Browsing by Author "Kovalev, Vladimir"

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Anthryl-1,2,4-oxadiazole-Substituted Calix[4]arenes as Highly Selective Fluorescent Chemodosimeters for Fe3+
(2015-04-01)
Chen, Ying-Jung
;
Yang, Shun-Chieh
;
Tsai, Chia-Chen
;
Chang, Kai-Chi
;
Chuang, Wen-Han
Fluorescent chemosensors 1 and 2, with 1,2,4-oxadiazoles as the binding ligands and anthracene as the fluorophore, were synthesized through sequential 1,3-dipolar cycloaddition reactions of 25,27-dioxyacetonitrilecalix[4]arenes 8 and 11. The fluorescence of 1 was severely quenched by both Fe3+ and Cu2+, whereas that of 2 was selectively quenched only by Fe3+. Control compound 4 was also selectively quenched by Fe3+, which implied the importance of anthryl-1,2,4-oxadiazole core; furthermore, it was shown to give various oxidation products such as oxanthrone 13, anthraquinone 14, and imidazolyl oxanthrone 15. In addition to product separation and identification, the fluorescent quenching mechanism of these 9-anthryl-1,2,4-oxadiazolyl derivatives by Fe3+ is also discussed. Furthermore, it should be noted that the oxadiazole-substituted anthracene 4 and calix[4]arene 2 are Fe3+-selective fluorescent chemodosimeters without the interference by Cu2+.
Constructing bridged multifunctional calixarenes by intramolecular indole coupling
(2019-10-07)
Bolshchikov, Boris
;
Volkov, Sergey
;
Sokolova, Dania
;
Gorbunov, Alexander
;
Serebryannikova, Alina
2,2 '-Bisindole units are suggested as new bridging motifs which can be easily created at calixarene cores. In TFA solutions, calix[4]arenes having pairs of indole groups originating from tryptamine or tryptophan residues are converted selectively into macrocycles bridged by indolylindoline moieties. The latter are easily transformed into fluorescent 2,2 '-bisindole bridges upon oxidation. The coupling/oxidation sequence works fine at bridging the cavities of the cone and 1,3-alternate (thia)calix[4]arenes in their distal positions. Ester groups, triazole units and crown ether loops, which are practically important functionalities in calixarene chemistry, are compatible with the bridging strategy thus making available diverse calixarene-based hosts comprising novel features provided by the 2,2 '-bisindole bridges. Of them the abilities to self-assembly and to bind anions through multiple hydrogen bonds were observed by X-ray crystallography, fluorescence measurements, and NMR experiments. When combined with a cation-binding site, the 2,2 '-bisindole units can turn the calixarene molecules into heteroditopic receptors being able to stabilize the anionic parts of the ion pairs. This feature was assessed by using the 1,3-alternate calix[4]arene having the 2,2 '-bisindole bridge and the crown-5-ether loop which was found to form neutral complexes with potassium acetate or potassium benzoate.