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Strong Fluorescence of Poly(Nvinylpyrrolidone) and Its Oxidized Hydrolyzate

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DOI: 10.1002/marc.201400516

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Macromolecular
Rapid Communications

Communication

Strong Fluorescence of Poly(N-vinylpyrrolidone)

and Its Oxidized Hydrolyzate
Guoshan Song, Yannan Lin, Zhongcheng Zhu, Heying Zheng, Jinping Qiao,
Changcheng He, Huiliang Wang*

PL Intensity

Discovering uorescence of existing compounds, which are generally regarded as non-uorescent, is of important academic and technical signicance. This article reports the uorescence of common compounds containing pyrrolidone ring(s) and their oxidized hydrolyzates.
Poly(N-vinylpyrrolidone) (PVP), polymerized from a very weak uorescent monomer N-vinyl2-pyrrolidone (NVP), exhibits strong intrinsic uorescence. Moreover, the uorescence of its
hydrolyzate is dramatically enhanced by about 1000 times. The hydrolyzate of N-methylpyrrolidone (NMP) also exhibits signicantly enhanced uorescence. By studying the chemical structures and uorescence of the hydrolyzates, the enhanced uorescence is attributed to
the formation of secondary amine oxide. The much stronger
1000
NVP, 1.0 wt.%
uorescence of the polymers compared to the corresponding
PVP, 1.0 wt.%
800
Oxidized PVP hydrolyzate
small molecular compounds is ascribed to the aggregation1.010 wt.%
600
induced emission (AIE) effect of the luminophores. PVP and
its oxidized hydrolyzate also show some phenomena dif400
ferent to the common AIE effect. The uorescence of PVP and
200
its oxidized hydrolyzate shows stimuli response to metal ions
0
and pH values. This study introduces novel uorescent mate350
400
450
500
550
(nm)
rials for various potential applications.

1. Introduction
Fluorescent materials have broad applications in biosensors,[1] cellular imaging,[2] drug delivery,[3] and so on. The
most commonly studied uorescent materials include
uorescent proteins (especially green uorescent proteins),[4] quantum dots (QDs),[5] and uorescent organic
dyes.[6] Many organic dyes containing benzene rings or
heterocyclic rings usually show aggregation-caused
quenching (ACQ) effect, which is harmful to their practical applications.[7] Tang and co-workers discovered the
G. S. Song, Y. N. Lin, Z. C. Zhu, H. Y. Zheng,
Dr. J. P. Qiao, Dr. C. C. He, Prof. H. L. Wang
College of Chemistry, Beijing Key Laboratory of Energy
Conversion and Storage Materials, Beijing Normal University,
Beijing 100875, China
E-mail: wanghl@bnu.edu.cn

-3

aggregation-induced emission (AIE) effect of some novel

types of organic or polymeric uorescent materials based
on silole derivatives.[8] The AIE uorescent materials are
nonemissive in dilute solutions but highly luminescent
when they are in concentrated solutions or casted into
solid lms.
Luminescent polymers are generally constructed by
-aromatic building blocks functioning as emitting units.
But in recent years it was found that the polymerization
of some nonuorescent monomers without incorporating
any uorescent units can produce uorescent polymers.[9]
The most investigated luminescent polymers are dendritic and hyperbranched polymers containing tertiary
amine moieties, such as poly(amido amine) (PAMAM),[10]
poly(amino ester)s (PAE),[11] poly(ether amide)s (PEA),[12]
and polyureas (PURE).[13] The N-branched tertiary amine
moiety is thought to be the luminogen of the polymers,
and the oxidation of the tertiary amine is attributed to

Macromol. Rapid Commun. 2014, DOI: 10.1002/marc.201400516

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photoluminescence. Meanwhile, some other polymers

containing only carbonyl and ester groups rather than
tertiary amine are also reported to be luminescent. For
example, Tang and co-workers observed an AIE effect in
colloidal nanoparticles of poly[(maleic anhydride)-alt(vinyl acetate)], and they thought that the reason may be
related to the molecular interactions between the vemembered dihydrofuran-2,5-dione rings.[14] A similar
AIE effect has also been observed for a polymer carrying
a succinic anhydride moiety[15] and a multiblock polymer
obtained via poly(trithiocarbonate) (PTTC)-mediated RAFT
polymerization of N-isopropyl acrylamide (NIPAM).[16]
Poly(N-vinylpyrrolidone) (PVP) is a commercially available water-soluble, uncharged and nontoxic polymeric
material, and it has been widely used in textile, pharmaceutical, and other industries.[17] The characteristic chemical structure of PVP is that pendant pyrrolidone rings (a
lactam) are attached to the main chain, which is linear
rather than hyperbranched. To our knowledge, photoluminescence of PVP has never been reported. Our work
proves that PVP exhibits intrinsic strong uorescence;
in addition, the oxidized hydrolyzates of both polymeric
and small molecular compounds containing pyrrolidone
ring(s) show much enhanced uorescence.

was carried out under magnetic stirring in air atmosphere, or

bubbling with O2, or adding with H2O2 (0.15 mol L1) at 50 C for
different periods.

2.4. Fluorescence Spectroscopy

The uorescence spectra of the aqueous solutions were recorded
on a Cary Eclipse uorescence spectrophotometer (Varian Inc.,
Walnut Creek, CA, USA) at room temperature, the excitation
wavelength (ex) was selected as 310 nm, the excitation and the
emission slit width was 10 nm, if not otherwise stated. Photographs of the solutions under UV illumination were taken with
a Canon D600 camera in a dark room. The exposure times were
automatically adjusted by the camera.

2.5. Characterization
1H

NMR spectra were recorded on a Bruker Avance III 400 MHz

with auto-sampler (Bruker BioSpin GmbH, Rheinstetten,
Germany) at ambient temperature, using D2O as solvent. Fourier
transform-infrared (FT-IR) spectra of the samples were measured
on a Nicolet Avatar E. S. P. 360 FT-IR spectrometer (Thermo Electron Corporation, USA). The number of scans was 32 at a resolution of 4 cm1.

3. Results and Discussion

2. Experimental Section

3.1. Fluorescence of PVP and Its Hydrolyzate

2.1. Materials
PVP (Mw = 40 000, high pure grade) was purchased from Alfa
Aesar Co., Inc. (MA, USA) and Amresco Inc. (OH, USA). N-vinyl2-pyrrolidone (NVP, AR grade) and 4-(methylamino)butyric
acid hydrochloride were purchased from Acros Organics (New
Jersey, USA), they were puried before use. N-methylpyrrolidone
(NMP, AR grade) was from Sinopharm Chemical Reagent Co., Ltd.
(Shanghai, China) and was used as received. The other chemicals
used were all AR grade.

2.2. PVP Synthesis

PVP was rstly prepared by radiation-induced polymerization of
NVP. NVP aqueous solution (8.0 wt%) was deaerated with highpurity nitrogen and then was sealed, and then the solution was
irradiated with 60Co gamma rays at a dose rate of 30 Gy s1 for
different times. In addition, PVP was also prepared by H2O2-initiated polymerization of NVP. NVP aqueous solution (30 wt%) with
H2O2 (0.18 wt%) was deaerated with high-purity nitrogen and
then was heated at 52 C for 72 h.

2.3. Hydrolysis and Oxidation

The hydrolysis of NMP and PVP was carried out in aqueous solutions (pH 14, adjusted with NaOH) under magnetic stirring in air
atmosphere at 50 C for different periods. The oxidation of 4-(methylamino) butanoate (MBA) in aqueous solutions (0.5 mol L1)

We found with some surprise that the aqueous solutions of

commercial PVP exhibit uorescence. A question arising is
that the uorescence of PVP solutions is from PVP or from
some unknown uorescent impurities. PVP is polymerized from the monomer NVP. We found that the puried
NVP exhibits very weak uorescence with a maximum
emission wavelength (em) at about 350 nm, whereas the
commercial PVP shows much stronger uorescence with a
em around 380 nm (Figure 1a). To prove the strong uorescence of PVP is its inherent properties, we employed
-ray-induced polymerization, which does not introduce
any uorescent impurities, to synthesize PVP. The irradiated solutions show similar uorescence spectra as that
of the purchased PVP, and the uorescent intensity of the
irradiated solution increases with increasing irradiation
time (Figure S1, Supporting Information). It is reported that
the conversion of NVP to PVP increases with increasing
irradiation time.[18] Therefore, the increased uorescent
intensity is due to the formation of PVP. We also synthesized PVP by convenient radical polymerization initiated
by hydrogen peroxide. Great care was taken in the process
to avoid introducing any uorescent impurities into the
solutions. After the polymerization, the uorescence intensity of the PVP solution increases dramatically (Figure 1a).
The commercial and self-made PVPs show very similar

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Figure 1. Fluorescence emission spectra of aqueous solutions of small molecular and polymeric compounds containing pyrrolidone ring(s)
and their hydrolyzates, ex = 310 nm. a) NVP, commercial PVP, and self-made PVP aqueous solutions (1 wt%); b) PVP solutions with different
concentrations; c) PVP and its hydrolyzate; d) NMP and its hydrolyzate. Hydrolysis conditions: air atmosphere, pH 14, 50 C, 30 d. The inset in
(a) shows the photographs of NVP (left) and PVP (right) solutions under UV illumination, the inset in (b) shows a linear relationship between
the uorescence intensity and PVP concentration, and the insets in (c) and (d) show the photographs of PVP and NMP before (left) and after
(right) hydrolysis under UV illumination, respectively.

uorescence emission spectra with em at around 380 nm,

and they have similar uorescence intensity at the same
concentration. Figure 1b shows that there is a linear relationship between the uorescence intensity and PVP concentration. These experiments prove that the increased
uorescence intensity is due to the formation of PVP, i.e.,
PVP is a uorescent material.
More impressively, when PVP is hydrolyzed in an alkaline (NaOH) solution in air atmosphere, its uorescence is
further dramatically enhanced. The uorescence intensity of the hydrolyzate at a concentration of 1.0 103 wt%
(Figure 1c) is similar to that of PVP at the concentration
of 1.0 wt% (Figure 1a), suggesting that the uorescence of
PVP hydrolyzate is about 1000 times that of PVP.
3.2. Fluorescence Mechanism
NVP contains a vinyl group and a pendant pyrrolidone
ring. The pyrrolidone ring should be the luminogen, since
after polymerization the formed PVP does not contain vinyl
group anymore. We used N-methyl pyrrolidone (NMP), the
simplest compound with a pyrrolidone ring, as the model
compound to study the uorescence of the compounds
with a pyrrolidone ring and their uorescence mechanism.

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Similar to NVP, NMP also exhibits very weak uorescence

with em at about 420 nm, but when it is hydrolyzed in air
atmosphere in a NaOH solution its uorescence is dramatically enhanced, showing em at about 425 nm (Figure 1d).
A blue uorescent emission can be seen when the solution
is irradiated with UV light (the inset in Figure 1d). Signicant enhancement in UVvis absorbance is also observed
for the hydrolyzates, and an additional absorption peak is
found in the UVvis spectra for PVP at 307 nm and NMP at
340 nm, respectively (Figure S2, Supporting Information).
The lactam bond linkage of a pyrrolidone ring can be
easily hydrolyzed in an alkaline solution, producing a
hydrolyzed product with a secondary amine and a carboxylate separated by three CH2 groups (Scheme 1).[19] For
NMP, its fully hydrolyzed anionic product is MBA.
MS analysis proves that NMP has been hydrolyzed to
MBA, as shown with a base peak at m/z = 115.8 (Figure S3,
Supporting Information). FTIR analyses also prove the
hydrolysis of NMP to MBA (Figure S4, Supporting Information). 1H NMR analyses of the solutions reacted for different times allow us to calculate the degree of hydrolysis
of NMP quantitatively. As shown in Figure 2a, with the
progress of hydrolysis, proton signals attributed to MBA
appear and they increase with the reaction time with

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O
H
N

Alkal.
R

O-

H2O
O

O
N
R

OH

O
-

N
R

Scheme 1. Hydrolysis of the pyrrolidone ring and oxidation of secondary amine.

comparison to those of NMP. The degree of hydrolysis of

NMP, calculated from the intensity of the proton signals
of MBA and NMP, increases quickly in the rst 2 d and
then slowly to about 90% at 7 d (Figure 2b).
If the hydrolyzed product of NMP, i.e., MBA, is the
luminophore responsible for the uorescence, then the
uorescent intensities of the solutions reacted for different times should show a similar pattern as that for the
degree of hydrolysis. However, the uorescence intensity
increases gradually with the reaction time (Figure 2b),
even when the degree of hydrolysis is almost con-

Figure 2. a) 1H NMR spectra of NMP reacted in an NaOH solution for different times. b) The degree of hydrolysis of NMP (open
square) and the corresponding uorescence intensity (closed
square) of the solutions as a function of reaction time, ex =
310 nm. Reaction conditions: CNMP = 0.33 mol L1, pH 14, 50 C, air
atmosphere.

stant after 4 d. Moreover, we tested the uorescence of

pure MBA in an aqueous solution, which is obtained by
reacting 4-(methylamino)butyric acid hydrochloride with
NaOH, but no uorescence was observed (Figure S5, Supporting Information). Therefore, we can infer that MBA
is not the luminophore, and some new luminophores
should have been formed during the hydrolysis of NMP.
It is known that secondary amines can be easily oxidized to produce hydroxylamine or NO compounds.[20]
As the hydrolysis of NMP was carried out in the air atmosphere, so the hydrolyzed product MBA may react with the
oxidative O2 in air to produce hydroxylamine and/or secondary amine oxide (Scheme 1). The new absorption peaks
found in the UVvis spectra of hydrolyzed PVP and NMP
indicate the formation of new chromophores (Figure S2,
Supporting Information). FTIR and MS characterizations prove the existence of oxidized products. Hydroxylamine is unstable and hence is difcult to be characterized. The MS spectrum of the oxidized MBA (MBAO)
shows a signal at m/z = 152 (MBAO + Na+) (Figure S6,
Supporting Information). The FTIR spectrum of MBAO
does not show the distinct characteristic NO absorption bands at 15851539 cm1 and 14201250 cm1,
which are overlapped with absorption bands at 1567 cm1
and 1411 cm1 attributed to antisymmetrical and symmetrical stretching of COO in carboxylic acid salts.[21]
Luckily, a new absorption band at 877 cm1[21] attributed
to C-NO stretching appears (Figure 3a). Similar hydrolysis
and oxidation reactions occur when PVP is hydrolyzed in
air atmosphere, as proven by the FTIR characterization
(Figure S7, Supporting Information).
When NMP is hydrolyzed in NaOH solution in air for
30 d, the excitation and emission spectra have the maximum excitation wavelength (ex) at 379 nm and em at
458 nm, respectively (Figure 3b). When the nonuorescent MBA solution is oxidized with O2 or H2O2, obvious
uorescence can be found, showing peaks with the ex
at 384 nm and em at about 465 nm (Figure 3c,d). Therefore, we conclude that the secondary amine oxide group
(NO) is the luminogen for the uorescence.
PVP and its oxidized hydrolyzate exhibit much stronger
uorescence than the small molecular molecules NVP,
NMP, and its oxidized hydrolyzate (MBAO). The major
difference between the polymers and the small molecules
is that the luminophores (pyrrolidone rings and the secondary amine oxides) are held together in the polymer
chains whereas for the small molecules they are separated
by water molecules in the aqueous solutions. In addition, it
is found that PVP and its hydrolyzate aggregate in aqueous
solutions to form nanoparticles, whereas NMP and its
hydrolyzate cannot aggregate even at a much higher
concentration (Figure S8, Supporting Information). It is
worthy of noting that both the maximum wavelengths of
uorescent emission (Figure 1c, d) and UVvis absorption

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Figure 3. a) FTIR spectra of MBA and its oxidized product reacted in air atmosphere for 30 d. bd) Excitation (dashed lines) and emission
(solid lines) spectra of NMP and MBA solutions reacted under different conditions: b) NMP (1.0 mol L1) and NaOH (3.0 mol L1) reacted in
air atmosphere at 50 C for 30 d; c) MBA (1.0 mol L1) solution in air atmosphere at 50 C for 30 d; d) MBA (1.0 mol L1) solution with H2O2
(0.15 mol L1) at 50 C for 1 d. The excitation and emission slit widths were 2.5 and 5 nm for (b, d), and 5 and 10 nm for (c), respectively.

(Figure S2, Supporting Information) for PVP and its oxidized hydrolyzate are lower than those for NMP and its
oxidized hydrolyzate, suggesting that the aggregation of
chromophores or luminophores leads to the intermolecular interactions between them and hence increases the
energies. It is known that the uorescence of tertiary aliphatic amines can be easily quenched by solvents, and collisional relaxation is a very important factor inuencing
the uorescence efciency.[22] Pan and co-workers demonstrated that tertiary aliphatic amine in branching units of
hyperbranched polymers exhibits high uorescence efciency, and they thought the reason is that the decreased
mobility of tertiary amine in the hyperbranched polymers
lowers the possibility of collisional relaxation.[11b] Very
possibly, for PVP and its oxidized hydrolyzate, the aggregation of luminophores in a polymer chain and in nanoparticles (a conned space) lowers their mobility and
hence decreases collisional relaxation with solvent molecules, leading to their very strong uorescence.
The excitation wavelength has a signicant effect on
the emission wavelength and intensity when scattering
phenomena due to aggregation are present. The uorescence intensity increases with excitation wavelength till
310 nm and then decreases (Figure S9a, Supporting Information). While the emission wavelengths keep almost

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constant at about 377 nm when the excitation wavelengths are less than 290 nm, and then they red-shift as
excitation wavelength increases to be more than 300 nm
(Figure S9b, Supporting Information). Similar results have
been reported for hyperbranched poly(amido amine)s
(HPAMAMs).[10d] In addition, temperature also affects
the uorescence intensity of the PVP aqueous solutions, which decreases with the increase of temperature
(Figure S10, Supporting Information), due to the high nonradiative decay rate of excited state at high temperatures.
It is necessary to mention that PVP and its oxidized
hydrolyzate show some phenomena different to common
AIE effect. For instance, AIE compounds emit strong uorescence when they are in the solid state or dispersed in
the mixed solvents containing a poor solvent.[8] PVP and
its oxidized hydrolyzate do not emit strong uorescence
in the solid state. In addition, when acetone, a poor solvent for PVP, is added, the uorescence intensity gradually decreases with the increase of the volume ratio of
acetone till 60%, but it increases when the volume ratio
of acetone is more than 80%, and it is even higher in
pure acetone than in pure water (Figure S11a, Supporting
Information). In addition, the em of PVP rstly red-shifts
with the increase of the volume ratio of acetone, from
387 nm in pure water to 410 nm in the mixed solvent

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with the water/acetone ratio of 50/50, while in the mixed

solvent with the water/acetone ratio of 20/80 and in
pure acetone, the em is blue-shifted to about 366 nm.
Dynamic light-scattering experiment results (Figure S11b,
Supporting Information) prove that there is not a direct
correlation between the uorescence intensity and the
size of aggregates. For hyperbranched PAMAMs[10d] and
poly(amine-ester) (HypET),[11b] their uorescence intensity increases with increasing the molecular weight. The
PL intensity of the PVP aqueous solutions rstly increases
with the increase of molecular weight till 3.0 104 and
then decreases (Figure S12, Supporting Information). The
possible reason is the strong physical entanglement of
very long, linear polymer chains prevents the formation
of PVP aggregates. These phenomena may suggest that
the polymers only emit strong uorescence when they
have proper conformations in the solutions, which allow
the intermolecular interactions among the luminogens.
3.3. Stimuli Response of Fluorescence of PVP and Its
Hydrolyzate
PVP can form complexes with many metal ions,[23] and the
stability of the metal complexes increases with increasing
of the metal ion charge/radius ratio.[24] Figure 4a shows the
uorescence spectra of the PVP solutions (1.0 wt%) added

with different metal ions. To avoid the inuence of anions,

the same anion Cl was chosen. The uorescence intensity
of the PVP solutions decreases in all cases, but the decrease
varies signicantly with the types of metal ions, i.e., the
uorescence of the PVP solution with the metal ion of a
higher charge/radius ratio is usually weaker. The decrease
in uorescence intensity is very small for Ba2+ and Cd2+,
but it becomes more signicant for Mn2+, Co2+, Ni2+, Cu2+,
and Cr3+ in an increasing order. Among the metal ions,
Fe3+ has the biggest charge/radius ratio, and therefore it
forms the strongest interaction with PVP. Impressively, the
uorescence of the PVP solution added with Fe3+ decreases
to nearly zero, suggesting that the uorescence of PVP is
extremely sensitive to Fe3+. The uorescence intensity of
the PVP solutions decreases dramatically with increasing
Fe3+ concentration. An obvious decrease can be found at a
concentration of 5.0 105 or 5.0 106 mol L1 (Figure 4b),
indicating the extremely low detection level of Fe3+.
pH-dependent uorescence has been reported for NH2terminated PAMAM dendrimers[25] and CO2H-terminated
hyperbranched poly(amido acids) (HBPAAs),[26] showing
maximum emissions at pH around 2.5 and 9, respectively.
We measured the emissions of the PVP hydrolyzate in
aqueous solutions with different pH values. Two maxima
are observed at the pH values around 4 and 9 (Figure 4c).
The possible reason is that the PVP hydrolyzate contains

Figure 4. a,b) Fluorescence emission spectra of PVP aqueous solutions (1.0 wt%) added with different metal ions of the same concentration (5.0 102 mol L1) (a), and added with Fe3+ ion of different concentrations (b). c) The uorescence intensity of the PVP hydrolyzate
(0.01 wt%) in aqueous solutions with different pH values, and d) multiple reversible acid-base response of the uorescent intensity of the
PVP hydrolyzate.

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both carboxyl (acidic) and secondary amine (basic) groups,

which have different pKa values. The pH value of the
aqueous solutions affects the protonation/deprotonation of the two groups oppositely and hence might affect
the aggregation and intermolecular interactions of the
PVP hydrolyzate. The uorescence of the PVP hydrolyzate
can be easily adjusted by adding an acid or a base, and it
undergoes reversible change in emission intensity upon
adding stoichiometric amounts of HCl and NaOH repeatedly (Figure 4d). In addition, it is also found that the uorescence of PVP in water (a protic solvent) and acetone
(an aprotic solvent) also responds to pH value, it decreases
slightly in water while increases signicantly in acetone
at the pH of 1 (Figure S13, Supporting Information).

4. Conclusion
We demonstrated that small molecular compounds containing a pyrrolidone ring (e.g., NMP) exhibit very weak
uorescence, but their hydrolyzates obtained by the
hydrolysis reaction in air atmosphere in an alkaline solutions exhibit dramatically enhanced uorescence, due
to the formation of secondary amine oxide (NO). More
importantly, the polymeric compound containing pendant
pyrrolidone rings (PVP) and its oxidized hydrolyzate exhibit
much stronger uorescence than the corresponding
small molecular compounds. Our work proves that linear
polymers containing pyrrolidone rings, different to those
mostly studied dendritic and hyperbranched polymers
containing tertiary amine moieties, can also exhibit
strong uorescence. In addition, the oxidation product
of secondary amine rather than tertiary amine is proved
to be the luminogen for the enhanced uorescence. Very
possibly, many other small molecular or polymeric compounds with pyrrolidone ring(s) and their oxidized hydrolyzates, or more widely amine oxides, might also emit
strong uorescence. Our preliminary study proves that
the oxidation of primary, secondary, and tertiary amines
all leads to signicant increase in uorescence. The uorescence of PVP and its oxidized hydrolyzate shows stimuli
response to metal ions and acidbase, and very possibly
some other chemicals. Further study on the uorescence
mechanism of these compounds will lead to the development of novel high-efcient uorescent materials for various applications.

Supporting Information
Supporting Information is available from the Wiley Online
Library or from the author.
Acknowledgements: This work is supported by the National
Science Foundation of China (grant number 21274013) and the
Fundamental Research Funds for the Central Universities.

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Received: September 11, 2014; Revised: October 24, 2014;

Published online: ; DOI: 10.1002/marc.201400516
Keywords: aggregation-induced
emission;
uorescence;
hydrolyzates; poly(N-vinylpyrrolidone); secondary amine oxides

[1] a) Z. Song, Y. Hong, R. T. K. Kwok, J. W. Y. Lam, B. Liu,

B. Z. Tang, J. Mater. Chem. B 2014, 2, 1717; b) W. Zhang, L. Xu,
J. Qin, C. Yang, Macromol. Rapid Commun. 2013, 34, 442.
[2] a) L. Bai, W. Li, J. Chen, F. Bo, B. Gao, H. Liu, J. Li, Y. Wu, X. Ba,
Macromol. Rapid Commun. 2013, 34, 539; b) Y.-X. Wu,
J.-B. Li, L.-H. Liang, D.-Q. Lu, J. Zhang, G.-J. Mao, L.-Y. Zhou,
X.-B. Zhang, W. Tan, G.-L. Shen, R.-Q. Yu, Chem. Commun.
2014, 50, 2040; c) H. Shi, H. Sun, H. Yang, S. Liu, G. Jenkins,
W. Feng, F. Li, Q. Zhao, B. Liu, W. Huang, Adv. Funct. Mater.
2013, 23, 3268; d) M. Chen, M. Yin, Prog. Polym. Sci. 2014, 39,
365.
[3] a) F. Qiu, D. Wang, Q. Zhu, L. Zhu, G. Tong, Y. Lu, D. Yan,
X. Zhu, Biomacromolecules 2014, 15, 1355; b) B. Kang,
M. M. A, L. A. Austin, M. A. El-Sayed, ACS Nano 2013, 7,
7420.
[4] J. N. Brantley, C. B. Bailey, J. R. Cannon, K. A. Clark,
D. A. Vanden Bout, J. S. Brodbelt, A. T. Keatinge-Clay,
C. W. Bielawski, Angew. Chem. Int. Ed. 2014, 53, 5088.
[5] a) A. P. Alivisatos, Science 1996, 271, 933; b) Y. Song, S. Zhu,
B. Yang, RSC Adv. 2014, 4, 27184; c) A. Lourenco, T. Casimiro,
V. D. B. Bonifacio, Talanta 2014, 125, 319.
[6] a) M. Li, L.-H. Feng, H.-Y. Lu, S. Wang, C.-F. Chen, Adv.
Funct. Mater. 2014, 24, 4405; b) A. Braganca, M. Araujo,
V. D. B. Bonifacio, Part. Part. Syst. Charact. 2014, DOI:
10.1002/ppsc.201400120.
[7] a) C. Munkholm, D. R. Parkinson, D. R. Walt, J. Am. Chem. Soc.
1990, 112, 2608; b) B.-P. Jiang, D.-S. Guo, Y.-C. Liu, K.-P. Wang,
Y. Liu, ACS Nano 2014, 8, 1609.
[8] a) J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu,
H. S. Kwok, X. Zhan, Y. Liu, D. Zhu, B. Z. Tang, Chem. Commun.
2001, 1740; b) Y. Hong, J. W. Y. Lam, B. Z. Tang, Chem. Soc.
Rev. 2011, 40, 5361; c) A. Qin, J. W. Y. Lam, B. Z. Tang, Prog.
Polym. Sci. 2012, 37, 182.
[9] T. Huang, Z. Wang, A. Qin, J. Z. Sun, B. Z. Tang, Acta Chim.
Sinica 2013, 71, 979.
[10] a) G. A. Crosby, J. N. Demas, J. Phys. Chem. 1971, 75, 991;
b) W. I. Lee, Y. Bae, A. J. Bard, J. Am. Chem. Soc. 2004, 126,
8358; c) L. Cao, W. Yang, C. Wang, S. Fu, J. Macromol. Sci.,
Part A 2007, 44, 417; d) W. Yang, C.-Y. Pan, Macromol. Rapid
Commun. 2009, 30, 2096; e) Y.-Z. You, Z.-Q. Yu, M.-M. Cui,
C.-Y. Hong, Angew. Chem. Int. Ed. 2010, 49, 1099; f) D. Wang,
Z.-Q. Yu, C.-Y. Hong, Y.-Z. You, Eur. Polym. J. 2013, 49, 4189.
[11] a) D. C. Wu, Y. Liu, C. B. He, S. H. Goh, Macromolecules 2005,
38, 9906; b) M. Sun, C.-Y. Hong, C.-Y. Pan, J. Am. Chem. Soc.
2012, 134, 20581.
[12] Y. Lin, J.-W. Gao, H.-W. Liu, Y.-S. Li, Macromolecules 2009, 42,
3237.
[13] R. B. Restani, P. I. Morgado, M. P. Ribeiro, I. J. Correia,
A. Aguiar-Ricardo, V. D. B. Bonifcio, Angew. Chem. Int. Ed.
2012, 51, 5162.
[14] C. M. Xing, J. W. Y. Lam, A. J. Qin, Y. Q. Dong, M. Haussler,
W. T. Yang, B. Z. Tang, Polym. Mater. Sci. Eng. 2007, 96,
418.
[15] A. Pucci, R. Rausa, F. Ciardelli, Macromol. Chem. Phys. 2008,
209, 900.
[16] J.-J. Yan, Z.-K. Wang, X.-S. Lin, C.-Y. Hong, H.-J. Liang,
C.-Y. Pan, Y.-Z. You, Adv. Mater. 2012, 24, 5617.

Macromol. Rapid Commun. 2014, DOI: 10.1002/marc.201400516

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Early View Publication; these are NOT the final page numbers, use DOI for citation !!

Macromolecular
Rapid Communications

G. S. Song et al.

www.mrc-journal.de

[17] T. Trellenkamp, H. Ritter, Macromolecules 2010, 43, 5538.

[18] D. Darwis, N. Hilmy, L. Hardiningsih, T. Erlinda, Radiat. Phys.
Chem. 1993, 42, 907.
[19] a) T. M. Zima, I. A. Vorsina, N. Z. Lyakhov, Inorg. Mater. 2009,
45, 524; b) M. Yin, Y. Ye, M. Sun, N. Kang, W. Yang, Macromol.
Rapid Commun. 2013, 34, 616.
[20] a) T.-H. Wu, C.-P. Liu, C.-T. Chien, S.-Y. Lin, Chem. Eur. J. 2013,
19, 11672; b) M. Thiverny, E. Demory, B. Baptiste, C. Philouze,
P. Y. Chavant, V. Blandin, Tetrahedron: Asymmetry 2011, 22,
1266; c) S.-I. Murahashi, T. Shiota, Tetrahedron Lett. 1987, 28,
2383.

[21] E. Pretsch, P. Bhlmann, C. Affolter, Structure Determination

of Organic Compounds: Tables of Spectral Data, Springer,
Berlin 2000, p. 295.
[22] C. G. Freeman, M. J. McEwan, R. F. C. Claridge, L. F. Phillips,
Chem. Phys. Lett. 1971, 8, 77.
[23] N. Tokman, S. Akman, C. Ozeroglu, Talanta 2004, 63, 699.
[24] T. aykara, R. nam, Z. ztrk, O. Gven, Colloid. Polym. Sci.
2004, 282, 1282.
[25] D. Wang, T. Imae, J. Am. Chem. Soc. 2004, 126, 13204.
[26] S.-F. Shiau, T.-Y. Juang, H.-W. Chou, M. Liang, Polymer 2013,
54, 623.

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