molecules

Communication
A New Determination Method of the Solubility
Parameter of Polymer Based on AIE
Shan Jiang 1 , Tian Ya Huang 1 , Ke Min Wang 1 , Ben Zhong Tang 2 and Qiang Yu 1, *
1 School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China;
[email protected] (S.J.); [email protected] (T.Y.H.); [email protected] (K.M.W.)
2 Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon,
Hong Kong, China; [email protected]
* Correspondence: [email protected]; Tel.: +86-1391-5023-269

Academic Editor: Youhong Tang

Received: 29 November 2016; Accepted: 21 December 2016; Published: 30 December 2016

Abstract: An accurate method of the fluorescence probe approach based on an aggregation-induced

emission (AIE) molecule (tetraphenylethylene) for measuring the solubility parameter of the polymer
is reported. This method is distinctive in that the approach can make the polymer chain conformation
in solution be related to the fluorescence intensity. Since the solubility parameter of the polymer is
also closely linked to its chain conformation in solution, the solubility parameter can be determined
by the fluorescence intensity. The range of the solubility parameter of polymethyl methacrylate
(PMMA) tested by this method was from 9.00 cal1/2 cm−3/2 to 10.00 cal1/2 cm−3/2 . The results are
more accurate than those obtained from the traditional turbidimetric titration method, ranging
from 8.60 cal1/2 cm−3/2 to 12.15 cal1/2 cm−3/2 . According to the photoluminescence (PL) intensities
spectra, the solubility parameters of PMMA and polyvinyl acetate (PVAc) are 9.19 cal1/2 cm−3/2 and
9.85 cal1/2 cm−3/2 , respectively.

Keywords: aggregation-induced emission; conformation transition; luminescence; solubility parameter

1. Introduction
Luminescent materials are rapidly being developed and have aroused great academic
interest [1–3]. Generally, a luminescent substance in the state of aggregation would produce
two different kinds of photoluminescence (PL) effects: aggregation-induced emission (AIE) and
aggregation-caused quenching (ACQ) [4–6]. When the AIE molecules aggregate in concentrated
solutions or on surfaces of solid materials, they become highly luminescent. Thus, the AIE phenomenon
can be applied in some special fields [7,8].
The solubility parameter is defined as the square root of the total energy of vaporization of the
liquid [9]. Since polymers would decompose before the heat of the vaporization could be measured,
the solubility parameter of polymer is measured indirectly, and it can be estimated from experimental
testing methods such as turbidimetric titration [10,11], viscometry [12], the swelling method [13], etc.
The interactions of polymer chains and solvent molecules are most conveniently described by the
Flory-Huggins (F-H) model [14,15], and the interaction parameters χ and the second virial coefficient
A2 are closely related to the conformations of polymer chains in solution [16]. When a polymer
dissolves in a good solvent, the polymer chains are in stretched conformations, A2 > 0, χ < 1/2; with a
bad solvent added, the polymer chains are in entangled conformations, A2 < 0, χ > 1/2. On the basis of
the Hildebrand approximation [17], polymer chains are in stretched conformations when the solubility
parameters of the solvent and polymer are similar. When choosing a good solvent for the polymer,
a mixed solvent is often adopted rather than a single solvent. The solubility parameter of the mixed
solvent δmix can be adjusted to an accurate value by Equation (1), as follows:

Molecules 2017, 22, 54; doi:10.3390/molecules22010054 www.mdpi.com/journal/molecules

Molecules 2017, 22, 54 2 of 6

Molecules 2017, 22, 54 2 of 6

δmix = δ1 φ1 + δ2 φ2 (1)

where δ1 , δ2 are the solubility parameters of δtwo mix =types

δ1φ1 +of
δ2φ
pure
2 solvents; φ1 , φ2 are the volume(1)fractions
of two types
where δ1, of pure
δ2 are thesolvents. In addition
solubility parameters of to
two considering
types of purewhether
solvents; the
φ1, φsolubility parameters of the
2 are the volume fractions
solvent and polymer are similar, some physical parameters such as the dispersion
of two types of pure solvents. In addition to considering whether the solubility parameters force, polarity
of theforce,
and hydrogen
solvent and bond should
polymer are be takensome
similar, into account
physical when choosing
parameters such aasgood solvent for
the dispersion polymers.
force, polarity
force,
In ourand hydrogen
work, bond shouldprobe
a luminescence be taken into on
based account when choosing
4-Acryloyl a good solvent for
tetraphenylethylene polymers.
(TPE-a) [18] was
introduced In into
our the
work, a luminescence
polymers polymethylprobe based on 4-Acryloyl tetraphenylethylene
methacrylate(PMMA) (TPE-a) [18]by
and polyvinyl acetate(PVAc) was
radical
introduced into the polymers polymethyl methacrylate(PMMA) and polyvinyl
copolymerizations, giving birth to AIE polymers P(MMA-co-TPE-a) (PMT) and P(VAc-co-TPE-a) (PVT)acetate(PVAc) by radical
copolymerizations, giving birth to AIE polymers P(MMA-co-TPE-a) (PMT) and P(VAc-co-TPE-a)
(Scheme 1). The solubility parameter of the solvent, in which the polymer chains are in fully stretched
(PVT) (Scheme 1). The solubility parameter of the solvent, in which the polymer chains are in fully
conformations, can serve as the solubility parameter of the polymer itself. The state of the polymer
stretched conformations, can serve as the solubility parameter of the polymer itself. The state of the
chains was observed
polymer chains wascontinuously by luminescent
observed continuously by luminescent intensity inina aseries
intensity ofsolvents
series of solvents with
with different
different
solubility parameters.
solubility parameters.

Scheme
Scheme 1. Synthesis
1. Synthesis ofofaggregation-induced
aggregation-induced emission
emission(AIE)
(AIE)polymers PMT
polymers andand
PMT PVT.PVT.

2. Results and Discussion

2. Results and Discussion
The PL spectra of PMT in THF-water mixtures with different water contents are shown in Figure 1.
The
When PLa spectra of PMT
large amount in THF-water
of water (50% vol.)mixtures
was added with different
to the water contents
THF solution, an emissionare peak
shown in Figure 1.
emerged
Whenata465 large
nm,amount of water
demonstrating (50% vol.)
a typical was added to
AIE phenomenon. the THF
Despite beingsolution,
weak, the anpolymer
emission is peak emerged
somewhat
at 465fluorescent in the THF solution.
nm, demonstrating TheAIE
a typical emission became stronger
phenomenon. Despiteprogressively
being weak, withthe
increasing
polymer theisamount
somewhat
of waterin
fluorescent in the
the mixed solvent. During
THF solution. The the process,became
emission the solubility of theprogressively
stronger PMT got worse with and the polymer the
increasing
amount of water in the mixed solvent. During the process, the solubility of the PMT got worsethe
chains changed from stretched conformations to curled conformations. At 90% vol. water content, and the
PL intensity is clearly higher than that of the 50% vol. water content solution, while the emission
polymer chains changed from stretched conformations to curled conformations. At 90% vol. water
maximum is still located at 465 nm.
content, the PL intensity is clearly higher than that of the 50% vol. water content solution, while the
Different kinds of solvents were chosen to dissolve PMT. Although all these solutions were
emission maximum is still located at 465 nm.
transparent, the PL spectra presented big differences. From the PL spectra (Figure 2), when PMT was
Different
dissolved in kinds of solvents (DCM),
dichloromethane were chosen to dissolve
the PL intensity PMT.
reached theAlthough
minimum all these
at 465 nm.solutions
Therefore, were
transparent, the PL spectra
DCM is considered presented
as a good solventbig fordifferences.
PMT. From the PL spectra (Figure 2), when PMT was
dissolvedThen,in dichloromethane
DCM was mixed with (DCM), the PL intensity
cyclohexane and ethyl reached
alcohol inthe minimum
varying at 465giving
proportions, nm. Therefore,
birth
to a series of solvents with different
DCM is considered as a good solvent for PMT. solubility parameters (Figure 3a). It was found that when the δ
of mixed solvent was below 9.00 cal 1/2cm−3/2 or above 10.00 cal1/2cm−3/2, the PL intensity and the relative
Then, DCM was mixed with cyclohexane and ethyl alcohol in varying proportions, giving birth
fluorescent
to a series quantum
of solvents withyielddifferent
(ln(I/I0)) (Figure
solubility3b) parameters
changed monotonically,
(Figure 3a). indicating that thethat
It was found polymer
when the
chains tend to shrink. Additionally, when 1/2 the−δ3/2
was below 8.50 cal1/2cm−3/21/2or above
− 3/212.00 cal1/2cm−3/2, the
δ of mixed solvent was below 9.00 cal cm or above 10.00 cal cm , the PL intensity and
polymer precipitated thoroughly. From the range of 9.00 cal1/2cm−3/2 to 10.00 cal1/2cm−3/2, the PL intensity
the relative fluorescent quantum yield (ln(I/I0 )) (Figure 3b) changed monotonically, indicating that
and ln(I/I0) decreased at first, and then they increased, indicating the minimum intensity must be in
the polymer chains tend to shrink. Additionally, when the δ was below 8.50 cal1/2 cm−3/2 or above
this range. Based on the analysis, the intersection point of the trendline on both sides of 9.50 cal1/2cm−3/2
cal1/2tocm
12.00refers −3/2 the polymer precipitated thoroughly. From the range of 9.00 cal1/2 cm−3/2 to
δ = 9.19, cal 1/2cm−3/2 (Figure 3b), which can be considered as the solubility parameter of PMT.
−
10.00 cal cm 3/2 , the PL intensity and ln(I/I0 ) decreased at first, and then they increased, indicating
1/2
Molecules 2017, 22, 54 3 of 6

the minimum intensity must be in this range. Based on the analysis, the intersection point of the
trendline on2017,
Molecules both
Molecules 54 54 of 9.50 cal1/2 cm−3/2 refers to δ = 9.19 cal1/2 cm−3/2 (Figure 3b), which
sides
22,22,
2017, 3 of36ofcan
6 be
considered as 2017,
Molecules the 22,
solubility
54 parameter of PMT. Furthermore, since the molar content of TPE 3 of 6 units is
Furthermore,
Furthermore, since the themolar
molarcontent
contentofofTPE
TPE units only 0.47%,
0.47%,which
whichisisextremely
extremely low,
itsits impact
only 0.47%, which issince extremely low, its impact units is only
on the solubility parameter low,
could be impact
neglected and the
on Furthermore,
thethe
on solubility
solubility parameter
parameter
since could
could
the molar be
beneglected
content neglected and is
of TPE units solubility
theonly
solubility parameters
0.47%, parameters
which ofofPMT
PMT
is extremely and
and
low, PMMA
PMMA
its areare
impact
solubility parameters
the same.
of PMT and PMMA are the same.
theon
same.
the solubility parameter could be neglected and the solubility parameters of PMT and PMMA are
the same.

Figure 1. Photoluminescence (PL) spectra of PMT in THF-water mixtures with different water contents
Figure 1. Photoluminescence (PL) spectra of PMT in THF-water mixtures with different water contents
(λex =1.310
Figure
Figure nm, [P] = 1 mg·mL(PL)
Photoluminescence
1. Photoluminescence
−1).
(PL)spectra
spectraof
of PMT
PMT in THF-watermixtures
in THF-water mixtureswith
withdifferent
different water
water contents
contents
(λex = 310 nm, [P] = 1 mg·mL−−11−1).
(λex(λ=ex310 nm,
= 310 [P][P]
nm, = 1= mg·mL
1 mg·mL ).).

Figure 2. PL spectra of PMT in different solvents (λex = 310 nm, [P] = 1 mg·mL−1).
Figure 2. PL spectra of PMT in different solvents (λex = 310 nm, [P] = 1 mg·mL−1).
Figure 2. PL spectra of PMT in different solvents (λex==310
Figure 2. PL spectra of PMT in different solvents (λex
310nm,
nm, [P] = 1 mg·mL−1 ).
[P] = 1 mg·mL−1).

(a) (b)
Figure 3. (a) PL spectra(a)
of PMT in mixed solvents with different solubility (b)
parameters (δ = 8.50~12.00
cal1/2cm3.
Figure
−3/2, λex = 310 nm, [P] = 1 mg·mL−1); (b) Plots of ln(I/I0) of PL spectra (a).
(a) PL spectra(a)of PMT in mixed solvents with different solubility parameters
(b) (δ = 8.50~12.00
cal cm , λex = 310 nm, [P] = 1 mg·mL−1); (b) Plots of ln(I/I0) of PL spectra (a).
1/2 −3/2

Figure 3. (a) PL spectra of PMT in mixed solvents with different solubility parameters (δ = 8.50~12.00
Figure 3. (a) PL spectra of PMT in mixed solvents with different solubility parameters (δ = 8.50~12.00
cal1/2cm−3/2, λex = 310 nm, [P] = 1 mg·mL−1); (b) Plots of ln(I/I0) of PL spectra (a).
cal1/2 cm−3/2 , λex = 310 nm, [P] = 1 mg·mL−1 ); (b) Plots of ln(I/I0 ) of PL spectra (a).
Molecules 2017, 22, 54 4 of 6

For comparing
Molecules 2017, 22, 54 the fluorescence probe technique with the turbidimetric titration method, 4 of which
6
is now the most commonly used method for determining the solubility parameter of a polymer, the
turbidimetricFor comparing
titration was the fluorescence
carried outprobe technique the
by measuring withluminousness
the turbidimetric of titration method,
the solutions towhich
estimateis the
now the most commonly used method for determining the solubility
cloud point. The solubility parameter of PMT obtained by the turbidimetric titration method rangedparameter of a polymer, the
from turbidimetric
8.60 cal1/2 cm titration
−3/2 towas12.15carried1/2
cal out cmby−3/2
measuring the luminousness of the solutions to estimate
, which is much wider than the range (9.00 cal1/2the cm−3/2
cloud point.
1/2 The
− solubility
3/2 parameter of PMT obtained by the turbidimetric titration method ranged from
to 10.00 cal 1/2 cm ) determined by our fluorescence method above.
8.60 cal cm−3/2 to 12.15 cal1/2cm−3/2, which is much wider than the range (9.00 cal1/2cm−3/2 to 10.00 cal1/2cm−3/2)
To further explore the application of the fluorescence method, the solubility parameter of PVT was
determined by our fluorescence method above.
also determined.
To furtherThe n-hexane,
explore DCM and
the application ethyl
of the alcohol were
fluorescence method,used
thefor preparing
solubility mixed
parameter of solvents
PVT was with
different solubility parameters
also determined. The n-hexane, to measure
DCM andthe solubility
ethyl parameter
alcohol were used forof PVT (Figure
preparing mixed4a). When
solvents the δ of
with
the mixed solvent was 10.00 cal 1/2 cm−3/2 , the PL intensity of solution reached the relative minimum
different solubility parameters to measure the solubility parameter of PVT (Figure 4a). When the δ of
at 463thenm.mixed solvent
The was 10.00
intensity andcal 1/2cm−3/2, the PL intensity of solution reached the relative
ln(I/I 1/2 cm −3/2 or at
minimum
0 ) changed monotonically below 9.50 cal above
10.50463 1/2
calnm.cm − 3/2
The intensity
. From andtheln(I/I 0) changed
range of 9.50 1/2
monotonically−
cal cm below3/2 9.50 cal
to 10.50 1/2 −
calcm cmor above
1/2 −3/2 3/2 10.50
, the PLcal 1/2cm−3/2.
intensity and
ln(I/IFrom the rangeatoffirst,
9.50 and
cal1/2cm −3/2 to 10.50 cal1/2cm−3/2, the PL intensity and ln(I/I0) decreased at first,
0 ) decreased then they increased, indicating the minimum intensity must be in this
and then they increased, indicating the minimum intensity must be in this range. Figure 4b shows −
range. Figure 4b shows that the intersection point of the trendline1/2on −3/2 both sides of 10.00 cal cm 3/2 1/2
that the intersection 1/2 point
− of the trendline on both sides of 10.00 cal cm refers to δ = 9.85 cal1/2cm−3/2,
3/2
refers to δ = 9.85 cal cm , which can be considered as the solubility parameter of PVT. Since the
which can be considered as the solubility parameter of PVT. Since the molar content of TPE units is only
molar0.37%,
content of TPE units is only 0.37%, which is extremely low, the solubility parameter of PVT
which is extremely low, the solubility parameter of PVT could be identical to the solubility
couldparameter
be identical to the solubility parameter of PVAc.
of PVAc.

(a) (b)
Figure 4. (a) PL spectra of PVT in mixed solvents with different solubility parameters (δ = 8.50~12.00
Figure 4. (a) PL spectra of PVT in mixed solvents with different solubility parameters (δ = 8.50~12.00
cal1/2cm−3/2, λex = 310 nm, [P] = 1 mg·mL−1); (b) Plots of ln(I/I0) of PL spectra (a).
cal1/2 cm−3/2 , λex = 310 nm, [P] = 1 mg·mL−1 ); (b) Plots of ln(I/I0 ) of PL spectra (a).
3. Materials and Methods
3. Materials and Methods
3.1. General
3.1. General
Tetrahydrofuran (THF), methyl methacrylate (MMA), vinyl acetate (VAc), and triethylamine (Et3N)
were freshly purified,
Tetrahydrofuran respectively.
(THF), methyl Azobisisobutyronitrile
methacrylate (MMA), (AIBN)
vinylwas purified
acetate by recrystallization.
(VAc), and triethylamine
4-hydroxylbenzophenone,
(Et3 N) were freshly purified, benzophenone, and acryloyl
respectively. chloride were purchased(AIBN)
Azobisisobutyronitrile from Aladdin
wasIndustrial
purified by
Co., (Fengxian, Shanghai, China) and used as received without further purification.
recrystallization. 4-hydroxylbenzophenone, benzophenone, and acryloyl chloride were purchased Number-average
frommolecular
Aladdinweight and polydispersity of polymers by GPC (Waters Co., Milford, MA, USA) and THF as
Industrial Co., (Fengxian, Shanghai, China) and used as received without further
the eluent. NMR spectra were measured on AVANCE III 400 MHz (Bruker Co., Fällanden, Switzerland).
purification. Number-average molecular weight and polydispersity of polymers by GPC (Waters Co.,
PL spectra were measured on a PerkinElmer LS45 spectrometer (Fremont, CA, USA).
Milford, MA, USA) and THF as the eluent. NMR spectra were measured on AVANCE III 400 MHz
(Bruker
3.2. Co., Fällanden,
Synthesis Switzerland).
of 4-Hydroxyl PL spectra were measured on a PerkinElmer LS45 spectrometer
Tetraphenylethylene
(Fremont, CA, USA).
Into a 500 mL two-necked round-bottom flask were added 4-hydroxylbenzophenone (1.9 g, 10
mmol), benzophenone (2.2 g, 12 mmol) and Zn powder (2.9 g, 44 mmol). The flask was evacuated under
3.2. Synthesis of 4-Hydroxyl Tetraphenylethylene
vacuum and flushed with dry N2 three times. Then 80 mL fresh dried THF was added. After all the
Into
solidsawere
500completely
mL two-necked
dissolved,round-bottom
the solution wasflask
cooledwere
to 0 °Cadded 4-hydroxylbenzophenone
and TiCl (1.9 g,
4 (2.4 mL, 22 mmol) was slowly

injected into the flask. After refluxing at 70 °C overnight, the mixture was cooled to
10 mmol), benzophenone (2.2 g, 12 mmol) and Zn powder (2.9 g, 44 mmol). The flask was evacuatedroom temperature
under vacuum and flushed with dry N2 three times. Then 80 mL fresh dried THF was added. After all
Molecules 2017, 22, 54 5 of 6

the solids were completely dissolved, the solution was cooled to 0 ◦ C and TiCl4 (2.4 mL, 22 mmol)
was slowly injected into the flask. After refluxing at 70 ◦ C overnight, the mixture was cooled to room
temperature and 80 mL dilute hydrochloric acid (1 mol·L−1 ) was added to it, which was extracted with
dichloromethane (3 × 80 mL). The collected organic layer was dried over anhydrous magnesium sulfate.
After solvent evaporated, the crude product was purified by a silica gel column chromatography using
petroleum ether (60–90 ◦ C)/ethyl acetate (40:1) as eluent. White crystal; yield 58% (2.4 g). 1 H-NMR
(400 MHz, CDCl3 , δ): 7.16–7.09 (m, 8H), 7.07–7.01 (m, 9H), 6.91 (d, 1H), 6.58 (d, 1H), 4.78 (s, 1H).

3.3. Synthesis of 4-Acryloyl Tetraphenylethylene

Into a 250 mL two-necked round-bottom flask were added 4-Hydroxyl Tetraphenylethylene
(TPE-OH) (1.0 g, 3 mmol), trimethylamine (2 mL) and fresh dried THF (30 mL). After all the solids
were completely dissolved, acryloyl chloride (0.3 mL, 3.6 mmol) was injected into the flask dropwise
over 20 min. After stirring at 0 ◦ C for 2 h, the reaction mixture was concentrated under vacuum.
The residue was dissolved in ethyl acetate and the resulting solution was washed with water and
brine, dried with Na2 SO4 and concentrated. The crude product was purified by a silica gel column
chromatography using petroleum ether (60–90 ◦ C)/ethyl acetate (100:1) as eluent. White crystal; yield
62% (0.83 g). 1 H-NMR (400 MHz, CDCl3 , δ):7.14–7.07 (m, 9H), 7.05–6.99 (m, 8H), 6.88 (d, 1H), 6.55
(d, 1H), 6.31–6.24 (q, 1H), 5.99 (d, 1H), 5.97 (d, 1H).

3.4. Synthesis of PMT and PVT

The polymerization reaction was carried out by radical polymerization under N2 and equipped
with a condenser and magnetic stirring. Into 500 mL three-necked round-bottom flask were added
TPE-a (0.3 g, 0.7 mmol), MMA (15 g, 150 mmol), AIBN (0.1 g, 0.6 mmol) and DMF (80 mL). The reaction
mixture was stirred on an oil bath at 70 ◦ C under nitrogen for 16 h. The solution was then cooled
to room temperature, concentrated under vacuum and added dropwise to 500 mL of methanol
under stirring to precipitate the polymer and meanwhile remove the unreacted reactants and solvent.
The polymer was filtered by Buchner funnel, washed with methanol several times, and dried in
vacuum overnight at 40 ◦ C to a constant weight. White solid; yield 86% (13.2 g). Mn : 16500, PDI: 1.78
(GPC); 1 H-NMR (400 MHz, CDCl3 , δ): 7.13–6.99 (multi-peak of TPE), molar ratio of TPE: 0.47%.
The PVT was synthesized using the same synthesis methods of PMT. White solid; yield 82%
(12.6 g). Mn : 12800, PDI: 1.68 (GPC); 1 H-NMR (400 MHz, CDCl3 , δ): 7.13–6.98 (multi-peak of TPE),
molar ratio of TPE: 0.37%.

4. Conclusions
We have demonstrated a luminescence probe approach based on the AIE molecule to measure
the solubility parameters of PMMA and PVAc. The solubility parameters of PMMA and PVAc are
9.19 cal1/2 cm−3/2 and 9.85 cal1/2 cm−3/2 , respectively. The measured parameter of PMMA ranges
from 9.00 cal1/2 cm−3/2 to 10.00 cal1/2 cm−3/2 , while the solubility parameter of PMMA measured
by the turbidimetric titration ranges from 8.6 cal1/2 cm−3/2 to 12.15 cal1/2 cm−3/2 . All these results
demonstrated that the values obtained from our method should be more accurate than those obtained
by the turbidimetric titration method, and the luminescence probe approach can also be applied to
other kinds of polymers.

Acknowledgments: The research was supported by the National Science Foundation of China (21304011).
Author Contributions: K.M.W., B.Z.T. and Q.Y. performed the research, analyzed the data and discussed the
results; S.J. and T.Y.H. designed and performed the research, and did the data analysis, manuscript writing and
revision. All authors read and approved the final manuscript.
Conflicts of Interest: The authors declare no conflict of interest.
Molecules 2017, 22, 54 6 of 6

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