With the development of the economy and the increasing demand for environmental protection,the efficient and selective recovery of Gd(Ⅲ)from actual wastewater is of critical importance.In this work,lanthanum-based me...With the development of the economy and the increasing demand for environmental protection,the efficient and selective recovery of Gd(Ⅲ)from actual wastewater is of critical importance.In this work,lanthanum-based metal-organic framework(LaBDC)materials were prepared by a hydrothermal method,and then polyethyleneimine(PEI)and LaBDC were combined by an impregnation method to form a novel LaBDC@xPEI composite.The prepared materials were characterized using Fourier transfo rm infrared spectroscopy(FTIR),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),B runauer-Emmett-Teller(BET),thermogravimetric analysis(TGA)and X-ray photoelectron spectroscopy(XPS).Experiments show that LaBDC@50%PEI has the highest adsorption capacity(181.77 mg/g)among lanthanum-based MOFs with different PEI loadings at pH=5.5,which is about 5.1 times that of bare LaBDC.The adsorption isotherm analysis shows that LaBDC@50%PEI follows the Langmuir model.In addition,the adsorption kinetics of LaBDC@50%PEI follows a pseudo-second-order kinetic model,indicating that the adsorption process is chemical adsorption.It is worth noting that LaBDC@50%PEI maintains good adsorption performance and stability after three recycling tests,and exhibits excellent selectivity in cation interference experiments.Overall,the LaBDC@50%PEI composites possess good stability and hold great promises in rapid recovery of Gd(Ⅲ)from practical aqueous environments.展开更多
The extraction behavior of N,N,N’,N’-tetrabutylglutaramide（TBGA）employing cyclohexane as diluent toward La（Ⅲ）,Pr（Ⅲ）,Gd（Ⅲ）and Er（Ⅲ） investigated.The effect of the concentrations of nitric acid,lithium n...The extraction behavior of N,N,N’,N’-tetrabutylglutaramide（TBGA）employing cyclohexane as diluent toward La（Ⅲ）,Pr（Ⅲ）,Gd（Ⅲ）and Er（Ⅲ） investigated.The effect of the concentrations of nitric acid,lithium nitrate and extractant and also the temperature on the extraction distribution ratio was studied.The stoichiometry of the extracted species was Found to be M（NO3）3·3TBGA（M=La,Pr,Gd,Er）.The extraction mechanism was also discussed and the values of the enthalpy of extraction reaction was calculated.展开更多
The sorption behavior and mechanism of a Macroporous weak acid resin, （D155 resin,） for Gd（Ⅲ） were investigated. The statically saturated sorption capacity is 283 mg/g resin at 298 K in HAc-NaAc medium. The Gd（...The sorption behavior and mechanism of a Macroporous weak acid resin, （D155 resin,） for Gd（Ⅲ） were investigated. The statically saturated sorption capacity is 283 mg/g resin at 298 K in HAc-NaAc medium. The Gd（Ⅲ） adsorbed on macroporous weak acid resin, （D155 resin,） could be reductively eluted with the mixed solution of HCl and NaCl, and the elution percentage was as high as 100%. The resin could be regenerated and reused without remarkable decrease in sorption capacity. The apparent sorption rate constant was k298=1.98×10^5 s^-1. The apparent activation energy was Ea=2.78 kJ/mol. The sorption behavior of D155 resin for Gd（Ⅲ） obeyed the Langmuir isotherm. The thermodynamic sorption parameters were △H=33.0 kJ/mol,△S=192 J/mol/K, and △G298=-24.3 kJ/mol. The sorption mechanism of D155 resin for Gd（Ⅲ） was examined by using chemical method and IR spectrometry. The coordination compound was formed between oxygen atoms in the functional group of D155 resin and Gd （Ⅲ）.展开更多
The title complex K [Gd~Ⅲ(edta)(H_2O)_3]·5H_2O was synthesized, where edta denotes ethylenediamine- tetraacetic acid. The crystal and molecular structure of the complex were determined by single-crystal X-ray st...The title complex K [Gd~Ⅲ(edta)(H_2O)_3]·5H_2O was synthesized, where edta denotes ethylenediamine- tetraacetic acid. The crystal and molecular structure of the complex were determined by single-crystal X-ray structure analysis. The crystal belongs to an orthorhombic crystal system and an Fdd2 space group. The complex anion [Gd~Ⅲ(edta)(H_2O)_3] has a pseudo-monocapped square antiprismatic nine-coordinate structure in which six coordinate atoms (two N and four O) are from an edta ligand and three water molecules coordinate to Gd~Ⅲ ion directly. It can be predicted that Gd~Ⅲ ion can also form a nine-coordinate complex with ttha (triethylenetetraminehexaacetic acid) li- gand, so the GdⅢ complex anion [Gd~?é¨(r)(Httha)]~￡¨2-￡(c) can supply a free non-coordinate carboxyl group (-C-CH_2COOH) used for molecular embellishment in some biological molecules to form a contrast agent of Magnetic Resonance Imagine (MRI) with targeting function.展开更多
Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the...Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, t55Gd, and 237Np Mtissbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds. In this article, the crystal structures of two novel Gd（Ⅲ） acetylacetonato complexes, Gd（pta）3 · 2H2O （pta = 1,1,1 -trifluoro-5,5-dimethy 1-2,4-hexanedione） and Gd（bfa）3 · 2H2O （bfa = 1, 1, 1 -trifluoro-4-phenyl-2-4-butanedione） were reported. Though both of them were dihydrate and had distorted square antiprismatical structure, Gd（pta）3 · 2H2O crystallizes in the P 2 1/n （#14） monoclinic space group and its lattice parameters are a = 1.4141（6） nm, b = 1.0708（3） nm, c =2.2344（4） nm, β =952.4（2）°, and Gd（bfa）3· 2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a = 1.322 （1） nm, b = 2.295 （1） nm, c = 1. 0786（8） nm. In the meantime, the authors had finished a systematic investigation on the ^155Gd Mossbauer isomer shift （δ） of various Gd（Ⅲ） metal complexes having a different coordination number （C.N.） and different ratios coordinating oxygen to nitrogen. A tendency for the 6 value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed. This indicated that the Gd-O and/or Gd-N bond in the investigated Gd（Ⅲ） metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the lisands donating electrons to 6s, 5d, and 4f orbitals of Gd.展开更多
Two long-chain multidentate ligands： 2,9-di-（n-2＇,5＇,8＇-triazanonyl）-1,10-phenanthroline （L^1） and 2,9-di- （n-4＇,7＇,10＇-triazaundecyl）-1,10-phenanthroline （L^2） were synthesized. The hydrolytic kinetics...Two long-chain multidentate ligands： 2,9-di-（n-2＇,5＇,8＇-triazanonyl）-1,10-phenanthroline （L^1） and 2,9-di- （n-4＇,7＇,10＇-triazaundecyl）-1,10-phenanthroline （L^2） were synthesized. The hydrolytic kinetics of 2-hydroxypropyl p-nitrophenyl phosphate （HPNP） catalyzed by the complexes of L^1 or L^2 with La（Ⅲ） or Gd（Ⅲ） have been studied in aqueous solution at （298.2±0.1） K, I=0.10 mol·dm^-3 KNO3 in pH 7.5-9.1, respectively, finding that the catalytic effect of GdL^1 was the best among the four complexes for hydrolysis of HPNP. Its kLnLH-1, kLnLand pKa are 0.047 mol^-1·L·s^-1, 0.000074 mol^-1·L·s^-1 and 8.90, respectively. This paper expounded the studied result with the structure of the ligands and the properties of the metal ions, and deduced the catalysis mechanism.展开更多
The present paper covers the synthesis and the characterization of ligand 2-decyl-3,6,9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid,H_5L,and its Gd(Ⅲ) chelate. The protonation constants for H_5L(lg K H_...The present paper covers the synthesis and the characterization of ligand 2-decyl-3,6,9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid,H_5L,and its Gd(Ⅲ) chelate. The protonation constants for H_5L(lg K H_ i =10.90,8.50,4.55,2.92,2.20) and the stability constant for GdL 2- (lg K _ GdL 2- =22.80) were determined by means of potentiometric titration. They are similar to the corresponding values of DTPA and Gd-DTPA,respectively. The results obtained show that the basicity of the ligand and the stability constant of its Gd(Ⅲ) chelate are not obviously altered after the introduction of a linear chain decyl group into the terminal acetic acid residue of DTPA. The Gd(Ⅲ) chelate may be a potential contrast agent with liver-specificity for magnetic resonance imaging(MRI).展开更多
Diethylenetriaminepentaacetic dianhydride was co-polymerized with dodecyl ester and benzyl ester of lysine,and octodecyl ester and benzyl ester of lysine respectively to give two terpolymers. These two terpolymer liga...Diethylenetriaminepentaacetic dianhydride was co-polymerized with dodecyl ester and benzyl ester of lysine,and octodecyl ester and benzyl ester of lysine respectively to give two terpolymers. These two terpolymer ligands were reacted with GdCl 3 to afford amphiphilic oligomers of Gd(Ⅲ) complexes. These new ligands and Gd(Ⅲ) complexes were characterized by IR, 1H NMR and elemental analysis. The oligomeric complexes show a higher relaxivity as compared to that of Gd(DTPA) which is widely used in clinic diagnoses. The Gd(Ⅲ) complex derived from octodecyl ester demonstrated liver-selective enhancement for MR imaging of Wistar rat. The ratios of signal to noise ( S/N ) in the proton intensity imaging were enhanced,respectively,by 15%,27%,and 36% at the time of 5,30 and 45 min after injection of this complex.展开更多
基金Project supported by the National Natural Science Foundation of China(41662004)。
文摘With the development of the economy and the increasing demand for environmental protection,the efficient and selective recovery of Gd(Ⅲ)from actual wastewater is of critical importance.In this work,lanthanum-based metal-organic framework(LaBDC)materials were prepared by a hydrothermal method,and then polyethyleneimine(PEI)and LaBDC were combined by an impregnation method to form a novel LaBDC@xPEI composite.The prepared materials were characterized using Fourier transfo rm infrared spectroscopy(FTIR),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),B runauer-Emmett-Teller(BET),thermogravimetric analysis(TGA)and X-ray photoelectron spectroscopy(XPS).Experiments show that LaBDC@50%PEI has the highest adsorption capacity(181.77 mg/g)among lanthanum-based MOFs with different PEI loadings at pH=5.5,which is about 5.1 times that of bare LaBDC.The adsorption isotherm analysis shows that LaBDC@50%PEI follows the Langmuir model.In addition,the adsorption kinetics of LaBDC@50%PEI follows a pseudo-second-order kinetic model,indicating that the adsorption process is chemical adsorption.It is worth noting that LaBDC@50%PEI maintains good adsorption performance and stability after three recycling tests,and exhibits excellent selectivity in cation interference experiments.Overall,the LaBDC@50%PEI composites possess good stability and hold great promises in rapid recovery of Gd(Ⅲ)from practical aqueous environments.
文摘The extraction behavior of N,N,N’,N’-tetrabutylglutaramide（TBGA）employing cyclohexane as diluent toward La（Ⅲ）,Pr（Ⅲ）,Gd（Ⅲ）and Er（Ⅲ） investigated.The effect of the concentrations of nitric acid,lithium nitrate and extractant and also the temperature on the extraction distribution ratio was studied.The stoichiometry of the extracted species was Found to be M（NO3）3·3TBGA（M=La,Pr,Gd,Er）.The extraction mechanism was also discussed and the values of the enthalpy of extraction reaction was calculated.
基金the Zhejiang Provincial Natural Science Foundation of China (Y404279)
文摘The sorption behavior and mechanism of a Macroporous weak acid resin, （D155 resin,） for Gd（Ⅲ） were investigated. The statically saturated sorption capacity is 283 mg/g resin at 298 K in HAc-NaAc medium. The Gd（Ⅲ） adsorbed on macroporous weak acid resin, （D155 resin,） could be reductively eluted with the mixed solution of HCl and NaCl, and the elution percentage was as high as 100%. The resin could be regenerated and reused without remarkable decrease in sorption capacity. The apparent sorption rate constant was k298=1.98×10^5 s^-1. The apparent activation energy was Ea=2.78 kJ/mol. The sorption behavior of D155 resin for Gd（Ⅲ） obeyed the Langmuir isotherm. The thermodynamic sorption parameters were △H=33.0 kJ/mol,△S=192 J/mol/K, and △G298=-24.3 kJ/mol. The sorption mechanism of D155 resin for Gd（Ⅲ） was examined by using chemical method and IR spectrometry. The coordination compound was formed between oxygen atoms in the functional group of D155 resin and Gd （Ⅲ）.
文摘The title complex K [Gd~Ⅲ(edta)(H_2O)_3]·5H_2O was synthesized, where edta denotes ethylenediamine- tetraacetic acid. The crystal and molecular structure of the complex were determined by single-crystal X-ray structure analysis. The crystal belongs to an orthorhombic crystal system and an Fdd2 space group. The complex anion [Gd~Ⅲ(edta)(H_2O)_3] has a pseudo-monocapped square antiprismatic nine-coordinate structure in which six coordinate atoms (two N and four O) are from an edta ligand and three water molecules coordinate to Gd~Ⅲ ion directly. It can be predicted that Gd~Ⅲ ion can also form a nine-coordinate complex with ttha (triethylenetetraminehexaacetic acid) li- gand, so the GdⅢ complex anion [Gd~?é¨(r)(Httha)]~￡¨2-￡(c) can supply a free non-coordinate carboxyl group (-C-CH_2COOH) used for molecular embellishment in some biological molecules to form a contrast agent of Magnetic Resonance Imagine (MRI) with targeting function.
基金Project supported by the Grants-in-Aid for Scientific Research from the Ministry of Education, Science and Culture, Japan andin Part by the Inter-University Joint Research Program for the Common Use of JAERI (Japan Atomic Energy Research Institute)Facilities
文摘Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, t55Gd, and 237Np Mtissbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds. In this article, the crystal structures of two novel Gd（Ⅲ） acetylacetonato complexes, Gd（pta）3 · 2H2O （pta = 1,1,1 -trifluoro-5,5-dimethy 1-2,4-hexanedione） and Gd（bfa）3 · 2H2O （bfa = 1, 1, 1 -trifluoro-4-phenyl-2-4-butanedione） were reported. Though both of them were dihydrate and had distorted square antiprismatical structure, Gd（pta）3 · 2H2O crystallizes in the P 2 1/n （#14） monoclinic space group and its lattice parameters are a = 1.4141（6） nm, b = 1.0708（3） nm, c =2.2344（4） nm, β =952.4（2）°, and Gd（bfa）3· 2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a = 1.322 （1） nm, b = 2.295 （1） nm, c = 1. 0786（8） nm. In the meantime, the authors had finished a systematic investigation on the ^155Gd Mossbauer isomer shift （δ） of various Gd（Ⅲ） metal complexes having a different coordination number （C.N.） and different ratios coordinating oxygen to nitrogen. A tendency for the 6 value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed. This indicated that the Gd-O and/or Gd-N bond in the investigated Gd（Ⅲ） metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the lisands donating electrons to 6s, 5d, and 4f orbitals of Gd.
基金Project supported by the National Natural Science Foundation of China （Nos. 20371028, 20671052）.
文摘Two long-chain multidentate ligands： 2,9-di-（n-2＇,5＇,8＇-triazanonyl）-1,10-phenanthroline （L^1） and 2,9-di- （n-4＇,7＇,10＇-triazaundecyl）-1,10-phenanthroline （L^2） were synthesized. The hydrolytic kinetics of 2-hydroxypropyl p-nitrophenyl phosphate （HPNP） catalyzed by the complexes of L^1 or L^2 with La（Ⅲ） or Gd（Ⅲ） have been studied in aqueous solution at （298.2±0.1） K, I=0.10 mol·dm^-3 KNO3 in pH 7.5-9.1, respectively, finding that the catalytic effect of GdL^1 was the best among the four complexes for hydrolysis of HPNP. Its kLnLH-1, kLnLand pKa are 0.047 mol^-1·L·s^-1, 0.000074 mol^-1·L·s^-1 and 8.90, respectively. This paper expounded the studied result with the structure of the ligands and the properties of the metal ions, and deduced the catalysis mechanism.
文摘The present paper covers the synthesis and the characterization of ligand 2-decyl-3,6,9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid,H_5L,and its Gd(Ⅲ) chelate. The protonation constants for H_5L(lg K H_ i =10.90,8.50,4.55,2.92,2.20) and the stability constant for GdL 2- (lg K _ GdL 2- =22.80) were determined by means of potentiometric titration. They are similar to the corresponding values of DTPA and Gd-DTPA,respectively. The results obtained show that the basicity of the ligand and the stability constant of its Gd(Ⅲ) chelate are not obviously altered after the introduction of a linear chain decyl group into the terminal acetic acid residue of DTPA. The Gd(Ⅲ) chelate may be a potential contrast agent with liver-specificity for magnetic resonance imaging(MRI).
文摘Diethylenetriaminepentaacetic dianhydride was co-polymerized with dodecyl ester and benzyl ester of lysine,and octodecyl ester and benzyl ester of lysine respectively to give two terpolymers. These two terpolymer ligands were reacted with GdCl 3 to afford amphiphilic oligomers of Gd(Ⅲ) complexes. These new ligands and Gd(Ⅲ) complexes were characterized by IR, 1H NMR and elemental analysis. The oligomeric complexes show a higher relaxivity as compared to that of Gd(DTPA) which is widely used in clinic diagnoses. The Gd(Ⅲ) complex derived from octodecyl ester demonstrated liver-selective enhancement for MR imaging of Wistar rat. The ratios of signal to noise ( S/N ) in the proton intensity imaging were enhanced,respectively,by 15%,27%,and 36% at the time of 5,30 and 45 min after injection of this complex.
