Protein-Framed Multi-Porphyrin Micelles for a Hybrid Natural–Artificial Light-Harvesting Nanosystem

Article abstract of DOI:10.1002/anie.201601516

A micelle-like hybrid natural–artificial light-harvesting nanosystem was prepared through protein-framed electrostatic self-assembly of phycocyanin and a four-armed porphyrin star polymer. The nanosystem has a special structure of pomegranate-like unimole

Full text of DOI:10.1002/anie.201601516

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201601516
German Edition: DOI: 10.1002/ange.201601516
Photochemistry
Protein-Framed Multi-Porphyrin Micelles for a Hybrid Natural–
Artificial Light-Harvesting Nanosystem
Yannan Liu, Jiyang Jin, Hongping Deng, Ke Li, Yongli Zheng, Chunyang Yu, and
Yongfeng Zhou*
Dedicated to Professor Deyue Yan on the occasion of his 80th birthday
Abstract: A micelle-like hybrid natural–artificial light-harvest-
ing nanosystem was prepared through protein-framed electro-
static self-assembly of phycocyanin and a four-armed porphy-
rin star polymer. The nanosystem has a special structure of
pomegranate-like unimolecular micelle aggregate with one
phycocyanin acceptor in the center and multiple porphyrin
donors in the shell. It can inhibit donor self-quenching
effectively and display efficient transfer of excitation energy
(about 80.1%) in water. Furthermore, the number of donors
contributing to a single acceptor could reach as high as about
179 in this nanosystem.
micelle aggregate (UMA), through the direct aggregation of
unimolecular micelles into a pomegranate-like micellar
structure.[13] In the present work, a four-arm star polymer
(THPD) with a porphyrin core and four poly(2-(Dimethyla-
mino)ethylmethacrylate) (PDMAEMA) arms was synthe-
sized, which also self-assembled into the pomegranate-like
UMAs in water (Scheme 1). Since the obtained THPD
Natural photosynthesis is the survival foundation of the
living beings. Light-harvesting antenna (LHA), as the initia-
tion of the photosynthesis, can capture light energy and then
funnel excitation energy to the reaction center where light
energy turns into chemical energy.[1] One of the most
remarkable feature of the natural LHA is that weak light
can be used by the reaction center because of their specific
structure where every acceptor molecule is surrounded by
a large number of donors (often ca. 200). Inspired by nature,
up to now, great progress has been made in artificial light-
harvesting systems.[1,2] The majority of them are worked in
organic solutions and are generally based on scaffolds like
dendrimers,[3] coordination polymers,[4] and cyclic arrays.[5] In
recent years, some aqueous artificial LHA scaffolds, such as
DNA,[6] MOFs,[7] gels,[8] virus,[9] proteins,[10] micelles[11] and
clay,[12] have also been developed. These LHA systems are
like nature ones working in aqueous environment, however, it
is difficult for them to obtain clear multi-donors to only one
acceptor structure, especially with a ratio more than 100 as the
nature does. In addition, it is still very challenging for these
aqueous LHAs to inhibit the self-quenching of donors in
water due to their great hydrophobicity.
Scheme 1. Self-assembly of the pomegranate-like porphyrin-phycocya-
nin light-harvesting nanosystem (Ex Light=exciting light; Em Light=
emitted light).
micelles have multi-porphyrin donors, a biomimetic LHA
system with multiple donors and one acceptor could be
constructed if an acceptor was able to be introduced into the
core of the THPD micelle. Herein, a natural LHA protein of
phycocyanin (PC) was selected as the acceptor. PC, a water-
soluble light-absorption protein in cyanobacteria, is com-
posed of two subunits of the a-chain and b-chain. The two
subunits form monomers, which aggregate into a3b3 trimers
and further into a6b6 hexamers (Scheme 1).[14] The PC was put
into the core of the pomegranate-like THPD UMA micelle
through a delicate protein-framed electrostatic assembly
process (Scheme 1).[15] In this as-prepared hybrid natural–
artificial LH system, the porphyrin donors are effectively
separated from each other by PDMAEMA arms, which
Herein, we report a novel aqueous LH system to address
these challenges. Previously, our group disclosed a special
multimolecular micelle structure, named as unimolecular
[*] Y. N. Liu, J. Y. Jin, H. P. Deng, K. Li, Dr. Y. L. Zheng, Dr. C. Y. Yu,
Prof. Y. F. Zhou
School of Chemistry and Chemical Engineering, State Key Laboratory
of Metal Matrix Composites, Shanghai Jiao Tong University
800 Dongchuan Road, Shanghai 200240 (China)
E-mail: yfzhou@sjtu.edu.cn
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201601516.
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inhibits self-quenching of donors and keep them stable in
water. In addition, like the natural system, a regular structure
with about 179 effective donors but one acceptor was
constructed in this synthetic LH system, which showed
excellent energy-funneling properties in water. Porphyrins
are stable and have broad absorption and large extinction
coefficient in the visible light region. Thus, they are not only
widely existed in chlorophyll a and chlorophyll b of the
natural LHAs, but also have been widely used as artificial
LHA chromophores.[16] Herein, a porphyrin-based four-arm
star polymer of THPD was constructed as donors through an
oxyanionic polymerization of PDMAEMA arms from the
core of 5,10,15,20-tetrakis(4-hydroxyphenyl) zinc porphyrin
(ZnTHPP).[17] The detailed syntheses and characterizations of
the synthetic intermediates as well as THPDs were shown in
the supporting information (see Figures S1–S5 in the Sup-
porting Information). As we know, short PDMAEMA arms
cannot support the total segregation of porphyrin chromo-
phores between THPDs, while too longer arms will prevent
THPDs from self-assembly. Therefore, the THPDs with
a moderate degree of polymerization of 21 for PDMAEMA
arms, a total molecular weight around 14 kD, and a polydis-
persity of 1.19 were synthesized.
THPDs can undergo self-assembly in aqueous solution at
a pH of 6.2 since each of them has a hydrophobic ZnTHPP
core and four hydrophilic PDMAEMA arms in this condition.
The critical micellar concentration (CMC) of THPDs was
determined to be 0.05 mgmLÀ1 (Figure S6). When the con-
centration was below CMC, for example 0.04 mgmLÀ1, the
typical transmission electron microscope (TEM) image in
Figure 1a showed that spherical particles with an average
diameter of about 3.8 nm existed in solution, which was also
supported by dynamic light scattering (DLS) analysis showing
an average hydrodynamic diameter (Dh) of 5.3 nm (inset of
Figure 1a). These results indicate THPDs form unimolecular
micelles below the CMC. In contrast, when the THPD
concentration was above the CMC, spherical micelles with an
average diameter of 76 nm, as counted from 200 particles in
the TEM images, were observed (Figures 1b and S7a), which
agreed well with the scanning electron microscope (SEM)
result (Figure S7b). However, the micelle size measured by
TEM was smaller than that from DLS measurement (Dh =
112 nm, Figure S7c) since the micelles were in a dried state
during the TEM measurement.
Most interestingly, the obtained micelles seemed to be
formed by the aggregation of small particles (Figure 1b), and
the size of these small particles inside the micelles were
ranging from 3 to 6 nm in diameter based on the statistical
analyses of 200 particles (Figure 1c), which matched well with
that of the THPD unimolecular micelles. Thus, the THPD
micelles should have a so-called UMA structure as shown in
Scheme 1.[13] In other words, the THPD micelles were formed
through the direct aggregation of THPD unimolecular
micelles.
Such a UMA structure can effectively inhibit the self-
quenching between porphyrin chromophores. ZnTHPPs are
not water-soluble and will undergo serious aggregation-
caused quenching (ACQ) with the increase of concentration.
The SEM measurement also showed the formation of large
aggregates from ZnTHPPs in water (Figure S8). As expected,
ZnTHPPs almost had no fluorescence emission in water
because of the strong ACQ effect (Figure 1d).[18] In contrast,
the fluorescent intensity of THPD aqueous solution increased
linearly with the concentration (Figures 1d and S9) up to
0.51 mgmLÀ1 (ten times higher than CMC). Besides, the UV
absorbance peaks of THPDs in water were almost kept at the
same positions in spite that they were in the unimolecular
micelle state below the CMC or in the UMA state above the
CMC (Figure S10). The time-resolved fluorescence analyses
showed no apparent change between the decay lifetime of
THPD unimolecular micelles (t = 1.35 ns) and UMA micelles
(t = 1.32 ns; Figure S11). All these data support the self-
quenching of porphyrins in THPD micelles is inhibited, which
should be attributed to the UMA structure in the micelles. In
such UMA micelles, each porphyrin chromophore was
spatially separated from one another by the PDMAEMA
shells, which greatly decreased the p–p stacking of chromo-
phores. However, when the concentration of THPD was
higher than 0.51 mgmLÀ1, the fluorescent intensity was
deviated from linear relationship with concentration probably
due to the common inner-filter effect of the fluorescence
between chromophores.[19]
As shown above, THPDs formed multi-porphyrin
micelles with a UMA structure and a good fluorescence
property in water. In addition, the energy migration ability
between porphyrins in the THPD micelles was also proved by
a small additional rise-time component in time-resolved
profile of THPD micelles (Figure S11).[20] Then, we wanted
to introduce PCs as the acceptors into THPD micelles to
construct hybrid LH systems. PCs formed spherical nano-
particles with a diameter of about 13 nm according to typical
TEM (Figures S12) and atomic force microscope (AFM)
images (Figure S13). The Zeta potential value of PCs at the
Figure 1. Characterizations of THPD micelles. a) Representative TEM
images as well as the DLS curve (inset) of THPD unimolecular
micelles. b) A typical TEM image of THPD multimolecular micelles at
a concentration of 0.50 mgmLÀ1. c) The size distribution of small
spherical particles inside the THPD multimolecular micelles from
image (b). d) The fluorescence emission intensity (exited at
l=426 nm) as a function of the concentration of ZnTHPP and THPD
aqueous solutions.
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pH of 6.2 is À31.1 mV (Figure S14), which means PC is
negatively charged. These results are consistent with litera-
tures.[14] In addition, the fluorescence emission spectrum of
THPDs and the UV absorption spectrum of PCs were well
overlapped (Figure S15). Thus, THPD and PC are comple-
mentary donor and acceptor candidates and might be
combined into a LH system through an electrostatic self-
assembly process since THPD micelles are positively charged
(the zeta potential value is 35.3 mV at pH 6.2, Figure S16).
We wanted to set up a LH system with only one PC
acceptor but multiple THPD donors. In order to ensure this,
a classical electrostatic self-assembly method as developed by
Grzybowski was adopted here.[21] A small amount of aqueous
solution of negatively charged PCs was added into the
aqueous solution of massive positively charged THPDs with
vigorous stirring (the concentration of THPDs is
0.04 mgmLÀ1). In this way, PCs were separated from each
other by many surrounding THPD molecules. We expected
that at the beginning THPD unimers in solution would be
immediately adsorbed onto the surface of every PC particle
though electrostatic interaction to form primary micelles, and
then every primary micelle would act as a nucleating agent to
take more and more THPD molecules to form a THPD-PC
complex micelle.
To prove the assumption, TEM measurements were
performed to track the intermediates during this electrostatic
self-assembly process. In the TEM image, PC particles look
much paler than THPDs since there is one Zn atom with
a high electron density in each THPD molecule. The TEM
image in Figure S17 displayed some particle intermediates at
the beginning of self-assembly process of THPDs and PCs
with a molar ratio of 200:1, and each of them has a light core
partly or completely covered with a dark thin layer. The light
cores have a diameter in the range from 10 nm to 15 nm,
which agrees well with the size of PCs, while the dark thin
layer should come from the adsorbed THPD molecules. In
other words, the PC-cored primary micelles did form at the
initial step of the co-assembly process. Finally, numerous
core–shell micelles (Figure 2a) with a Dh of 93 nm (Fig-
ure 2b) were obtained. The light core was assigned to the PC,
while the dark shell was formed by the aggregation of small
nanoparticles according to the magnified view (Figure 2c).
The diameter of these small particles in the micelle shell is
ranging from 3 nm to 6 nm when counted from 100 particles
(Figure 2d), which agrees well with the size of THPD
unimers. So, the final THPD-PC complex micelle should be
composed of a PC core and a shell of THPD molecules with
a UMA structure (Scheme 1).
The core–shell structure of the THPD-PC complex
micelles was much clearer (Figure 2e) under high-resolution
TEM (HRTEM) in spite that the details in the shell as shown
in the biological TEM (Figure 2a and c) were lost. Fortu-
nately, the line scanning element analyses of one selected
THPD-PC micelle show the micelle shell has more zinc and
carbon contents derived from ZnTHPP moieties, while the
micelle core has more nitrogen content derived from the
peptide bonds of PC (Figure 2 f) under HRTEM. Thus, as
a support of the biological TEM, the HRTEM results also
Figure 2. Structural characterizations of THPD-PC complex micelles.
a) A typical biological TEM image of THPD-PC micelles. b) The DLS
curve of THPD-PC micelles. c) The magnified view of a typical THPD-
PC micelle. d) A statistical size distribution of small particles inside
the shell of THPD-PC micelles. e) The HRTEM image of THPD-PC
micelles, f) Line scanning element analyses of one THPD-PC micelle
(bottom left), including carbon element (top left), zinc element (top
right) and nitrogen element (bottom right).
prove the THPD-PC micelle has a structure of one-PC core
and a multi-THPD shell.
Besides the morphology observation, the self-assembly
process between PCs and THPDs was further tracked by
time-dependent DLS and fluorescence emission measure-
ments (Figure S18), and all results support an electrostatic
self-assembly process as summarized in Scheme 1. At the
beginning, each PC was worked as a core to frame the coating
of a thin layer of THPD molecules driven by the electrostatic
interactions, and thus a primary micelle was obtained. Since
the positive charge of the THPD layer in the primary micelle
was partly neutralized by the PC core, the hydrophobicity of
these coated THPD molecules increased. As a result, the
primary micelles further attracted the aggregation of more
THPD molecules onto the surface driven by the hydrophobic
interactions to form a core–shell complex micelle. This
process was similar to the self-assembly process of THPDs
except that a primary micelle pre-existed in here, and thus
a UMA structure was also formed in the shell of the complex
micelle. Since the final obtained core–shell micelle was
framed by the PC protein, we called it as a protein-framed
multi-porphyrin micelle.
There are also some factors that play important roles in
the self-assembly of PC-THPD micelles. First, the concen-
tration of THPD is very important. If the concentration was
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too low (much lower than 0.04 mgmLÀ1), only small core–
shell micelles with thin THPD shells were obtained. While, if
the concentration of THPDs was higher than the CMC,
THPDs themselves formed the micelles with a UMA struc-
ture, and the PC-THPD core–shell micelles were difficult to
form. Second, the feed ratios of THPD:PC is also important.
A series of PC-THPD core–shell complex micelles were also
obtained by changing the ratios from 500:1 to 2000:1 through
the same PC-framed electrostatic self-assembly process, and
the micelle size increased with the increase of the ratios
(Figures S19 and S20). However, there is a size self-limiting
mechanism in the self-assembly of THPD-PC micelles,[22] and
they will stop growing when the feed ratio is above 1000:1,
which is probably attributed to the equilibrium of the
hydration repulsion and hydrophobic attraction interactions
between the free THPD molecules and the already existing
micelles at the critical condition.
maximum absorption wavelength of THPDs (lmax = 426 nm).
However, PCs have the weakest absorption at this excitation
wavelength (Figure S22), which can better avoid the emission
interference for the energy-transfer process. The FRET
efficiency of these LH systems was calculated and listed in
Table S1, which reached the maximum of 80.1% in the
complex micelle system with a THPD:PC molar ratio of 200:1
(see the Supporting Information).
The time-resolved fluorescence spectra for THPD-PC LH
system at a feed ratio of 200:1 and excited at 456 nm were
examined to further reveal the energy-transfer process (Fig-
ure 3c). The obtained emission spectrum was similar to that
of THPDs at the beginning (set as 0 ns), and then with the
continuous excitation, the spectrum transferred to that of PCs
after 2 ns, which directly supported the energy was transferred
from the excited THPD donors to PC acceptors effectively.
Furthermore, the fluorescence lifetime decay curves of
THPD donors and PC acceptors at 620 nm were fitted as
a single exponential decay with a lifetime of tD = 1.32 ns
(Figure 3d) and tA = 1.43 ns (Figure S23), respectively. How-
ever, the lifetime of THPD-PC micelles exhibited a typically
biexponential decay with t1 = 0.51 ns and t2 = 1.46 ns, respec-
tively (Figure 3d). The long lifetime t2 is close to that of
acceptors, and thus we believe the short lifetime t1 is from the
donors. Such a prominent shortening of the donor lifetime
suggests that nonradiative energy transfer takes the dominant
place in the energy-transfer mechanism from the donors to
the acceptors in the THPD-PC complex micelles. The time-
resolved fluorescence curves of the THPD-PC micelles and
PC acceptors monitored at 680 nm support the same results
(Figure S24).
The light-harvesting property of the as-prepared THPD-
PC complex micelles was also carefully investigated. Com-
pared with the fluorescent emission of THPDs and PCs
(Figure 3a), the fluorescence emission spectra of THPD-PC
In addition, in the THPD-PC micellar LH system with
a THPD/PC ratio of 200:1, the energy-transfer rate constant
kET between THPD donor and PC acceptor was calculated to
be 3.03 ꢀ 109 sÀ1 (see the Supporting Information). The over-
lap integral J was calculated to be 1.40 ꢀ 1013 mÀ1 cmÀ1 nm4 for
energy transfer between THPD and PC (JD-A), and 1.16 ꢀ
1012 mÀ1 cmÀ1 nm4 for energy transfer between THPDs (JD-D
;
see the Supporting Information). Herein, both the kET and J
are large enough to keep the effective energy migration
among donors and energy transfer from the donor to the
acceptor.[2,12] The Fçrster radius between donor and acceptor
(R0(D-A)) was estimated to be 2.90 nm (see the Supporting
Information), which indicates that PC acceptors are very
closely surrounded by THPD donors in PC-THPD hybrid LH
nanosystem. The average number of THPD molecules that
quenched by each PC was calculated to be 179 (see the
Supporting Information), which is comparable to that in
natural LHA systems.
Figure 3. Optical property characterizations of THPD-PC complex
micelles. a) Normalized absorption (solid lines) and fluorescence
emission (dashed lines) spectra of PC and THPD. b) The fluorescence
spectra of PC-THPD complex micelles excited at 456 nm in aqueous
solution at the different donor-to-acceptor ratios. c) The time-resolved
fluorescence spectra of PC-THPD complex micelles at 0 ns, 0.5 ns,
1 ns, 1.5 ns and 2 ns after excitation. d) The fluorescence decay
profiles of pure THPD (black) and PC-THPD complex micelles (blue).
The excitation wavelength was 456 nm in images (b)–(d), and the
monitored wavelength in image (d) is 620 nm (the donor emission
maxima). The ratio between THPD and PC is 200:1 for the complex
micelles in images (c) and (d).
In summary, the work reports a novel core–shell micellar
light-harvesting nanosystem consisting of one phycocyanin
acceptor in the center and many porphyrin donors packed in
a pomegranate-like model in the shell through the protein-
framed aqueous electrostatic self-assembly. It can avoid self-
quenching among the porphyrin donors and afford efficient
energy transfer from up to 179 porphyrin donors to one
phycocyanin acceptor in water. Such a regular multi-donor
and one-acceptor structure is similar to that of natural light-
harvesting antenna. Thus, we believe this work might throw
complex micelles excited at 456 nm showed a typical Fçrster
resonance energy transfer (FRET) phenomenon with one
isoemissive point: the fluorescence emission peak of THPD
donors at 620 nm decreased, while that of PC acceptors at
660 nm increased with the increase of the PC concentrations
(Figure 3b and the corresponding peak-differentiation-imi-
tating analyses in Figure S21). The excitation wavelength was
set at 456 nm for the FRET measurements, which is not the
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Acknowledgements
This work was supported by the National Basic Research
Program (grant number 2013CB834506), China National
Funds for Distinguished Young Scholar (grant number
21225420), Jiangsu Collaborative Innovation Center of Bio-
medical Functional Materials, and the National Natural
Science Foundation of China (grant numbers 91527304,
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Received: February 12, 2016
Revised: March 31, 2016
Published online: && &&, &&&&
6
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Communications
Photochemistry
Y. N. Liu, J. Y. Jin, H. P. Deng, K. Li,
Y. L. Zheng, C. Y. Yu,
Y. F. Zhou*
&&&& — &&&&
Protein-Framed Multi-Porphyrin Micelles
for a Hybrid Natural–Artificial Light-
Harvesting Nanosystem
Nanopomegranate: A micellar light-har-
vesting nanosystem was prepared con-
sisting of one phycocyanin protein
acceptor in the core and many porphyrin
donors packed in a pomegranate-like
manner in the shell. The system inhibited
donor self-quenching effectively and dis-
played efficient transfer of excitation
energy in water.
Angew. Chem. Int. Ed. 2016, 55, 1 – 7
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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7
These are not the final page numbers!