Fifteen isomers of [Si,N,C,O]2+ system are obtained at UB3LYP/6-311G(d) and UCCSD(T)/6-311+G(2df) (single-point) levels. The analyses are made for predicting the structures of optimized isomers, while ionic fragments ...Fifteen isomers of [Si,N,C,O]2+ system are obtained at UB3LYP/6-311G(d) and UCCSD(T)/6-311+G(2df) (single-point) levels. The analyses are made for predicting the structures of optimized isomers, while ionic fragments with lower energies are suggested. The calculated results indicate that linear isomer SiNCO2+(2Π) is thermodynamically the most stable species in [Si,N,C,O]2+ system, followed by linear SiOCN2+ (2Π), SiCNO2+ (2Π), and SiC(NO) (2A) with NCO three-membered ring. The order of stability of several kinetically stable isomers is SiNCO2> SiCNO2+ (2Π)>SiOCN2+>SiC(NO)2+>OSiNC2+ (2Π). The obtained results by analyzing the isomerizations and ionic fragment patterns show that the signal peaks of [Si,N,C,O]2+ are attributed to the contribution of linear SiNCO2+ species, which is metastable and can dissociate to the ionic fragments in the mass spectrometry experiments.展开更多
Using molecular mechanics method,values of the heat of formation (HF) of different conformations,of perylenequinonoid photosensitizes hypocrellin A (HA) and hypocrellin B (HB) were calculated and the variance of HF af...Using molecular mechanics method,values of the heat of formation (HF) of different conformations,of perylenequinonoid photosensitizes hypocrellin A (HA) and hypocrellin B (HB) were calculated and the variance of HF after phenolic protons' dissociation were calculated as well The following was found:(i) The HF values of lour conformational isomers of HA and HB are similar to each other,so the four isomcrs can transform to each other room temperature,(ii) There exists the difference between the ability of dissociation of phenolic protons of HA and that of HB,the former is higher than the latter (iii) There exist two intramolecular hydrogen bonds in HA and HB The bond energy is approximately 8 kJ/mol and the energy of conformation Ⅰ is lower than that of conformationⅡ The bond energy of HA is lower than that of HB.(iv) There exists a low energy snot when phenolic hydroxyl bond twists 180° from the position where hydrogen bond is formed,which suggests that this kind of conformation probably exists,(v) The phenolic hydrogen of HBMC forms hydrogen bond with the neighbouring nitrogen,which is its striticture basis of possessing photosensitizing activity.展开更多
The volatilisation of perfluorooctanoic acid(PFOA)was measured experimentally at a range of pH values using a previously published laboratory method.Water-to-air transfer was studied for five structural isomers,namely...The volatilisation of perfluorooctanoic acid(PFOA)was measured experimentally at a range of pH values using a previously published laboratory method.Water-to-air transfer was studied for five structural isomers,namely:the linear isomer(n-PFOA)and the four most commonly occurring branched isomers(3-,4-,5-and 6-PFOA).The influence of water concentration and water type on the pH-dependent waterto-air transfer was also investigated for n-PFOA.The water-to-air transfer was studied over the course of 48 h at pH values ranging from 0.2 to 5.5.Under all experimental conditions tested,the volatilisation of PFOA was negligible at pH>2.5.In experiments performed with MilliQ water,volatilisation increased with decreasing water pH.In experiments performed with tap water and lake water,maximum volatilisation was observed at pH 1.The concentration of PFOA in water had no influence on the pH value at which water-to-air transfer was observed(i.e.at pH<2.5)for the concentration range tested(0.1e50 mg/L PFOA in deionised water).Although the percentage of PFOA volatilised was significantly different for the four branched isomers at low pH,volatilisation was not observed above pH 2.5 for any branched isomer suggesting that all PFOA isomers have a low pKa.Overall,these laboratory results demonstrate that volatilisation of any structural isomer of PFOA from water is negligible at environmentally-relevant conditions.It is unlikely that PFOA isomers will be fractionated in the environment as a result of volatilisation because it is a process of negligible environmental relevance.展开更多
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.20171015,20171016)Science Foundation for Excellent Youths of Heilongjiang University(2002) and the Natural Science Foundation of Heilongjiang Province(Grant No.E0
文摘Fifteen isomers of [Si,N,C,O]2+ system are obtained at UB3LYP/6-311G(d) and UCCSD(T)/6-311+G(2df) (single-point) levels. The analyses are made for predicting the structures of optimized isomers, while ionic fragments with lower energies are suggested. The calculated results indicate that linear isomer SiNCO2+(2Π) is thermodynamically the most stable species in [Si,N,C,O]2+ system, followed by linear SiOCN2+ (2Π), SiCNO2+ (2Π), and SiC(NO) (2A) with NCO three-membered ring. The order of stability of several kinetically stable isomers is SiNCO2> SiCNO2+ (2Π)>SiOCN2+>SiC(NO)2+>OSiNC2+ (2Π). The obtained results by analyzing the isomerizations and ionic fragment patterns show that the signal peaks of [Si,N,C,O]2+ are attributed to the contribution of linear SiNCO2+ species, which is metastable and can dissociate to the ionic fragments in the mass spectrometry experiments.
基金Project supported by the National Natural Science Foundation of China
文摘Using molecular mechanics method,values of the heat of formation (HF) of different conformations,of perylenequinonoid photosensitizes hypocrellin A (HA) and hypocrellin B (HB) were calculated and the variance of HF after phenolic protons' dissociation were calculated as well The following was found:(i) The HF values of lour conformational isomers of HA and HB are similar to each other,so the four isomcrs can transform to each other room temperature,(ii) There exists the difference between the ability of dissociation of phenolic protons of HA and that of HB,the former is higher than the latter (iii) There exist two intramolecular hydrogen bonds in HA and HB The bond energy is approximately 8 kJ/mol and the energy of conformation Ⅰ is lower than that of conformationⅡ The bond energy of HA is lower than that of HB.(iv) There exists a low energy snot when phenolic hydroxyl bond twists 180° from the position where hydrogen bond is formed,which suggests that this kind of conformation probably exists,(v) The phenolic hydrogen of HBMC forms hydrogen bond with the neighbouring nitrogen,which is its striticture basis of possessing photosensitizing activity.
基金the Swedish Research Council Formas(project number 2011-1345).
文摘The volatilisation of perfluorooctanoic acid(PFOA)was measured experimentally at a range of pH values using a previously published laboratory method.Water-to-air transfer was studied for five structural isomers,namely:the linear isomer(n-PFOA)and the four most commonly occurring branched isomers(3-,4-,5-and 6-PFOA).The influence of water concentration and water type on the pH-dependent waterto-air transfer was also investigated for n-PFOA.The water-to-air transfer was studied over the course of 48 h at pH values ranging from 0.2 to 5.5.Under all experimental conditions tested,the volatilisation of PFOA was negligible at pH>2.5.In experiments performed with MilliQ water,volatilisation increased with decreasing water pH.In experiments performed with tap water and lake water,maximum volatilisation was observed at pH 1.The concentration of PFOA in water had no influence on the pH value at which water-to-air transfer was observed(i.e.at pH<2.5)for the concentration range tested(0.1e50 mg/L PFOA in deionised water).Although the percentage of PFOA volatilised was significantly different for the four branched isomers at low pH,volatilisation was not observed above pH 2.5 for any branched isomer suggesting that all PFOA isomers have a low pKa.Overall,these laboratory results demonstrate that volatilisation of any structural isomer of PFOA from water is negligible at environmentally-relevant conditions.It is unlikely that PFOA isomers will be fractionated in the environment as a result of volatilisation because it is a process of negligible environmental relevance.
