At present, the use of rare earth elements（REEs） has become an inevitable necessity in many modern industries. In general, liquid extraction is the best commercial method for extracting REEs due to its ability to co...At present, the use of rare earth elements（REEs） has become an inevitable necessity in many modern industries. In general, liquid extraction is the best commercial method for extracting REEs due to its ability to control high volumes of liquids with electrical load. With the aim of improving a separation technology that would be superior to the existing extraction systems, the extraction behaviors of La（Ⅲ）,Pr（Ⅲ）, and Nd（Ⅲ） from an HCI medium with Cyanex 272 in the presence of the complexing agent lactic acid（HLac） and auxiliary agents citric acid（H3 Cit）, acetic acid（HAc）, and Titriplex Ⅲ have been reported.The effect of pH and lactic acid concentration has been examined. The use of lactic acid as a complexing agent leading to a high extraction of REEs with Cyanex 272 at pH = 5 was compared with systems without lactic acid. The results show that the use of acetic acid along with lactic acid leads to an increase in the extraction percentage of LREEs. While use of citric acid and Titriplex Ⅲ reduces the extraction percentage of LREEs. Finally, the presence of Titriplex Ⅲ together with lactic acid could lead to an increase in the separation factor of Pr and Nd.展开更多
The metal-organic framework（MOF）{[Cu（L1）_（0.5）（CN）]·4H_2O·3DMSO}_n（1） was assembled by 1,4-bis（3？,5？-dicyano-2？,6？-di（pyrid-4-yl）-1？,4？-dihydropyridyl）benzene（L1） together with copper c...The metal-organic framework（MOF）{[Cu（L1）_（0.5）（CN）]·4H_2O·3DMSO}_n（1） was assembled by 1,4-bis（3？,5？-dicyano-2？,6？-di（pyrid-4-yl）-1？,4？-dihydropyridyl）benzene（L1） together with copper cyanide at room temperature. In 1,the Cu~＋ ions are linked by CN-anions into a 1D helical chain,which is further fused together by tetradentate L1 ligands to build an extended 3D porous framework with two different types of functionalized channels. 1 crystallizes in the monoclinic,space group P21/c with a = 17.8729（6）,b = 8.7298（3）,c = 22.7524（9） ？,β = 96.072（4）o,V = 3530.1（2） ？~3,μ = 0.845 mm-1,Dc = 1.352 Mg/m^3,Z = 4,Mr = 718.35,F（000） = 1500,S = 1.081,the final R = 0.0877 and wR = 0.2275 for 6975 observed reflections with I 〉 2σ（I）.展开更多
The interaction of iodine as an cr-acceptor with a synthetic ligand,benzene-1,3-disulfonylamid-kriptofix[22]（BDSAK） as a π-donor has been investigated spectrophotometrically in chloroform（CHCl3） and dichlorometh...The interaction of iodine as an cr-acceptor with a synthetic ligand,benzene-1,3-disulfonylamid-kriptofix[22]（BDSAK） as a π-donor has been investigated spectrophotometrically in chloroform（CHCl3） and dichloromethane（DCM） solutions.The results of mole ratio plots and Job＇s method show the stoichiometry of complexation I2/BDSAK is 1：1.Stability constants have been calculated in various temperatures and thermodynamic parameters have also been determined from the temperatures dependence of the stability constants by using van＇t Hoff equation.The results indicate the iodine complex with BDSAK is enthalpy stabilized but entropy destabilized.展开更多
Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co（en）312[Zr2（C2O4）7]·2H2O （1） has been obtained. The title complex crystall...Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co（en）312[Zr2（C2O4）7]·2H2O （1） has been obtained. The title complex crystallizes in the monoclinic, space group P21/n （No. 14） with a = 7.7448（10）, b = 14.5683（19）, c = 19.375（3） A, fl = 92.124（2）°, V= 2184.5（5） A3, Z = 4, Dc = 1.996 gcm-3, F（000） = 1332, μ = 1.328 mm＂1, R = 0.0353 and wR = 0.0718 （1 〉 2α（I））. Single-crystal structure analysis reveals that the title complex possesses a 3D network assembled through a multitude of charge-assisted hydrogen bonds between the in situ generated anionic coordination complexes [Zr2（C204）7]6- and metal complexes Co（en）33＋.展开更多
The building of safe and high energy-density lithium batteries is strongly dependent on the electrochemical performance of working electrolytes, in which ion–solvent interactions play a vital role. Herein, the ion–s...The building of safe and high energy-density lithium batteries is strongly dependent on the electrochemical performance of working electrolytes, in which ion–solvent interactions play a vital role. Herein, the ion–solvent chemistry is developed from mono-solvent to multi-solvent complexes to probe the solvation structure and the redox stability of practical electrolytes. The decrease in energies of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of solvents in lithium-ion solvation shells becomes less significant as the number of coordinated solvents increases, but both the HOMO and LUMO energies of the coordinated solvents remain lower than those of free solvents. A positive and approximately linear relationship was found between the decrease in the HOMO/LUMO energy and the average binding energy between Li+ and the coordinated solvents. A binary-solvent complex model further highlight the significant importance of the electrolyte solvation environment in regulating electrolyte stability, and it is essential to consider electrolyte stability from the perspective of ion–solvent complexes. These fresh insights into the energy chemistry of multi-solvent complexes provide critical references for electrolyte design and cell optimization.展开更多
Photodynamic therapy(PDT)has long been receiving increasing attention for the minimally invasive treatment of cancer.The performance of PDT depends on the photophysical and biological properties of photosensitizers(PS...Photodynamic therapy(PDT)has long been receiving increasing attention for the minimally invasive treatment of cancer.The performance of PDT depends on the photophysical and biological properties of photosensitizers(PSs).The always-on fluorescence signal of conventional PSs makes it difficult to realtime monitor phototherapeutic efficacy in the PDT process.Therefore,functional PSs with good photodynamic therapy effect and self-reporting properties are highly desired.Here,two nonemissive iridium(III)solvent complexes,[(dfppy)2Ir-(DMSO)]Cl(Ir-DMSO,dfppy=2,4-difluorophenyl)pyridine,DMSO=dimethyl sulfoxide)and[(dfppy)_(2)Ir(ACN)]Cl(Ir-ACN,ACN=acetonitrile)as PSs,were synthesized.Both of them exhibit intense high-energy absorption bands,low photoluminescence(PL)emission,and low dark toxicity.Thanks to the lower dark toxicity of Ir-DMSO,we chose it as a PS for further PDT.In this work,Ir-DMSO functions as a specific PL“signal on”PS for self-reporting therapeutic efficacy during its own PDT process.Colocalization experiments indicated that Ir-DMSO accumulated in the endoplasmic reticulum and mitochondria.Under light irradiation,Ir-DMSO not only exhibited the ability to kill cancer cells but also presented a“signal on”PL response toward cell death.During Ir-DMSO-induced PDT,cell death modality was further investigated and immunogenic cell death was revealed,in which main hallmarks,including ROS generation,upregulation of surface-exposed calreticulin,high-mobility group box 1,and adenosine triphosphate secretion,were observed.Thanks to the specific coordination reaction between Ir-DMSO and histidine(His)/Hiscontaining proteins,the phototherapeutic efficacy can be monitored in real time without other signal probes.This work provides a new and promising strategy for the development of PSs with self-reporting ability,which is of great importance for imaging-guided PDT.展开更多
基金Project supported by Anguran Lead and Zinc Company(55/G/93)
文摘At present, the use of rare earth elements（REEs） has become an inevitable necessity in many modern industries. In general, liquid extraction is the best commercial method for extracting REEs due to its ability to control high volumes of liquids with electrical load. With the aim of improving a separation technology that would be superior to the existing extraction systems, the extraction behaviors of La（Ⅲ）,Pr（Ⅲ）, and Nd（Ⅲ） from an HCI medium with Cyanex 272 in the presence of the complexing agent lactic acid（HLac） and auxiliary agents citric acid（H3 Cit）, acetic acid（HAc）, and Titriplex Ⅲ have been reported.The effect of pH and lactic acid concentration has been examined. The use of lactic acid as a complexing agent leading to a high extraction of REEs with Cyanex 272 at pH = 5 was compared with systems without lactic acid. The results show that the use of acetic acid along with lactic acid leads to an increase in the extraction percentage of LREEs. While use of citric acid and Titriplex Ⅲ reduces the extraction percentage of LREEs. Finally, the presence of Titriplex Ⅲ together with lactic acid could lead to an increase in the separation factor of Pr and Nd.
基金supported by the Natural Science Foundation of Fujian Province(2012J06006,2014J05026,2006L2005)
文摘The metal-organic framework（MOF）{[Cu（L1）_（0.5）（CN）]·4H_2O·3DMSO}_n（1） was assembled by 1,4-bis（3？,5？-dicyano-2？,6？-di（pyrid-4-yl）-1？,4？-dihydropyridyl）benzene（L1） together with copper cyanide at room temperature. In 1,the Cu~＋ ions are linked by CN-anions into a 1D helical chain,which is further fused together by tetradentate L1 ligands to build an extended 3D porous framework with two different types of functionalized channels. 1 crystallizes in the monoclinic,space group P21/c with a = 17.8729（6）,b = 8.7298（3）,c = 22.7524（9） ？,β = 96.072（4）o,V = 3530.1（2） ？~3,μ = 0.845 mm-1,Dc = 1.352 Mg/m^3,Z = 4,Mr = 718.35,F（000） = 1500,S = 1.081,the final R = 0.0877 and wR = 0.2275 for 6975 observed reflections with I 〉 2σ（I）.
文摘The interaction of iodine as an cr-acceptor with a synthetic ligand,benzene-1,3-disulfonylamid-kriptofix[22]（BDSAK） as a π-donor has been investigated spectrophotometrically in chloroform（CHCl3） and dichloromethane（DCM） solutions.The results of mole ratio plots and Job＇s method show the stoichiometry of complexation I2/BDSAK is 1：1.Stability constants have been calculated in various temperatures and thermodynamic parameters have also been determined from the temperatures dependence of the stability constants by using van＇t Hoff equation.The results indicate the iodine complex with BDSAK is enthalpy stabilized but entropy destabilized.
基金supported by the National Natural Science Foundation of China(Nos.21301024,21103017)the Fundamental Research Funds for the Central Universities(N120305003)
文摘Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co（en）312[Zr2（C2O4）7]·2H2O （1） has been obtained. The title complex crystallizes in the monoclinic, space group P21/n （No. 14） with a = 7.7448（10）, b = 14.5683（19）, c = 19.375（3） A, fl = 92.124（2）°, V= 2184.5（5） A3, Z = 4, Dc = 1.996 gcm-3, F（000） = 1332, μ = 1.328 mm＂1, R = 0.0353 and wR = 0.0718 （1 〉 2α（I））. Single-crystal structure analysis reveals that the title complex possesses a 3D network assembled through a multitude of charge-assisted hydrogen bonds between the in situ generated anionic coordination complexes [Zr2（C204）7]6- and metal complexes Co（en）33＋.
基金This work was supported by the National Natural Science Foundation of China(21825501)Beijing Municipal Natural Science Foundation(Z20J00043)+2 种基金National Key Research and Development Program(2016YFA0200102)Grant 2020GQG1006 from the Guoqiang Institute at Tsinghua UniversityX.Chen appreciates the support from the Shuimu Tsinghua Scholar Program of Tsinghua University and the Project funded by China Postdoctoral Science Foundation(2021TQ0161 and 2021M691709).
文摘The building of safe and high energy-density lithium batteries is strongly dependent on the electrochemical performance of working electrolytes, in which ion–solvent interactions play a vital role. Herein, the ion–solvent chemistry is developed from mono-solvent to multi-solvent complexes to probe the solvation structure and the redox stability of practical electrolytes. The decrease in energies of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of solvents in lithium-ion solvation shells becomes less significant as the number of coordinated solvents increases, but both the HOMO and LUMO energies of the coordinated solvents remain lower than those of free solvents. A positive and approximately linear relationship was found between the decrease in the HOMO/LUMO energy and the average binding energy between Li+ and the coordinated solvents. A binary-solvent complex model further highlight the significant importance of the electrolyte solvation environment in regulating electrolyte stability, and it is essential to consider electrolyte stability from the perspective of ion–solvent complexes. These fresh insights into the energy chemistry of multi-solvent complexes provide critical references for electrolyte design and cell optimization.
基金supported by the National Natural Science Foundation of China(Nos.22074087,22374094,and 22274093)the Fundamental Research Funds for the Central Universities(No.GK202202002).
文摘Photodynamic therapy(PDT)has long been receiving increasing attention for the minimally invasive treatment of cancer.The performance of PDT depends on the photophysical and biological properties of photosensitizers(PSs).The always-on fluorescence signal of conventional PSs makes it difficult to realtime monitor phototherapeutic efficacy in the PDT process.Therefore,functional PSs with good photodynamic therapy effect and self-reporting properties are highly desired.Here,two nonemissive iridium(III)solvent complexes,[(dfppy)2Ir-(DMSO)]Cl(Ir-DMSO,dfppy=2,4-difluorophenyl)pyridine,DMSO=dimethyl sulfoxide)and[(dfppy)_(2)Ir(ACN)]Cl(Ir-ACN,ACN=acetonitrile)as PSs,were synthesized.Both of them exhibit intense high-energy absorption bands,low photoluminescence(PL)emission,and low dark toxicity.Thanks to the lower dark toxicity of Ir-DMSO,we chose it as a PS for further PDT.In this work,Ir-DMSO functions as a specific PL“signal on”PS for self-reporting therapeutic efficacy during its own PDT process.Colocalization experiments indicated that Ir-DMSO accumulated in the endoplasmic reticulum and mitochondria.Under light irradiation,Ir-DMSO not only exhibited the ability to kill cancer cells but also presented a“signal on”PL response toward cell death.During Ir-DMSO-induced PDT,cell death modality was further investigated and immunogenic cell death was revealed,in which main hallmarks,including ROS generation,upregulation of surface-exposed calreticulin,high-mobility group box 1,and adenosine triphosphate secretion,were observed.Thanks to the specific coordination reaction between Ir-DMSO and histidine(His)/Hiscontaining proteins,the phototherapeutic efficacy can be monitored in real time without other signal probes.This work provides a new and promising strategy for the development of PSs with self-reporting ability,which is of great importance for imaging-guided PDT.
