Self-assembly, conductivity and chemosensor behavior of biphenylsulfone based Janus polycatenar

Article abstract of DOI:10.1016/j.molliq.2018.05.053

A novel Janus polycatenar JP-I bearing a bisphenylsulfone central core, with a hydrophobic 3,4,5-tridodecyloxybenzylether unit at one side and a hydrophilic trioligoethylene oxide benzyl triazoly unit at another side has been synthesized via copper(I)-cat

Full text of DOI:10.1016/j.molliq.2018.05.053

Accepted Manuscript
Self-assembly, conductivity and chemosensor behavior of
biphenylsulfone based Janus polycatenar
Huifang Cheng, Hongfei Gao, Yulong Xiao, Bei Zhang, Wei
Xing, Xiaohong Cheng
PII:
DOI:
Reference:
S0167-7322(17)36032-4
doi:10.1016/j.molliq.2018.05.053
MOLLIQ 9108
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Accepted date:
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10 May 2018
12 May 2018
Please cite this article as: Huifang Cheng, Hongfei Gao, Yulong Xiao, Bei Zhang, Wei
Xing, Xiaohong Cheng , Self-assembly, conductivity and chemosensor behavior of
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ACCEPTED MANUSCRIPT
Self-assembly, conductivity and chemosensor behavior of
biphenylsulfone based Janus polycatenar
Huifang Cheng,a,1 Hongfei Gao,a,1 Yulong Xiao,a Bei Zhang,a Wei Xing,a Xiaohong Chenga,*
[a]
Key Laboratory of Medicinal Chemistry for Natural Resources, Chemistry
School of Chemical Science and Technology, Yunnan University
Kunming,
Yunnan 650091,
P. R. China
Fax: (+86) 871 65032905
E-mail: xhcheng@ynu.edu.cn
1 Both authors contributed equally to this work
Abstract: A novel Janus polycatenar JP-I bearing a bisphenylsulfone central core, with a
hydrophobic 3,4,5-tridodecyloxybenzylether unit at one side and a hydrophilic trioligoethylene
oxide benzyl triazoly unit at another side has been synthesized via copper(I)-catalyzed
azide-alkyne cycloaddition (CuAAC) reaction. JP-I can display SmA2 phase triggered by the
addition of alkali metal ions. The LC property of the doped system was well demonstrated by
polarized optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray
diffraction (XRD) experiments. The conductivity of the doped system (JP-I : LiOTf) is 4.0 × 10−8
S cm-1. JP-I could gel both in ethanol and aqueous ethanol. Such gel which formed in ethanol
showed a helical nanostructure. The XRD displayed that the JP-I could self-assemble into a
monolayer structure which had a small tilt angle in the layers. Furthermore, the gel system could
be established to remove iodine from water. Additionally, JP-I could recognize Fe3+ with lower
detection limit in aqueous ethanol. Finally, JP-I could self-assemble into micelles in aqueous
solution and the critical micelle concentration CMC was determined to be 0.002 mg mL-1 with the
diameter of the spherical micelles about 15-20 nm.
Key words: liquid crystal, self-assembly, organogels, chemosensor, micelles
1. Introduction
Polycatenar liquid crystals [1] consist of a long rod-like rigid core ending in two half-disc moieties.
The core contains in general, five rings and each ‘half-disc’ is usually composed of two or three
alkyl chains grafted on both terminal phenyl rings in meta and/or para positions. Now the concept
of polycatenar mesogens has been extended, besides linear alkyl chains, also branched chains
(swallow tail chains) [2 ] and other bulky groups, such as strongly coiled chains (e.g.,
poly(ethylene oxide) (PEO), oligo-(propylene oxides) [3], oligosiloxanes) [4] and fluorinated
chains [5], were attached in terminal position to calamitic or bent aromatic cores [6] to form
columnar mesophases [7,8,9].
Janus molecules consist of two different functional blocks which are covalently attached at a
central unit [10,11]. Hydrophilic blocks are commonly constructed of poly(ethylene glycol) [12],
amino [13] hydroxyl [14] and carboxyl groups etc. [15]. Hydrophobic blocks are often composed
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of aliphatic chains with varying poly(benzyl ether) [16,17]. Janus molecules can self-assemble
into nanostructures driven by different non-covalent interactions such as π-π stacking, hydrogen
bonding, hydrophobic interactions and van der Waals force between the periphery units. This type
of compounds could be utilized to construct more complex superstructure, which leading to the
revolution in material science [18,19]. Considering the important and wide applications of Janus
molecules in drug delivery [20] gene delivery [21], catalysts [22], sensor [23], bioimaging [24]
and liquid crystals [25], the development of novel Janus molecules is emergency. Till now only
few examples of Janus polycatenars (JPs) [26] with flexible alkyl chains at one terminal but
flexible PEO at another terminal [27] were reported.
Bisphenylsulfone moiety has large dipole moments (1.6-6.2 D) [28,29] and strong thermal
stability, it could be used as an aromatic monomeric unit for engineering plastics such as
liquid-crystalline polyesters [30] poly(ether sulfone)s etc. [31]. Its derivatives have wide
application as self-assembled monolayers [28], electrolytes for lithium-ion batteries [32], electron
acceptors for organic semiconductors [29,33], and water purification membranes [34]. However
there is no report on the synthesis and application of Janus polycatenar with biphenylsulfonly as
central unit. It could be predicted that full benefit could be achieved by incorporating rigid polar
biphenylsulfonly into the structure of JP because of its unique chemophysical property.
Therefore in this contribution, we designed a novel Janus polycatenar containing
biphenylsulfonly core to bridge a hydrophobic 3,4,5-tridodecyloxybenzylether unit at one side and
a hydrophilic PEO [35] benzyl triazoly unit at another side (Fig. 1).
Fig. 1 The molecular structure of Janus polycatenar JP-I.
The copper-catalyzed azide-alkyne cycloaddition (CuAAC) was used to synthesize JP-I in this
report, which allowing us to easily control the relative ratio of terminal block. Due to the
incorporation of triazole into the molecule, chemosensor and gel properties could be imparted. The
PEO tails can interact with alkali metal ions through ion-dipole interactions. Ion-dipole
interactions as well as ionic interactions among alkali metal salts could also drive the
self-assembly of the molecules. There are a few examples that liquid-crystalline phases such as
lamellar, cubic and cylindrical phases can be induced in PEO based polymers [36], taper shaped
molecules [37], rod-coil molecules [38] by complexation with alkali metal ions. Additionally,
polyether networks based on PEO have been extensively studied as polymer matrices in
complexes with inorganic alkali salts in view of their potential application as electrolytes in
solid-state batteries [39]. It was reported that PEO based compounds (polymers) have ionic
conductivity, they are one of the most studied conductors [40] in which PEO forms the conductive
phase, while the other components act as mechanical supports [41].
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2. Results and discussion
2.1. Synthesis
The target JP-I was synthesized via CuAAC reaction as a key step, as shown in Scheme 1.
Compound
3
was obtained by mono-etherification of 4,4'-sulfonyldiphenol 2 with
3,4,5-trialkoxybenzyl chlorides 1 [42] in DMF in the presence of K2CO3. Compound 4 was
synthesized by etherification of 3 with propargyl bromide in acetone in the presence of K2CO3.
Etherification between propyl gallate 7 and tosylated diethylene glycol monomethyl ether
(Me-DEG-Ts) 8 gave 9 [43]. The obtained compound 9 was reduced with lithium aluminum
hydride, and the obtained benzyl alcohol 10 reacted with SOCl2 yielded the benzyl chloride 11.
The nucleophilic substitution of benzyl chloride 11 with sodium azide produced the benzyl azide
IN [44]. Finally click reaction between 4 and aromatic azide IN produced the target compound
JP-I. JP-I was purified by column chromatography. The detailed procedures and corresponding
analysis data are collected in the Supporting Information (SI).
Scheme 1 Synthesis of JP-I: Reagents and conditions: (i) K2CO3, DMF, 80 °C, 4 h, 59%; (ii) K2CO3, acetone,
propargyl bromide, 45 °C, 12 h, 92%; (iii) CH2Cl2, pyridine, 25 °C, 8 h, 80%; (iv) K2CO3, DMF, 90 °C, 8 h, 88%;
(v) LiAlH4, THF, 25 °C, 2 h; (vi) SOCl2, THF, 25 °C, 1 h; (vii) NaN3, KI, DMF, 45 °C, 10 h, 66%; (viii)
tert-butanol, THF, H2O, sodium ascorbate, CuSO4·5H2O, 25 °C, 20 h, 61%.
2.2. Mesomorphic properties
The liquid-crystalline property of the synthesized JP-I was studied by polarizing optical
microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD)
techniques. The phase transition temperatures of JP-I is collected in Table 1.
Table 1 The phase type and phase transition temperatures of compound JP-Ia
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Comp.
T/°C
JP-I
Cr 43 Iso
Cr < 20 SmA2 110 Iso (67 SmA2 < 20 Cr)
JP-I:LiOTf(0.5eq)
a Transition temperatures were determined by POM. Abbreviations: Cr = crystal; SmA2 = smectic A phase with
intercalated bilayer structure; Iso = isotropic liquid.
As shown in Table 1, the pure JP-I is only a crystal. However, upon doping with CF3SO3Li
(LiOTf), the obtained ionic samples displayed liquid-crystalline properties. The doped ratios of
LiOTf between 0 - 1.5 were tested (Fig. S2). The result showed that the LC properties of the
obtained ionic samples occurred when the doped ratio of LiOTf is  0.3. With the doped ratio
between 0.3 - 0.8, the isotropic temperatures of doped system increased with increasing the doped
ratio of LiOTf. It suggested that lithium salts intermolecularly interact with PEO moieties by
ion-dipole interactions [45]. The LC phase of ionic sample was identified as smectic A phase by
its typical texture observed under POM (Fig. 1a). The doped sample showed two reflection peaks
in the small angle region with a ratio of d001/d002 ≈ 2, which confirmed the smectic organization.
The layer spacing was calculated to be d = 5.35 nm at 60 °C (Table 1), while the molecular length
is Lmax = 4.59 nm (calculated by the MM2 method [46] and assuming a molecule in the most
stretched conformation). The ratio of the layer spacing (d) and the molecule length (Lmax) is 1.17,
this value is larger than the molecular length but significantly smaller than twice the molecular
length, indicating a bilayer structure (as shown in the inset of Fig. 1b). Annealing NVT molecular
dynamics was carried out on the model of JP-I with 18 molecules in a box 8.7 × 0.45 × 5.35 nm3
with periodic boundary conditions [47]. The molecular dynamics (MD) annealed model of the
smectic A phase shows that the bisphenylsulfone cores are randomly tilted in the bilayer, and the
alkyl chains and PEO chains are completely disordered and strongly interdigitated (Fig. 2).
(10)
(a)
(b)
Iq 2
(20)
1
2
3
q/nm
Fig. 1 Liquid-crystalline phase of ionic sample of JP-I: (a) The texture of SmA2 phase triggered by the addition of
0.5 equiv of LiOTf on cooling at T = 60 °C; (b) SAXS diffractogram of the SmA2 phase at T = 60 °C.
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Fig. 2 Snapshot of the structure of the SmA2 phase of ionic sample JP-I after MD annealing. Annealing NVT
molecular dynamics was carried out on the model of ionic sample JP-I with 18 molecules in a box 8.7 × 0.45 ×
5.35 nm3 with periodic boundary conditions.
2.3 Conductivity measurements
The measurement of conductivities of ionic samples could provide evidence for understanding
morphological properties, such as domain connectivity [48]. The results are usually based on the
equivalent circuits composing of electrical components such as resistors, capacitors, and inductors
[49]. Therefore, impedance measurements were made to obtain the information about the
conductivity of the compound in the LC state. Fig. 3 shows the complex impedance diagram (Z″
vs Z′) of ionic sample JP-I in the SmA2 phase. It shows a typical semicircle of a circuit consisting
of a parallel connection of a resistor and a capacitor, where R is shown as the bulk resistance.
Conductivity can be calculated from R values using σ = d/(R·A), where d is the thickness of the
sample, which corresponds the distance between the electrodes (0.026 mm). The letter A
represents the surface area of the cell (about 0.896 cm2). Thus the electrical conductivity σ in the
SmA2 phase is calculated to be 4.0 × 10−8 S cm-1. Remarkably, this value is lower than the
reported analogues which containing an unpolar core to bridge hydrophobic blocks and
hydrophilic aliphatic ether blocks with different degrees of branching [48a,50]. It is reasonable to
assume that the stronger the electrostatic interaction within a cation-anion pair in this doped
sample leading to the higher viscosity of this sample and therefore the lower ionic conductivity
[51].
60000
50000
40000
30000
20000
10000
0
0
10000 20000 30000 40000 50000 60000 70000
Z'()
Fig. 3 Impedance Z'' vs Z' plot of ionic sample JP-I captured in its SmA2 phase.
2.4 Gel properties
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The gelation property of the JP-I was examined in different organic solvents with a concentration
of 5.0 mg/mL, the results were listed in Table 2. The organic solvent (1 mL) containing JP-I was
heated in a test tube until the solid was completely dissolved. Then the solution was cooled at
room temperature. Gel formation was observed during the cooling process or immediately after
the cooling process (about 1 min). The organogel exhibited gel-sol reversible trans process upon
application of environmental stimuli such as temperature and shear etc. (Fig. 4a). Such
stimuli-responsive behaviors maybe favourable for various applications such as sensors, drug
controlled release [52] and hardeners of solvents and etc. [53]. JP-I could form gels in both
ethanol and aqueous ethanol solution (ethanol : H2O = 1 : 2). To assess the gel stability, we
measured Tgel (the temperature at which the gel is broken) values for the gel of JP-I in ethanol
(Fig. S3). The Tgel values for JP-I increased with increasing gelator concentration, which is a
general trend observed for low molecular weight gelators [54]. The helical nanobelts with three
dimensional superstructure of 30 to 75 μm in size (Fig. 4b) of the xerogel formed from JP-I in
ethanol was observed by scanning electron microscopy (SEM) images.
To our knowledge, this is the first time for JPs to represent morphology with such twist
nanobelts. The interaction between the solvents and the triazole units or PEO, intermolecular
hydrogen bonds, π-π interactions and van der Waals forces may play an essential role in
aggregation types [55].
Table 2 Gelation test results of compound JP-Ia
Solvent
JP-I
S
Solvent
JP-I
S
Ethyl acetate
Acetone
Chloroform
n-Hexane
Cyclohexane
1,4-Dioxane
Ethanol
P
P
DMF
S
S
Toluene
P
P
Acetonitrile
Ethanol : H2O (1 : 2)
S
G
PG
a G = stable gel at room temperature; S = soluble; P = precipitation; PG = partial gelation.
(b)
(a)
Cooling
Rest
Heating
Shaking
Fig. 4 (a) Multistimuli responsive organogels of JP-I in ethanol (5.0 mg/mL); (b) Selected SEM image of the
xerogels made from JP-I in ethanol with scale bar is 50 μm.
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To further investigate the helicity of the aggregates of JP-I gel, we performed the CD
measurements for JP-I gel and its ethanol solution. The CD spectrum of JP-I gel exhibits a
negative Cotton effect, while JP-I ethanol solution shows no Cotton effect. This suggests that the
JP-I gel has a helical nanostructure with preferential left handedness (Fig. 5a). In order to further
study the molecular aggregation mechanism, XRD experiment was carried out (Fig. 5b). The XRD
curve of JP-I shows sharp peaks with 2θ values of 2.74°, 5.44°, 7.84° and 11.04o corresponding to
d values of 32.21, 16.22, 11.26 and 8.00 Å, respectively. The corresponding d values follow a ratio
of 1 : 1/2 : 1/3 : 1/4, which was consistent with the lamellar structure of the aggregates in the gel.
In the high-angle regions, there is only one diffuse broad peak, with a maximum at about 4.09 Å,
which is a typical angle for diffraction from partly disordered alkyl chains [56]. This result
illustrated that the interlayer distance is 32.21 Å in the gel phase. Lamellar structure is slightly
shorter than the calculated molecular length (Lmax = 4.59 nm) of the largest extended conformation.
Considering this result the molecules should self-assemble into a monolayer structure with a small
tilt angle in layers [57]. Based on those result, a possible helical structure model for the system of
JP-I gel is proposed, and the result is schematically shown in the inset of Fig. 5a.
(a)
(b)
Fig. 5 (a) CD spectrum of JP-I gel and JP-I ethanol solution (10-5 M) at room temperature. The inset shows the
possible helical structure model of the system of JP-I gel; (b) XRD pattern of JP-I xerogel from ethanol.
The UV-vis absorption spectra of JP-I shows a maxima at 206 nm in ethanol solution at 25 ℃,
and a maxima at 211 nm in gel state. The absorption peak in the gel state was red-shift by 5 nm,
which suggested the formation of π-stacked aggregates with a J-type parallel stacking mode in the
gel state (Fig. S4) [58]. With increasing the temperature the absorption of JP-I in gel state has
slightly bathochromic shift by about 3 nm. Additionally, the intensity of emission peak increased
with decreasing the temperature (Fig. S5).
2.5. Gel application in water purification
As mentioned above, biphenylsulfone derivatives, low molecular-mass gelators (LMMGs) and
their relevant molecular gels can be found application as water purification membranes [59].
However, due to the limited contact of the gel phase (or LMMGs) with the liquid phase, it is
usually time-consuming to completely remove contaminants from water. In this contribution,
xerogel system of JP-I can be established for purification of wastewater by removing of iodine (I2)
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from wastewater as an example. Thus the xerogel of JP-I (about 5 mg) was put into 1.0 mL of the
saturated aqueous solution of I2. After vigorous shaking, the mixture turned into a turbid liquid.
Standing for a while, the precipitate appeared at the bottom. Simultaneously, the water layer
became clear, indicating the effective extraction of I2 from water to gel phase. Then, the residue
gel was filtered. The separation process was illustrated in Fig. 6a. As demonstrated by UV-vis
spectroscopy, 78.5% of I2 was removed from water after such treatment (Fig. 6b). This strategy is
convenient and of great significance for enhancing the practical applications of LMMGs and their
related molecular gels.
(a)
(b)
Saturated solution of I2
Liquid-solid separation
After shaking
Fig. 6 (a) Adsorption of I2 from water by JP-I gel; (b) Absorption spectra of water contaminated with I2 before
(black curve) and after purification (red curve).
2.6. Chemosensor behavior
The metal-binding ability of the JP-I was examined by various metal ions, including Ag+, Cd2+,
Co2+, Cu2+, Fe3+, Hg2+, K+, Li+, Mg2+, Ni2+, Pb2+, Zn2+. The emission of JP-I gradually decreased
with an increase in the amount of 10 equiv. metal ions. JP-I displayed a good selectivity to Fe3+
(Fig. 7). After Fe3+ was added to the solution of JP-I (quenching upon the addition of 12 equiv. of
Fe3+) (Fig. S6), strong quenching of the emission was observed, which results from a heavy metal
ion effect or a reverse PET [60]. In detail, the association constants (Ka) of JP-I for Fe3+ was
evaluated to be 2.12 × 104 M-1 by plotting 1/(F0-F) against 1/[Fe3+] (Fig. S7a) [61], indicating that
the JP-I had a strong interaction with Fe3+. To elucidate the different molecular assembly between
JP-I-Fe3+, we first studied the binding stoichiometries by Job’s plot method. The stoichiometric
ratios of JP-I : Fe3+ was determined to be 2 : 1 (Fig. S8). In order to further determine the
sensitivity level, the detection limit [62] for JP-I with Fe3+ was assessed to 3.42 × 10-6 mol/L
based on a 3σ/slope analysis under these experimental conditions (Fig. S7b). This detection limit
value of JP-I is not very low [63], but it is enough for JP-I to detect the submillimolar
concentrations of Fe3+ ion found in many chemical and biological systems.
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4000
(a)
(b) 1.0
blank
Cd2+
Co2+
Cu2+
Fe3+
Hg2+
K+
0.8
0.6
0.4
0.2
0.0
3000
2000
1000
0
Li+
Mg2+
Ni2+
Pb2+
Zn2+
Hg2+ K+ Li+ Mg2+ Ni2+
Cd2+
Cu2+ Fe3+
Pb2+ Zn2+
Co2+
300
350
400
Wavelength/nm
450
500
Fig. 7 (a) Fluorescence spectra at room temperature at pH = 7.0 in CH3CH2OH : H2O = 1 : 1 mixture (λex = 280
nm) of JP-I (8.6 × 10-6 M); (b) (F0-F)/F0×100% depicts the cation selective fluorescence quenching efficiency
namely the fluorescence responses of different metal ions of JP-I; abbreviation: F0 = the fluorescence emission
maximum of the blank sample; F = the fluorescence emission maximum of samples after addition of different
metal ions.
In order to investigate the binding site of compound JP-I with Fe3+, FTIR spectra of solid JP-I,
JP-I + Fe3+ were performed. The spectrum in Fig. 8a (black line) indicates that the characteristic
peaks at 1300-990 cm-1 are assigned to the stretching vibrations of the C-O-C stretch in JP-I. In
addition, the peaks at 1257 cm-1 and 1108 cm-1 are characterized by the antisymmetric stretching
mode of C-O-C entities [64], the N=N, C-N of triazole ring at 1508 cm-1 and 592cm-1 respectively
[65]. After adding Fe3+, the peaks of C-O-C vibration shift to lower wave numbers of 1248 cm-1
and 1087 cm-1, respectively. While, the peak of N=N naturally cannot be found in the spectrum and
the peak of C-N vibration shifts to lower wave numbers of 585 cm-1 [66]. This result means that
Fe3+ in the JP-I + Fe3+ complex had a strong interaction with the benzyl oxygen, PEO oxygen, as
well as triazolyl N. Based on these results, the binding model of JP-I + Fe3+ is proposed in Fig.
8b.
(a)
(b)
592
C-N
JP-I
JP-I+Fe3+
1257
1508
1108
C-O-C
N=N
585
1087
1248
500
1000
1500
2000
2500
3000
3500
4000
wavelength(cm-1)
Fig. 8 (a) FTIR spectra of the samples JP-I and JP-I + Fe3+; (b) Possible Fe3+-binding mode of JP-I.
2.7. Determination of critical micelle concentration (CMC)
Since JP-I is composed of a hydrophobic block at one side and a hydrophilic block at another side,
it could self-assemble into micelles in an aqueous solution. The micellar structure of JP-I is
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confirmed by the fluorescence technique using pyrene as a probe. The ratios did not change
significantly below a certain concentration, while the ratios increase remarkably above this
concentration, suggesting that pyrene molecules are bound to the hydrophobic core region upon
micellar aggregation. The critical micelle concentration (CMC) was obtained from the intersection
of two straight lines: the baseline and the rapidly increasing I393/I373 line. The CMC of JP-I was
determined to be 0.002 mg mL-1 (Fig. 9a). The transmission electron microscopy (TEM) image of
JP-I displayed well-defined spherical micelles (Fig. 9b). The spherical micelles are sometimes
overlapped with one another. The diameter of the spherical micelles is about 15-20 nm. The
formation of those regular-shaped aggregates may be due to the highly hydrophobic content
promote the formation of more well-defined aggregates. Such spherical micelles may have many
potential applications in drug delivery [67], membrane separation etc. [68].
(a)
(b)
Fig. 9 (a) Plot of I393/I373 of pyrene emission spectra versus logarithm of concentration for JP-I; (b) TEM images
of the formed micelles by JP-I.
3. Conclusion
Therefore a novel Janus polycatenar JP-I bearing a bisphenylsulfone core has been successfully
synthesized. JP-I can display SmA2 phase triggered by the addition of lithium salt with a
conductivity value of 4.0 × 10−8 S cm-1. The xerogel formed by JP-I in ethanol which displaying
helical nanobelt morphologies, could be established for water purification. Additionally, JP-I can
act as chemosensor for Fe3+ ion. Furthermore, JP-I can form micelles in aqueous solution with a
micelle diameter of 15-20 nm and CMC of 0.002 mg/mL. The multi-characteristics of JP-I
highlight the potential for Janus polycatenars in the field of functional materials.
Acknowledgements
This work was supported by National Natural Science Foundation of China (Nos. 21664015,
21364017 and 21602195) and the Yunnan Provincial Department of Education Foundation (Nos.
ZD2015001, 2016FD008 and 2017FB011). We thank beamline 1W2A at Beijing Synchrotron
Radiation Facility (BSRF) and beamline BL16B1 at Shanghai Synchrotron Radiation Facility
(SSRF), China.
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Graphical abstract
Target Janus polycatenar can self-assemble into SmA2 phase triggered by lithium salt, and helical
nanobelt gel with application for water purification.
Highlights
1. A novel Janus polycatenar JP-I was synthesized via CuAAC click reaction.
2. JP-I displays SmA2 phase triggered by the addition of alkali metal ions.
3. JP-I forms helical gel in ethanol, and the gel can remove iodine from water.
4. JP-I could recognize Fe3+ with lower detection limit in aqueous ethanol.
5. JP-I could self-assemble into micelles in aqueous solution.
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