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Papers by Alessandro Casnati
Solvent Extraction and Ion Exchange, Dec 26, 2017
Proceedings of the National Academy of Sciences of the United States of America, Apr 16, 2002
Journal of Organic Chemistry, Feb 23, 2022
Inorganic Chemistry, Feb 2, 2017
J. Chem. Soc., Perkin Trans. 2, 1996
Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2001
Cesium possesses two long lived isotopes 135Cs and 137Cs and the first one has a very long (2.3 ×... more Cesium possesses two long lived isotopes 135Cs and 137Cs and the first one has a very long (2.3 × 106 y) half life and is one of the most mobile nuclides in a repository.Calix[4]arene-crowns-6 in the 1,3-alternate conformation areemerging as a new class of ionophores exhibiting a very high efficiency and selectivity in the complexation of cesium ion and itsremoval
Tetrahedron Letters, 1997
... Giuseppe Arena,* Alessandro Casnati, Annalinda Contino,t Domenico Sciotto** and Rocco Ungarot... more ... Giuseppe Arena,* Alessandro Casnati, Annalinda Contino,t Domenico Sciotto** and Rocco Ungarot * Dipartimento di Scienze Chimiche, Universit di Catania, Viale ... Casnati, A.; Ting, Y.; Berti, D.; Fabbi, M.; Poehini, A.; Ungaro, R.; Sciotto, D.; Lombardo, GG Tetrahedron, 1993, 49 ...
Tetrahedron, 2004
The reaction of O-alkylated p-aminocalix[n]arenes (n=4, 6, 8) with N,N′-di(tert-butoxycarbonyl )t... more The reaction of O-alkylated p-aminocalix[n]arenes (n=4, 6, 8) with N,N′-di(tert-butoxycarbonyl )thiourea in the presence of HgCl 2 and subsequent removal of the protective groups with hydrochloric acid led to the new water soluble calix[n]guanidinium derivatives (p-guanidiniumcalix[n] ...
Supramolecular Chemistry, 2002
Two novel cone calix[4]arene ligands 11a and 11b bearing two iminodiacetic chelating units and tw... more Two novel cone calix[4]arene ligands 11a and 11b bearing two iminodiacetic chelating units and two C 6 or C 5 substituted 2,2'-bipyridine chromophores in diametral position at the lower rim were synthesized. These ligands form complexes with lanthanide ions in methanol solution whose stability (4.5<log K ass <6.2) depends on the substitution pattern (C 6 or C 5 ) of
Org. Biomol. Chem., 2003
The thiourea group has been exploited to link two or four carbohydrate units at the upper rim of ... more The thiourea group has been exploited to link two or four carbohydrate units at the upper rim of tetrapropoxycalix[4]arene derivatives in the cone conformation. Two synthetic methodologies were used, the first one consisting of the condensation of di- and tetraminocalix[4]arenes with the isothiocyanate of monosaccharides in dry CH2Cl2 at room temperature and the second one exploiting the condensation of an aminolactoside with a calixarene isothiocyanate. The first method allows the glycoconjugates to be obtained in 75-80% overall yields. The disfunctionalized derivatives exist in a closed flattened cone conformation in CDCl3 and CD3OD due to the formation of intramolecular hydrogen bonds involving the thiourea groups which are broken in DMSO-d6 to give an open flattened cone conformation. The thiourea groups act not only as linkers but also as binding units for anionic substrates as evidenced by solution 1H NMR and ESI-MS experiments. Turbidimetric analysis indicates that the tetraglucoside and tetragalactoside clusters give specific interactions with Concanavalin A (Con A) and peanut lectin (PNA), respectively. Both features show that the neoglycoconjugates could also be used as site specific molecular delivery systems.
Journal of the American Chemical Society, 2001
Three novel lower rim hexamide derivatives 5(6), 7(6), and 9(6) of p-hydroxycalix[6]arene and fou... more Three novel lower rim hexamide derivatives 5(6), 7(6), and 9(6) of p-hydroxycalix[6]arene and four octamides 5(8), 7(8)-9(8) derived from the corresponding p-hydroxycalix[8]arene were synthesized, and their potential as extractants in radioactive waste treatment was evaluated, in comparison with upper rim analogues 12(6) and 12(8) and other existing selective neutral ionophores currently used in radioactive waste treatment. Extraction of alkali and alkaline earth metal picrates from water to dichloromethane, and of the corresponding nitrates from acidic water solution simulating radioactive waste, to 2-nitrophenyl hexyl ether (NPHE), showed that the lower rim amides extract divalent cations much better than monovalent ones. The upper rim hexa-12(6) and octamide 12(8) are very inefficient ligands, hardly extracting any cation. In all cases, p-alkoxy octamides are more efficient and selective extractants than the corresponding hexamides. In the case of simulated waste solutions, the distribution coefficients for strontium removal by octamides (6.5 < D(Sr) < 30) are much higher than the corresponding value (D(Sr)) found for dicyclohexyl-18-crown-6 (DC18C6), and the same applies for the strontium/sodium selectivity, which is 6500 < D(Sr)/D(Na) < 30 000 for octamides and 47 for DC18C6. ESI-MS, UV-vis, and X-ray crystal structure studies give consistent results and indicate the formation of 2:1 (cation/ligand) strontium complexes for all octamides tested. Stability constants were determined in homogeneous methanol solution for alkali metal (log beta(11) < or = 2), calcium (4.3 < or = log beta(11) < or = 6.0; 9.4 < or = log beta(21) < or = 12.0), and strontium (5.6 < or = log beta(11) < or = 12.3) ions using a UV-vis competition method with 1-(2-pyridylazo)-2-naphthol (PAN). They confirm the high efficiency and high divalent/monovalent selectivity found in metal ion extraction experiments for the new octamide ligands. Evidence for a positive cooperative effect between the two metal ion binding sites was obtained in the case of the Ca(2+) complex of octamide 1(8).
Journal of the American Chemical Society, 1994
The Journal of Organic Chemistry, 1995
Inorganica Chimica Acta, 2007
Inorganica Chimica Acta, 1996
Several new calix [4] arene-crowns have been synthesized and their complexation of the Eu3+ and T... more Several new calix [4] arene-crowns have been synthesized and their complexation of the Eu3+ and Tb3+ ions has been studied in order to obtain compounds exhibiting metal luminescence. Whereas ligands 3 and 5 gave no indication of complex formation with ...
European Journal of Organic Chemistry, 2003
The 8‐alkoxy‐5‐chloroquinoline fluorophore was appended at the lower rim of a calix[4]arene triam... more The 8‐alkoxy‐5‐chloroquinoline fluorophore was appended at the lower rim of a calix[4]arene triamide with two different orientations. In ligand 1 the quinoline part is linked to the calixarene skeleton through the pyridine C2 atom, while in 2 it is linked through the phenolic oxygen atom of the chromophore. The binding properties of both ligands, investigated in chloroform and methanol solutions, indicate that they are efficient fluoroionophores, with selectivity for sodium and strontium ions among alkali and alkaline earth metal ions. Combined NMR, photophysical, and modeling studies disclosed the peculiar conformational and coordination features of monovalent and divalent metal ion complexes. Lanthanide metal ion complexes were prepared and studied in acetonitrile solution showing good luminescence in the case of Nd3+, Yb3+, and Er3+ ions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Solvent Extraction and Ion Exchange, Dec 26, 2017
Proceedings of the National Academy of Sciences of the United States of America, Apr 16, 2002
Journal of Organic Chemistry, Feb 23, 2022
Inorganic Chemistry, Feb 2, 2017
J. Chem. Soc., Perkin Trans. 2, 1996
Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2001
Cesium possesses two long lived isotopes 135Cs and 137Cs and the first one has a very long (2.3 ×... more Cesium possesses two long lived isotopes 135Cs and 137Cs and the first one has a very long (2.3 × 106 y) half life and is one of the most mobile nuclides in a repository.Calix[4]arene-crowns-6 in the 1,3-alternate conformation areemerging as a new class of ionophores exhibiting a very high efficiency and selectivity in the complexation of cesium ion and itsremoval
Tetrahedron Letters, 1997
... Giuseppe Arena,* Alessandro Casnati, Annalinda Contino,t Domenico Sciotto** and Rocco Ungarot... more ... Giuseppe Arena,* Alessandro Casnati, Annalinda Contino,t Domenico Sciotto** and Rocco Ungarot * Dipartimento di Scienze Chimiche, Universit di Catania, Viale ... Casnati, A.; Ting, Y.; Berti, D.; Fabbi, M.; Poehini, A.; Ungaro, R.; Sciotto, D.; Lombardo, GG Tetrahedron, 1993, 49 ...
Tetrahedron, 2004
The reaction of O-alkylated p-aminocalix[n]arenes (n=4, 6, 8) with N,N′-di(tert-butoxycarbonyl )t... more The reaction of O-alkylated p-aminocalix[n]arenes (n=4, 6, 8) with N,N′-di(tert-butoxycarbonyl )thiourea in the presence of HgCl 2 and subsequent removal of the protective groups with hydrochloric acid led to the new water soluble calix[n]guanidinium derivatives (p-guanidiniumcalix[n] ...
Supramolecular Chemistry, 2002
Two novel cone calix[4]arene ligands 11a and 11b bearing two iminodiacetic chelating units and tw... more Two novel cone calix[4]arene ligands 11a and 11b bearing two iminodiacetic chelating units and two C 6 or C 5 substituted 2,2&amp;amp;amp;#39;-bipyridine chromophores in diametral position at the lower rim were synthesized. These ligands form complexes with lanthanide ions in methanol solution whose stability (4.5&amp;amp;amp;amp;lt;log K ass &amp;amp;amp;amp;lt;6.2) depends on the substitution pattern (C 6 or C 5 ) of
Org. Biomol. Chem., 2003
The thiourea group has been exploited to link two or four carbohydrate units at the upper rim of ... more The thiourea group has been exploited to link two or four carbohydrate units at the upper rim of tetrapropoxycalix[4]arene derivatives in the cone conformation. Two synthetic methodologies were used, the first one consisting of the condensation of di- and tetraminocalix[4]arenes with the isothiocyanate of monosaccharides in dry CH2Cl2 at room temperature and the second one exploiting the condensation of an aminolactoside with a calixarene isothiocyanate. The first method allows the glycoconjugates to be obtained in 75-80% overall yields. The disfunctionalized derivatives exist in a closed flattened cone conformation in CDCl3 and CD3OD due to the formation of intramolecular hydrogen bonds involving the thiourea groups which are broken in DMSO-d6 to give an open flattened cone conformation. The thiourea groups act not only as linkers but also as binding units for anionic substrates as evidenced by solution 1H NMR and ESI-MS experiments. Turbidimetric analysis indicates that the tetraglucoside and tetragalactoside clusters give specific interactions with Concanavalin A (Con A) and peanut lectin (PNA), respectively. Both features show that the neoglycoconjugates could also be used as site specific molecular delivery systems.
Journal of the American Chemical Society, 2001
Three novel lower rim hexamide derivatives 5(6), 7(6), and 9(6) of p-hydroxycalix[6]arene and fou... more Three novel lower rim hexamide derivatives 5(6), 7(6), and 9(6) of p-hydroxycalix[6]arene and four octamides 5(8), 7(8)-9(8) derived from the corresponding p-hydroxycalix[8]arene were synthesized, and their potential as extractants in radioactive waste treatment was evaluated, in comparison with upper rim analogues 12(6) and 12(8) and other existing selective neutral ionophores currently used in radioactive waste treatment. Extraction of alkali and alkaline earth metal picrates from water to dichloromethane, and of the corresponding nitrates from acidic water solution simulating radioactive waste, to 2-nitrophenyl hexyl ether (NPHE), showed that the lower rim amides extract divalent cations much better than monovalent ones. The upper rim hexa-12(6) and octamide 12(8) are very inefficient ligands, hardly extracting any cation. In all cases, p-alkoxy octamides are more efficient and selective extractants than the corresponding hexamides. In the case of simulated waste solutions, the distribution coefficients for strontium removal by octamides (6.5 < D(Sr) < 30) are much higher than the corresponding value (D(Sr)) found for dicyclohexyl-18-crown-6 (DC18C6), and the same applies for the strontium/sodium selectivity, which is 6500 < D(Sr)/D(Na) < 30 000 for octamides and 47 for DC18C6. ESI-MS, UV-vis, and X-ray crystal structure studies give consistent results and indicate the formation of 2:1 (cation/ligand) strontium complexes for all octamides tested. Stability constants were determined in homogeneous methanol solution for alkali metal (log beta(11) < or = 2), calcium (4.3 < or = log beta(11) < or = 6.0; 9.4 < or = log beta(21) < or = 12.0), and strontium (5.6 < or = log beta(11) < or = 12.3) ions using a UV-vis competition method with 1-(2-pyridylazo)-2-naphthol (PAN). They confirm the high efficiency and high divalent/monovalent selectivity found in metal ion extraction experiments for the new octamide ligands. Evidence for a positive cooperative effect between the two metal ion binding sites was obtained in the case of the Ca(2+) complex of octamide 1(8).
Journal of the American Chemical Society, 1994
The Journal of Organic Chemistry, 1995
Inorganica Chimica Acta, 2007
Inorganica Chimica Acta, 1996
Several new calix [4] arene-crowns have been synthesized and their complexation of the Eu3+ and T... more Several new calix [4] arene-crowns have been synthesized and their complexation of the Eu3+ and Tb3+ ions has been studied in order to obtain compounds exhibiting metal luminescence. Whereas ligands 3 and 5 gave no indication of complex formation with ...
European Journal of Organic Chemistry, 2003
The 8‐alkoxy‐5‐chloroquinoline fluorophore was appended at the lower rim of a calix[4]arene triam... more The 8‐alkoxy‐5‐chloroquinoline fluorophore was appended at the lower rim of a calix[4]arene triamide with two different orientations. In ligand 1 the quinoline part is linked to the calixarene skeleton through the pyridine C2 atom, while in 2 it is linked through the phenolic oxygen atom of the chromophore. The binding properties of both ligands, investigated in chloroform and methanol solutions, indicate that they are efficient fluoroionophores, with selectivity for sodium and strontium ions among alkali and alkaline earth metal ions. Combined NMR, photophysical, and modeling studies disclosed the peculiar conformational and coordination features of monovalent and divalent metal ion complexes. Lanthanide metal ion complexes were prepared and studied in acetonitrile solution showing good luminescence in the case of Nd3+, Yb3+, and Er3+ ions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)