The sorption study of La(Ⅲ) was carried out on poly[dibenzo-18-crown-6] and L-valine medium. The quantitative adsorption of La(Ⅲ) was found at 1×10-2 to 1×10-5 mol/L L-valine. The various eluting agents we...The sorption study of La(Ⅲ) was carried out on poly[dibenzo-18-crown-6] and L-valine medium. The quantitative adsorption of La(Ⅲ) was found at 1×10-2 to 1×10-5 mol/L L-valine. The various eluting agents were found efficient eluents for La(Ⅲ). The capacity of crown polymer for La(Ⅲ) was found to be 0.43 ±0.01 mmol/g. The tolerance limit of various cations and anions for La(Ⅲ) was determined. La(Ⅲ) was quantitatively separated from other metal ions in binary as well as multicomponent mixtures. The study was extended to sequential separation of La(Ⅲ), U(VI) and Th(IV). The good separation yields were obtained and had good reproducibility (±2%). The method incorporated the determination of La(Ⅲ) in real sample. The method was simple, rapid and selective.展开更多
used－silical capillary columns containing heptakis（2、3、6－tri－o－pentyl）-β-cyclodextrinand dibenzo-18-crown-6 were prepared．By studying the selectivity of mixed stationary phases forsome solute pairs.as well a...used－silical capillary columns containing heptakis（2、3、6－tri－o－pentyl）-β-cyclodextrinand dibenzo-18-crown-6 were prepared．By studying the selectivity of mixed stationary phases forsome solute pairs.as well as comparing with the heptakis（2．3、6-tri-O-pentyl）-β-cyclodextrin and thedibenzo-18-crown-6 used as individual stationary phase、the synergistic effects were observed.These effects were affected by the column temperature．mixed ratio and linear velocity of carrier gas．展开更多
3,3′-Dimethyl-dibenzo-18-crown-6 was synthesized and characterized by elemental analysis, FT-IR, ^1H NMR, UV, MS spectra and X-ray single-crystal diffraction. It belongs to orthorhombic, space group Pna21 with a = 8....3,3′-Dimethyl-dibenzo-18-crown-6 was synthesized and characterized by elemental analysis, FT-IR, ^1H NMR, UV, MS spectra and X-ray single-crystal diffraction. It belongs to orthorhombic, space group Pna21 with a = 8.0790（18）, b = 16.780（4）, c = 15.222（3） .A, Z= 4, V= 2063.6（8） A3 Dc = 1.250 g/cm^3,μ = 0.090 mm^-1, F（000） = 832, R = 0.0474 and wR = 0.1103. According to structural analysis, the title compound possesses a boat-like configuration.展开更多
A simple and selective method for the separation of Be（Ⅱ） was developed using poly[dibenzo-18-crown-6] as a stationary phase in column chromatography. The study was carried out in L-arginine medium. 1.0-8.0 M HCl a...A simple and selective method for the separation of Be（Ⅱ） was developed using poly[dibenzo-18-crown-6] as a stationary phase in column chromatography. The study was carried out in L-arginine medium. 1.0-8.0 M HCl and CH3COOH, 0.5-8.0 M HBr, HClO4 and H2SO4, 0.2-1.0 M EDTA and 0.02-0.12 M ammonium oxalate were found to be an efficient eluents for Be（Ⅱ）. The capacity of polymer was 0.554-0.01 mmol/g of crown polymer. The tolerance limit of various cations and anions were reported. Be（Ⅱ） was quantitatively separated from Mg（Ⅱ）, Ca（Ⅱ）, Sr（Ⅱ） and Ba（Ⅱ）. The selective separation of Be（Ⅱ） was possible from multicomponent mixtures. The method was extended to determine Be（Ⅱ） from geological samples. Method was simple, rapid and selective having good reproducibility （approximately4-2%）.展开更多
A combination of molecular dynamics （MD） and density functional theory （DFT） calculations were used to study the hydration structures of K＋ and Na＋ ions under the confinement of 18-crown-6 in order to identify t...A combination of molecular dynamics （MD） and density functional theory （DFT） calculations were used to study the hydration structures of K＋ and Na＋ ions under the confinement of 18-crown-6 in order to identify the role of water in the selectivity of 18-crown-6 towards K＋.The radial distribution functions,coordination num-bers,orientation structures and interaction energies were analyzed to investigate the hydration of K＋ and Na＋ in 18-crown-6/cation complexes.All calculations of K＋ and Na＋ in bulk water were also conducted for comparison.The simulation results show that the orientation distributions of the water molecules in the first coordination shell of K＋ are more sensitive to the confinement of 18-crown-6 than those of Na＋.It is more favorable to confine a K＋ in 18-crown-6 than a Na＋ in terms of interaction energy.Good agreement is obtained between MD results and DFT results.展开更多
It is well-known that primary amines form inclusive complexes with crown ethers. This kind of noncovalently inclusive complexes, exemplified tryptophan complex with 18-crown-6, was studied by combination of two experi...It is well-known that primary amines form inclusive complexes with crown ethers. This kind of noncovalently inclusive complexes, exemplified tryptophan complex with 18-crown-6, was studied by combination of two experimental methods, fluorimetry and mass spectrometry, with theoretical calculation. Fluorescence intensity of tryptophan in the absence and the presence of 18-crown-6 in aqueous HAc-NaAc buffer solution at pH=3.73 has been studied by fluorometry. The fuorescence intensity decreases significantly with increasing the concentration of 18-crown-6. The association constant K for the 1：1 complex of tryptophan ion-18-crown-6 was determined by means of fuorimetry. Mass spectrometric study of the complex gives direct evidence of the complex in the gas phase whose structure and binding energy are properly predicted by ab initio calculation.展开更多
The trinuclear complex bis（18-crown-6）thallium tetracyanoplatinate [Tl2（1 8-crown- 6）2Pt（CN）4]·2H2O was prepared and its structure was determined by X-ray diffraction analysis. The compound （C28H52N4O14PtT...The trinuclear complex bis（18-crown-6）thallium tetracyanoplatinate [Tl2（1 8-crown- 6）2Pt（CN）4]·2H2O was prepared and its structure was determined by X-ray diffraction analysis. The compound （C28H52N4O14PtTl2, Mr = 1272.57） crystallizes in monoclinic, space group P21/n with a = 10.5180（10）, b = 8.6162（8）, c = 21.118（2） A, β= 92.577（2）°, V= 1911.9（3） A^3, Z = 2, Dc = 2.211 g/cm^3, F（000） = 1200,μ= 12.123 mm^-1, R = 0.0181 and wR = 0.0427. The linearly arranged three metals are sandwiched by two 18-crown-6 molecules.展开更多
{[K.18-Crown-6]Br3}n,a unique tribromide-type catalyst,was utilized for the N-boc protection of amines and trimethylsilylation(TMS)and tetrahydropyranylation(THP)of alcohols.The method is general for the preparation o...{[K.18-Crown-6]Br3}n,a unique tribromide-type catalyst,was utilized for the N-boc protection of amines and trimethylsilylation(TMS)and tetrahydropyranylation(THP)of alcohols.The method is general for the preparation of N-boc derivatives of aliphatic(acyclic and cyclic)and aromatic,and primary and secondary amines and also various TMS-ethers and THP-ethers.The simple separation of the catalyst from the product is one of the many advantages of this method.展开更多
Diaza Crown ethers are versatile complexing reagents, their complexing abilities are dramatically modified by the electron donating atoms on substituents attached to the nitrogen if they can give a three-dimensional c...Diaza Crown ethers are versatile complexing reagents, their complexing abilities are dramatically modified by the electron donating atoms on substituents attached to the nitrogen if they can give a three-dimensional cavity as in cryptates. Hence the synthesis and characterization of bibracchial lariat ethers (BIBLES) have received much attention. In the preparation of new BIBLES, a complex Ⅱ was unexpectedly obtained.展开更多
the regioselectivity in the oxidation of different types of ketone compounds 1--6 with an oxidative reagent system,KH/O_2/18- Crown-6/THF is described.From these oxidative products,the various lactones have been prepa...the regioselectivity in the oxidation of different types of ketone compounds 1--6 with an oxidative reagent system,KH/O_2/18- Crown-6/THF is described.From these oxidative products,the various lactones have been prepared.展开更多
CdI2 in water was extracted with 18-crown-6 ether (L) into 10 diluents at 298 K. The following equilibrium constants were determined or evaluated: some extraction constants (Kex/mol-3·dm9 & Kex,ip/mol-2·...CdI2 in water was extracted with 18-crown-6 ether (L) into 10 diluents at 298 K. The following equilibrium constants were determined or evaluated: some extraction constants (Kex/mol-3·dm9 & Kex,ip/mol-2·dm6 for CdLI2, Kex±/mol-2·dm6 for CdLI+ with I-, & Kex2±/mol-1·dm3 for CdL2+ with 2I-), conditional distribution constants (KD,I for I-, KD,CdLI for CdLI+, & KD,CdL for CdL2+) between the two phases, and an ion-pair formation constant (K1,org/mol-1·dm3) for CdLI+ and that (K2,org/mol-1·dm3) for CdLI2 in the organic (org) phases. Using the K1,org and K2,org values, acidities of the complex ions, CdL2+ and CdLA+ (A- = I-, Br-, & Cl-), in the 11 diluents were classified by applying the HSAB rule. Especially, the CdLA+ ions were classified as the soft acids in 9 diluents. Also, molar volumes (Vj/cm3·mol-1) of j = CdLI2 and CdL2+ were determined with the regular-solution-theory plot of logKex,ip vs. logKD,L and its pseudo-plot of logKD,CdL, respectively. Here, KD,L denotes the distribution constant of L between the two phases. So, sizes among CdLA2 and CdL2+ were compared by using the Vj values. Additionally, some distribution equilibrium potentials (dep/V) between the water and org bulk phases were topically calculated from an equation of KD,I with KSD,I, where the symbol KSD,I shows a standard distribution constant of I- at dep = 0 V for a given diluent.展开更多
The complexe{[K(DB18-crown-6)]_(2)(CH_(3)CN)}[Pt(SCN)_(4)]was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complexe belongs to monoclinic,space group c2/c with cel...The complexe{[K(DB18-crown-6)]_(2)(CH_(3)CN)}[Pt(SCN)_(4)]was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complexe belongs to monoclinic,space group c2/c with cell dimensions,a=2.5904(8),6=1.3653(4),c-1.84706(6)nm,β=123.811(4)°,V=5-339(3)nm^(3),Z=4,.Dcalcd=l.577 g/cm^(3),F(000)=2552,R_(1)=0.051 l,wR_(2)=0.1411.The complexe shows one-dimensional chain of{[K(DB18-crown-6)]+complex cation and[Pt(SCN),i]2-complex anion bridged by N atom of CHaCN moleculer between two[K(DB18-crown-6)]_(2)[Pt(SCN)_(4)]groups respectively.展开更多
基金Project supported by the University Grants Commission,New Delhi
文摘The sorption study of La(Ⅲ) was carried out on poly[dibenzo-18-crown-6] and L-valine medium. The quantitative adsorption of La(Ⅲ) was found at 1×10-2 to 1×10-5 mol/L L-valine. The various eluting agents were found efficient eluents for La(Ⅲ). The capacity of crown polymer for La(Ⅲ) was found to be 0.43 ±0.01 mmol/g. The tolerance limit of various cations and anions for La(Ⅲ) was determined. La(Ⅲ) was quantitatively separated from other metal ions in binary as well as multicomponent mixtures. The study was extended to sequential separation of La(Ⅲ), U(VI) and Th(IV). The good separation yields were obtained and had good reproducibility (±2%). The method incorporated the determination of La(Ⅲ) in real sample. The method was simple, rapid and selective.
文摘used－silical capillary columns containing heptakis（2、3、6－tri－o－pentyl）-β-cyclodextrinand dibenzo-18-crown-6 were prepared．By studying the selectivity of mixed stationary phases forsome solute pairs.as well as comparing with the heptakis（2．3、6-tri-O-pentyl）-β-cyclodextrin and thedibenzo-18-crown-6 used as individual stationary phase、the synergistic effects were observed.These effects were affected by the column temperature．mixed ratio and linear velocity of carrier gas．
基金This project was supported by the Natural Science Foundation of Shandong Province (No.Y2003 D01)
文摘3,3′-Dimethyl-dibenzo-18-crown-6 was synthesized and characterized by elemental analysis, FT-IR, ^1H NMR, UV, MS spectra and X-ray single-crystal diffraction. It belongs to orthorhombic, space group Pna21 with a = 8.0790（18）, b = 16.780（4）, c = 15.222（3） .A, Z= 4, V= 2063.6（8） A3 Dc = 1.250 g/cm^3,μ = 0.090 mm^-1, F（000） = 832, R = 0.0474 and wR = 0.1103. According to structural analysis, the title compound possesses a boat-like configuration.
文摘A simple and selective method for the separation of Be（Ⅱ） was developed using poly[dibenzo-18-crown-6] as a stationary phase in column chromatography. The study was carried out in L-arginine medium. 1.0-8.0 M HCl and CH3COOH, 0.5-8.0 M HBr, HClO4 and H2SO4, 0.2-1.0 M EDTA and 0.02-0.12 M ammonium oxalate were found to be an efficient eluents for Be（Ⅱ）. The capacity of polymer was 0.554-0.01 mmol/g of crown polymer. The tolerance limit of various cations and anions were reported. Be（Ⅱ） was quantitatively separated from Mg（Ⅱ）, Ca（Ⅱ）, Sr（Ⅱ） and Ba（Ⅱ）. The selective separation of Be（Ⅱ） was possible from multicomponent mixtures. The method was extended to determine Be（Ⅱ） from geological samples. Method was simple, rapid and selective having good reproducibility （approximately4-2%）.
基金Supported by the National Natural Science Foundation of China （20706029） the National Basic Research Program of China （2009CB623407 2009CB219902） Jiangsu Applied Chemistry and Materials Graduate Center for Innovation and Academic Communication foundation （2010ACMC03）
文摘A combination of molecular dynamics （MD） and density functional theory （DFT） calculations were used to study the hydration structures of K＋ and Na＋ ions under the confinement of 18-crown-6 in order to identify the role of water in the selectivity of 18-crown-6 towards K＋.The radial distribution functions,coordination num-bers,orientation structures and interaction energies were analyzed to investigate the hydration of K＋ and Na＋ in 18-crown-6/cation complexes.All calculations of K＋ and Na＋ in bulk water were also conducted for comparison.The simulation results show that the orientation distributions of the water molecules in the first coordination shell of K＋ are more sensitive to the confinement of 18-crown-6 than those of Na＋.It is more favorable to confine a K＋ in 18-crown-6 than a Na＋ in terms of interaction energy.Good agreement is obtained between MD results and DFT results.
基金Supported by the Foundation of President of the Chinese Academy of Sciences and the Key(Keygrant) Project of Chinese Ministry of Education(No.106064)
文摘It is well-known that primary amines form inclusive complexes with crown ethers. This kind of noncovalently inclusive complexes, exemplified tryptophan complex with 18-crown-6, was studied by combination of two experimental methods, fluorimetry and mass spectrometry, with theoretical calculation. Fluorescence intensity of tryptophan in the absence and the presence of 18-crown-6 in aqueous HAc-NaAc buffer solution at pH=3.73 has been studied by fluorometry. The fuorescence intensity decreases significantly with increasing the concentration of 18-crown-6. The association constant K for the 1：1 complex of tryptophan ion-18-crown-6 was determined by means of fuorimetry. Mass spectrometric study of the complex gives direct evidence of the complex in the gas phase whose structure and binding energy are properly predicted by ab initio calculation.
基金This project was supported by the Zhejiang Provincial Natural Science Foundation of China (R405066)
文摘The trinuclear complex bis（18-crown-6）thallium tetracyanoplatinate [Tl2（1 8-crown- 6）2Pt（CN）4]·2H2O was prepared and its structure was determined by X-ray diffraction analysis. The compound （C28H52N4O14PtTl2, Mr = 1272.57） crystallizes in monoclinic, space group P21/n with a = 10.5180（10）, b = 8.6162（8）, c = 21.118（2） A, β= 92.577（2）°, V= 1911.9（3） A^3, Z = 2, Dc = 2.211 g/cm^3, F（000） = 1200,μ= 12.123 mm^-1, R = 0.0181 and wR = 0.0427. The linearly arranged three metals are sandwiched by two 18-crown-6 molecules.
基金support for this work from the research affairs of Hamedan University of Medical Sciences,Hamedan,I.R.Iranpartial support of this work by the Research Affairs Office of Bu-Ali Sina UniversityCenter of Excellence in Development of Chemical Method(CEDCM)Hamedan,I.R.Iran
文摘{[K.18-Crown-6]Br3}n,a unique tribromide-type catalyst,was utilized for the N-boc protection of amines and trimethylsilylation(TMS)and tetrahydropyranylation(THP)of alcohols.The method is general for the preparation of N-boc derivatives of aliphatic(acyclic and cyclic)and aromatic,and primary and secondary amines and also various TMS-ethers and THP-ethers.The simple separation of the catalyst from the product is one of the many advantages of this method.
基金Supported by the National Natural Science foundation of China Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics, Academic Soinica, Wuhan
文摘Diaza Crown ethers are versatile complexing reagents, their complexing abilities are dramatically modified by the electron donating atoms on substituents attached to the nitrogen if they can give a three-dimensional cavity as in cryptates. Hence the synthesis and characterization of bibracchial lariat ethers (BIBLES) have received much attention. In the preparation of new BIBLES, a complex Ⅱ was unexpectedly obtained.
文摘the regioselectivity in the oxidation of different types of ketone compounds 1--6 with an oxidative reagent system,KH/O_2/18- Crown-6/THF is described.From these oxidative products,the various lactones have been prepared.
文摘CdI2 in water was extracted with 18-crown-6 ether (L) into 10 diluents at 298 K. The following equilibrium constants were determined or evaluated: some extraction constants (Kex/mol-3·dm9 & Kex,ip/mol-2·dm6 for CdLI2, Kex±/mol-2·dm6 for CdLI+ with I-, & Kex2±/mol-1·dm3 for CdL2+ with 2I-), conditional distribution constants (KD,I for I-, KD,CdLI for CdLI+, & KD,CdL for CdL2+) between the two phases, and an ion-pair formation constant (K1,org/mol-1·dm3) for CdLI+ and that (K2,org/mol-1·dm3) for CdLI2 in the organic (org) phases. Using the K1,org and K2,org values, acidities of the complex ions, CdL2+ and CdLA+ (A- = I-, Br-, & Cl-), in the 11 diluents were classified by applying the HSAB rule. Especially, the CdLA+ ions were classified as the soft acids in 9 diluents. Also, molar volumes (Vj/cm3·mol-1) of j = CdLI2 and CdL2+ were determined with the regular-solution-theory plot of logKex,ip vs. logKD,L and its pseudo-plot of logKD,CdL, respectively. Here, KD,L denotes the distribution constant of L between the two phases. So, sizes among CdLA2 and CdL2+ were compared by using the Vj values. Additionally, some distribution equilibrium potentials (dep/V) between the water and org bulk phases were topically calculated from an equation of KD,I with KSD,I, where the symbol KSD,I shows a standard distribution constant of I- at dep = 0 V for a given diluent.
文摘The complexe{[K(DB18-crown-6)]_(2)(CH_(3)CN)}[Pt(SCN)_(4)]was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complexe belongs to monoclinic,space group c2/c with cell dimensions,a=2.5904(8),6=1.3653(4),c-1.84706(6)nm,β=123.811(4)°,V=5-339(3)nm^(3),Z=4,.Dcalcd=l.577 g/cm^(3),F(000)=2552,R_(1)=0.051 l,wR_(2)=0.1411.The complexe shows one-dimensional chain of{[K(DB18-crown-6)]+complex cation and[Pt(SCN),i]2-complex anion bridged by N atom of CHaCN moleculer between two[K(DB18-crown-6)]_(2)[Pt(SCN)_(4)]groups respectively.
