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Femtosecond to Second Studies of a Water-Soluble Porphyrin Derivative in Chemical and Biological Nanocavities
journal contribution
posted on 2012-03-06, 00:00 authored by Yilun Wang, Boiko Cohen, Laszlo Jicsinszky, Abderrazzak DouhalThe interactions of 5,10,15,20-tetrakis(4-sulfonatophenyl)-porphyrin
(TSPP) with a quaternary ammonium modified β-cyclodextrin (QA-β-CD)
and human serum albumin (HSA) protein in aqueous solutions at pH 7
were studied using steady-state, stopped-flow, and femtosecond to
millisecond spectroscopy. TSPP forms 1:1 and 1:2 complexes with QA-β-CD
(K1 = 1.9 × 105 M–1 and K2 = 7 × 103 M–1) at 293 K, whereas with the HSA protein
only 1:1 complex (K1 = 1.7 × 106 M–1) has been found. The chemical and biological
nanocavities have notable effects on the fluorescence lifetimes of
the Qx state (from 9.3
to 11.1 ns in QA-β-CD and 11.6 ns in HSA). Furthermore, the
rotational times (400 ps for the free TSPP, 1.6 and 19 ns for QA-β-CD
and HSA protein complexes, respectively) clearly indicate the robustness
of the formed entities. The confined environment does not affect much
the fs dynamics (0.1–0.2 ps) of the encapsulated molecule.
However, it clearly affect the ps one (1–2 ps (H2O) and 5–10 ps (QA-β-CD and HSA)). The effect of O2 on the relaxation of the triplet state of the free and encapsulated
TSPP is also studied and the obtained results are discussed in light
of the shielding effect provided by the chemical and biological cavities.
The observed difference, longer triplet lifetime upon encapsulation,
might be relevant to the efficiency of this porphyrin in photodynamic
therapy. The presteady-state kinetics of the TSPP:HSA has been studied
by the stopped-flow spectrometer, and a two-step model was proposed
for the complexation processes. The results show the importance of
the initial association step for the overall ligand recognition process.
This first step occurs with rate constant of ∼4 × 105 M–1 s–1, which is about
5 orders of magnitude larger than the rate constant of the consecutive
relaxation processes. We believe that our observations of molecular
interaction between TSPP, QA-β-CD, and HSA protein from femtosecond
to second at both ground and electronically first excited state give
detailed information to improve our understanding of this kind of
system and thus for a better design of drug delivery nanocarriers.