Porphyrin and Tetrabenzoporphyrin Dendrimers: Tunable Membrane-Impermeable Fluorescent pH Nanosensors

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Porphyrin and Tetrabenzoporphyrin Dendrimers: Tunable Membrane-Impermeable Fluorescent pH Nanosensors. / Finikova, Olga; Galkin, Alexander; Rozhkov, Vladimir; Cordero, Maria; Hägerhäll, Cecilia; Vinogradov, Sergei.

I: Journal of the American Chemical Society, Vol. 125, Nr. 16, 2003, s. 4882-4893.

Forskningsoutput: TidskriftsbidragÖversiktsartikel

Harvard

Finikova, O, Galkin, A, Rozhkov, V, Cordero, M, Hägerhäll, C & Vinogradov, S 2003, 'Porphyrin and Tetrabenzoporphyrin Dendrimers: Tunable Membrane-Impermeable Fluorescent pH Nanosensors', Journal of the American Chemical Society, vol. 125, nr. 16, s. 4882-4893. https://doi.org/10.1021/ja0341687

APA

Finikova, O., Galkin, A., Rozhkov, V., Cordero, M., Hägerhäll, C., & Vinogradov, S. (2003). Porphyrin and Tetrabenzoporphyrin Dendrimers: Tunable Membrane-Impermeable Fluorescent pH Nanosensors. Journal of the American Chemical Society, 125(16), 4882-4893. https://doi.org/10.1021/ja0341687

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MLA

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Author

Finikova, Olga ; Galkin, Alexander ; Rozhkov, Vladimir ; Cordero, Maria ; Hägerhäll, Cecilia ; Vinogradov, Sergei. / Porphyrin and Tetrabenzoporphyrin Dendrimers: Tunable Membrane-Impermeable Fluorescent pH Nanosensors. I: Journal of the American Chemical Society. 2003 ; Vol. 125, Nr. 16. s. 4882-4893.

RIS

TY - JOUR

T1 - Porphyrin and Tetrabenzoporphyrin Dendrimers: Tunable Membrane-Impermeable Fluorescent pH Nanosensors

AU - Finikova, Olga

AU - Galkin, Alexander

AU - Rozhkov, Vladimir

AU - Cordero, Maria

AU - Hägerhäll, Cecilia

AU - Vinogradov, Sergei

PY - 2003

Y1 - 2003

N2 - The pH dependencies of the UV-vis and fluorescent spectra of new water-soluble dendritic porphyrins and tetrabenzoporphyrins were studied. Because of extended -conjugation and nonplanar distortion, the absorption and the emission bands of tetraaryltetrabenzoporphyrins (Ar4TBP) are red-shifted and do not overlap with those of regular tetraarylporphyrins (Ar4P). When encapsulated inside dendrimers with hydrophilic outer layers, Ar4Ps and Ar4TBPs become water soluble and can serve as pH indicators, with pK's adjustable by the peripheral charges on the dendrimers. Two new dendritic porphyrins, Gen 4 polyglutamic porphyrin dendrimer H2P-Glu4OH (1) with 64 peripheral carboxylates and Gen 1 poly(ester amide) Newkome-type tetrabenzoporphyrin dendrimer H2TBP-Nw1OH (2) with 36 peripheral carboxylates, were synthesized and characterized. The pK's of the encapsulated porphyrins (pKH2P-Glu4OH = 6.2 and pKH2TBP-Nw1OH = 6.3) were found to be strongly influenced by the dendrimers, revealing significant electrostatic shielding of the cores by the peripheral charges. The titration curves obtained by differential excitation using the mixtures of the dendrimers were shown to be identical to those determined for the dendrimers individually. Due to their peripheral carboxylates and nanometric molecular size, porphyrin dendrimers cannot penetrate through phospholipid membranes. Dendrimer 1 was captured inside phospholipid liposomes, which were suspended in a solution containing dendrimer 2. No response from 1 was detected upon pH changes in the bulk solution, while the response from 2 was predictably strong. When proton channels were created in the liposome walls, both compounds responded equally to the bulk pH changes. These results suggest that porphyrin dendrimers can be used as fluorescent pH indicators for proton gradient measurements.

AB - The pH dependencies of the UV-vis and fluorescent spectra of new water-soluble dendritic porphyrins and tetrabenzoporphyrins were studied. Because of extended -conjugation and nonplanar distortion, the absorption and the emission bands of tetraaryltetrabenzoporphyrins (Ar4TBP) are red-shifted and do not overlap with those of regular tetraarylporphyrins (Ar4P). When encapsulated inside dendrimers with hydrophilic outer layers, Ar4Ps and Ar4TBPs become water soluble and can serve as pH indicators, with pK's adjustable by the peripheral charges on the dendrimers. Two new dendritic porphyrins, Gen 4 polyglutamic porphyrin dendrimer H2P-Glu4OH (1) with 64 peripheral carboxylates and Gen 1 poly(ester amide) Newkome-type tetrabenzoporphyrin dendrimer H2TBP-Nw1OH (2) with 36 peripheral carboxylates, were synthesized and characterized. The pK's of the encapsulated porphyrins (pKH2P-Glu4OH = 6.2 and pKH2TBP-Nw1OH = 6.3) were found to be strongly influenced by the dendrimers, revealing significant electrostatic shielding of the cores by the peripheral charges. The titration curves obtained by differential excitation using the mixtures of the dendrimers were shown to be identical to those determined for the dendrimers individually. Due to their peripheral carboxylates and nanometric molecular size, porphyrin dendrimers cannot penetrate through phospholipid membranes. Dendrimer 1 was captured inside phospholipid liposomes, which were suspended in a solution containing dendrimer 2. No response from 1 was detected upon pH changes in the bulk solution, while the response from 2 was predictably strong. When proton channels were created in the liposome walls, both compounds responded equally to the bulk pH changes. These results suggest that porphyrin dendrimers can be used as fluorescent pH indicators for proton gradient measurements.

U2 - 10.1021/ja0341687

DO - 10.1021/ja0341687

M3 - Review article

VL - 125

SP - 4882

EP - 4893

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 1520-5126

IS - 16

ER -