A new two-step synthetic method was successfully developed to simplify the recrystallization process of lithium difluoro(oxalate)borate(LiODFB).Meanwhile,the purity of LiODFB as-prepared was determined by NMR,ICP-AES ...A new two-step synthetic method was successfully developed to simplify the recrystallization process of lithium difluoro(oxalate)borate(LiODFB).Meanwhile,the purity of LiODFB as-prepared was determined by NMR,ICP-AES and Karl Fisher measurements,respectively.The as-prepared LiODFB presents a high purity up to 99.95%.Its metal ions and water contents are under good control as well.Besides,its structure information and thermal properties were confirmed by FTIR,Raman and DSC-TGA analyses,respectively.LiODFB exerts fine thermostability and hypo-water-sensitivity and its structure information agrees well with previous literature.Furthermore,a combination of phase diagram and Raman spectroscopy were utilized to study the thermal phase behavior and ions coordination of LiODFB-DMC binary system to optimize the synthesis and recrystallization process.Although there are three types of molecular interaction forms(CIPs,AGG-IIa,AGG-IIIb)in LiODFB-DMC binary system,LiODFB can only be isolated as large single crystal solvate as LiODFB·(DMC)3/2 by slowly cooling subjected to the nucleation kinetics.Therefore,the fundamental information of our work is helpful in accelerating the application of LiODFB in Li-ion secondary batteries.展开更多
We previously isolated a natural product, namely guaiazulene-2,9-dione showing strong antibacterial activity against Vibrio anguillarum, from a gorgonian Muriceides collaris collected in South China Sea. In this exper...We previously isolated a natural product, namely guaiazulene-2,9-dione showing strong antibacterial activity against Vibrio anguillarum, from a gorgonian Muriceides collaris collected in South China Sea. In this experiment, guaiazulene-2,9-dione was quantitatively synthesized with an optimized one-step bromine oxidation method using guaiazulene as the raw material. The key reaction condition including reaction time and temperature, drop rate of bromine, concentration of aqueous THF solution, respective molar ratio of guaiazulene to bromine and acetic acid, and concentration of guaiazulene in aqueous THF solution, were investigated individually at five levels each for optimization. Combined with the verification test to show the absolute yield of each optimization step, the final optimal condition was determined as: when a solution of 0.025 mmol m L-1 guaiazulene in 80% aqueous THF was treated with four volumes of bromine at a drop rate of 0.1 m L min-1 and four volumes of acetic acid at-5℃ for three hours, the yield of guaiazulene-2,9-dione was 23.72%. This was the first report concerning optimized one-step synthesis to provide a convenient method for the large preparation of guaiazulene-2,9-dione.展开更多
基金Project(51371198)supported by the National Natural Science Foundation of ChinaProject(K1202039-11)supported by the Science and Technology Project of Changsha,China
文摘A new two-step synthetic method was successfully developed to simplify the recrystallization process of lithium difluoro(oxalate)borate(LiODFB).Meanwhile,the purity of LiODFB as-prepared was determined by NMR,ICP-AES and Karl Fisher measurements,respectively.The as-prepared LiODFB presents a high purity up to 99.95%.Its metal ions and water contents are under good control as well.Besides,its structure information and thermal properties were confirmed by FTIR,Raman and DSC-TGA analyses,respectively.LiODFB exerts fine thermostability and hypo-water-sensitivity and its structure information agrees well with previous literature.Furthermore,a combination of phase diagram and Raman spectroscopy were utilized to study the thermal phase behavior and ions coordination of LiODFB-DMC binary system to optimize the synthesis and recrystallization process.Although there are three types of molecular interaction forms(CIPs,AGG-IIa,AGG-IIIb)in LiODFB-DMC binary system,LiODFB can only be isolated as large single crystal solvate as LiODFB·(DMC)3/2 by slowly cooling subjected to the nucleation kinetics.Therefore,the fundamental information of our work is helpful in accelerating the application of LiODFB in Li-ion secondary batteries.
基金supported by National Natural Science Foundation of China (No. 21102136)Changjiang Scholars and Innovative Research Team in University (PCSIRT,No. IRT0944)
文摘We previously isolated a natural product, namely guaiazulene-2,9-dione showing strong antibacterial activity against Vibrio anguillarum, from a gorgonian Muriceides collaris collected in South China Sea. In this experiment, guaiazulene-2,9-dione was quantitatively synthesized with an optimized one-step bromine oxidation method using guaiazulene as the raw material. The key reaction condition including reaction time and temperature, drop rate of bromine, concentration of aqueous THF solution, respective molar ratio of guaiazulene to bromine and acetic acid, and concentration of guaiazulene in aqueous THF solution, were investigated individually at five levels each for optimization. Combined with the verification test to show the absolute yield of each optimization step, the final optimal condition was determined as: when a solution of 0.025 mmol m L-1 guaiazulene in 80% aqueous THF was treated with four volumes of bromine at a drop rate of 0.1 m L min-1 and four volumes of acetic acid at-5℃ for three hours, the yield of guaiazulene-2,9-dione was 23.72%. This was the first report concerning optimized one-step synthesis to provide a convenient method for the large preparation of guaiazulene-2,9-dione.
