Preparation and properties of a linked porphyrin–cyclodextrin

Abstract

. Can. J . Chem. 63, 602 (1985).The synthesis of the linked porphyrin-cyclodextrin 3 and its zinc complex 4 is described and their characterization by ' H nmr, ''C nmr, circular dichroism, ultraviolet, and infrared spectroscopy is reported. The linked porphyrin-cyclodextrin compounds exhibited perturbed electronic absorption and emission spectra which are consistent with their adopting two conformations, one extended with little interaction between the porphyrin and cyclodextrin, and the other folded with the cyclodextrin weakly complexed to the porphyrin. Quenching of the porphyrin excited state of 3 by benzoquinone was examined by measurement of the fluorescence lifetime as a function of quinone concentration; the results suggest that the porphyrin excited state can be quenched intermolecularly by benzoquinone and also intramolecularly by quinone complexed within the cyclodextrin cavity.MONICA C. GONZALEZ et ALAN C. WEEDON. Can. J. Chem. 63, 602 (1985).On dCcrit la synthkse du composC 3 (cyclodcxtrine-porphyrine liees) et de son complexe de zinc (4) ainsi que leur caractkrisation par les spectroscopies infrarouge, ultraviolette et rmn ' H et ' " ainsi que par leur dichroi'sme circulaire. Les composCs lies de cyclodextrine-porphyrine presentent des spectres d'absorption et d'kmission electronique qui sont perturb& et qui sont en accord avec le fait qu'ils adoptent deux conformations: une ktendue, dans laquelle il n'existe que peu d'interactions entre la cyclodextrine et la porphyrine, et une autre replike, dans laquelle la cyclodextrine est faiblement complexCe par la porphyrine. En mesurant le temps de vie de la fluorescence en fonction de la concentration de quinone, on a examine la reaction de p~tgeage, par la benzoquinone, de I'etat excite de la porphyrine presente dans 3; les resultats suggkrent que I'Ctat excite de la porphyrine peut &tre piCgC d'une facon intermoleculaire par la benzoquinone et aussi d'une facon intramolCculaire par de la quinone qui est complexee dans la cavitC de la cyclodextr~ne.[Traduit par le journal]

Probing the Interactions of Porphyrins with Macromolecules Using NMR Spectroscopy Techniques

“…Initial studies on phenyl-substituted porphyrin-CD inclusion complexes were inspired by mimicking photosynthetic reaction centers [ 170 ] or protein containing porphyrins such as hemoglobin, myoglobin or cytochromes where the CD cavity mimics the protein hydrophobic pockets to obtain water-soluble artificial analogues for mechanistic investigations [ 171 , 172 , 173 , 174 ]. Numerous studies have addressed the CD inclusion of meso -tetrakis (4-sulfonatophenyl) porphyrin (TPPS 4 ) and its metal complexes that exhibit aggregation in aqueous solutions [ 175 , 176 ].…”

Synthesis and reactions of meso-(p-nitrophenyl)porphyrins

“…Furthermore, nitro and amino groups can be easily functionalized, 11,13,14 and conjugated with bioactive molecules, such as monoclonal antibodies, 15 oligomeric carboranyl phosphate diesters, 16 polymer backbones, 17 and cyclodextrins. 18 Current synthetic routes to mono-, di-and tri-nitro functionalized meso-tetraphenylporphyrins involve total synthesis via a crossed Rothemund approach, 17 or by electrophilic nitration of the p-phenyl groups of mesotetraphenylporphyrin (TPP, 1). 19,20 In the first method co-condensation of pyrrole, benzaldehyde and nitrobenzaldehyde, results in low to moderate yields of the targeted porphyrins, which can be tedious to purify from the resulting reaction mixtures.…”

Synthesis of Water-Soluble Non-Aggregated Porphyrin-β-Cyclodextrin Tetraconjugate

“…[1][2][3][4][5][6][7][8][9][10][11][12]19,21] The several porphyrin derivatives covalently linked with cyclodextrins were synthesized and investigated. [2][3][4][6][7][8][9][10][11][12]20,[22][23][24][25][26][27][28][29][30][31][32][33][34] Most of these conjugates contain one or two cyclodextrin units on periphery of porphyrin macrocycle. In general, as evidenced from experimental data, the cyclodextrin containing porphyrins with one and two cyclodextrin fragments are formed supramolecular complexes due to deep inclusion of unsubstituted phenyl groups in the CD cavity.…”