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Abstract: Porphyrin and pyrene photoactive cores have been encapsulated within an isolating polymeric shell
using an efficient and general strategy based on the use of dendritic initiators for the ring-opening polymerization
of -caprolactone to yield functional core star polymers. The isolation of the core functionalities has been
studied using fluorescence quenching and fluorescence resonance energy transfer (FRET) techniques as well
as solvatochromic probes. With increasing chain length as well as solvent polarity, enhanced site isolation of
the core has been observed. These findings have been correlated to actual molecular dimensions independently
measured by pulsed field gradient spin-echo (PGSE) NMR. The developed synthetic methodology offers a
rapid route to efficient encapsulation of functional moieties and therefore has potential for the design of new
materials.
Introduction
In recent years, one of the major objectives in dendrimer
chemistry1 has been the encapsulation of active core functionalities within dendritic backbones.2 Numerous examples of such
structures have shown profound effects of the dendrimer shell
on the core properties, and impressively demonstrated the
importance of this site isolation concept.3 The use of dendritic
nonnatural building blocks to mimic enzyme functions4 will
ultimately provide a more detailed understanding of biological
processes, and facilitate the design of artificial nanoscale
molecular devices by creating specific microenvironments
around active units.5 Porphyrin core dendrimers6 have received
special attention due to their potential as hemeprotein mimics
for electron transport,6a-f dioxygen binding,6g,h and oxidation
catalysis.6i,j
The preparation of structurally perfect dendrimers traditionally
suffers from its time-consuming nature due to the required
repetitive coupling and activation steps, and the necessity for
extensive purification. Although accelerated synthetic protocols7
and the construction of less perfect analogues8 have been
(1) (a) Newkome, G. R.; Moorefield, C. N.; Vogtle, F. Dendritic
Molecules: Concepts, Synthesis, PerspectiVes; VCH: Weinheim, 1996. (b)
Bosman, A. W.; Jansen, H. M.; Meijer, E. W. Chem. ReV. 1999, 99, 1665.
(c) Fischer, M.; Vogtle, F. Angew. Chem., Int. Ed. 1999, 38, 885. (d)
Matthews, O. A.; Shipway, A. N.; Stoddart, J. F. Prog. Polym. Sci. 1998,
23, 1. (e) Frechet, J. M. J.; Hawker, C. J. In ComprehensiVe Polymer
Science, 2nd Suppl.; Aggarwal, S. L., Russo, S., Eds.; Pergamon Press:
Oxford, 1996; p 140. (f) Frechet, J. M. J. Science, 1994, 263, 1710. (g)
Tomalia, D. A.; Naylor, A. M.; Goddard, W. A., III Angew. Chem., Int.
Ed. 1990, 29, 138.
(2) Functional dendrimers have been comprehensively reviewed by: (a)
Chow, H.-F.; Mong, T. K.-K.; Nongrum, M. F.; Wan, C.-W. Tetrahedron
1998, 54, 8543. Other reviews include: (b) Newkome, G. R..; He, E..;
Moorefield, C. N. Chem. ReV. 1999, 99, 1689. (c) Archut, A.; Vogtle, F.
Chem. Soc. ReV. 1999, 27, 233.
(3) Hecht, S.; Frechet, J. M. J. Angew. Chem., Int. Ed. 2001, 40, 74.
(4) Dendrimers as biological mimics have been reviewed in: Smith, D.
K.; Diederich, F. Chem. Eur. J. 1998, 4, 1353.
(5) (a) Wang, P.-W.; Liu, Y.-J.; Devadoss, C.; Bharathi, P.; Moore, J.
S. AdV. Mater. 1996, 8, 237. (b) Kawa, M.; Frechet, J. M. J. Chem. Mater.
1998, 10, 286. (c) Halim, M.; Pillow, J. N. G.; Samuel, I. D. W.; Burn, P.
L. AdV. Mater. 1999, 11, 371. (d) Freeman, A. W.; Koene, S. C.; Malenfant,
P. R. L.; Thompson, M. E.; Frechet, J. M. J. J. Am. Chem. Soc. In press.
DP(NMR)
M
h n(NMR)
M
h W/M
h n(GPC)
26.6
33.3
44.6
54.2
24.9
31.9
41.0
50.4
24.9
31.9
41.0
50.4
33.7
56.8
84.5
116.3
31.5
53.6
82.4
107.3
25 400
31 600
41 800
50 600
47 200
59 900
76 600
93 700
50 000
62 700
79 400
96 500
8 000
13 300
19 600
26 900
14 700
24 800
38 000
49 300
1.14
1.13
1.17
1.19
1.18
1.14
1.12
1.10
1.18
1.14
1.12
1.10
1.35
1.37
1.32
1.26
1.21
1.17
1.16
1.18
Hecht et al.
Scheme 3
Scheme 4
in the less polar solvents that are good solvents for the
investigated polymers. Rather than employing different neutral
quenchers,6k,q we sought to take advantage of the unique design
of the system with its multiple reactive chain ends to attach an
internal probe enabling the study of site isolation as a function
of solvent.
FRET Studies. FRET involves the nonradiative transfer of
singlet excitation energy from a donor chromophore to an
acceptor chromophore. According to Forsters mechanism,21a
the magnitude of the interaction, i.e., the FRET efficiency
(FRET), is inversely proportional to the sixth power of the
donor-acceptor separation.13,21 Mainly due to this sensitive
distance dependence, FRET has proven to be an exceptional
tool for the study of the conformation and motion of biological
macromolecules.22 To monitor interactions over the range of
several nanometers, a high intrinsic probability of FRET and
therefore maximized spectral overlap between the emission of
the donor and the absorption of the acceptor is required.13,21
In the present study, the porphyrin core served as acceptor,
whereas multiple donors were introduced by modification of
the chain ends (Scheme 3). In our system, coumarin-3carboxylates were chosen as the donor chromophores since their
emission centered around 420 nm strongly overlaps with the
Soret absorption band (max ) 420 nm) of the porphyrin acceptor
core (Figure 2).23 In addition, coumarin-3-carboxylic acid is a
commercially available, rather inexpensive dye that can be
conveniently linked to the hydroxyl-chain ends via esterification.9 When the coumarin donors in polymers 3a-d were
excited selectively (exc ) 350 nm), emission from both the
coumarins and the porphyrin acceptor was observed, demon(21) (a) Forster, T. Fluoreszenz Organischer Verbindungen; Vandenhoech
and Ruprech: Gottingen, 1951. (b) Van der Meer, W. B.; Coker, G., III;
Chen, S.-Y. Resonance Energy Tranfer, Theory and Data; VCH: Weinheim,
1994.
(22) Representative recent reviews are given in the following: (a) Weiss,
S. Science 1999, 283, 1676. (b) Szollosi, J.; Damjanovich, S.; Matyus, L.
Cytometry 1998, 34, 159.
(23) To our knowledge, this is the first time the emission originating
from a coumarin dye is quenched by the porphyrin Soret absorption. One
example of energy transfer from a coumarin donor (7-diethylaminocoumarin3-carboxylate) to a metalloporphyrin acceptor (palladium(II) tetraarylporphyrin) has been reported by: Kaschak, D. M.; Lean, J. T.; Waraksa, C.
C.; Saupe, G. B.; Usami, H.; Mallouk, T. E. J. Am. Chem. Soc. 1999, 121,
3435. However, due to the red-shifted emission of the employed coumarin,
sensitization of the Q-band and not the Soret band of the metalloporphyrin
most likely occurred.
strating that FRET was facile but not quantitative in this system.
In a separate control experiment, excitation of a porphyrin core
star polymer having no coumarin donor chromophores attached
led to no observable emission due to the negligible absorption
at this particular excitation wavelength. It is important to note
that at concentrations above 0.2 mM, the extremely high
extinction coefficient of the Soret band ( ) 519 000 M-1 cm-1)
promotes self-absorption, i.e., trivial radiative energy transfer.
Since the coumarin emission spectrum is very indicative of this
effect (Figure 2), it could be shown that the portion of the
radiative energy transfer increased linearly with increasing
concentration and therefore optical density, assuming constant
efficiency of the nonradiative transfer, i.e., FRET. In all
experiments concentrations of approximately 0.1 mM were
employed to avoid this self-absorption process, and to enable
the use of both good and poor solvents in the experiments. On
the basis of the very low concentrations employed, aggregation
phenomena are unlikely to occur. Further experimental evidence
for this assumption arises from the excellent agreement of the
MW determined independently by light scattering and 1H NMR
as well as the constant gel permeation chromatography (GPC)
elution volume of polymers 3a-d within a wide concentration
range (10-8-10-4 M in THF and CHCl3). The exclusion of
aggregation is essential since only intramolecular FRET provides
valuable information about the intrinsic polymer dynamics.
The dependence of FRET on polymer chain length was
investigated (Figure 3). As the chain length increases and the
donor chromophores are placed at further average distances from
the acceptor core, the donor emission intensity increases as the
result of the reduced probability of FRET in the system. In one
extreme case, quantitative FRET is observed in 3e due to
extremely short average donor-acceptor distances. In contrast,
no FRET occurs in 4 as a result of the absence of an acceptor
chromophore.
The values of FRET were determined by the method of
quenched donor emission,24 which compares the coumarin
emission in the presence of the acceptor (3a-e) to the emission
in the absence of an acceptor, as in model compound 4.25 The
results shown in Figure 4 obtained with different solvents reflect
the chain length dependence, as described above, and complement our earlier findings using fluorescence quenching (vide
supra). Interestingly, a pronounced solvent effect is observed.
In good solvents for the poly(-caprolactone) stars, such as
CHCl3 or toluene, a steep decline of FRET is observed with
Hecht et al.
Figure 3. Corrected emission of the terminal coumarin donor chromophores in compounds 3a-e and model compound 4 in chloroform as
a function of chain length (DP).
R0 )
0.52912J
n4NA
(1)
Figure 7. Plot of polymer peak area versus g222( - /3) and linear
fit for star polymers 3 in CDCl3 (open symbol, dotted lines) and CD3CN
(solid symbols, solid lines) at 298 ( 1 .
I ) I0eg (-/3)D
(2)
RH )
kBT
6D
(3)
Hecht et al.
polymer
D (m2/s)
RH (nm)
CDCl3
3a
3b
3c
3d
3a
3b
3c
3d
8.62 10-11
7.31 10-11
5.86 10-11
4.40 10-11
3.20 10-10
2.36 10-10
1.85 10-10
1.39 10-10
4.7
5.5
6.9
9.2
2.0
2.7
3.4
4.6
CD3CN
JA003304U