In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations we...In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations were used to study the thermal reactions of pyrene,1-methylpyrene,7,8,9,10-tetrahydrobenzopyrene,and mixtures of pyrene with 1-octene,cyclohexene,or styrene.The reactant conversion rates,reaction rates,and product distributions were calculated and compared,and the mechanisms were analyzed and discussed.The results demonstrated that methyl and naphthenic structures in aromatics might improve the conversion rates of reactants in hydrogen transfer processes,but their steric hindrances prohibited the generation of high polymers.The naphthenic structures could generate more free radicals and presented a more obvious inhibition effect on the condensation of polymers compared with the methyl side chains.It was discovered that when different olefins were mixed with pyrene,1-octene primarily underwent pyrolysis reactions,whereas cyclohexene mainly underwent hydrogen transfer reactions with pyrene and styrene,mostly producing superconjugated biradicals through condensation reactions with pyrene.In the mixture systems,the olefins scattered aromatic molecules,hindering the formation of pyrene trimers and higher polymers.According to the reactive molecular dynamics simulations,styrene may enhance the yield of dimer and enable the controlled polycondensation of pyrene.展开更多
<span style="line-height:1.5;">Polycyclic aromatic hydrocarbons (PAHs) are important pollutants, whose biodegradation and bioremediation with microorganisms are the promising ways to clean environments...<span style="line-height:1.5;">Polycyclic aromatic hydrocarbons (PAHs) are important pollutants, whose biodegradation and bioremediation with microorganisms are the promising ways to clean environments and reduce their exposure to humans. Although the transportation of PAHs across bacterial membrane is the first step forwards their biodegradation, it receives less attention. In this mini-review, we explore which transport system for uptake of carbon sources can serve for </span><span style="line-height:1.5;">uptake of PAHs in bacteria, and try to uncover some patterns in their transport mechanisms. Collectively, 1) the major carbohydrate transport system, PTS, is unlikely to take PAHs because PAHs lack a hydroxy group for phosphorylation but aromatic acids are good candidates;2) PAHs could probably go through H<sup>+</sup> symporters, especially the low-molecular-weight PAHs, which are partially dissolvable in water;3) it is unlikely that PAHs can produce chemiosmotic ion gradients to go through uniporters;and 4) antiporters could serve as transporters to transport PAHs across bacterial membrane only after the metabolism of PAHs generates extra H<sup>+</sup> inside cell. Accordingly, the basic mechanism for uptake of PAHs is whether they can donate H<sup>+</sup> in order to generate an electrochemical proton gradient to go through symporters.展开更多
Two-dimensional molecular recognition studies of the six polyaromatic hydro-carbons that can be formed from the combination of four benzene rings: tetracene, pyrene, 1,2-benzanthracene, 3,4-benzphenanthrene, triphenyl...Two-dimensional molecular recognition studies of the six polyaromatic hydro-carbons that can be formed from the combination of four benzene rings: tetracene, pyrene, 1,2-benzanthracene, 3,4-benzphenanthrene, triphenylene, and chrysene were explored for each of these six molecules interacting with six different graphene layer site-specific nanopores. Computational studies were done for the gas phase adsorption on single layer graphene, bilayer graphene, and six molecule-specific graphene bilayer nanopores. Molecular mechanics MM2 parameters have been shown previously to provide good comparisons to experimental adsorption energies for aromatic hydrocarbons adsorption on graphitic surfaces. These binding energies are dominated by van der Waals forces. Just as a jigsaw puzzle hole can accommodate only a specific piece, two-dimensional shape specific sites were created in the top layer of a graphene bilayer to match each one of the six adsorbate molecules. The purpose of this study was to examine the molecular recognition possibilities of site specific adsorption in these simple two-dimensional nanopores based on dispersion forces and molecular shape. For example, triphenylene has a calculated surface binding energy of 24.5 kcal/mol on the graphene bilayer and 30.2 kcal/mol in its own site specific pore. The interaction energy of this molecule in the other five sites ranged from 17.6 to 23.8 kcal/mol. All the molecules tetracene, pyrene, 1,2-benzanthracene, triphenylene and chrysene had higher binding energies in their matched molecule bilayer sites than on either single or double layer graphene. In addition, each one of these five molecules had a stronger binding in their own shape specific (puzzle-ene) site than any of the other molecular sites. The results suggest that two-dimensional molecular recognition based on shape specific pores may allow selectivity useful for applications such as sensors, separations, nanofabrication, or information storage.展开更多
The stability of Zn anode in various Znbased energy storage devices is the key problem to be solved.Herein,aromatic aldehyde additives are selected to modulate the interface reactions between the Zn anode and electrol...The stability of Zn anode in various Znbased energy storage devices is the key problem to be solved.Herein,aromatic aldehyde additives are selected to modulate the interface reactions between the Zn anode and electrolyte.Through comprehensively considering electrochemical measurements,DFT calculations and FEA simulations,novel mechanisms of one kind of aromatic aldehyde,veratraldehyde in inhibiting Zn dendrite/by-products can be obtained.This additive prefers to absorb on the Zn surface than H_(2)O molecules and Zn^(2+),while competes with hydrogen evolution reaction and Zn plating/stripping proces s via redox reactions,thus preventing the decomposition of active H_(2)O near the interface and uncontrollable Zn dendrite growth via a synactic absorption-competition mechanism.As a result,Zn-Zn symmetric cells with the veratraldehyde additive realize an excellent cycling life of 3200 h under 1 mA cm^(-2)/1 mAh cm^(-2)and over 800 h even under 5 mA cm^(-2)/5 mAh cm^(-2).Moreover,Zn-Ti and Zn-MnO_(2)cells with the veratraldehyde additive both obtain elevated performance than that with pure ZnSO_(4)electrolyte.Finally,two more aromatic aldehyde additives are chosen to prove their universality in stabilizing Zn anodes.展开更多
Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system,and the characteristics of the products were analyzed to find out the fractionation mecha...Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system,and the characteristics of the products were analyzed to find out the fractionation mechanism of carbon isotopes and the causes of abnormal carbon isotopic compositions of natural gas.At the heating rates of 2℃/h(slow)and 20℃/h(rapid),the low maturity coal samples of the Ordos Basin had the maximum yields of alkane gas of 302.74 mL/g and 230.16 mL/g,theδ13C1 ranges of-34.8‰to-23.6‰and-35.5‰to-24.0‰;δ13C2 ranges of-28.0‰to-9.0‰and-28.9‰to-8.3‰;andδ13C3 ranges of-25.8‰to-14.7‰and-26.4‰to-13.2‰,respectively.Alkane gas in the thermal simulation products of rapid temperature rise process showed obvious partial reversal of carbon isotope series at 550℃,and at other temperatures showed positive carbon isotope series.In the two heating processes,theδ13C1 turned lighter first and then heavier,and the non-monotonic variation of theδ13C1 values is because the early CH4 is from different parent materials resulted from heterogeneity of organic matter or the carbon isotope fractionation formed by activation energy difference of early enriched 12CH4 and late enriched 13CH4.The reversal of carbon isotope values of heavy hydrocarbon gas can occur not only in high to over mature shale gas(oil-type gas),but also in coal-derived gas.Through thermal simulation experiment of toluene,it is confirmed that the carbon isotope value of heavy hydrocarbon gas can be reversed and inversed at high to over mature stage.The isotope fractionation effect caused by demethylation and methyl linkage of aromatic hydrocarbons may be an important reason for carbon isotope inversion and reversal of alkane gas at the high to over mature stage.展开更多
The geometry and the potential curve of thermal decomposition for 2,2′dimethyl-5,5′-azotetraol (2-DMAT) are calculated by ab initio quantum chemistry method. The structural characteristics and decomposition mechanis...The geometry and the potential curve of thermal decomposition for 2,2′dimethyl-5,5′-azotetraol (2-DMAT) are calculated by ab initio quantum chemistry method. The structural characteristics and decomposition mechanism are carefully studied. It is found that the terrazzo ring satisfies 4n+2 rule and it is a conjugated π-systems for 2-DMAT. The azotetrazol has aromaic characteristic and its thermal decomposition can proceed in two steps: ring opening and N2 separation. The activation energies of the two steps are 152.3kJ/mol and 44.67kJ/mol respectively. The ring opening is the rate-controlling step.展开更多
Aromaticity,in general,can promote a given reaction by stabilizing a transition state or a product via a mobility ofπelectrons in a cyclic structure.Similarly,such a promotion could be also achieved by destabilizing ...Aromaticity,in general,can promote a given reaction by stabilizing a transition state or a product via a mobility ofπelectrons in a cyclic structure.Similarly,such a promotion could be also achieved by destabilizing an antiaromatic reactant.However,both aromaticity and transition states cannot be directly measured in experiment.Thus,computational chemistry has been becoming a key tool to understand the aromaticity-driven reaction mechanisms.In this review,we will analyze the relationship between aromaticity and reaction mechanism to highlight the importance of density functional theory calculations and present it according to an approach via either aromatizing a transition state/product or destabilizing a reactant by antiaromaticity.Specifically,we will start with a particularly challenging example of dinitrogen activation followed by other small-molecule activation,Csingle bondF bond activation,rearrangement,as well as metathesis reactions.In addition,antiaromaticity-promoted dihydrogen activation,CO_(2)capture,and oxygen reduction reactions will be also briefly discussed.Finally,caution must be cast as the magnitude of the aromaticity in the transition states is not particularly high in most cases.Thus,a proof of an adequate electron delocalization rather than a complete ring current is recommended to support the relatively weak aromaticity in these transition states.展开更多
The cold plasma(CP)technique was applied to alleviate the contamination of polycyclic aromatic hydrocarbon(PAH)in this investigation.Two different CP treatments methods were implemented in the production of beef patti...The cold plasma(CP)technique was applied to alleviate the contamination of polycyclic aromatic hydrocarbon(PAH)in this investigation.Two different CP treatments methods were implemented in the production of beef patties,to investigate their inhibition and degradation capacity on PAHs.With 5 different cooking oils and fats addition,the inhibition mechanism of in-package cold plasma(ICP)pretreatment was explored from the aspect of raw patties fatty acids composition variation.The results of principal component analysis showed that the first two principal components accounted for more than 80%of the total variation in the original data,indicating that the content of saturated fatty acids was significantly positively correlated with the formation of PAHs.ICP pretreatment inhibited the formation of PAHs by changing the composition of fatty acids,which showed that the total amount of polyunsaturated fatty acids decreased and the total amount of monounsaturated fatty acids increased.Sensory discrimination tests demonstrated there were discernable differences between 2 CP treated samples and the controls,utilization of the ICP pretreatment in meat products processing was expected to achieve satisfying eating quality.In conclusion,CP treatment degraded PAHs through stepwise ring-opening oxidation in 2 reported pathways,the toxicity of PAHs contaminated products was alleviated after CP treatment.展开更多
基金financially supported by the National Natural Science Foundation of China(Approval No.42172168).
文摘In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations were used to study the thermal reactions of pyrene,1-methylpyrene,7,8,9,10-tetrahydrobenzopyrene,and mixtures of pyrene with 1-octene,cyclohexene,or styrene.The reactant conversion rates,reaction rates,and product distributions were calculated and compared,and the mechanisms were analyzed and discussed.The results demonstrated that methyl and naphthenic structures in aromatics might improve the conversion rates of reactants in hydrogen transfer processes,but their steric hindrances prohibited the generation of high polymers.The naphthenic structures could generate more free radicals and presented a more obvious inhibition effect on the condensation of polymers compared with the methyl side chains.It was discovered that when different olefins were mixed with pyrene,1-octene primarily underwent pyrolysis reactions,whereas cyclohexene mainly underwent hydrogen transfer reactions with pyrene and styrene,mostly producing superconjugated biradicals through condensation reactions with pyrene.In the mixture systems,the olefins scattered aromatic molecules,hindering the formation of pyrene trimers and higher polymers.According to the reactive molecular dynamics simulations,styrene may enhance the yield of dimer and enable the controlled polycondensation of pyrene.
文摘<span style="line-height:1.5;">Polycyclic aromatic hydrocarbons (PAHs) are important pollutants, whose biodegradation and bioremediation with microorganisms are the promising ways to clean environments and reduce their exposure to humans. Although the transportation of PAHs across bacterial membrane is the first step forwards their biodegradation, it receives less attention. In this mini-review, we explore which transport system for uptake of carbon sources can serve for </span><span style="line-height:1.5;">uptake of PAHs in bacteria, and try to uncover some patterns in their transport mechanisms. Collectively, 1) the major carbohydrate transport system, PTS, is unlikely to take PAHs because PAHs lack a hydroxy group for phosphorylation but aromatic acids are good candidates;2) PAHs could probably go through H<sup>+</sup> symporters, especially the low-molecular-weight PAHs, which are partially dissolvable in water;3) it is unlikely that PAHs can produce chemiosmotic ion gradients to go through uniporters;and 4) antiporters could serve as transporters to transport PAHs across bacterial membrane only after the metabolism of PAHs generates extra H<sup>+</sup> inside cell. Accordingly, the basic mechanism for uptake of PAHs is whether they can donate H<sup>+</sup> in order to generate an electrochemical proton gradient to go through symporters.
文摘Two-dimensional molecular recognition studies of the six polyaromatic hydro-carbons that can be formed from the combination of four benzene rings: tetracene, pyrene, 1,2-benzanthracene, 3,4-benzphenanthrene, triphenylene, and chrysene were explored for each of these six molecules interacting with six different graphene layer site-specific nanopores. Computational studies were done for the gas phase adsorption on single layer graphene, bilayer graphene, and six molecule-specific graphene bilayer nanopores. Molecular mechanics MM2 parameters have been shown previously to provide good comparisons to experimental adsorption energies for aromatic hydrocarbons adsorption on graphitic surfaces. These binding energies are dominated by van der Waals forces. Just as a jigsaw puzzle hole can accommodate only a specific piece, two-dimensional shape specific sites were created in the top layer of a graphene bilayer to match each one of the six adsorbate molecules. The purpose of this study was to examine the molecular recognition possibilities of site specific adsorption in these simple two-dimensional nanopores based on dispersion forces and molecular shape. For example, triphenylene has a calculated surface binding energy of 24.5 kcal/mol on the graphene bilayer and 30.2 kcal/mol in its own site specific pore. The interaction energy of this molecule in the other five sites ranged from 17.6 to 23.8 kcal/mol. All the molecules tetracene, pyrene, 1,2-benzanthracene, triphenylene and chrysene had higher binding energies in their matched molecule bilayer sites than on either single or double layer graphene. In addition, each one of these five molecules had a stronger binding in their own shape specific (puzzle-ene) site than any of the other molecular sites. The results suggest that two-dimensional molecular recognition based on shape specific pores may allow selectivity useful for applications such as sensors, separations, nanofabrication, or information storage.
基金support by National Natural Science Foundation of China(51271205,50801070)‘‘Project of Science and Technology Plan’’by Qingyuan city(DZXQY052,2018C005,2019A026)+2 种基金Project of results transformation achievement fund by Sun Yat-sen University(31000-18843232)‘‘Tian’e Plan’’by Huizhou city(20170220011822281,20170220085037390)the Scientifc Technology Project of Guangzhou City(202103000003).
文摘The stability of Zn anode in various Znbased energy storage devices is the key problem to be solved.Herein,aromatic aldehyde additives are selected to modulate the interface reactions between the Zn anode and electrolyte.Through comprehensively considering electrochemical measurements,DFT calculations and FEA simulations,novel mechanisms of one kind of aromatic aldehyde,veratraldehyde in inhibiting Zn dendrite/by-products can be obtained.This additive prefers to absorb on the Zn surface than H_(2)O molecules and Zn^(2+),while competes with hydrogen evolution reaction and Zn plating/stripping proces s via redox reactions,thus preventing the decomposition of active H_(2)O near the interface and uncontrollable Zn dendrite growth via a synactic absorption-competition mechanism.As a result,Zn-Zn symmetric cells with the veratraldehyde additive realize an excellent cycling life of 3200 h under 1 mA cm^(-2)/1 mAh cm^(-2)and over 800 h even under 5 mA cm^(-2)/5 mAh cm^(-2).Moreover,Zn-Ti and Zn-MnO_(2)cells with the veratraldehyde additive both obtain elevated performance than that with pure ZnSO_(4)electrolyte.Finally,two more aromatic aldehyde additives are chosen to prove their universality in stabilizing Zn anodes.
基金Supported by the National Natural Science Foundation of China(41902160,41625009)the China Postdoctoral Science Foundation(2019M650967,2020T130721)the China National Science and Technology Major Project(2016ZX05007-001)
文摘Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system,and the characteristics of the products were analyzed to find out the fractionation mechanism of carbon isotopes and the causes of abnormal carbon isotopic compositions of natural gas.At the heating rates of 2℃/h(slow)and 20℃/h(rapid),the low maturity coal samples of the Ordos Basin had the maximum yields of alkane gas of 302.74 mL/g and 230.16 mL/g,theδ13C1 ranges of-34.8‰to-23.6‰and-35.5‰to-24.0‰;δ13C2 ranges of-28.0‰to-9.0‰and-28.9‰to-8.3‰;andδ13C3 ranges of-25.8‰to-14.7‰and-26.4‰to-13.2‰,respectively.Alkane gas in the thermal simulation products of rapid temperature rise process showed obvious partial reversal of carbon isotope series at 550℃,and at other temperatures showed positive carbon isotope series.In the two heating processes,theδ13C1 turned lighter first and then heavier,and the non-monotonic variation of theδ13C1 values is because the early CH4 is from different parent materials resulted from heterogeneity of organic matter or the carbon isotope fractionation formed by activation energy difference of early enriched 12CH4 and late enriched 13CH4.The reversal of carbon isotope values of heavy hydrocarbon gas can occur not only in high to over mature shale gas(oil-type gas),but also in coal-derived gas.Through thermal simulation experiment of toluene,it is confirmed that the carbon isotope value of heavy hydrocarbon gas can be reversed and inversed at high to over mature stage.The isotope fractionation effect caused by demethylation and methyl linkage of aromatic hydrocarbons may be an important reason for carbon isotope inversion and reversal of alkane gas at the high to over mature stage.
基金Sponsored by National Basic Research Programof China Throughthe Grant(2004CB217802) Educational Committee of Beijing(XK114140479)
文摘The geometry and the potential curve of thermal decomposition for 2,2′dimethyl-5,5′-azotetraol (2-DMAT) are calculated by ab initio quantum chemistry method. The structural characteristics and decomposition mechanism are carefully studied. It is found that the terrazzo ring satisfies 4n+2 rule and it is a conjugated π-systems for 2-DMAT. The azotetrazol has aromaic characteristic and its thermal decomposition can proceed in two steps: ring opening and N2 separation. The activation energies of the two steps are 152.3kJ/mol and 44.67kJ/mol respectively. The ring opening is the rate-controlling step.
基金the National Natural Science Foundation of China(22073079,22025105 and 21873079)the Ministry of Education of China(H20200504)+2 种基金the Top-Notch Young Talents Program of China is gratefully acknowledgedM.S.thanks the Ministerio de Ciencia e Innovación of Spain(project PID2020-113711GB-I00)the Generalitat de Catalunya(project 2017SGR39).
文摘Aromaticity,in general,can promote a given reaction by stabilizing a transition state or a product via a mobility ofπelectrons in a cyclic structure.Similarly,such a promotion could be also achieved by destabilizing an antiaromatic reactant.However,both aromaticity and transition states cannot be directly measured in experiment.Thus,computational chemistry has been becoming a key tool to understand the aromaticity-driven reaction mechanisms.In this review,we will analyze the relationship between aromaticity and reaction mechanism to highlight the importance of density functional theory calculations and present it according to an approach via either aromatizing a transition state/product or destabilizing a reactant by antiaromaticity.Specifically,we will start with a particularly challenging example of dinitrogen activation followed by other small-molecule activation,Csingle bondF bond activation,rearrangement,as well as metathesis reactions.In addition,antiaromaticity-promoted dihydrogen activation,CO_(2)capture,and oxygen reduction reactions will be also briefly discussed.Finally,caution must be cast as the magnitude of the aromaticity in the transition states is not particularly high in most cases.Thus,a proof of an adequate electron delocalization rather than a complete ring current is recommended to support the relatively weak aromaticity in these transition states.
基金supported by the Key Scientific and Technological Research Projects of Xinjiang Production and Construction Corps(2022AB001)the Henan Key Laboratory of Cold Chain Food Quality and Safety Control(CCFQ2022)+2 种基金the National Key R&D Program of China(2019YFC1606200),funded by Ministry of Science and Technology of the People’s Republic of Chinathe China Agriculture Research System(CARS-41)funded by the Chinese Ministry of Agriculture,and the Priority Academic Program Development of Jiangsu Higher Education Institution(PAPD).
文摘The cold plasma(CP)technique was applied to alleviate the contamination of polycyclic aromatic hydrocarbon(PAH)in this investigation.Two different CP treatments methods were implemented in the production of beef patties,to investigate their inhibition and degradation capacity on PAHs.With 5 different cooking oils and fats addition,the inhibition mechanism of in-package cold plasma(ICP)pretreatment was explored from the aspect of raw patties fatty acids composition variation.The results of principal component analysis showed that the first two principal components accounted for more than 80%of the total variation in the original data,indicating that the content of saturated fatty acids was significantly positively correlated with the formation of PAHs.ICP pretreatment inhibited the formation of PAHs by changing the composition of fatty acids,which showed that the total amount of polyunsaturated fatty acids decreased and the total amount of monounsaturated fatty acids increased.Sensory discrimination tests demonstrated there were discernable differences between 2 CP treated samples and the controls,utilization of the ICP pretreatment in meat products processing was expected to achieve satisfying eating quality.In conclusion,CP treatment degraded PAHs through stepwise ring-opening oxidation in 2 reported pathways,the toxicity of PAHs contaminated products was alleviated after CP treatment.
