite increase remarkably,and the recruitments caused by collectors also follow the order of DENDPNDRN.The results of dynamics simulation show that the geometries of substituent groups bonding to N are deflected and twisted,and some of bond angles are changed when tertiary amines cations adsorb on kaolinite（001） surface.Based on the results of dynamics simulations and quantum chemistry calculations,the electrostatic forces between three tertiary amines cations and 4×4×3（001） plane of kaolinite are 1.38×10？7 N（DRN12H＋）,1.44×10-6 N（DEN12H＋）,1.383×10-6 N（DPN12H＋）,respectively.展开更多
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
The flotation of diaspore and kaolinite by one of a series of tertiary amines（DRN,DEN,DPN and DBN） was investigated.The tertiary amines show better floating recovery for kaolinite compared to diaspore.The maximum re...The flotation of diaspore and kaolinite by one of a series of tertiary amines（DRN,DEN,DPN and DBN） was investigated.The tertiary amines show better floating recovery for kaolinite compared to diaspore.The maximum recovery D-value is 45%over a pH range from 3 to 8.FT-IR spectra confirm the presence of hydroxyl groups on the surface of kaolinite and diaspore.Zeta potential measurements show that the mineral surfaces are negatively charged over a wide pH range.Ionization of hydroxyl groups mainly accounts for the surface charging mechanism.The adsorption of tertiary amines onto the mineral surface is due mainly to electrostatic effects and the difference in electrostatic effect between a collector and the two minerals can explain the flotation separation.Inductive electronic and steric effects from the substituent groups result in different collecting powers for the four tertiary amines.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
Trace amines(TAs)are metabolically related to catecholamine and associated with cancer and neurological disorders.Comprehensive measurement of TAs is essential for understanding pathological processes and providing pr...Trace amines(TAs)are metabolically related to catecholamine and associated with cancer and neurological disorders.Comprehensive measurement of TAs is essential for understanding pathological processes and providing proper drug intervention.However,the trace amounts and chemical instability of TAs challenge quantification.Here,diisopropyl phosphite coupled with chip two-dimensional(2D)liquid chromatography tandem triple-quadrupole mass spectrometry(LC-QQQ/MS)was developed to simultaneously determine TAs and associated metabolites.The results showed that the sensitivities of TAs increased up to 5520 times compared with those using nonderivatized LC-QQQ/MS.This sensitive method was utilized to investigate their alterations in hepatoma cells after treatment with sorafenib.The significantly altered TAs and associated metabolites suggested that phenylalanine and tyrosine metabolic pathways were related to sorafenib treatment in Hep3B cells.This sensitive method has great potential to elucidate the mechanism and diagnose diseases considering that an increasing number of physiological functions of TAs have been discovered in recent decades.展开更多
Presented in several types of food, bioactive amines are described as organic bases of low molecular weight. They have vasoactive, psychoactive and toxicological characteristics and constitute a potential health risk....Presented in several types of food, bioactive amines are described as organic bases of low molecular weight. They have vasoactive, psychoactive and toxicological characteristics and constitute a potential health risk. The concentration of amines formed in foods depends on the type of microorganisms present, the action of decarboxylase enzymes produced by microorganisms on specific amino acids and favorable conditions for enzymatic activity. The presence of these chemical metabolites has been suggested as a quality indicator in routine analyzes for food production and marketing monitoring. The detection of bioactive amines can be performed by chromatographic methods, fluorometric and enzymatic kits. Bioactive amine formation can be prevented mainly through the adoption of good manufacturing practices, but the industry can also use other methods such as temperature control in the production chain, modified atmosphere packaging and food irradiation. This review aims to address the formation of bioactive amines in foods, emphasizing the formation and classification of these metabolites, aspects related to health, acceptable limits, detection methods and control methods used in the industry to ensure food safety and quality. The success of this approach is linked to the importance of bioactive amines as quality indicators, as well as the discussion on the development of methodologies for determining these substances and discussion of acceptable parameters in food.展开更多
N-Arylation of a wide variety of amines with phenylboronic acid catalyzed by copper acetate under 20%aqueous solution of n-Bu_4NOH was accomplished in good to excellent yields（up to 92%） and substrate conversions（u...N-Arylation of a wide variety of amines with phenylboronic acid catalyzed by copper acetate under 20%aqueous solution of n-Bu_4NOH was accomplished in good to excellent yields（up to 92%） and substrate conversions（up to 96%）.展开更多
The regulation of three biogenic amines over the reproductive neuroendoerine activity of the male Scylla serrata was investigated by in vivo injection and in vitro incubation. The testicular index, the ratio of the ma...The regulation of three biogenic amines over the reproductive neuroendoerine activity of the male Scylla serrata was investigated by in vivo injection and in vitro incubation. The testicular index, the ratio of the mature sections in testes, and the ratio of Type B cells in androgenic gland were taken as the quantitative indexes. The in vivo injections indicated that： 5-HT can significantly promote the testicular development and the secretion of the androgenic gland in S. serrata; DA can inhibit the testicular development, but no influence on the secretion of the androgenic gland was found; no significant difference was observed between the OA-injected group and the concurrent control group. In vitro incubations showed that： 5-HT can stimulate the secretion of the brain and the thoracic ganglia, thus accelerating that of the androgenic gland; however, neither OA nor DA showed any significant influence on the secretion of the brain and the thoracic ganglionic mass. As to the optic ganglia, the three biogenic amines hardly have any effect on its secretion. It is the first time to report the regulation of biogenic amines over the reproductive neuroendocrine of male crustaceans through vitro experiments. Results corroborate that 5-HT activates the brain and the thoracic ganglia to secret GSH first, then promote the testicular development through the activity of the androgenic gland.展开更多
The liquid-phase hydrogenation of butyronitrile to saturated amines was studied on silica- supported Ni catalysts prepared by either incipient-wetness impregnation (Ni/SiO2-I) or ammonia (Ni/SiO2-A) methods. A Ni/SiO2...The liquid-phase hydrogenation of butyronitrile to saturated amines was studied on silica- supported Ni catalysts prepared by either incipient-wetness impregnation (Ni/SiO2-I) or ammonia (Ni/SiO2-A) methods. A Ni/SiO2-Al2O3-I sample was also used. Ni/SiO2-I was a non-acidic catalyst containing large Ni^0 particles of low interaction with the support, while Ni/SiO2-A was an acidic catalyst due to the presence of Ni^2+ species in Ni phyllosilicates of low reducibility. Ni/SiO2-I formed essentially butylamine (80%), and dibutylamine as the only byproduct. In contrast, Ni/SiO2-A yielded a mixture of dibutylamine (49%) and tributylamine (45%), being the formation of butylamine almost completely suppressed. The selective formation of secondary and tertiary amines on Ni/SiO2-A was explained by considering that butylamine is not release to the liquid phase during the reaction because it is strongly adsorbed on surface acid sites contiguous to Ni^0 atoms, thereby favoring the butylimine/butylamine condensation to higher amines between adsorbed species.展开更多
This study was carried out to investigate the biogenic amines(BAs), physicochemical property and microorganisms in dry salted fish, a traditional aquatic food consumed in China. Forty three samples of dry salted fish ...This study was carried out to investigate the biogenic amines(BAs), physicochemical property and microorganisms in dry salted fish, a traditional aquatic food consumed in China. Forty three samples of dry salted fish were gathered from retail and wholesale markets and manufacturers, which had been produced in various regions in China. Cadaverine(CAD) and putrescine(PUT) were quantitatively the most common biogenic amines. About 14% of the samples exceeded the histamine content standards established by the FDA and/or EU. The highest histamine content was found in Silver pomfret(Pampus argenteus)(347.79 mg kg^(-1)). Five of forty three samples exceeded the acceptable content of TYR(100 mg kg^(-1)), and 23.26% of dried-salted fish contained high contents of biogenic amines(above 600 mg kg^(-1)). In addition, species, regions, pickling processes and drying methods made the physicochemical property, microorganisms and biogenic amines in dry salted fish to be different to some extents. The total plate count(TPC) was much higher than that of total halophilic bacteria in all samples. The biogenic amines, physicochemical property and microbiological counts exhibited large variations among samples. Furthermore, no significant correlation between biogenic amines and physicochemical property and TPC was observed. This study indicated that dry salted fish may still present healthy risk for BAs, depending on the processing methods, storage conditions among others.展开更多
As more attention is being paid to the characteristics of atmospheric amines,there is also an increasing demand for reliable detection technologies.Herein,a method was developed for simultaneous detection of atmospher...As more attention is being paid to the characteristics of atmospheric amines,there is also an increasing demand for reliable detection technologies.Herein,a method was developed for simultaneous detection of atmospheric amines in both gaseous and particulate phases using gas chromatography-mass spectrometry(GC-MS).The amine samples were collected with and without phosphoric acid filters,followed by derivatization with benzenesulfonyl chloride under alkaline condition prior to GC-MS analysis.Furthermore,the method was optimized and validated for determining 14 standard amines.The detection limits ranged from0.0408-0.421μg/mL(for gaseous samples)and 0.163-1.69μg/mL(for particulate samples),respectively.The obtained recoveries ranged from 68.8%-180%and the relative standard deviation was less than 30%,indicating high precision and good reliability of the method.Seven amines were simultaneously detected in gaseous and particulate samples in an industrial park using the developed method successfully.Methylamine,dimethylamine and diethylamine together accounted for 76.7%and 75.6%of particulate and gaseous samples,respectively.By comparing the measured and predicted values of gas-particle partition fractions,it was found that absorption process of aqueous phase played a more important role in the gas-partition of amines than physical adsorption.Moreover,the reaction between unprotonated amines and acid(aq.)in water phase likely promoted water absorption.Higher measured partition fraction of dibutylamine was likely due to the reaction with gaseous HCl.The developed method would help provide a deeper understanding of gas-particle partitioning as well as atmospheric evolution of amines.展开更多
The hydrolysis process of the anticancer agents novel non-classical transplatinum（ Ⅱ ） with aliphatic amines and the influence of solvent models therein have been studied by using hybrid density functional theory ...The hydrolysis process of the anticancer agents novel non-classical transplatinum（ Ⅱ ） with aliphatic amines and the influence of solvent models therein have been studied by using hybrid density functional theory （B3LYP）. In this study, the stepwise hydrolysis, trans[PtCl2（Am）（isopropylamine）] ＋ 2H2O → trans-[Pt（Am）（isopropylamine）（OH2）2]^2＋＋ 2Cl^-, was explored. Implicit solvent effects were incorporated through polarized continuum models. The stationary points on the potential energy surfaces for the first and second hydrolysis steps,proceeding via a general SN2 pathway, were fully optimized and characterized. It was found that the first hydrolysis reaction is easier than the second one and the hydrolysis of trans- [PtCl2-（isopropylamine）2] is the easiest in our studying systems. The result can assist in under- tanding the hydrolysis mechanism of trans-[PtCl2（Am）（isopropylamine）] and designing novel Pt-based anticancer drugs.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
Enhancing the selectivity of imines for the oxidative self-coupling of primary amines was found to be challenging in the heterogeneous catalysis.Three different manganese oxides(M-3,M-4,M-5) were synthesized by contro...Enhancing the selectivity of imines for the oxidative self-coupling of primary amines was found to be challenging in the heterogeneous catalysis.Three different manganese oxides(M-3,M-4,M-5) were synthesized by controlling the calcination temperature using a simple template-free oxalate route.The prepared manganese oxides were systematically characterized using XRD,N2 sorption,SEM,TEM,XPS,H2-TPR techniques.M-4 gave 96.2% selectivity of imine at 100% conversion of benzylamine,which was far more superior than other existing protocols.Mn^3+/Mn^4+ ratio was found to affect the selectivity of the imines.The probable reaction pathway for amines oxidation catalyzed by manganese oxides was proposed for the first time.展开更多
Amines have been considered as promising candidates for post-combustion CO2 capture. A mechanistic understanding for the chemical processes involved in the capture and release of CO2 is important for the rational desi...Amines have been considered as promising candidates for post-combustion CO2 capture. A mechanistic understanding for the chemical processes involved in the capture and release of CO2 is important for the rational design of amines. In this study, the structural effects of amines on the kinetic competition among three typical products（carbamates, carbamic acids and bicarbonate） from amines ＋ CO2 were investigated, in contrast to previous thermodynamic studies to tune the reaction of amines with CO2 based on desirable reaction enthalpy and reaction stoichiometry. We used a quantum chemical method to calculate the activation energies（Ea） for the reactions of a range of substituted monoethanolamines with CO2 covering three pathways to the three products. The results indicate that the formation of carbamates is the most favorable, among the three considered products. In addition, we found that the Eavalues for all pathways linearly correlate with pK aof amines, and more importantly, the kinetic competition between carbamate and bicarbonate absorption pathways varies with p Kaof the amines, i.e. stronger basicity results in less difference in Ea. These results highlight the importance of the consideration of kinetic competition among different reaction pathways in amine design.展开更多
基金supported financially by the Excellent Going Abroad Expert's Training Program in Hebei Province (No. 201940)the Hebei Natural Science Foundation of China (No. H2020208030)the S & T Program of Hebei (No. 22567607H) for financial support。
文摘A nickel-catalyzed C(sp^(2))–H alkynylation of unprotected α-substituted benzylamines is achieved by utilizing a transient directing group. The combination of a TDG with a nickel catalyst significantly improves the reaction step and atom economy. It has been investigated that the 2,4,6-trimethylpyridine ligand was critical to achieve the optimized reactivity. This protocol provides a straightforward route for synthesizing the alkynylated free benzylamines, featuring good substrate compatibility and monoselectivity.
基金supported by the Key R&D Program of Yunnan Province(No.202303AC100008)the National Natural Science Foundation of China(No.52100133)the Major Science and Technology-Special Plan“Unveiling and Leading”Project of Shanxi Province(No.202201050201011).
文摘The biphasic solvent is a promising solution to reduce regeneration energy consumption in CO_(2) capture.However,most current biphasic solvents suffer from high viscosity and poor desorption of the rich phase.To the issues,a novel pentamethyldiethylenetriamine(PMDETA)-2-amino-2-methyl-1-propanol(AMP)/diethylenetriamine(DETA)-sulfolane biphasic solvent was developed.The mechanism of AMP affecting CO_(2) recycling capacity was analyzed.By adjusting the ratio of AMP and DETA,the absorption and desorption performance were balanced,and the recycling capacity and renewable energy consumption of the absorbent were improved.For the P_(2.4)A_(0.8)D_(0.8)S_(2) biphasic solvent,the CO_(2) loading of the rich phase was 5.87 mol/L,and the proportion of the rich phase volume ratio was 35%,which surpasses most reported biphasic solvents.The viscosity of the absorbent significantly decreased from 527.00 mPa·s to 92.26 mPa·s,attributed to the beneficial effect of AMP.Thermodynamic analysis showed that the biphasic solvent produced a lower regeneration energy consumption of 1.70 GJ/t CO_(2),which was 57%lower than that of monoethanolamine(MEA).Overall,the PMDETA-AMP/DETA-sulfolane biphasic solvent exhibited cycle capacity,which provided new insights for the designing of biphasic solvent.
基金supported by the CAMS Innovation Fund for Medical Sciences(CIFMS,No.2023-I2M-2-009).
文摘An electronic circular dichroism(ECD)-based chiroptical sensing method has been developed forβ-andγ-chiral primary amines via a C-H activation reaction.With the addition of Pd(OAc)_(2),the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex,producing an intense ECD response.The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed,together with theoretical verification using timedependent density functional theory(TDDFT).Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity.This work introduces an alternative perspective of C-H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
文摘N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imine reductase from Streptomyces albidoflavus(SaIRED)for the reductive amination of biobased furans.A simple,fast and interference-resistant high-throughput screening(HTS)method was developed,based on the coloration reaction of carbonyl compounds with 2,4-dinitrophenylhydrazine.The reductive amination activity of IREDs can be directly indicated by a colorimetric assay.With the reductive amination of furfural with allylamine as the model reaction,SaIRED with the activity of 4.8 U mg^(-1) was subjected to three rounds of protein engineering and screening by this HTS method,affording a high-activity tri-variant I127V/D241A/A242T(named M3,20.2 U mg^(-1)).The variant M3 showed broad substrate scope,and enabled efficient reductive amination of biobased furans with a variety of amines including small aliphatic amines and sterically hindered amines,giving the target FAs in yields up to>99%.In addition,other variants were identified for preparative-scale synthesis of commercially interesting amines such as N-2-(methylsulfonyl)ethyl-FA by the screen method,with isolated yields up to 87%and turnover numbers up to 9700 for enzyme.Gram-scale synthesis of N-allyl-FA,a valuable building block and potential polymer monomer,was implemented at 0.25 mol L^(-1) substrate loading by a whole-cell catalyst incorporating variant M3,with 4.7 g L^(-1) h^(-1) space-time yield and 91%isolated yield.
基金Project (2005CB623701) supported by the National Basic Research Program of China Project (201011031) supported by National Department Public Benefit Research Foundation from Ministry of Land and Resources of China+1 种基金 Project (2935) supported by the Foundation for the Author of Zhengzhou Institute of Multipurpose Utilization of Mineral Resources CAGS, China Project (1212011120304) supported by the Geological Surrey Program
文摘The collecting power of tertiary amines（DRN,DEN and DPN） on kaolinite follows the order of DENDPNDRN.After reacting with DRN,DEN and DPN,the surface potentials of kaolinite increase remarkably,and the recruitments caused by collectors also follow the order of DENDPNDRN.The results of dynamics simulation show that the geometries of substituent groups bonding to N are deflected and twisted,and some of bond angles are changed when tertiary amines cations adsorb on kaolinite（001） surface.Based on the results of dynamics simulations and quantum chemistry calculations,the electrostatic forces between three tertiary amines cations and 4×4×3（001） plane of kaolinite are 1.38×10？7 N（DRN12H＋）,1.44×10-6 N（DEN12H＋）,1.383×10-6 N（DPN12H＋）,respectively.
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 National Key Fundamental Research and Development Program(No.2005CB623701)the National Department Public Benefit Research Foundation from Ministry of Land and Resources(No.201011031 )the Foundation for the Author of Zhengzhou Institute of Multipurpose Utilization of Mineral Resources CAGS(No.2935)
文摘The flotation of diaspore and kaolinite by one of a series of tertiary amines（DRN,DEN,DPN and DBN） was investigated.The tertiary amines show better floating recovery for kaolinite compared to diaspore.The maximum recovery D-value is 45%over a pH range from 3 to 8.FT-IR spectra confirm the presence of hydroxyl groups on the surface of kaolinite and diaspore.Zeta potential measurements show that the mineral surfaces are negatively charged over a wide pH range.Ionization of hydroxyl groups mainly accounts for the surface charging mechanism.The adsorption of tertiary amines onto the mineral surface is due mainly to electrostatic effects and the difference in electrostatic effect between a collector and the two minerals can explain the flotation separation.Inductive electronic and steric effects from the substituent groups result in different collecting powers for the four tertiary amines.
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 the Science and Technology Development Fund,Macao,China(Grant No.:FDCT0044/2018/AFJ).
文摘Trace amines(TAs)are metabolically related to catecholamine and associated with cancer and neurological disorders.Comprehensive measurement of TAs is essential for understanding pathological processes and providing proper drug intervention.However,the trace amounts and chemical instability of TAs challenge quantification.Here,diisopropyl phosphite coupled with chip two-dimensional(2D)liquid chromatography tandem triple-quadrupole mass spectrometry(LC-QQQ/MS)was developed to simultaneously determine TAs and associated metabolites.The results showed that the sensitivities of TAs increased up to 5520 times compared with those using nonderivatized LC-QQQ/MS.This sensitive method was utilized to investigate their alterations in hepatoma cells after treatment with sorafenib.The significantly altered TAs and associated metabolites suggested that phenylalanine and tyrosine metabolic pathways were related to sorafenib treatment in Hep3B cells.This sensitive method has great potential to elucidate the mechanism and diagnose diseases considering that an increasing number of physiological functions of TAs have been discovered in recent decades.
文摘Presented in several types of food, bioactive amines are described as organic bases of low molecular weight. They have vasoactive, psychoactive and toxicological characteristics and constitute a potential health risk. The concentration of amines formed in foods depends on the type of microorganisms present, the action of decarboxylase enzymes produced by microorganisms on specific amino acids and favorable conditions for enzymatic activity. The presence of these chemical metabolites has been suggested as a quality indicator in routine analyzes for food production and marketing monitoring. The detection of bioactive amines can be performed by chromatographic methods, fluorometric and enzymatic kits. Bioactive amine formation can be prevented mainly through the adoption of good manufacturing practices, but the industry can also use other methods such as temperature control in the production chain, modified atmosphere packaging and food irradiation. This review aims to address the formation of bioactive amines in foods, emphasizing the formation and classification of these metabolites, aspects related to health, acceptable limits, detection methods and control methods used in the industry to ensure food safety and quality. The success of this approach is linked to the importance of bioactive amines as quality indicators, as well as the discussion on the development of methodologies for determining these substances and discussion of acceptable parameters in food.
文摘N-Arylation of a wide variety of amines with phenylboronic acid catalyzed by copper acetate under 20%aqueous solution of n-Bu_4NOH was accomplished in good to excellent yields（up to 92%） and substrate conversions（up to 96%）.
基金supported by the National Natural Science Foundation of China under contract No.30300269the National High Technology Research and Development Program("863"program)of China under contract No.2002AA603013.
文摘The regulation of three biogenic amines over the reproductive neuroendoerine activity of the male Scylla serrata was investigated by in vivo injection and in vitro incubation. The testicular index, the ratio of the mature sections in testes, and the ratio of Type B cells in androgenic gland were taken as the quantitative indexes. The in vivo injections indicated that： 5-HT can significantly promote the testicular development and the secretion of the androgenic gland in S. serrata; DA can inhibit the testicular development, but no influence on the secretion of the androgenic gland was found; no significant difference was observed between the OA-injected group and the concurrent control group. In vitro incubations showed that： 5-HT can stimulate the secretion of the brain and the thoracic ganglia, thus accelerating that of the androgenic gland; however, neither OA nor DA showed any significant influence on the secretion of the brain and the thoracic ganglionic mass. As to the optic ganglia, the three biogenic amines hardly have any effect on its secretion. It is the first time to report the regulation of biogenic amines over the reproductive neuroendocrine of male crustaceans through vitro experiments. Results corroborate that 5-HT activates the brain and the thoracic ganglia to secret GSH first, then promote the testicular development through the activity of the androgenic gland.
基金the Universidad Nacional del Litoral (UNL)Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET)Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT ), Argentina, for the financial support of this work
文摘The liquid-phase hydrogenation of butyronitrile to saturated amines was studied on silica- supported Ni catalysts prepared by either incipient-wetness impregnation (Ni/SiO2-I) or ammonia (Ni/SiO2-A) methods. A Ni/SiO2-Al2O3-I sample was also used. Ni/SiO2-I was a non-acidic catalyst containing large Ni^0 particles of low interaction with the support, while Ni/SiO2-A was an acidic catalyst due to the presence of Ni^2+ species in Ni phyllosilicates of low reducibility. Ni/SiO2-I formed essentially butylamine (80%), and dibutylamine as the only byproduct. In contrast, Ni/SiO2-A yielded a mixture of dibutylamine (49%) and tributylamine (45%), being the formation of butylamine almost completely suppressed. The selective formation of secondary and tertiary amines on Ni/SiO2-A was explained by considering that butylamine is not release to the liquid phase during the reaction because it is strongly adsorbed on surface acid sites contiguous to Ni^0 atoms, thereby favoring the butylimine/butylamine condensation to higher amines between adsorbed species.
基金financially supported by the National Natural Science Foundation of China (No.31371800)the National Science-Technology Support Plan Project (2012BAD28B05)
文摘This study was carried out to investigate the biogenic amines(BAs), physicochemical property and microorganisms in dry salted fish, a traditional aquatic food consumed in China. Forty three samples of dry salted fish were gathered from retail and wholesale markets and manufacturers, which had been produced in various regions in China. Cadaverine(CAD) and putrescine(PUT) were quantitatively the most common biogenic amines. About 14% of the samples exceeded the histamine content standards established by the FDA and/or EU. The highest histamine content was found in Silver pomfret(Pampus argenteus)(347.79 mg kg^(-1)). Five of forty three samples exceeded the acceptable content of TYR(100 mg kg^(-1)), and 23.26% of dried-salted fish contained high contents of biogenic amines(above 600 mg kg^(-1)). In addition, species, regions, pickling processes and drying methods made the physicochemical property, microorganisms and biogenic amines in dry salted fish to be different to some extents. The total plate count(TPC) was much higher than that of total halophilic bacteria in all samples. The biogenic amines, physicochemical property and microbiological counts exhibited large variations among samples. Furthermore, no significant correlation between biogenic amines and physicochemical property and TPC was observed. This study indicated that dry salted fish may still present healthy risk for BAs, depending on the processing methods, storage conditions among others.
基金supported from the National Natural Science Foundation of China(Nos.42020104001 and 41805103)Local Innovative and Research Team Project of Guangdong Pearl River Talents Program(No.2017BT01Z032)the Fund from Chemistry and Chemical Engineering Guangdong Laboratory(No.1922009)
文摘As more attention is being paid to the characteristics of atmospheric amines,there is also an increasing demand for reliable detection technologies.Herein,a method was developed for simultaneous detection of atmospheric amines in both gaseous and particulate phases using gas chromatography-mass spectrometry(GC-MS).The amine samples were collected with and without phosphoric acid filters,followed by derivatization with benzenesulfonyl chloride under alkaline condition prior to GC-MS analysis.Furthermore,the method was optimized and validated for determining 14 standard amines.The detection limits ranged from0.0408-0.421μg/mL(for gaseous samples)and 0.163-1.69μg/mL(for particulate samples),respectively.The obtained recoveries ranged from 68.8%-180%and the relative standard deviation was less than 30%,indicating high precision and good reliability of the method.Seven amines were simultaneously detected in gaseous and particulate samples in an industrial park using the developed method successfully.Methylamine,dimethylamine and diethylamine together accounted for 76.7%and 75.6%of particulate and gaseous samples,respectively.By comparing the measured and predicted values of gas-particle partition fractions,it was found that absorption process of aqueous phase played a more important role in the gas-partition of amines than physical adsorption.Moreover,the reaction between unprotonated amines and acid(aq.)in water phase likely promoted water absorption.Higher measured partition fraction of dibutylamine was likely due to the reaction with gaseous HCl.The developed method would help provide a deeper understanding of gas-particle partitioning as well as atmospheric evolution of amines.
基金This work was supported by the Science Foundation of Jinan University (639)
文摘The hydrolysis process of the anticancer agents novel non-classical transplatinum（ Ⅱ ） with aliphatic amines and the influence of solvent models therein have been studied by using hybrid density functional theory （B3LYP）. In this study, the stepwise hydrolysis, trans[PtCl2（Am）（isopropylamine）] ＋ 2H2O → trans-[Pt（Am）（isopropylamine）（OH2）2]^2＋＋ 2Cl^-, was explored. Implicit solvent effects were incorporated through polarized continuum models. The stationary points on the potential energy surfaces for the first and second hydrolysis steps,proceeding via a general SN2 pathway, were fully optimized and characterized. It was found that the first hydrolysis reaction is easier than the second one and the hydrolysis of trans- [PtCl2-（isopropylamine）2] is the easiest in our studying systems. The result can assist in under- tanding the hydrolysis mechanism of trans-[PtCl2（Am）（isopropylamine）] and designing novel Pt-based anticancer drugs.
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.
基金Financial support from the National Natural Science Foundation of China (NSFC,Nos.21776258,21476207,91534113,21406199, 21566013,21875220)Program from Science and Technology Department of Zhejiang Province (Nos.2015C31042, LY17B060006)+1 种基金Education Science Planning Project of Jiangxi Province (No.18YB243)Natural Science Foundation of Jiangxi Province (No.20181BAB216032)
文摘Enhancing the selectivity of imines for the oxidative self-coupling of primary amines was found to be challenging in the heterogeneous catalysis.Three different manganese oxides(M-3,M-4,M-5) were synthesized by controlling the calcination temperature using a simple template-free oxalate route.The prepared manganese oxides were systematically characterized using XRD,N2 sorption,SEM,TEM,XPS,H2-TPR techniques.M-4 gave 96.2% selectivity of imine at 100% conversion of benzylamine,which was far more superior than other existing protocols.Mn^3+/Mn^4+ ratio was found to affect the selectivity of the imines.The probable reaction pathway for amines oxidation catalyzed by manganese oxides was proposed for the first time.
基金supported by the National Natural Science Foundation of China (Nos. 21207016, 21325729)the Fundamental Research Funds for the Central Universities (No. DUT12RC(3)07)+1 种基金the Liaoning Provincial Education Department (No. L2012021)Program for Changjiang Scholars and Innovative Research Team in University (No. IRT_13R05)
文摘Amines have been considered as promising candidates for post-combustion CO2 capture. A mechanistic understanding for the chemical processes involved in the capture and release of CO2 is important for the rational design of amines. In this study, the structural effects of amines on the kinetic competition among three typical products（carbamates, carbamic acids and bicarbonate） from amines ＋ CO2 were investigated, in contrast to previous thermodynamic studies to tune the reaction of amines with CO2 based on desirable reaction enthalpy and reaction stoichiometry. We used a quantum chemical method to calculate the activation energies（Ea） for the reactions of a range of substituted monoethanolamines with CO2 covering three pathways to the three products. The results indicate that the formation of carbamates is the most favorable, among the three considered products. In addition, we found that the Eavalues for all pathways linearly correlate with pK aof amines, and more importantly, the kinetic competition between carbamate and bicarbonate absorption pathways varies with p Kaof the amines, i.e. stronger basicity results in less difference in Ea. These results highlight the importance of the consideration of kinetic competition among different reaction pathways in amine design.
