Thermodynamics of Calixarene-Ion Interactions

Namor, Angela F. Danil de

doi:10.1007/0-306-47522-7_19

Cited by 21 publications

(44 citation statements)

References 36 publications

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“…The p-tert-butyl-calix [4]arene, 18-crown-6, potassium carbonate (K 2 CO 3 ) and 2-chloro-N,Ndiethylacetamide were purchased from Aldrich and were used without further purification.…”

Section: Experimental Section Chemicalsmentioning

confidence: 99%

“…Metal cation salts as perchlorates, LiClO 4 .H 2 O, NaClO 4 4 NClO 4 (Aldrich) were dried over P 4 O 10 under vacuum for several days before use. The absence of a water signal on the NMR spectra upon the addition of metal cation salts indicated the removal of water from these salts.…”

Section: Experimental Section Chemicalsmentioning

confidence: 99%

“…p-tert-Butyl calix [4]arene (5 g), 18-crown-6 (0.53 g), potassium carbonate (10.66 g) and MeCN (250 ml) were mixed in a 500 ml three-necked-round bottom flask equipped with a condenser. 34 The mixture was stirred for one hour under a nitrogen atmosphere.…”

Section: Synthesis Of 5111723-p-tert-butyl-25262728-tetradiethymentioning

confidence: 99%

“…An ion pair receptor is that with the capability of complexing the cation and the anion by offering different active sites. A representative example for a calix [4]pyrrole amide derivative is shown in Figure 2 where the pyrrole NH proton interacts with the anion while the amide functionalities interact with the cation, ii) The behaviour of the ligand in solution. Hardly any attempts have been made to establish it.…”

Section: Selection Of the Solventmentioning

confidence: 99%

“…Unlike calix[n]arene esters 13−26 and to some extent calix[n]arene ketones, 27−29 no detailed thermodynamics have been reported on calix[n]arene tertiary amide derivatives and ionic species (by detailed thermodynamics the authors refer to processes in which the speciation in solution, the solution thermodynamics for reactants and product and the composition of the complex are investigated and the scope and limitations of the methodology used are considered in the determination of stability constants and enthalpies of complexation as discussed below). Recently a detailed study on the interactions of a lower rim calix [4]arene containing secondary amide functionalities with alkali-metal cations involving thermodynamic, structural and computational studies has been reported. 30 Even though the receptor does not involve a tertiary amide it is worth mentioning this paper given that an integrated approach has been taken for complexation studies.…”

Section: Introductionmentioning

confidence: 99%

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An Enchiridion of Supramolecular Thermodynamics: Calix[N]arene (N=4,5,6) Tertiary Amide Derivatives and their Ionic Recognition

Namor¹,

Matsufuji-Yasuda²,

Zegarra-Fernandez³

et al. 2013

Croat. Chem. Acta

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Abstract. The importance of detailed thermodynamic studies in assessing the selective behaviour of macrocyclic receptors for one species relative to another in a given solvent and the medium effect on complexation processes involving ionic species are emphasised. Factors to be considered in the determination of thermodynamic parameters of complexation in non-aqueous solvents are highlighted. Particular reference is made to the need for considering the bulk of information available in the literature on the solution properties of electrolytes in non-aqueous medium in the selection of the solvent for ion complexation processes involving macrocycles.A detailed thermodynamic study on the interaction of p-tert-butyl calix[n]arene (n = 4−6) tertiary amide derivatives with uni-and bivalent cations in protic (methanol) and dipolar aprotic (acetonitrile) media is reported. It is demonstrated that as the number of phenyl units in the macrocycle increases, the vital feature of the cyclic tetramer receptor for selective recognition of cations decreases significantly for the cyclic pentamer and almost disappears for the hexamer. Concluding remarks are included. (doi: 10.5562/cca2170)

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“…The p-tert-butyl-calix [4]arene, 18-crown-6, potassium carbonate (K 2 CO 3 ) and 2-chloro-N,Ndiethylacetamide were purchased from Aldrich and were used without further purification.…”

Section: Experimental Section Chemicalsmentioning

confidence: 99%

Section: Experimental Section Chemicalsmentioning

confidence: 99%

Section: Synthesis Of 5111723-p-tert-butyl-25262728-tetradiethymentioning

confidence: 99%

Section: Selection Of the Solventmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

An Enchiridion of Supramolecular Thermodynamics: Calix[N]arene (N=4,5,6) Tertiary Amide Derivatives and their Ionic Recognition

Namor¹,

Matsufuji-Yasuda²,

Zegarra-Fernandez³

et al. 2013

Croat. Chem. Acta

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Viscosity Formation Mechanism and Viscosity Reduction Strategy for Ammoniated Slurry of Nitrophosphate Fertilizer

Yin

Tang

Zhang

et al. 2023

Ind. Eng. Chem. Res.

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Wet-process phosphoric acid (WPA) preparation by the nitric acid method (WPA-HNO 3 ) is a green technology with broad development prospects. However, in the process of preparing nitrophosphate fertilizer (NP) by WPA-HNO 3 ammonification, the NP ammoniated slurry has high viscosity and poor fluidity, resulting in the shutdown of the production process. There is an urgent problem in NP production to study the formation mechanism of the high viscosity slurry and provide effective guidance for reducing the viscosity. In this paper, based on the composition of actual WPA-HNO 3 in NP production, the equilibrium species variation with pH in the ammoniated slurry was simulated by using HSC software. The viscosity and composition of the NP slurry and the hygroscopicity and microtopography of the solid products were analyzed. The mechanism of viscosity formation and the strategy of viscosity reduction were proposed. The results showed that the micron-scale CaHPO 4 formed in the NP slurry provided nucleation sites for the crystallization of the soluble ammonium salt, which promoted the precipitation of unsaturated NH 4 NO 3 and NH 4 H 2 PO 4 in large quantities. The strong hygroscopic NH 4 NO 3 solid reduced the free water content in the slurry. In addition, the NH 4 NO 3 underwent crystalline transformation with the increase in the pH, and the specific surface area of the solid was increased. The coated CaHPO 4 particles were stripped from the ammonium salt and hydrated to form CaHPO 4 •2H 2 O. The slurry viscosity increased sharply with the increase in the solid content and the decrease in free water. The large amount of Ca 2+ in WPA-HNO 3 was the inducible factor for the formation of the high viscosity slurry. By adding 2.5% (wt) sodium hexametaphosphate as the Ca 2+ complexing agent in WPA-HNO 3 to avoid the formation of micron-sized CaHPO 4 , the maximum viscosity of the slurry decreased from 1361.00 ± 128.47 mPa• s to 351.24 ± 15.87 mPa•s.

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Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative

et al. 2017

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The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

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Thermodynamics of Calixarene-Ion Interactions

Abstract: General information on calixarenes is readily obtained [2-5] and only structures of derivatives directly discussed are given here. (See Chart 1) Chart 1. Narrow rim functionalised calix[4]arenes.

Cited by 21 publications

References 36 publications

An Enchiridion of Supramolecular Thermodynamics: Calix[N]arene (N=4,5,6) Tertiary Amide Derivatives and their Ionic Recognition

An Enchiridion of Supramolecular Thermodynamics: Calix[N]arene (N=4,5,6) Tertiary Amide Derivatives and their Ionic Recognition

Viscosity Formation Mechanism and Viscosity Reduction Strategy for Ammoniated Slurry of Nitrophosphate Fertilizer

Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative

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