Acetylacetone(AcAc)is a typical class ofβ-diketones with broad industrial applications due to the property of the keto-enol isomers,but its isomerization and chemical reactions at the air-droplet interface are still ...Acetylacetone(AcAc)is a typical class ofβ-diketones with broad industrial applications due to the property of the keto-enol isomers,but its isomerization and chemical reactions at the air-droplet interface are still unclear.Hence,using combined molecular dynamics and quantum chemistry methods,the heterogeneous chemistry of AcAc at the air-droplet interface was investigated,including the attraction of AcAc isomers by the droplets,the distribution of isomers at the air-droplet interface,and the hydration reactions of isomers at the air-droplet interface.The results reveal that the preferential orientation of two AcAc isomers(keto-and enol-AcAc)to accumulate and accommodate at the acidic air-droplet interface.The isomerization of two AcAc isomers at the acidic air-droplet interface is more favorable than that at the neutral air-droplet interface because the“water bridge”structure is destroyed by H_(3)O^(+),especially for the isomerization from keto-Ac Ac to enol-AcAc.At the acidic air-droplet interface,the carbonyl or hydroxyl O-atoms of two AcAc isomers display an energetical preference to hydration.Keto-diol is the dominant products to accumulate at the air-droplet interface,and excessive keto-diol can enter the droplet interior to engage in the oligomerization.The photooxidation reaction of AcAc will increase the acidity of the air-droplet interface,which indirectly facilitate the uptake and formation of more keto-diol.Our results provide an insight into the heterogeneous chemistry ofβ-diketones and their influence on the environment.展开更多
Personal care products(PCPs)inevitably come into contact with the skin in people’s daily life,potentially causing adverse effects on human health.The adverse effects can be exacerbated under UV irradiation but are ra...Personal care products(PCPs)inevitably come into contact with the skin in people’s daily life,potentially causing adverse effects on human health.The adverse effects can be exacerbated under UV irradiation but are rarely studied.In this study,to clearly understand the damage of representative PCPs to human skin and their photochemical transformation behaviors,fragrance tonalide(AHTN)was measured in the presence of amino acids as a basic building block of human tissue.The results showed that amino acids could decelerate the photochemical transformation rate of AHTN,increasing the likelihood of AHNT persisting on the skin surface and the health risk to the human being.Further,the interaction between amino acids and AHTN was investigated.AHTN could play bidirectional roles in damaging amino acids:the photosensitizer and reactive activator.As a photosensitizer,the ^(1)O_(2) generated from the AHTN photosensitization was partly employed to oxidative damage amino acids.Furthermore,by combining experiments with quantum chemical computation,the carbonyl group of the activator AHTN was found to be the active site to activate the N-containing group of amino acids.The activation mechanism was the electron transfer between AHTN and amino acids.Imines formed during the photochemical transformation of AHTN with histidine/glycine were the molecular initiating event for potential skin sensitization.This study reported for the first time that skin photosensitizer formation threatens human health during the photochemical transformation of AHTN.展开更多
Organosulfate (OSA) nanoparticles,as secondary organic aerosol (SOA) compositions,are ubiquitous in urban and rural environments.Hence,we systemically investigated the mechanisms and kinetics of aqueous-phase reaction...Organosulfate (OSA) nanoparticles,as secondary organic aerosol (SOA) compositions,are ubiquitous in urban and rural environments.Hence,we systemically investigated the mechanisms and kinetics of aqueous-phase reactions of 1-butanol/1-decanol (BOL/DOL) and their roles in the formation of OSA nanoparticles by using quantum chemical and kinetic calculations.The mechanism results show that the aqueous-phase reactions of BOL/DOL start from initial protonation at alcoholic OH^(-)groups to form carbenium ions (CBs),which engage in the subsequent esterification or oligomerization reactions to form OSAs/organosulfites (OSIs) or dimers.The kinetic results reveal that dehydration to form CBs for BOL and DOL reaction systems is the rate-limiting step.Subsequently,about 18%of CBs occur via oligomerization to dimers,which are difficult to further oligomerize because all reactive sites are occupied.The rate constant of BOL reaction system is one order of magnitude larger than that of DOL reaction system,implying that relative short-chain alcohols are more prone to contribute OSAs/OSIs than long-chain alcohols.Our results reveal that typical long-chain alcohols contribute SOA formation via esterification rather than oligomerization because OSA/OSI produced by esterification engages in nanoparticle growth through enhancing hygroscopicity.展开更多
As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-conta...As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes(such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite(NS) were investigated. The results show that around 63% of ethylparaben could be absorbed onto NS within 38 hr, whereas the maximum adsorption capacity was 0.45 mg/g under room temperature. High temperature could improve the adsorption performance of ethylparaben using NS. In particular, for the temperature of 313 K, the adsorption turned spontaneous. The well-fitted adsorption kinetics indicated that both the surface adsorption and intra-particle diffusion contribute to the overall adsorption process. The monolayer adsorption on the surface of NS was primarily responsible for the elimination of ethylparaben. The adsorption mechanism showed that hydrophobic partitioning into organic matter could largely govern the adsorption process, rather than the Zn S that was the main component of NS. Furthermore, the ethylparaben adsorbed on the surface of NS was stable, as only less than 2% was desorbed and photochemically degraded under irradiation of simulated sunlight for 5 days. This study revealed that NS might serve as a potential natural remediation agent for some hydrophobic EOCs including parabens, and emphasized the significant role of naturally abundant minerals on the remediation of EOCs-contaminated water bodies.展开更多
Rapid economic development and industrialization have left many risk sites around the world with significant or potential soil contamination due to industrial production or the shutdown or relocation of industrial fac...Rapid economic development and industrialization have left many risk sites around the world with significant or potential soil contamination due to industrial production or the shutdown or relocation of industrial facilities.Soil pollutants pose significant threats to human health,especially at sites used by the chemical,mining,and metalworking industries,among others[1].展开更多
基金supported by the Guangdong Basic and Applied Basic Research Foundation(No.2019B151502064)the National Natural Science Foundation of China(Nos.42077189,42020104001,and 42277081)+3 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01Z032)the Science and Technology Key Project of Guangdong ProvinceChina(No.2019B110206002)the Guangdong Provincial Key R&D Program(No.2022-GDUT-A0007)。
文摘Acetylacetone(AcAc)is a typical class ofβ-diketones with broad industrial applications due to the property of the keto-enol isomers,but its isomerization and chemical reactions at the air-droplet interface are still unclear.Hence,using combined molecular dynamics and quantum chemistry methods,the heterogeneous chemistry of AcAc at the air-droplet interface was investigated,including the attraction of AcAc isomers by the droplets,the distribution of isomers at the air-droplet interface,and the hydration reactions of isomers at the air-droplet interface.The results reveal that the preferential orientation of two AcAc isomers(keto-and enol-AcAc)to accumulate and accommodate at the acidic air-droplet interface.The isomerization of two AcAc isomers at the acidic air-droplet interface is more favorable than that at the neutral air-droplet interface because the“water bridge”structure is destroyed by H_(3)O^(+),especially for the isomerization from keto-Ac Ac to enol-AcAc.At the acidic air-droplet interface,the carbonyl or hydroxyl O-atoms of two AcAc isomers display an energetical preference to hydration.Keto-diol is the dominant products to accumulate at the air-droplet interface,and excessive keto-diol can enter the droplet interior to engage in the oligomerization.The photooxidation reaction of AcAc will increase the acidity of the air-droplet interface,which indirectly facilitate the uptake and formation of more keto-diol.Our results provide an insight into the heterogeneous chemistry ofβ-diketones and their influence on the environment.
基金This work was supported by the National Key Research and Development Program of China(2019YFC1804503 and 2019YFC1804501)the Key-Area Research and Development Program of Guangdong Province(2020B1111350002)+2 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01Z032)the National Natural Science Foundation of China(41977365 and 41425015)the Key Project of Guangdong-Guangxi Joint Fund(2020B1515420002).
文摘Personal care products(PCPs)inevitably come into contact with the skin in people’s daily life,potentially causing adverse effects on human health.The adverse effects can be exacerbated under UV irradiation but are rarely studied.In this study,to clearly understand the damage of representative PCPs to human skin and their photochemical transformation behaviors,fragrance tonalide(AHTN)was measured in the presence of amino acids as a basic building block of human tissue.The results showed that amino acids could decelerate the photochemical transformation rate of AHTN,increasing the likelihood of AHNT persisting on the skin surface and the health risk to the human being.Further,the interaction between amino acids and AHTN was investigated.AHTN could play bidirectional roles in damaging amino acids:the photosensitizer and reactive activator.As a photosensitizer,the ^(1)O_(2) generated from the AHTN photosensitization was partly employed to oxidative damage amino acids.Furthermore,by combining experiments with quantum chemical computation,the carbonyl group of the activator AHTN was found to be the active site to activate the N-containing group of amino acids.The activation mechanism was the electron transfer between AHTN and amino acids.Imines formed during the photochemical transformation of AHTN with histidine/glycine were the molecular initiating event for potential skin sensitization.This study reported for the first time that skin photosensitizer formation threatens human health during the photochemical transformation of AHTN.
基金financially supported by the Natural Science Foundation of Guangdong Province,China (No.2019B151502064)the National Natural Science Foundation of China (Nos.42077189 and 4201001008)+2 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No.2017BT01Z032)the Innovation Team Project of Guangdong Provincial Department of Education(No.2017KCXTD012)the Science and Technology Key Project of Guangdong Province,China (No.2019B110206002)。
文摘Organosulfate (OSA) nanoparticles,as secondary organic aerosol (SOA) compositions,are ubiquitous in urban and rural environments.Hence,we systemically investigated the mechanisms and kinetics of aqueous-phase reactions of 1-butanol/1-decanol (BOL/DOL) and their roles in the formation of OSA nanoparticles by using quantum chemical and kinetic calculations.The mechanism results show that the aqueous-phase reactions of BOL/DOL start from initial protonation at alcoholic OH^(-)groups to form carbenium ions (CBs),which engage in the subsequent esterification or oligomerization reactions to form OSAs/organosulfites (OSIs) or dimers.The kinetic results reveal that dehydration to form CBs for BOL and DOL reaction systems is the rate-limiting step.Subsequently,about 18%of CBs occur via oligomerization to dimers,which are difficult to further oligomerize because all reactive sites are occupied.The rate constant of BOL reaction system is one order of magnitude larger than that of DOL reaction system,implying that relative short-chain alcohols are more prone to contribute OSAs/OSIs than long-chain alcohols.Our results reveal that typical long-chain alcohols contribute SOA formation via esterification rather than oligomerization because OSA/OSI produced by esterification engages in nanoparticle growth through enhancing hygroscopicity.
基金financial supports from the National Natural Science Foundation of China (Nos.41977365and 41425015)the National Key Research and Development Program of China (No.2019YFC1804503)+4 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No.2017BT01Z032) Natural Sciences and Engineering Research Council of Canadathe Canada Research Chairs ProgramAlberta InnovatesAlberta Health for their supportsupport of Guangdong University of Technology for her visiting scholarship.
文摘As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes(such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite(NS) were investigated. The results show that around 63% of ethylparaben could be absorbed onto NS within 38 hr, whereas the maximum adsorption capacity was 0.45 mg/g under room temperature. High temperature could improve the adsorption performance of ethylparaben using NS. In particular, for the temperature of 313 K, the adsorption turned spontaneous. The well-fitted adsorption kinetics indicated that both the surface adsorption and intra-particle diffusion contribute to the overall adsorption process. The monolayer adsorption on the surface of NS was primarily responsible for the elimination of ethylparaben. The adsorption mechanism showed that hydrophobic partitioning into organic matter could largely govern the adsorption process, rather than the Zn S that was the main component of NS. Furthermore, the ethylparaben adsorbed on the surface of NS was stable, as only less than 2% was desorbed and photochemically degraded under irradiation of simulated sunlight for 5 days. This study revealed that NS might serve as a potential natural remediation agent for some hydrophobic EOCs including parabens, and emphasized the significant role of naturally abundant minerals on the remediation of EOCs-contaminated water bodies.
基金This work was supported by the National Key Research and Development Project of China(2019YFC1804500).
文摘Rapid economic development and industrialization have left many risk sites around the world with significant or potential soil contamination due to industrial production or the shutdown or relocation of industrial facilities.Soil pollutants pose significant threats to human health,especially at sites used by the chemical,mining,and metalworking industries,among others[1].