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Cite this: DOI: 10.1039/c5tc00318k

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Photoluminescent nanoparticles in water with

tunable emission for coating and ink-jet printing
Chao Deng,a Zhening Yang,a Zhicheng Zheng,b Na Liua and Jun Ling*a
We report a novel fluorescent polyfluorene-containing methacrylate macromonomer (PFMA) and its
well-defined copolymers with 2-(dimethylamino)ethyl methacrylate (DMAEMA) [P(PFMA-r-DMAEMA)s]
via reversible additionfragmentation chain transfer (RAFT) polymerization. These copolymers self-

Received 31st January 2015,

Accepted 21st February 2015
DOI: 10.1039/c5tc00318k

assemble into photoluminescent nanoparticles in aqueous solutions and act as an excellent scaffold for
the incorporation of various pigments to emit tunable colors, including white, through Fo
rster resonance
energy transfer with high quantum yield up to 0.80. The directly cast films of these NPs after
evaporation of water exhibit strong colorful emission on both smooth quartz and rough plaster surfaces.

www.rsc.org/MaterialsC

The NP aqueous solutions are ready for ink-jet printing to produce exquisite fluorescent pictures.

1. Introduction
Over the past few decades, conjugated polymers have been
meticulously studied for their versatile applications in electronic
and optoelectronic fields, such as organic memory devices, lightemitting diodes and photovoltaic devices.17 On the one hand,
much research attention is focused on p-conjugated polymers
prepared by Suzuki or Yamamoto coupling reactions which have
satisfactory performance in optoelectronic devices.811 However,
their poor solubility limits further processing and applications.
On the other hand, vinyl backbone polymers with pendant
p-conjugated oligomers are synthesized from styrene- and
methacrylate-based monomers via conventional radical (co)polymerization.1217 These vinyl conjugated polymers have a considerable advantage as they exhibit excellent solubility and easily form
uniform films.18,19 Furthermore, it is feasible to design macromolecular architectures or change the composition to adjust their
electronic and optoelectronic properties, which is a challenge in
the above-mentioned main chain p-conjugated polymers.2027
In the molecular construction of vinyl p-conjugated polymers,
the pendant p-conjugated oligomers are of great importance since
they determine electronic and optoelectronic properties. Polyfluorenes (PFs) are the most interesting pendant p-conjugated
units due to their thermal/chemical stability, high fluorescence
quantum yield and significant charge carrier mobility.2830
Supported by both experiments17,31 and density functional

theory calculations,32,33 short PF oligomers with the degree of

polymerization (DP) from 6 to 10 emit strong and steady blue
light with the wavelength very close to that of the main chain
p-conjugated polymers. Only a few attempts have been reported
to polymerize PF-styrene derivatives. The corresponding
polymers obtained from macromonomers show unique selfassembly behavior and tunable properties.14,17,19,3436
In this work, we report novel amphiphilic vinyl p-conjugated
copolymers containing PF pendant groups (Scheme 1) as functional scaolds for photoluminescent nanoparticles (NPs) in
aqueous solution. Hydrophobic dyes including coumadin 6
(C6), Nile red (NR) and (4-(dicyanomethylene)-2-methyl-6-(2dimethylaminostyryl)-4H-pyran) (DCM) are loaded into the core
of NPs to induce their characteristic emissions after receiving
rster resonance energy transfer (FRET, Scheme 2)
energy via Fo
when the PF moiety is excited by near-ultraviolet light with the
wavelength of 370 nm. The photoluminescent NPs in aqueous

MOE Key Laboratory of Macromolecular Synthesis and Functionalization,

Department of Polymer Science and Engineering, Zhejiang University,
Hangzhou 310027, China. E-mail: lingjun@zju.edu.cn
b
nster, Germany
Hensenstrae 152, D-48161 Mu
Electronic supplementary information (ESI) available. See DOI: 10.1039/
c5tc00318k

This journal is The Royal Society of Chemistry 2015

Scheme 1

Synthesis of PFMA.

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Scheme 2

Synthesis of P(PFMA-r-DMAEMA) via RAFT and preparation of fluorescent nanoparticles.

solution can be directly cast to uniform solid films, coated on

any irregular surface, and ink-jet printed.

2. Experimental section
2.1.

Materials

Tetrahydrofuran (THF) was refluxed over potassium/benzophenone

ketyl prior to use. Anisole was purified by distillation under reduced
pressure after stirring over CaH2. Cumyl dithiobenzoate (CDB) was
synthesized as reported.37 N,N-Azobisisobutyronitrile (AIBN) was
purified by recrystallization in 95% ethanol. 2-(Dimethylamino)ethyl methacrylate (DMAEMA) was purified by distillation under
reduced pressure. 2,7-Dibromofluorene, 4-formylbenzeneboronicacid, tetrabutylammonium bromide, tetrakis(triphenylphosphine)
palladium(0), and 2-isopropoxy-4,4,5,5-tetramethyl-[1,3,2]-dioxaborolane were purchased from Adamas Company. The other
chemicals were purchased from J&K Company, China, and used
as received.
2.2.

Synthesis of macromonomers

Hydroxymethyl-functionalized polyfluorene (PFCH2OH).

Aldehyde-functionalized polyfluorene (PFCHO) was synthesized
by Suzuki coupling reaction according to the procedure
described before.17 A mixture of PFCHO (0.1 g, 0.05 mmol)
and sodium borohydride (NaBH4) (0.05 g, 1.3 mmol) was
dissolved in 30 mL THF and heated under reflux for 12 h.
After cooling to room temperature, 10 mL ethanol and 10 mL
2 mol L 1 HCl were carefully added to the mixture. The
aqueous solution was extracted by chloroform twice. After
drying over magnesium sulfate, the organic phase was concentrated and precipitated in cold methanol to give 85 mg (85%)
of PFCH2OH. 1H NMR (400 MHz, CDCl3), d (ppm): 7.957.30
(50H, ArH), 4.78 (2H, CH2OH), 2.10 (24H, CH2CH2C3H6CH3),
1.13 (80H, CH2CH2C3H6CH3), 0.78 (64H, CH2CH2C3H6CH3,
CH2CH2C3H6CH3).
Methacrylate-functionalized polyfluorene (PFMA). PFCH2OH
(0.4 g, 0.2 mmol) was dissolved in 15 mL dry THF followed by
triethylamine (0.15 mL, 1.05 mmol). Methacryloylchloride
(0.1 mL, 1.05 mmol) was added dropwise at 0 1C, and the
reaction was carried out overnight at 25 1C. Saturated aqueous

J. Mater. Chem. C

NaHCO3 was added and the mixture was extracted with dichloromethane. The organic phase was washed with aqueous NaHCO3,
HCl, brine and water, successively. After drying over magnesium
sulfate, the organic phase was concentrated and precipitated in
cold methanol to give 0.38 g (95%) of PMFA. 1H NMR (400 MHz,
CDCl3), d (ppm): 7.95-7.30 (46H, ArH), 6.20 (1H, CH3CQCH2),
5.61 (1H, CH3CQCH2), 5.27 (2H, CH2OH), 2.102.00 (26H,
CH2CH2C3H6CH3, CH3CQCH2), 1.13 (68H, CH2CH2C3H6CH3),
0.78 (58H, CH2CH2C3H6CH3, CH2CH2C3H6CH3).
2.3.

Polymerization

P(PFMA-r-DMAEMA) was synthesized via RAFT using CDB as

the chain transfer agent (CTA) and AIBN as the initiator. In a
typical example, PFMA (0.16 g, 0.1 mmol), DMAEMA (1.7 mL,
10 mmol), CDB (6.8 mg, 0.025 mmol) and AIBN (1.3 mg,
0.008 mmol) were dissolved in 3 mL anisole to form a crimson
transparent solution. After deoxygenation by three freeze
pumpthaw cycles, the flask was sealed and heated at 80 1C
for 6 h. Then the reaction mixture was cooled to room temperature and precipitated into cold hexane. The precipitate was
separated by filtration and dried in vacuum for 24 h (0.48 g,
27%). Other copolymers were synthesized using different
[PFMA]/[DMAEMA] feeding ratios.
2.4.

Preparation of nanoparticles

10 mg of P(PFMA-r-DMAEMA) was dissolved in 2 mL DMF, after

which 2 mL water was added dropwise to the solution under
vigorous stirring and the mixture was kept under stirring for
1 h. Then the mixture was dialyzed against water for 2 days.
After dialysis, the mixture was filtered and the volume was set
to 25 mL for further testing.
Nanoparticles containing chromophores were also prepared
via dialysis. In a typical run, 10 mg of P(PFMA-r-DMAEMA) was
dissolved in 2 mL DMF, after which coumadin 6 (60 mL, 0.25 mg
mL 1 in DMF) and Nile red solution (80 mL, 0.25 mg mL 1 in
DMF) were added. After 1 h, 2 mL water was added dropwise
to the solution under vigorous stirring and the mixture
was kept under stirring for another 1 h. Then the mixture was
dialyzed against water for 2 days. After dialysis, the mixture was
filtered and the volume was set to 25 mL for further testing.

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Nanoparticles containing coumadin 6, Nile red and DCM

respectively were prepared in the same way.
The nanoparticle solution was dropped onto quartz glass
directly and dried at 40 1C to give thin films.

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2.5.

Crosslinking of nanoparticles

100 mL of TMOS was added into 5 mL dilute NaOH solution

under stirring. Then 200 mL of this solution was added into
2 mL NP solution. The cross-linking procedure of TMOS was
carried out for several minutes, and the solution became
viscous. A uniform film was formed on the surface of plaster
models after painting and drying of the pretreated solution.
2.6.

Measurements

Nuclear magnetic resonance (NMR) spectra were recorded on a

Bruker Avance spectrometer (1H: 400 MHz) using tetramethylsilane as an internal reference. Molecular weights (MWs) and
polydispersity indices (PDIs) were determined by size-exclusion
chromatography (SEC) on two kinds of Waters instruments. One
is Waters-150C apparatus equipped with a Waters 2414 refractive
index (RI) detector and Waters Styragel HR3 and HR4 columns.
The elution solvent was THF with a flow rate of 1.0 mL min 1 at
40 1C and using polystyrene as standards. The other is Waters
1515 system, which was equipped with a Waters 1515 isocratic
high performance liquid chromatograph pump, two columns of
Styragel (HT3 and HT4) and a Wayatt Opitlab DSP interferometric
refractometer. DMF containing 0.05 mol L 1 LiBr was used as
an eluent at a flow rate of 1.0 mL min 1 at 60 1C and using
commercial poly(methyl methacrylate) samples as the calibration
standards. UV-Vis and steady-state fluorescence emission
measurements were carried out on a UV-2450 spectrometer
(SHIMADZU) and a FluoroMax-4 spectrofluorometer (HORIBA),
respectively. Fluorescence quantum yields for PF were obtained by
comparing the integrated fluorescence spectra of the polymers in
THF solutions to the fluorescence spectrum of quinine sulfate in
0.5 mol L 1 H2SO4 (F = 0.55, excitation wavelength of 365 nm)
with a correction of refractive index dierences.31 The hydrodynamic diameters of the nanoparticles were measured by dynamic
light scattering (DLS) using a particle size analyzer (Nano-ZS,
Malvern) at 25 1C. The morphologies of nanoparticles in aqueous
solution were observed using a JEOL JEM-1230 transmission
electron microscope (TEM) with an accelerating voltage of 80 kV.
The samples were prepared by placing 0.5 mg mL 1 of nanoparticle
dispersion on copper grids coated with carbon-film. The printing
process was carried on a common inkjet printer (HP deskjet 1010
inkjet printer) and the NP solution was directly used as the ink
without any extra treatment by being injected into an empty 802
ink-box which matched the printer.

Fig. 1 1H NMR spectra of PFCHO (A), PFCH2OH (B) and PFMA (C) in
CDCl3.

been reported yet. Given the plenty of intensively studied

methacrylate co-monomers with similar reactivity ratios, PFMA
is better than styrene derivatives.17
As shown in Scheme 1, the PFMA macromonomer was
synthesized from benzaldehyde-endcapped PFCHO oligomers
as reported in our previous work.17 The formyl group of PFCHO
was converted to the hydroxymethyl group after reduction
by NaBH4. PMFA was finally obtained by esterification of
PFCH2OH with methacryloyl chloride.
The products were confirmed by 1H NMR (Fig. 1). The
reduction of the formyl group was proved by the emergence
of the He signal at 4.78 ppm of the hydroxymethyl group
(Fig. 1B) and the disappearance of Hd. In Fig. 1C, the signals
Hf (2.0 ppm) and Hg (6.20 and 5.61 ppm) and the shift of He

3. Results and discussion

3.1. Synthesis of the PFMA macromonomer and vinyl
backbone copolymers
To the best of our knowledge, methacrylate-type macromonomers containing PF units (PFMA in short, Scheme 1) have not

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Fig. 2 SEC traces of P(PFMA-r-DMAEMA) copolymers PD1 (A), PD2 (B),

PD3 (C) and PD4 (D).

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from 4.78 to 5.27 ppm indicate successful esterification of

PFCH2OH with methacryloyl chloride to form the PFMA macromonomer. The molecular weight (MW) of PFMA was calculated
by integration of the vinyl proton relative to the aromatic signal
as 2250, indicating a DP of 6.2 fluorene units in average. In SEC
analysis, PFMA showed an Mn of 1900, an Mw of 2500 and a PDI
of 1.32 (Fig. S1, ESI), which is in good correspondence with the
1
H NMR results.
Although the polymer of PFMA is soluble in most organic
solvents, it cannot be dissolved in water. We introduced
2-(dimethylamino)ethyl methacrylate (DMAEMA) as a co-monomer

Table 1

Copolymerization of PFMA and DMAEMA via RAFT at 80 1C for 6 h

Entry

[D]0/[F]0/[C]0a

Yield (%)

Mn,SECb

PDIb

D : Fc

PD1
PD2
PD3
PD4

1600 : 4 : 1
800 : 4 : 1
400 : 4 : 1
200 : 4 : 1

20
27
36
28

43 900
44 000
35 800
16 200

1.52
1.45
1.43
1.42

910 : 1
360 : 1
210 : 1
100 : 1

a
The ratios of [DMAEMA]0/[PFMA]0/[CTA]0 in the feed. b Measured by
SEC. c The ratio of [DMAEMA]/[PFMA] in copolymers calculated by
1
H NMR.

Fig. 3

to statistically polymerize with PFMA taking advantage of the watersolubility of PDMAEMA.

As illustrated in Scheme 2, P(PFMA-r-DMAEMA) copolymers
(PD1PD4) were synthesized in THF at 80 1C via RAFT polymerization using AIBN as an initiator and CDB as a chain
transfer agent (CTA). By varying the [DMAEMA]0/[PFMA]0/
[CTA]0 ratio, we obtained copolymers with MWs ranging from
44 to 16 kDa (Fig. 2). Detailed experimental conditions and
analysis of the four copolymers are summarized in Table 1.
Monomer conversions were kept low (2040%) to control the
polymerization. The PDIs of the four copolymers were close to
1.5 because the PDI of PFMA was already 1.32 from Suzuki
condensation and PFMA units randomly distribute in copolymer
chains.
Fig. 3 illustrates the 1H NMR spectra of P(PFMA-r-DMAEMA)
samples. The signals at 7.97.3 ppm are attributed to the
aromatic protons of fluorene units. Hd, He and Hf observed
at 4.06, 2.57 and 2.28 ppm are the protons of PDMAEMA.
Compositions of the copolymers are calculated from the intensity ratio of the signal Hk at 5.03 ppm (the ester methylene
protons of PFMA) to Hd at 4.06 ppm (the ethyl protons of
DMAEMA). The results are summarized in Table 1.

H NMR spectra of PD1 (A), PD2 (B) PD3 (C) and PD4 (D) in CDCl3.

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Table 2 DLS results and photophysical properties of functional scaolds
formed by PD1PD4 in aqueous solution

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DLS results

Photophysical parameters

Sample

Diameter
(nm)

PDI

Absorption,
lmax (nm)

Emission,
lmax (nm)

Quantum
yield

PD1
PD2
PD3
PD4

75.0
70.6
64.4
28.3

0.30
0.28
0.28
0.27

370
371
371
371

417,
419,
418,
419,

0.80
0.75
0.74
0.65

441
443
443
443

Fig. 4 UV-Vis and photoluminescence spectra at the excitation wavelength of 370 nm of copolymers PD1 (A), PD2 (B), PD3 (C), PD4 (D) and
macromonomer PFMA (E). The concentrations cPD1PD4 = 2.5  10 3 mg mL 1
and cPFMA = 5  10 6 mg mL 1.

3.2. Photophysical properties of the PFMA macromonomer

and P(PFMA-r-DMAEMA) copolymers (PD) in solution
The photophysical characteristics of PFMA and the copolymers
in THF solution were investigated. Fig. 4 shows the UV-Vis
absorption and photoluminescence spectra of PFMA and
PD1PD4. The absorption maxima of PFMA and all the four
copolymers are observed at the wavelength of 370  2 nm, which
is attributed to the pp* transition of the fluorene units.38 This
wavelength was then chosen as the exciting wavelength in the
photoluminescence studies. As illustrated in Fig. 4, all of the
samples exhibit characteristic blue emission between 380 and
500 nm with two emission maxima observed. A quantum yield of
0.86 of PFMA is in good accordance with that of the analogue
oligofluorene reported.31 The quantum yields of PD1PD4 are
measured as 0.84, 0.87, 0.82 and 0.85, respectively. It suggests a
random distribution of PFMA units along polymer chains which
are thus well separated by DMAEMA units.
3.3 Preparation and characterization of functional scaolds
using P(PFMA-r-DMAEMA) copolymers (PD)
Upon dialyzing DMF solutions of PD1PD4 against water,
stable nanoscale coreshell self-assemblies are readily formed
due to the amphiphilic characteristics of the copolymers.
In aqueous medium, the hydrophobic polyfluorene units constitute the core, while the hydrophilic PDMAEMA segments
serve as the shell. The self-assembly formation is confirmed by
dynamic light scattering (DLS) measurements and transmission electron microscopy (TEM). As shown in Table 2, the
average particle sizes (hydrodynamic diameters) of the nanoparticles (NPs) show a general decrease in the order of PD1 4
PD2 4 PD3 4 PD4, while the PDI values are low indicating
narrow size distribution of the self-assemblies. TEM images of
the NPs formed by PD1PD4 (Fig. 6A and Fig. S2, ESI) reveal
that they are approximately spherical in shape with the average
diameters between 20 and 100 nm which agree with DLS
measurements (Table 2).

This journal is The Royal Society of Chemistry 2015

Fig. 5 Photoluminescence spectra at the excitation wavelength of 370 nm

of functional scaolds formed by PD1 (A), PD2 (B), PD3 (C) and PD4 (D).

The photophysical characteristics of the copolymer NPs in

aqueous medium were studied by conducting photoluminescence measurements. As shown in Fig. 5 and Table 2, the
emission spectra of NPs are the same as those of PD copolymers
in THF solution. Strong blue light is emitted upon excitation at
370 nm.
An exciting feature is the high fluorescence quantum yield of
the aqueous NPs. In the case of PD1 NP, the quantum yield is
0.80, which is almost as high as that of PD1 in THF solution.
It indicates that PFMA chromophores are very well separated in
the self-assemblies, which prevents the aggregation-induced
quenching. The fact may be that a few PDMAEMA segments
are included into the core of NPs. To prove this point, the
pH value of PD2 NP aqueous solution was adjusted from its
original condition (pH = 5.8) to an acidic condition (pH = 2.0).
The quantum yield of PB solution decreased sharply from 0.75
to 0.33. This is induced by the protonization of DAMEMA
segments under acidic conditions which makes them more
hydrophilic and thus be excluded from the hydrophobic core.
The resulting increased aggregation of PFMA in the core leads
to a dramatic decrease of the quantum yield. In our previous work
on the styrene-derivative of PF (PFS),17 P(PFS-r-AA) copolymers
were also able to form NPs in water. However, their quantum yield
was only about 0.1, which was much lower than that of P(PFMA-rDMAEMA) NPs in this work. DMAEMA units are far less hydrophilic than carboxyl groups of AA units and induce a less compact
core to dramatically decrease the quenching of PFMA segments.

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The quantum yield shows a trend of decrease in the order of

PD1 to PD4, which is in accordance with the decrease of
particle size. A smaller size may have a tendency to form
stronger aggregates with a relatively close packing of chromophores and thus lead to the decrease of quantum yield.38

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3.4. Preparation of various photoluminescent nanoparticles

by incorporating dyes into functional scaolds
The blue emission and high quantum yield make the polymers
excellent functional scaolds to prepare photoluminescent
NPs. On the one hand, hydrophobic dye molecules can be
incorporated into the core of NP through hydrophobic interactions in aqueous solution. On the other hand, PFMA units are
able to absorb UV light at a certain wavelength and transfer the
energy via FRET to nearby acceptors, i.e. the loaded dyes.17,3845
Green, red and white colors can be easily achieved by carefully
selecting the doped dyes, i.e. the energy acceptors. White
emission is especially important because of its wide applications.17,4244 Thus, multi-color emissions can be realized upon
excitation of only one wavelength for PFMA.
Organic dyes including C6, NR and DCM are selected to
dope into the functional PD2 NP scaold. The choice of these
three organic dyes meets the following two requirements. First,
the absorption bands of the dyes overlap the emission band of
PFMA (Fig. S3, ESI), which allows FRET from excited PFMA
Table 3

3.5. Photoluminescent behavior of NPs in solution and in

bulk (as thin films)
1

rsters law (R0 = 9.78  103[k2n 4QDJ(l)]6), FRET

According to Fo
from an energy donor to an acceptor is ecient only when the
distance between them is shorter than 10 nm.46 As measured
above, the average diameters of NPs are between 80 and 140 nm

Composition and DLS results of PB, PG, PO, PR and PW NPs

NP

Composition

PB
PG
PR
PO
PW

PD2
PD2
PD2
PD2
PD2

units (energy donors) to dyes (energy acceptors). Second, upon

excitation, C6, NR and DCM show green, red and orange
emissions, respectively, which enables the construction of
photoluminescent NPs with various emission colors. It is to
be noted that undoped PD2 scaolds give a blue emission upon
excitation and provide thereby photoluminescent NPs with blue
color, short as PB, while other NPs containing C6, NR, and
DCM dyes are named as PG (green), PR (red) and PO (orange),
respectively. Another type of NPs (PW) is prepared by incorporating a mixture of C6 and NR into PD2 scaolds to generate
white emission. The loading ratios of the photoluminescent
NPs, particle sizes and morphologies are shown in Table 3 and
Fig. 6. DLS analysis shows relatively narrow dispersions of NPs
whose diameters are between 70 and 140 nm. TEM images
reveal that NPs are approximately spherical in shape. The
average diameters of the particles obtained from TEM analysis
are between 60 and 120 nm which are in good agreement with
the DLS results.

scaolds
scaolds
scaolds
scaolds
scaolds

without doping
doped with C6 (0.3 wt%)a
doped with NR (0.27 wt%)a
doped with DCM (0.25 wt%)a
doped with C6 (0.15 wt%) and NR (0.2 wt%)a

Diameter (nm)

PDI

70.6
81.9
107.0
96.2
136.7

0.28
0.29
0.35
0.28
0.31

Weight percentage compared to PD2.

Fig. 6 TEM images of PB (A, undoped PD2 NP), PG (B, NPs containing C6), PR (C, NPs containing NR), PO (D, NPs containing DCM) and PW (E, NPs
containing C6 and NR). The detailed compositions are listed in Table 3.

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and hydrophobic dyes located close to PFMA. Thus, the intraparticle FRET from PFMA units to doped dyes can occur, while
the inter-particle FRET should be negligible since the distance
between the cores of two NPs is much larger than 10 nm.
Successful intra-particle FRET is confirmed by measuring
the photoluminescent behavior of aqueous solutions of NPs, as
shown in Fig. 7A. Their UV-Vis spectra are shown in Fig. S4
(ESI). Upon exciting at 370 nm (excitation wavelength for
PFMA), both the characteristic emission of PFMA and that of

Paper

individual dyes are observed. In the emission photograph

(Fig. 7E), PG, PR and PO NPs generate green, red and orange
light, respectively. The blue emission of PFMA units remains in
the doped NPs, which is stronger in the case of PR and PO due
to the limited overlap of PFMA emission band with the NR and
DCM absorption bands (Fig. S3, ESI). Fortunately, this remaining
blue emission is needed for the white emission NPs. PW is
prepared by doping a mixture of C6 and NR of appropriate ratio
(3 : 4) into the scaold. The FRET in PW NPs is more complicated

Fig. 7 Photoluminescence spectra of NPs in aqueous solution (A) and in bulk as films (B). Photos of NPs in solution and their films under sunlight (C and
D) and UV light (365 nm) (E and F). Samples a and a* (PB), b and b* (PG), c and c* (PR), d and d* (PO), and e and e* (PW) represent NPs in solution and in
bulk as films, respectively.

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Fig. 8 1931 CIE coordinate diagram of NPs in solution (A) and in bulk as films (B). All sample names are the same as those given in Fig. 7.

than that in the single component NPs, since the energy transfers
occur simultaneously from PFMA to C6, PFMA to NR, and C6 to
NR. The photoluminescence spectrum of PW shows strong white
emission composed of balanced green, red and blue lights
(Fig. 7A).
The emission stability of PW NP was investigated by comparing a sample stored for three months in the dark with a freshly
prepared one. The PL spectra are shown in Fig. S5 (ESI). As the
emission is almost the same after storage for three months,
excellent stability of the PW NP can be concluded.
As an advantage of aqueous solution, NPs are able to form
homogeneous fluorescent films when being cast directly on the
quartz surface. Their emission spectra and the photograph in
the film form are included in Fig. 7B and F. Similar to the
behavior in aqueous solutions, ecient and steady energy
transfers from PFMA to doped dyes occur in NP films. The
emissions of PR and PO films exhibit a slight blue shift and a
little decrease of intensity compared to the emissions of the
corresponding NPs in solution (Fig. 7A and B). This may be
caused by slight intra-particle phase separation of dyes, which
results in a slight aggregation quenching. Fortunately, this
phenomenon leads to a positive eect on the PW film whose
color output is more balanced than that of PW NP solution. The
1931 CIE coordinates of all the NP solutions and their films are
summarized in Fig. 8. The CIE coordinates of both PW solution
and PW film locate in the white emission region. Moreover, the
CIE coordinates of the film at this particular composition are
found to be (0.30, 0.33), which are very close to the center of
(0.33, 0.33).
3.6. Application of photoluminescent NPs in functional
coating and ink-jet printing
PDMAEMA segments can be crosslinked by tetramethoxysilane
(TMOS).47 It extends the application of NPs as fluorescenceactive coating materials. The crosslinking of interparticles
by TOMS guarantee a tolerant film formed on the surface of

J. Mater. Chem. C

Fig. 9 Photos of plaster models coated with PB, PG and PR NPs under
sunlight (A and C) and UV light (365 nm) (B and D). The object sizes are
ranging from 5 to 10 cm.

plaster models. After crosslinking, a solid silica shell on the

photoluminescent NPs retains the color of NPs and restricts the
mobilization of incorporated dyes, and thus improves the
endurability of NPs. As an example, we use the crosslinked
NPs to coat plaster models with a rather rough surface. Fig. 9
shows the photos of the plaster models coated with crosslinked
PB, PG and PR NPs in patterns simply by using a painting
brush. The thin and transparent coating does not change
the appearance of plaster models at all under sunlight, but
presents strong and colorful emission under UV light at the
wavelength of 365 nm. It is worth mentioning that the uncoated
area remains dark (invisible) under UV light.
One of the major advantages of water-soluble fluorescent
materials is that they can be feasibly processed by printing
technology to build electric or optical devices.4851 We apply NP
solutions in an color ink-jet printer directly by replacing the
blue, green and red inks with PB, PG and PR NP aqueous
solutions and print different patterns on a piece of paper.

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Fig. 10 Schematic illustration of the ink-jet printing process by using the NP solutions. Photographs of the paper printed with dierent patterns under
sunlight and UV light (365 nm). The first line of the patterns contains four Chinese characters from left to right printed by PB, PG, PR solutions and the
original black ink, respectively. The pattern below is the university badge printed by PB solution.

As illustrated in Fig. 10, four Chinese characters are colored by

PB, PG, PR solutions and the original black ink from left to
right, respectively. The first three characters cannot be seen
under sunlight. In contrast, they emit blue, green and red light
under UV excitation with very exquisite printing edges.
A further pattern of the university badge (below the character
lines) is also successfully printed by using the blue-emitting
PB NP ink. Based on the results above, our NPs possess a high
application potential as photoluminescent materials for functional coating and printing technology.

4. Conclusions
A novel polyfluorene-containing methacrylate macromonomer
(PFMA) is synthesized and polymerized with DMAEMA via
RAFT to random copolymers. NPs in aqueous solution prepared
from the amphiphilic copolymers give out blue emission with
high quantum yields over 80%. These PFMA-involved NPs serve
as functional scaolds to bear various dyes. By incorporating
C6, NR and DCM dyes, photoluminescent NPs emit predominantly green, red and orange light upon excitation. NPs with
white emission are obtained by doping C6 and NR with the
ratio of 3 : 4 into the scaolds. All of the NPs show eective
energy transfer and robust photoluminescence both in solution
and in bulk as thin films. NPs can be painted on plaster models
forming a fascinating fluorescent coating. In another example,
the blue, green and red NP solutions are directly used as
fluorescent inks and processed by an ink-jet printer. We
demonstrate promising applications of the PFMA-containing
polymers and more are in progress.

Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (No. 21374093). J. L. thanks Prof.
Dr. Thieo E. Hogen-Esch of the University of Southern California
for helpful discussions.

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