Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene...Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.展开更多
Tetrabromoalkylthiacalix[4]arenes（1a and 1b） reacted with excess bis（tetraethylammonium）-bis（1,3- dithiole-2-thione-4,5-dithiol）zincate（2） to give thiacalix[4]arene-thiones（3a and 3b） in the presence of Na2S...Tetrabromoalkylthiacalix[4]arenes（1a and 1b） reacted with excess bis（tetraethylammonium）-bis（1,3- dithiole-2-thione-4,5-dithiol）zincate（2） to give thiacalix[4]arene-thiones（3a and 3b） in the presence of Na2S. Two novel bistetrathiafulvalene-attached thiacalix[4]arene assemblies（5a and 5b） formed via triethyl phosphite-mediated cross-coupling of thiacalix[4]arene-thiones（3a and 3b） and 4,5-biscyanoethylthio-1,3-dithiole-2-one（4）. All the four new compounds were characterized by 1H NMR, 13C NMR, IR, MS spectra and elemental analysis. Meanwhile, the structures of thiacalix[4]arene-thiones（3a and 3b） were identified by X-ray analysis. In addition, the cyclic voltammograms of the resulting thiacalix[4]arenes containing electroactive TTF units（5a and 5b） were provided.展开更多
Introduction Calixarenes are versatile host molecules for molecular recognition and supramolecular assembly because its functional groups can be readily introduced into the phenolic OH or the para position to realize...Introduction Calixarenes are versatile host molecules for molecular recognition and supramolecular assembly because its functional groups can be readily introduced into the phenolic OH or the para position to realize a wide variety of functions calixarenes-based polymers tion as these polymers can During the past decade, received increasing attenbe used to synthesize the materials that are suitable for the preparation of chemical sensor devices such as ion-selective electrodes or transport membranes.展开更多
Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reacti...Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature, lariat calix[4]-1,3-aza-crown（6） with chiral amino acid group as branched chain was synthesized via ＂1＋ 1＂ addition in a yield of 70%. The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities for a-amino acids.展开更多
Two novel heteroatom-bridged his (benzo-12-crown-4 ether)s, i.e. his [2-nitro-4,5 (1,4,7,10-tetraoxadecamethylene) disulfide 1 and diselenide 2, have been synthesized. X ray crystallographic structure was obtained for...Two novel heteroatom-bridged his (benzo-12-crown-4 ether)s, i.e. his [2-nitro-4,5 (1,4,7,10-tetraoxadecamethylene) disulfide 1 and diselenide 2, have been synthesized. X ray crystallographic structure was obtained for 1. Ion selective electrodes (ISE) for Ag+, containing 1 and 2 in PVC membrane as neutral carriers, were prepared, and their selectivity coefficients for Ag^+ (K_(Ag.M)^(pot)) were determined against other heavy metal ions, alkali and alkaline-earth metal ions. and ammonium ion. These ISEs showed excellent Ag^+ selectivities, log K_(Ag.M)^(pot) ≤ -3.8, against most of the interfering canons examined, except for Hg^+.展开更多
Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,B...Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.展开更多
A diester-calix[4]crown-4-ether bearing mono (azophenol) moiety shows a larger spectral change toward Ca2+ than other alkali and alkaline eafth cations.
A new chiral multidenate ligand (S, S)-1,7-bis(4-benzyloxazolin-2-yl-methyl)-1, 7-diaza- 12-crown-4 1 has been synthesized and used as ligand in the copper catalyzed asymmetric cyclopropanation of 1, 1-diphenylethylene.
基金supported by the National Natural Science Foundation of China(U20A20268)Natural Science Foundation of Hunan Province(2020JJ1004)Hunan Provincial Innovation Foundation for Postgraduate(CX20211190)。
文摘Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.
基金Supported by the National Natural Science Foundation of China(Nos.201172105, 20872058)
文摘Tetrabromoalkylthiacalix[4]arenes（1a and 1b） reacted with excess bis（tetraethylammonium）-bis（1,3- dithiole-2-thione-4,5-dithiol）zincate（2） to give thiacalix[4]arene-thiones（3a and 3b） in the presence of Na2S. Two novel bistetrathiafulvalene-attached thiacalix[4]arene assemblies（5a and 5b） formed via triethyl phosphite-mediated cross-coupling of thiacalix[4]arene-thiones（3a and 3b） and 4,5-biscyanoethylthio-1,3-dithiole-2-one（4）. All the four new compounds were characterized by 1H NMR, 13C NMR, IR, MS spectra and elemental analysis. Meanwhile, the structures of thiacalix[4]arene-thiones（3a and 3b） were identified by X-ray analysis. In addition, the cyclic voltammograms of the resulting thiacalix[4]arenes containing electroactive TTF units（5a and 5b） were provided.
基金the Research Foundation of Tongji Medical College,Huazhong University of Science and Technology(No.25514107)Project Chenguang of Wuhan City(No.200750731267)for financial support.
基金Financial support from the National Natural Science Foundation of China(No:20402002)Fujian Natural Science Foundation of China(No:E0220002)were greatly acknowledged.
基金the National Natural Science Foundation of China(No 29971023)
文摘Introduction Calixarenes are versatile host molecules for molecular recognition and supramolecular assembly because its functional groups can be readily introduced into the phenolic OH or the para position to realize a wide variety of functions calixarenes-based polymers tion as these polymers can During the past decade, received increasing attenbe used to synthesize the materials that are suitable for the preparation of chemical sensor devices such as ion-selective electrodes or transport membranes.
基金Supported by the National Natural Science Foundation of China(No.20402002)Natural Science Foundation of Fujian Province,China(No.2009J01019)
文摘Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature, lariat calix[4]-1,3-aza-crown（6） with chiral amino acid group as branched chain was synthesized via ＂1＋ 1＂ addition in a yield of 70%. The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities for a-amino acids.
文摘Two novel heteroatom-bridged his (benzo-12-crown-4 ether)s, i.e. his [2-nitro-4,5 (1,4,7,10-tetraoxadecamethylene) disulfide 1 and diselenide 2, have been synthesized. X ray crystallographic structure was obtained for 1. Ion selective electrodes (ISE) for Ag+, containing 1 and 2 in PVC membrane as neutral carriers, were prepared, and their selectivity coefficients for Ag^+ (K_(Ag.M)^(pot)) were determined against other heavy metal ions, alkali and alkaline-earth metal ions. and ammonium ion. These ISEs showed excellent Ag^+ selectivities, log K_(Ag.M)^(pot) ≤ -3.8, against most of the interfering canons examined, except for Hg^+.
基金Financial support from the National Natural Science Foundation of China(No.20802049) and Program for New Century Excellent Talents in University of Tianjin City
基金the National Natural Science Foundation of China (No. 20371040) the Foundation (031-A21-004)of Gansu province and the Foundation (No. 02-18) of Northwest Normal University.
文摘Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.
文摘A diester-calix[4]crown-4-ether bearing mono (azophenol) moiety shows a larger spectral change toward Ca2+ than other alkali and alkaline eafth cations.
基金the National Natural Science Foundation of China (No. 20371040) the Foundation (031-A21-004)of Gansu province and the Foundation (No. 02-18) of Northwest Normal University.
文摘A new chiral multidenate ligand (S, S)-1,7-bis(4-benzyloxazolin-2-yl-methyl)-1, 7-diaza- 12-crown-4 1 has been synthesized and used as ligand in the copper catalyzed asymmetric cyclopropanation of 1, 1-diphenylethylene.
