There is a generally accepted conclusion that trifluoroacetic acid (TFA) does occur naturally, in part based on the large quantities of TFA in the oceans (61 - 205 million tonnes, measured in 1998-2002). However, the ...There is a generally accepted conclusion that trifluoroacetic acid (TFA) does occur naturally, in part based on the large quantities of TFA in the oceans (61 - 205 million tonnes, measured in 1998-2002). However, the recent review paper “Insufficient evidence for the existence of natural trifluoroacetic acid” concludes that “the presence of TFA in the deep ocean and lack of closed TFA budget is not sufficient evidence that TFA occurs naturally, especially without a reasonable mechanism of formation”. Industrial sources of TFA can only result from the use of fluoride minerals in industrial processes. Major industrial uses of fluorspar started significant expansion from about the same time (1930s). Over 190 million tonnes of fluorspar have been mined in the period 1930 to 1999. An inventory has been developed (1930-1999), accounting for most of the fluorspar production (86%) and estimating emissions of TFA. Industrial emissions of TFA are estimated as 230,000 to 470,000 tonnes. Significant other industrial uses of fluorides have not been identified that could account for the large burden of TFA in the oceans. This inventory provides complementary evidence that the quantity of TFA in the oceans must include a large natural burden.展开更多
The present paper covers the actional mechanism of trifluoroacetic acid for the separation of biopolymers investigated by using the parameters of stoichiometric displacement model for retention(SDM-R) in reversed-phas...The present paper covers the actional mechanism of trifluoroacetic acid for the separation of biopolymers investigated by using the parameters of stoichiometric displacement model for retention(SDM-R) in reversed-phase liquid chromatography. It was found that the trifluoroacetic acid(TFA) may participate in, or stimulate the association among displacing agent molecules in mobile phase, and decrease the affinity of both the associate molecules of the displacing agent and the TFA-protein ion-pairing. The former dominates over the separation selectivity of biopolymers as the concentration of TFA is lower than a given value, and the two contrary functions partly offset to each other and the latter dominates as its concentration is greater than the given value.展开更多
探讨了BiVO_4-BiIO_3光催化剂(BVBI)降解水体中有机污染物(甲基橙为模拟污染物)过程中,体系中的助剂三氟乙酸(TFA)的促进效果及理论机理。实验结果表明,TFA可明显提高光催化降解甲基橙的效率:反应0.5 h后加入0.25 m L TFA后降解率达到92...探讨了BiVO_4-BiIO_3光催化剂(BVBI)降解水体中有机污染物(甲基橙为模拟污染物)过程中,体系中的助剂三氟乙酸(TFA)的促进效果及理论机理。实验结果表明,TFA可明显提高光催化降解甲基橙的效率:反应0.5 h后加入0.25 m L TFA后降解率达到92.58%,而不加TFA降解率仅为25.50%。借助电化学分析与自由基捕获实验,我们推测TFA的助催化机理在于其有效地捕获催化剂的光生空穴(h+),促进其与光生电子(e-)的分离,提高e-利用率从而提高催化降解有机物的能力。首次利用TFA为光生空穴h+的捕获剂以提高光催化反应效率,研究成果可为光催化助剂高效降解水体中有机污染物的相关研究提供有益的借鉴。展开更多
Effect of acidic catalysis having carboxylic acid group was studied on properties of conductive copolymer films made of pyrrole (Py) and 2-formyl pyrrole (FPy). It was noted that trifluoroacetic acid (TFA) and trichlo...Effect of acidic catalysis having carboxylic acid group was studied on properties of conductive copolymer films made of pyrrole (Py) and 2-formyl pyrrole (FPy). It was noted that trifluoroacetic acid (TFA) and trichloroacetic acid (TCA) were suitable for the preparation of copolymer films, which showed good properties in its strength and electrical conductivity of the copolymer films. When the concentration of TFA or TCA was increased in the monomer feed, the copolymerization yield became higher and the obtained films showed electrical conductivity in the range of 10–4 - 10–3 S/cm. FT-IR and UV-Vis spectra confirmed the formation of conjugate chemical structure in the copolymer film.展开更多
We report the first trifluoroacetic anhydride- and trifluoroacetic acid-promoted cascade reaction with phtoroglucinoltribenzyl ether and carboxylic acid as starting materials. By simply varying the temperature of syst...We report the first trifluoroacetic anhydride- and trifluoroacetic acid-promoted cascade reaction with phtoroglucinoltribenzyl ether and carboxylic acid as starting materials. By simply varying the temperature of systems containing the same starting materials, different products were produced in high yields. A three-step consecutive reaction process was also proposed.展开更多
This paper is concerned with the interaction of ethyl benzoate (EBA) and trifluoroaceticacid (TFA) molecules in the excited state by measurements of steady--state and transient fluo-rescence spectra at room and low te...This paper is concerned with the interaction of ethyl benzoate (EBA) and trifluoroaceticacid (TFA) molecules in the excited state by measurements of steady--state and transient fluo-rescence spectra at room and low temperatures. The results show that not only the 1:1 exci-plex but also the 2:1 triplex between EBA and TFA was formed. The formation pathway ofthe triplex is that the exciplex formed at first, then by the interaction with the EBA mole-cule it transformed into triplex. But it could not be formed by the dimer of EBA by interac-tion with TFA. The dimer of EBA is confirmed in the concentrated solution. So there arefour components in EBA/TFA--concentrated solution and their fluorescence lifetimes aremeasured respectively.展开更多
Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have re...Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have reported the side reactions induced by it.We present here the application of in situ 1H-NMR techniques to explore its effect on the hydroxyl end-groups,which are usually used for the molecular weight determination of polyesters by end-group estimation method.Using bis(2-hydroxyethyl)terephthalate(BHET)as model compound,quantitative NMR results show the peak integration of hydroxyethyl end-groups decreased with time via a pseudo-first-order kinetics in d-trifluoroacetic acid/d-chloroform mixture solvent(1:10,V:V).This is due to the esterification of hydroxyethyl groups with trifluoroacetic acid,revealed by the H-^(13)C gradient-enhanced heteronuclear multiple bond correlation(gHMBC)spectrum.The mixtures of dimethyl terephthalate and BHET with different molar ratios were used to represent poly(ethylene terephthalate)(PET)with different degrees of polymerization,and the effect of trifluoroacetic acid on the estimation of hydroxyethyl groups and subsequent molecular weight determination of polyesters was studied.Our results show that if a relative error of 5%is allowed,the NMR measurements must be finished within 1.3 h of solution preparation at 25℃ in the mixture solve nt.The results were confirmed in PET sample,while in poly(ethyle ne adipate),the obtained esterifaction con stant is faster that those in aromatic system.The results can be applied to other polymer systems with alcohol functionalized groups,and used as a guideline for the characterization of polyesters and polyethers by end-group estimation method.展开更多
文摘There is a generally accepted conclusion that trifluoroacetic acid (TFA) does occur naturally, in part based on the large quantities of TFA in the oceans (61 - 205 million tonnes, measured in 1998-2002). However, the recent review paper “Insufficient evidence for the existence of natural trifluoroacetic acid” concludes that “the presence of TFA in the deep ocean and lack of closed TFA budget is not sufficient evidence that TFA occurs naturally, especially without a reasonable mechanism of formation”. Industrial sources of TFA can only result from the use of fluoride minerals in industrial processes. Major industrial uses of fluorspar started significant expansion from about the same time (1930s). Over 190 million tonnes of fluorspar have been mined in the period 1930 to 1999. An inventory has been developed (1930-1999), accounting for most of the fluorspar production (86%) and estimating emissions of TFA. Industrial emissions of TFA are estimated as 230,000 to 470,000 tonnes. Significant other industrial uses of fluorides have not been identified that could account for the large burden of TFA in the oceans. This inventory provides complementary evidence that the quantity of TFA in the oceans must include a large natural burden.
基金Supported by the National Natrual Science Foundation of China
文摘The present paper covers the actional mechanism of trifluoroacetic acid for the separation of biopolymers investigated by using the parameters of stoichiometric displacement model for retention(SDM-R) in reversed-phase liquid chromatography. It was found that the trifluoroacetic acid(TFA) may participate in, or stimulate the association among displacing agent molecules in mobile phase, and decrease the affinity of both the associate molecules of the displacing agent and the TFA-protein ion-pairing. The former dominates over the separation selectivity of biopolymers as the concentration of TFA is lower than a given value, and the two contrary functions partly offset to each other and the latter dominates as its concentration is greater than the given value.
文摘探讨了BiVO_4-BiIO_3光催化剂(BVBI)降解水体中有机污染物(甲基橙为模拟污染物)过程中,体系中的助剂三氟乙酸(TFA)的促进效果及理论机理。实验结果表明,TFA可明显提高光催化降解甲基橙的效率:反应0.5 h后加入0.25 m L TFA后降解率达到92.58%,而不加TFA降解率仅为25.50%。借助电化学分析与自由基捕获实验,我们推测TFA的助催化机理在于其有效地捕获催化剂的光生空穴(h+),促进其与光生电子(e-)的分离,提高e-利用率从而提高催化降解有机物的能力。首次利用TFA为光生空穴h+的捕获剂以提高光催化反应效率,研究成果可为光催化助剂高效降解水体中有机污染物的相关研究提供有益的借鉴。
文摘Effect of acidic catalysis having carboxylic acid group was studied on properties of conductive copolymer films made of pyrrole (Py) and 2-formyl pyrrole (FPy). It was noted that trifluoroacetic acid (TFA) and trichloroacetic acid (TCA) were suitable for the preparation of copolymer films, which showed good properties in its strength and electrical conductivity of the copolymer films. When the concentration of TFA or TCA was increased in the monomer feed, the copolymerization yield became higher and the obtained films showed electrical conductivity in the range of 10–4 - 10–3 S/cm. FT-IR and UV-Vis spectra confirmed the formation of conjugate chemical structure in the copolymer film.
基金Supported by the National Natural Science Foundation of China（No.51209024）.
文摘We report the first trifluoroacetic anhydride- and trifluoroacetic acid-promoted cascade reaction with phtoroglucinoltribenzyl ether and carboxylic acid as starting materials. By simply varying the temperature of systems containing the same starting materials, different products were produced in high yields. A three-step consecutive reaction process was also proposed.
基金Project supported by the National Natural Science Foundation of China and the National Laboratory for Structural Chemistry.
文摘This paper is concerned with the interaction of ethyl benzoate (EBA) and trifluoroaceticacid (TFA) molecules in the excited state by measurements of steady--state and transient fluo-rescence spectra at room and low temperatures. The results show that not only the 1:1 exci-plex but also the 2:1 triplex between EBA and TFA was formed. The formation pathway ofthe triplex is that the exciplex formed at first, then by the interaction with the EBA mole-cule it transformed into triplex. But it could not be formed by the dimer of EBA by interac-tion with TFA. The dimer of EBA is confirmed in the concentrated solution. So there arefour components in EBA/TFA--concentrated solution and their fluorescence lifetimes aremeasured respectively.
基金by the National Natural Science Foundation of China(No.21774090)National Key R&D Program of China(No.2018YFB1105700)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have reported the side reactions induced by it.We present here the application of in situ 1H-NMR techniques to explore its effect on the hydroxyl end-groups,which are usually used for the molecular weight determination of polyesters by end-group estimation method.Using bis(2-hydroxyethyl)terephthalate(BHET)as model compound,quantitative NMR results show the peak integration of hydroxyethyl end-groups decreased with time via a pseudo-first-order kinetics in d-trifluoroacetic acid/d-chloroform mixture solvent(1:10,V:V).This is due to the esterification of hydroxyethyl groups with trifluoroacetic acid,revealed by the H-^(13)C gradient-enhanced heteronuclear multiple bond correlation(gHMBC)spectrum.The mixtures of dimethyl terephthalate and BHET with different molar ratios were used to represent poly(ethylene terephthalate)(PET)with different degrees of polymerization,and the effect of trifluoroacetic acid on the estimation of hydroxyethyl groups and subsequent molecular weight determination of polyesters was studied.Our results show that if a relative error of 5%is allowed,the NMR measurements must be finished within 1.3 h of solution preparation at 25℃ in the mixture solve nt.The results were confirmed in PET sample,while in poly(ethyle ne adipate),the obtained esterifaction con stant is faster that those in aromatic system.The results can be applied to other polymer systems with alcohol functionalized groups,and used as a guideline for the characterization of polyesters and polyethers by end-group estimation method.
