Interactions of a water-soluble calix[4]arene with spermine: solution and solid-state characterisation. Issue 5 (2nd June 2016)

• Record Type: Journal Article
• Authors: D'Urso, Alessandro; Brancatelli, Giovanna; Hickey, Neal; Farnetti, Erica; De Zorzi, Rita; Bonaccorso, Carmela; Purrello, Roberto; Geremia, Silvano
• Is Part Of: Supramolecular chemistry. Volume 28:Issue 5/6(2016)
• Page Start: 499
• Page End: 505
• Publication Date: 2016-06-02
• Subjects: Spermine -- calixarene -- fluorescence titration -- X-ray crystallography -- supramolecular complexes; Macromolecules -- Periodicals; Supramolecular chemistry -- Periodicals; 547.005
• DOI: 10.1080/10610278.2015.1125900
• Languages: English
• ISSNs: 1061-0278

Abstract

Abstract: The octaanionic 5, 11, 17, 23-tetrasulfonato-25, 26, 27, 28-tetrakis(hydroxycarbonylmethoxy)-calix[4]arene (cone conformation) (C4 TsTc) was investigated as a sensor for the biogenic tetracationic polyamine, spermine. (H4 Spe 4+ ). Fluorescence titration experiments of the water-soluble calixarene with spermine showed the formation of the 2:1 and 1:1 calixarene:spermine complexes in solution. The single crystal X-ray diffraction analysis of [(NaC4 TsTc)4 ·(H4 Spe)7 ] confirmed the formation of 2:1 and 1:1 calixarene:spermine species and showed that the water-soluble calixarene binds the spermine either by partially hosting it in the inner cavity or through the carboxylate groups on the lower rim. In order to investigate the effect of multivalent systems, supramolecular assemblies of octaanionic calixarene molecules templated by meso -tetrakis(4- N -methylpyridyl)porphyrin (H2 T4 ) in different stoichiometric porphyrin:calixarene ratios (1:4 and 3:4) were also tested for spermine binding in solution. Fluorescence titration experiments with the 1:4 and 3:4 H2 T4 :C4 TsTc supramolecular complexes showed that the multivalent assemblies are more sensitive to the presence of spermine than the calixarene alone. Abstract :