2 research outputs found
Fluorescence Resonance Energy Transfer in Partially and Fully Labeled Pyrene Dendronized Porphyrins Studied with Model Free Analysis
A series of dendronized porphyrins
were synthesized and their photophysical
properties were determined by UVāvis absorption, steady-state
fluorescence, and time-resolved fluorescence. The constructs contained
a porphyrin core connected to a first generation FreĢchet-type
dendron (Py<sub>2</sub>G1) with or without a C<sub>4</sub>-butanoate
linker, and to a second generation dendron (Py<sub>4</sub>G2) with
a C<sub>4</sub>-linker. Pyrene and porphyrin were selected as donor
and acceptor, respectively, for fluorescence resonance energy transfer
or FRET. FRET occurred efficiently within the dendronized porphyrins
as determined from the extremely weak fluorescence of pyrene. The
number of pyrene groups present in the constructs was varied from
two to eight, but was found to have little effect on FRET as FRET
took place efficiently from an excited pyrene to a ground-state porphyrin.
The parameter that was found to affect FRET the most was the distance
separating pyrene from porphyrin within a construct. This effect was
probed successfully by fitting the pyrene and porphyrin fluorescence
decays according to the model free analysis (MFA) which yielded the
average rate constant āØ<i>k</i><sub>ET</sub>ā©
for FRET. āØ<i>k</i><sub>ET</sub>ā© increased
continuously with decreasing distance separating porphyrin and pyrene
as determined by conducting molecular mechanics optimizations on the
constructs. The āØ<i>k</i><sub>ET</sub>ā© values
were used to determine the through-space distance <i>d</i><sub>PorāPy</sub><sup>TS</sup> separating porphyrin from pyrene. <i>d</i><sub>PorāPy</sub><sup>TS</sup> was
found to scale as (<i>d</i><sub>PorāPy</sub><sup>EXT</sup>)<sup>0.5</sup>, where <i>d</i><sub>PorāPy</sub><sup>EXT</sup> represents the distance separating porphyrin and pyrene when the
construct adopts its most extended conformation. This relationship
suggests that FRET occurs intramolecularly inside the constructs between
pyrene and porphyrin where both dyes are linked by a string of freely
jointed Kuhn segments of length <i>l</i><sub>K</sub> = 9
Ć
Synthesis and Characterization of Novel Pyrene-Dendronized Porphyrins Exhibiting Efficient Fluorescence Resonance Energy Transfer: Optical and Photophysical Properties
A novel series of pyrene dendronized porphyrins bearing
two and
four pyrenyl groups (Py<sub>2</sub>-TMEG1 and Py<sub>4</sub>-TMEG2)
were successfully synthesized. First and second generation FreĢchet
type dendrons (Py<sub>2</sub>-G1OH and Py<sub>4</sub>-G2OH) were prepared
from 1-pyrenylbutanol and 3,5-dihydroxybenzyl alcohol. These compounds
were further linked to a trimesitylphenylporphyrin containing a butyric
acid spacer via an esterification reaction to obtain the desired products.
Dendrons and dendronized porphyrins were fully characterized by FTIR
and <sup>1</sup>H NMR spectroscopy and their molecular weights were
determined by matrix-assisted laser desorption ionization time of
flight mass spectrometry. Their optical and photophysical properties
were studied by absorption and fluorescence spectroscopies. The formation
of dynamic excimers was detected in the pyrene-labeled dendrons, with
more excimer being produced in the higher generation dendron. The
fluorescence spectra of the pyrene dendronized porphyrins exhibited
a significant decrease in the amount of pyrene monomer and excimer
emission, jointly with the appearance of a new emission band at 661
nm characteristic of porphyrin emission, an indication that fluorescence
resonance energy transfer (FRET) occurred from one of the excited
pyrene species to the porphyrin. The FRET efficiency was found to
be almost quantitative ranging between 97% and 99% depending on the
construct. Model Free analysis of the fluorescence decays acquired
with the pyrene monomer, excimer, and porphyrin core established that
only residual pyrene excimer formation in the dendrons could occur
before FRET from the excited pyrene monomer to the ground-state porphyrin
core