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
Calix[n]arenes was utilized to detect PABA,the primary sunscreen component.This study investigates the interaction of calix[4]arene(C4),calix[6]arene(C6),and PABA using the Langmuir method and first-principle density ...Calix[n]arenes was utilized to detect PABA,the primary sunscreen component.This study investigates the interaction of calix[4]arene(C4),calix[6]arene(C6),and PABA using the Langmuir method and first-principle density functional theory(DFT).Using the Langmuir-Schaefer(LS)technique,an ultrathin film composed of calix[n]arenes and their complexes with PABA was deposited on various substrates.Based on the Langmuir study,the PABA molecule was bonded to the lower rims of both C4 and C6 with the host-guest ratio of 1:1.All of the LS films formed were then characterized by ultravioletvisible spectroscopy(UV-Vis),Fourier-transform infrared spectroscopy(FTIR)and carbon,hydrogen,nitrogen,sulfur elemental analyzer(CHNS).The band gap reduction obtained in the DFT study denotes the charge transfer interaction with promising reactivity between the calix[n]arenes and PABA.The sensing of PABA by C4 and C6 is successful based on the formation of bonding between them due to the hosts’effective trapping capacity.The outcomes of this study could be applied to drug delivery systems for future pharmaceutical and medical applications.展开更多
Tetra-bromo-methyl-resorcin[4]arene cavitands were synthesized and C-2 position amine functionalized to obtain C-propyl-o-toluidine-methyl-resorcin[4]arene cavitand 4, and the crystal containing one solvate molecule o...Tetra-bromo-methyl-resorcin[4]arene cavitands were synthesized and C-2 position amine functionalized to obtain C-propyl-o-toluidine-methyl-resorcin[4]arene cavitand 4, and the crystal containing one solvate molecule of ethanol was obtained in a dichloromethane-ethanol solvent system, its structure crystallized in the monoclinic space group P2<sub>1</sub>/n, with a = 12.521(3) Å, b = 21.738(6) Å, c = 25.353(6) Å, α = 90˚, β = 102.372(4)˚, γ = 90˚, and Z = 4. The compound was determined by single-crystal X-ray diffraction and characterized by <sup>1</sup>H NMR, FT-IR and elemental analyses.展开更多
The title complex (C50H44C14O8) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/n with a = 19.7768(4), b =10.2085(2), c = 21...The title complex (C50H44C14O8) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/n with a = 19.7768(4), b =10.2085(2), c = 21.2721(4)A,β= 97.153(1)°, V = 4261.23(14)A^3, Z = 4, Mr = 914.65, F(000) = 1904, Dc = 1.426 g/cm^3,μ = 0.336, the final R = 0.0550 and wR = 0.1647. The compound was structurally characterized by IR and ^1H NMR. The molecules are stacked through C-H...π interactions and intermolecular C-H...O hydrogen bonds.展开更多
Salbutamol,which increases the muscle mass and decreases the adipose tissue,is misused as nutrient repartitioning agent in the livestock.The novelty of this work is the determination of salbutamol in the livestock mea...Salbutamol,which increases the muscle mass and decreases the adipose tissue,is misused as nutrient repartitioning agent in the livestock.The novelty of this work is the determination of salbutamol in the livestock meat via new bonded-phases bearing eight derivatives of p-tert-calix[4]arene in partial-cone conformation.The new synthesized bonded-phases were characterized and optimized.The bonding interactions of solute and stationary-phases were examined and the main interactions were reported.The salbutamol levels in six samples of livestock meat were analyzed and the results reveal that for the best bonded-phases,the limit of detection(LOD) and limit of quantitation(LOQ) were 0.02 and 0.06 μg/mL,respectively.展开更多
Introduction Calixarenes are one of the most important supra- molecular building blocks, which can be modified by introducing different functional and/or structural groups to create a specific interaction between the...Introduction Calixarenes are one of the most important supra- molecular building blocks, which can be modified by introducing different functional and/or structural groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry.展开更多
New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was e...New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was examined.For K+ ion transfer,preserving phenolic hydroxyl in the lower rim of calix[4]arene could enhance its transport ability.When benzoyl replaced phenolic hydroxyl,the transport would fall off,because benzoyl caused steric hindrance on the K+ transfer.The study also revealed that the group having the electron-withdrawing conjugative effect on phenolic hydroxyl,-NO2 in the upper rim of calix[4]arene,made transport ability of calix[4]arene fall off.On the contrary,-NH2 that had electron-repulsive conjugative effect enhanced the transport ability of the compound.For Hg2+ ion,only -NH2 in the upper rim of calix[4]arenes had high affinity for it and contributed to Hg2+ transfer.Transport amount of Hg2+ ion increased with increasing calix[4]arene5 concentration and ΔpH in BLM.展开更多
Calix resorcinarenes bearing four hydrophobic side chains ( Ar-Rn, Ar-Ph, and Ar-N) orient stably on water oil interface and show high solubilization capacities for organic compounds, such as long chain alcohols...Calix resorcinarenes bearing four hydrophobic side chains ( Ar-Rn, Ar-Ph, and Ar-N) orient stably on water oil interface and show high solubilization capacities for organic compounds, such as long chain alcohols, benzene, toluene and dyes. The capacities are high even near the cmc of polyalkylated calix resorcinarenes, but the solubilities of organic compounds(solubilizates) decrease with the increase of the size of the solubilizates. Ar-R 6, with a chain length of six carbons, is the most effective among Ar-R n , Ar-Ph, and Ar-N; 11 fold mol of hexanol is dissolved in 2×10 -3 mol/L Ar-R 6. Moreover, Ar-R n bearing four alkyl side chains solubilizes the chain alcohols of the same chain length mostly. The solubilization capacities are presumably brought by inclusion in a large cavity of the polyalkylated calix resorcinarenes and by an efficient orientation of the solubilizates.展开更多
A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described. The compound is an useful intermediates for the introduction of other functional groups to obtain N containi...A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described. The compound is an useful intermediates for the introduction of other functional groups to obtain N containing substituted calix[4]arene. The reaction mechanism is briefly discussed.展开更多
This letter reports the synthesis of Schiff base calix[4]arene crowns containing m-xylylene phenol subunit, in which calix[4]arene Schiff base crowns 2a, 2b and 2c were formed by 1:1 condensation of calix[4]arene diam...This letter reports the synthesis of Schiff base calix[4]arene crowns containing m-xylylene phenol subunit, in which calix[4]arene Schiff base crowns 2a, 2b and 2c were formed by 1:1 condensation of calix[4]arene diamine 1 with dialdehydes (2, 6-diformyl-4-chlorophenol 3a, 2, 6-diformyl-4-methylphenol 3b, 2, 6-diformyl-4-tert-butylphenol 3c) under high dilute condition in refluxing anhydrous ethanol in 65-70% yield.展开更多
Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg^(2+)and Pb^(2+),calix[4]arene derivatives containing hydroxyl,bro...Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg^(2+)and Pb^(2+),calix[4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg^(2+)and Pb^(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix[4]arene improved the extraction ability on Hg^(2+)by promoting the formation of the negative oxygen ions that could bind with Hg^(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix[4]arene(calix[4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb^(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb^(2+)with higher charge-to-radius ratio than Hg^(2+)was coordinated and extracted by the calix[4]arene thia derivative more easily.Furthermore,extraction rates of the calix[4]arene thia derivative on both ions(Hg^(2+)and Pb^(2+))increased with the increase of pH value in acidic aqueous system(pH<7).展开更多
Calixarenes are excellent scaffolds that can De modified by introducing various functional groups to create specific interactions between the host and guest molecules. Thus, many calixarene derivatives containing spec...Calixarenes are excellent scaffolds that can De modified by introducing various functional groups to create specific interactions between the host and guest molecules. Thus, many calixarene derivatives containing special functional groups, such as ester, amide and thiourea, have been synthesized and their excellent complexing capability for cations have also been studled. Lately, calixarene derivatives containing two or more sorts of functional groups have attracted much attention.展开更多
A novel fluorescent ionophore derived from calix[4]arene and pyrazoline was designed and synthesized.Its molecular structure was confirmed by ^1H NMR and element analysis.The resulting material shows specific fluoresc...A novel fluorescent ionophore derived from calix[4]arene and pyrazoline was designed and synthesized.Its molecular structure was confirmed by ^1H NMR and element analysis.The resulting material shows specific fluorescent behavior toward the Zn^2+ion among the other divalent metal ions,such as Co^2+,Ni^2+,Cu^2+.The primary results indicate this ionophore material is a potential material for developing efficient fluorescent Zn^2+ chemosensors.展开更多
An adsorbent calix[4]arene carboxylic acid was employed as the adsorption material for on-line flow in jection(FI) micro-column preconcentration coupled with flame atomic absorption spectrometry(FAAS) determinatio...An adsorbent calix[4]arene carboxylic acid was employed as the adsorption material for on-line flow in jection(FI) micro-column preconcentration coupled with flame atomic absorption spectrometry(FAAS) determination of trace heavy metals(Cu, Pb, Co, Ni and Cd). Parameters such as the pH, loading time and flow rate of sample, and the concentration, volume and flow rate of eluent were optimized. The enrichment factors are 50.0, 56.5, 11.6, 12.1 and 19.1 for Cu, Pb, Co, Ni, and Cd, respectively, and a sample throughput of 20 h–1 was obtained. The limits of de tection for Cu, Pb, Co, Ni, and Cd were in a range of 1.56―3.91 μg/L, and the relative standard deviations(RSDs) were less than 2.76%(n=7). Furthermore, the proposed method was successfully applied to the determination of Cu, Pb, Co, Ni, and Cd in certified reference materials and various water samples.展开更多
The title compound (C50H.44010) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a = 16.713(4), b --- 13.189(3), c = 1...The title compound (C50H.44010) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a = 16.713(4), b --- 13.189(3), c = 19.434(5) A, β = 104.411(4)°, Mr = 804.85, Dc = 1.288 g/cm3, V = 4149.2(17) A3, Z = 4, F(000) = 1696, #(MoKa) = 0.089 mm-1T = 296(2) K, 7279 independent reflections with 3172 observed ones (I 〉 2δ(/)), R = 0.0520 and wR = 0.1203 with GOF = 0.928 (R = 0.1464 and wR = 0.1657 for all data). The calixarene moiety maintains the symmetric cone conformation through intramolecular O-H…O hydrogen bonds. Preliminary bioassays indicated that the title compound has a potent inhibitory activity against the strand transfer process of HIV-1 integrase.展开更多
X-ray crystal structures of the inclusion complexes of calix[4]arene monomethoxycarboxylic acid 1 (C30H2606) with acetontrile and acetone are reported. The crystal of C30H26O6·CH3CN is of monoclinic, space grou...X-ray crystal structures of the inclusion complexes of calix[4]arene monomethoxycarboxylic acid 1 (C30H2606) with acetontrile and acetone are reported. The crystal of C30H26O6·CH3CN is of monoclinic, space group P2 1/c with a = 11.691(5), b = 13.753(5), c = 17.072(7)A, β = 100.104(7)°, C32H29NO6, Mr = 523.56, V = 2702.4(18)A^3, Z = 4, De= 1.287 g/cm^3, μ(MoKα) = 0.089 mm^-1, T = 293(2) K, 5570 independent reflections with 3220 observed ones (1 〉 2σ(I)), R = 0.0521 and wR = 0.1132 with GOF = 1.042 (R = 0.1055 and wR = 0.1350 for all data). The data for C30H26O6·CH3COCH3: monoclinic, space group P2 1/c, α = 12.366(4), b = 12.119(4), c = 18.796(6) A, β = 90.871(6)°, C33H32O7, Mr = 540.59, V = 2816.6(16)A^3, Z = 4, Dc = 1.275 g/cm^3, μ(MoKα) = 0.089 mm^-1, T = 293(2) K, 5783 independent reflections including 2580 observed ones (I 〉 2σ(I)), R = 0.0555 and wR = 0.1424 with GOF= 0.975 (R = 0.1601 and wR = 0.1884 for all data). Their architectures exhibit one-dimensional inclusion polymers which are mediated head-to-tail by the guests.展开更多
Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in c...Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in calix[4]arene on the catalytic activity was first investigated.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
Two novel polymeric complexes, [Gd(HsTCAS)(H2O)7]·4H2O 1 and [Gd(HsTCAS) (CH3COCH3)(H2O)6]·6H2O 2 (H4TCAS = p-sulfonatothiacalix[4]arene), have been synthesized and characterized by single-crysta...Two novel polymeric complexes, [Gd(HsTCAS)(H2O)7]·4H2O 1 and [Gd(HsTCAS) (CH3COCH3)(H2O)6]·6H2O 2 (H4TCAS = p-sulfonatothiacalix[4]arene), have been synthesized and characterized by single-crystal X-ray diffraction analyses. Complex 1 crystallizes in monoclinic, space group C2/m with a = 20.2308(12), b = 19.0894(10), c = 12.2448(7)A, β = 101.847(3)°, V = 4628.1(5)A^3, C24H43GdO27S8, Mr = 1169.25, Z = 4, Dc = 1.690 g/cm^3, F(000) = 2380,μ = 1.879 mm^-1, the final R = 0.0404 and wR = 0.1038 for 5127 observed reflections with I 〉 2σ(I). Complex 2 is pseudo-isostructural with complex 1.展开更多
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Funded by the Sultan Idris Education University(UPSI)(No.2020-0256-103-02(FRGS/1/2020/STG07/UPSI/02/2))provided by the Ministry of Higher Education,Malaysia。
文摘Calix[n]arenes was utilized to detect PABA,the primary sunscreen component.This study investigates the interaction of calix[4]arene(C4),calix[6]arene(C6),and PABA using the Langmuir method and first-principle density functional theory(DFT).Using the Langmuir-Schaefer(LS)technique,an ultrathin film composed of calix[n]arenes and their complexes with PABA was deposited on various substrates.Based on the Langmuir study,the PABA molecule was bonded to the lower rims of both C4 and C6 with the host-guest ratio of 1:1.All of the LS films formed were then characterized by ultravioletvisible spectroscopy(UV-Vis),Fourier-transform infrared spectroscopy(FTIR)and carbon,hydrogen,nitrogen,sulfur elemental analyzer(CHNS).The band gap reduction obtained in the DFT study denotes the charge transfer interaction with promising reactivity between the calix[n]arenes and PABA.The sensing of PABA by C4 and C6 is successful based on the formation of bonding between them due to the hosts’effective trapping capacity.The outcomes of this study could be applied to drug delivery systems for future pharmaceutical and medical applications.
文摘Tetra-bromo-methyl-resorcin[4]arene cavitands were synthesized and C-2 position amine functionalized to obtain C-propyl-o-toluidine-methyl-resorcin[4]arene cavitand 4, and the crystal containing one solvate molecule of ethanol was obtained in a dichloromethane-ethanol solvent system, its structure crystallized in the monoclinic space group P2<sub>1</sub>/n, with a = 12.521(3) Å, b = 21.738(6) Å, c = 25.353(6) Å, α = 90˚, β = 102.372(4)˚, γ = 90˚, and Z = 4. The compound was determined by single-crystal X-ray diffraction and characterized by <sup>1</sup>H NMR, FT-IR and elemental analyses.
基金the Scientific Research Fund Projects of China West Normal University(No.06B003)the Youth Fund Projects of Sichuan Educational Department(No.2006B039)
文摘The title complex (C50H44C14O8) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/n with a = 19.7768(4), b =10.2085(2), c = 21.2721(4)A,β= 97.153(1)°, V = 4261.23(14)A^3, Z = 4, Mr = 914.65, F(000) = 1904, Dc = 1.426 g/cm^3,μ = 0.336, the final R = 0.0550 and wR = 0.1647. The compound was structurally characterized by IR and ^1H NMR. The molecules are stacked through C-H...π interactions and intermolecular C-H...O hydrogen bonds.
基金Supported by the Project of Islamic Azad University(Shahreza Branch)the Iran Nanotechnology Initiative Council
文摘Salbutamol,which increases the muscle mass and decreases the adipose tissue,is misused as nutrient repartitioning agent in the livestock.The novelty of this work is the determination of salbutamol in the livestock meat via new bonded-phases bearing eight derivatives of p-tert-calix[4]arene in partial-cone conformation.The new synthesized bonded-phases were characterized and optimized.The bonding interactions of solute and stationary-phases were examined and the main interactions were reported.The salbutamol levels in six samples of livestock meat were analyzed and the results reveal that for the best bonded-phases,the limit of detection(LOD) and limit of quantitation(LOQ) were 0.02 and 0.06 μg/mL,respectively.
基金Supported by the National Natural Science Foundation of China(No. 20402002) Natural Science Foundation of FujianProvince, China(Nos. E0220002 and 2006J0155).
文摘Introduction Calixarenes are one of the most important supra- molecular building blocks, which can be modified by introducing different functional and/or structural groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry.
基金Natural Science Foundation of Education Department of Anhui Province,China(No. KJ2011B021)
文摘New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was examined.For K+ ion transfer,preserving phenolic hydroxyl in the lower rim of calix[4]arene could enhance its transport ability.When benzoyl replaced phenolic hydroxyl,the transport would fall off,because benzoyl caused steric hindrance on the K+ transfer.The study also revealed that the group having the electron-withdrawing conjugative effect on phenolic hydroxyl,-NO2 in the upper rim of calix[4]arene,made transport ability of calix[4]arene fall off.On the contrary,-NH2 that had electron-repulsive conjugative effect enhanced the transport ability of the compound.For Hg2+ ion,only -NH2 in the upper rim of calix[4]arenes had high affinity for it and contributed to Hg2+ transfer.Transport amount of Hg2+ ion increased with increasing calix[4]arene5 concentration and ΔpH in BLM.
文摘Calix resorcinarenes bearing four hydrophobic side chains ( Ar-Rn, Ar-Ph, and Ar-N) orient stably on water oil interface and show high solubilization capacities for organic compounds, such as long chain alcohols, benzene, toluene and dyes. The capacities are high even near the cmc of polyalkylated calix resorcinarenes, but the solubilities of organic compounds(solubilizates) decrease with the increase of the size of the solubilizates. Ar-R 6, with a chain length of six carbons, is the most effective among Ar-R n , Ar-Ph, and Ar-N; 11 fold mol of hexanol is dissolved in 2×10 -3 mol/L Ar-R 6. Moreover, Ar-R n bearing four alkyl side chains solubilizes the chain alcohols of the same chain length mostly. The solubilization capacities are presumably brought by inclusion in a large cavity of the polyalkylated calix resorcinarenes and by an efficient orientation of the solubilizates.
文摘A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described. The compound is an useful intermediates for the introduction of other functional groups to obtain N containing substituted calix[4]arene. The reaction mechanism is briefly discussed.
文摘This letter reports the synthesis of Schiff base calix[4]arene crowns containing m-xylylene phenol subunit, in which calix[4]arene Schiff base crowns 2a, 2b and 2c were formed by 1:1 condensation of calix[4]arene diamine 1 with dialdehydes (2, 6-diformyl-4-chlorophenol 3a, 2, 6-diformyl-4-methylphenol 3b, 2, 6-diformyl-4-tert-butylphenol 3c) under high dilute condition in refluxing anhydrous ethanol in 65-70% yield.
基金Natural Science Foundation of Education Department of Anhui Province,China(No.KJ2013B028)Textile Science and Technology Key Discipline in Anhui Polytechnic University,China
文摘Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg^(2+)and Pb^(2+),calix[4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg^(2+)and Pb^(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix[4]arene improved the extraction ability on Hg^(2+)by promoting the formation of the negative oxygen ions that could bind with Hg^(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix[4]arene(calix[4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb^(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb^(2+)with higher charge-to-radius ratio than Hg^(2+)was coordinated and extracted by the calix[4]arene thia derivative more easily.Furthermore,extraction rates of the calix[4]arene thia derivative on both ions(Hg^(2+)and Pb^(2+))increased with the increase of pH value in acidic aqueous system(pH<7).
基金Supported by the National Natural Science Foundation of China(No.20402002) the Natural Science Foundation of FujianProvince(No. E0020002).
文摘Calixarenes are excellent scaffolds that can De modified by introducing various functional groups to create specific interactions between the host and guest molecules. Thus, many calixarene derivatives containing special functional groups, such as ester, amide and thiourea, have been synthesized and their excellent complexing capability for cations have also been studled. Lately, calixarene derivatives containing two or more sorts of functional groups have attracted much attention.
基金supported by the National Natural Science Foundation of China(No.20802033)NaturalScience Foundation of Jiangxi Province(No.2007GZC1552)Scientific Research Foundation of NanchangHangkong University(No.EA200802012).
文摘A novel fluorescent ionophore derived from calix[4]arene and pyrazoline was designed and synthesized.Its molecular structure was confirmed by ^1H NMR and element analysis.The resulting material shows specific fluorescent behavior toward the Zn^2+ion among the other divalent metal ions,such as Co^2+,Ni^2+,Cu^2+.The primary results indicate this ionophore material is a potential material for developing efficient fluorescent Zn^2+ chemosensors.
基金Supported by the Fund of State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemi-stry, Chinese Academy of Sciences(No.RERU2011006)
文摘An adsorbent calix[4]arene carboxylic acid was employed as the adsorption material for on-line flow in jection(FI) micro-column preconcentration coupled with flame atomic absorption spectrometry(FAAS) determination of trace heavy metals(Cu, Pb, Co, Ni and Cd). Parameters such as the pH, loading time and flow rate of sample, and the concentration, volume and flow rate of eluent were optimized. The enrichment factors are 50.0, 56.5, 11.6, 12.1 and 19.1 for Cu, Pb, Co, Ni, and Cd, respectively, and a sample throughput of 20 h–1 was obtained. The limits of de tection for Cu, Pb, Co, Ni, and Cd were in a range of 1.56―3.91 μg/L, and the relative standard deviations(RSDs) were less than 2.76%(n=7). Furthermore, the proposed method was successfully applied to the determination of Cu, Pb, Co, Ni, and Cd in certified reference materials and various water samples.
基金supported by the National Natural Science Foundation of China(No.21102003)National Students'Innovation and Entrepreneurship Training Program(No.201210361094)Scientific Research Foundation for the Introduction of Talent and Young Teachers Scientific Research Foundation of Anhui University of Science&Technology(11214,2012QNY27)
文摘The title compound (C50H.44010) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a = 16.713(4), b --- 13.189(3), c = 19.434(5) A, β = 104.411(4)°, Mr = 804.85, Dc = 1.288 g/cm3, V = 4149.2(17) A3, Z = 4, F(000) = 1696, #(MoKa) = 0.089 mm-1T = 296(2) K, 7279 independent reflections with 3172 observed ones (I 〉 2δ(/)), R = 0.0520 and wR = 0.1203 with GOF = 0.928 (R = 0.1464 and wR = 0.1657 for all data). The calixarene moiety maintains the symmetric cone conformation through intramolecular O-H…O hydrogen bonds. Preliminary bioassays indicated that the title compound has a potent inhibitory activity against the strand transfer process of HIV-1 integrase.
基金supported by the 973 program (2006CB932900)NNSFC (Nos. 20572048 and 20421202)NSF of Tianjin (07QTPTJC29700)
文摘X-ray crystal structures of the inclusion complexes of calix[4]arene monomethoxycarboxylic acid 1 (C30H2606) with acetontrile and acetone are reported. The crystal of C30H26O6·CH3CN is of monoclinic, space group P2 1/c with a = 11.691(5), b = 13.753(5), c = 17.072(7)A, β = 100.104(7)°, C32H29NO6, Mr = 523.56, V = 2702.4(18)A^3, Z = 4, De= 1.287 g/cm^3, μ(MoKα) = 0.089 mm^-1, T = 293(2) K, 5570 independent reflections with 3220 observed ones (1 〉 2σ(I)), R = 0.0521 and wR = 0.1132 with GOF = 1.042 (R = 0.1055 and wR = 0.1350 for all data). The data for C30H26O6·CH3COCH3: monoclinic, space group P2 1/c, α = 12.366(4), b = 12.119(4), c = 18.796(6) A, β = 90.871(6)°, C33H32O7, Mr = 540.59, V = 2816.6(16)A^3, Z = 4, Dc = 1.275 g/cm^3, μ(MoKα) = 0.089 mm^-1, T = 293(2) K, 5783 independent reflections including 2580 observed ones (I 〉 2σ(I)), R = 0.0555 and wR = 0.1424 with GOF= 0.975 (R = 0.1601 and wR = 0.1884 for all data). Their architectures exhibit one-dimensional inclusion polymers which are mediated head-to-tail by the guests.
文摘Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in calix[4]arene on the catalytic activity was first investigated.
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This work was supported by the National Natural Science Foundation of China,Natural Science Foundation of Fujian Province,and the Young Scientist Funds of Fujian Province (No. 2006F3130)
文摘Two novel polymeric complexes, [Gd(HsTCAS)(H2O)7]·4H2O 1 and [Gd(HsTCAS) (CH3COCH3)(H2O)6]·6H2O 2 (H4TCAS = p-sulfonatothiacalix[4]arene), have been synthesized and characterized by single-crystal X-ray diffraction analyses. Complex 1 crystallizes in monoclinic, space group C2/m with a = 20.2308(12), b = 19.0894(10), c = 12.2448(7)A, β = 101.847(3)°, V = 4628.1(5)A^3, C24H43GdO27S8, Mr = 1169.25, Z = 4, Dc = 1.690 g/cm^3, F(000) = 2380,μ = 1.879 mm^-1, the final R = 0.0404 and wR = 0.1038 for 5127 observed reflections with I 〉 2σ(I). Complex 2 is pseudo-isostructural with complex 1.