Perylene diimide derivative: Via ionic self-assembly: Helical supramolecular structure and selective detection of ATP

Article abstract of DOI:10.1039/c9tc05792g

A novel perylene diimide material (perylene diimide tetracid-dihexadecyldimethylammonium bromide, PDTA-DHAB) with a unique hierarchical structure was designed and prepared by an ionic self-assembly (ISA) method. The self-assembly behavior and aggregated s

Full text of DOI:10.1039/c9tc05792g

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DOI: 10.1039/C9TC05792G
Perylene diimide derivative via ionic self-assembly: helical
supramolecular structure and selective detection of ATP
Lin Lu,a,1 Hai-Jun Sun,a,1 Yu-Ting Zeng,a Yu Shao,b Maxim V. Bermeshev,c Yang Zhao,a Bin Sun,*,b
Zhi-Jian Chen,a Xiang-Kui Ren*,a and Meifang Zhu*,b
a School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P. R. China
b State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of
Materials Science and Engineering, Donghua University, Shanghai 201620, P. R. China
c A.V. Topchiev Institute of Petrochemical Synthesis Russian Academy of Sciences, Moscow, 119991,
Russia
E-mail: renxiangkui@tju.edu.cn, zmf@dhu.edu.cn, sunbin@dhu.edu.cn
1 Lin Lu and Hai-Jun Sun contributed equally to this work.
1

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Abstract
A novel perylene diimide material (perylene diimide tetracid- dihexadecyldimethylammonium bromide,
PDTA-DHAB) with unique hierarchical structure was designed and prepared by ionic self-assembly
(ISA) method. The self-assembly behavior and aggregated structure of the complex were then studied
by a variety of techniques such as UV-Vis absorption spectra, differential scanning calorimetry, and
two-dimensional X-ray diffraction. With the presence of a rigid linkage, the complex can self-assemble
into highly ordered helical columns which further pack into a monoclinic crystalline lattice with
dimensions of a = 4.02 nm, b =3.40 nm, c = 2.90 nm, α = β = 90º, γ = 92º. During heating, the helical
supramolecular structure was destroyed and transformed to a lamellar liquid crystalline phase.
Furthermore, the complex solution upon addition of ATP showed a remarkable absorption and
fluorescence intensity decrease compared with other anions. These results will provide insight into the
rational design of functional materials with helical supramolecular structure through ISA method.
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1. Introduction
Perylene diimides (PDIs), as an important class of fluorophores, have been intensively studied owing
to their excellent properties, such as high thermal and photochemical stability,1 extraordinary
spectroscopical and electrochemical property.2-4 The dyes and their derivatives have a wide range of
practical applications in organic photovoltaic cells,5 organic field-effect transistors,6,7 liquid-crystal
displays8 and fluorescent chemosensors.9,10 In order to further optimize the properties of PDIs, the
introduction of substituent groups at the imide position or bay region of the perylene core is an effective
strategy. In the past decade, many researches have been working on enhancing the performance of PDI
materials by purposeful molecular designing.11-14 For example, we and other laboratories have reported
that the bulky nanoparticle substituents connected to perylene cores can restrain their strong self-
assembly by the spatially steric hindrance, which consistently improve the solubility and the
fluorescence quantum yield both in solution and in solid state.15-18 The chemical modification of PDIs
would modulate their physical and chemical properties, which further offers more possibilities for the
applications in different fields. However, most of the chemical methods require harsh synthesis
conditions, and often the yield is relatively low.
Ionic self-assembly (ISA) is a simple non-covalent strategy to construct novel functional materials
based on the combination of charged functional species with opposite charged surfactants.19-23 This
synthetic method has been widely used to fabricate PDI materials with diverse supramolecular
structures owing to its advantages of feasibility, green, and high yield.19 The ISA process utilizes
electrostatic interactions between charged PDIs and oppositely charged surfactants as the primary
interaction to drive structure formation. Other noncovalent interactions such as π–π interactions,
hydrophobic interactions, hydrogen bonding, and geometric factor can be used as secondary driving
force to further promote and stabilize the organization of the assemblies.20 By careful selection of both
components involved in complex formation, functional PDI materials that are endowed with a variety of
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supramolecular structures have been prepared.24-27 For example, non-chiral surfactants tethered PDI
connected with a flexible alkyl linkage, named as PDIC-DOAB (Fig. S1), has been reported in our
previous work.28 The PDIC-DOAB possesses interesting multiple thermally-induced phase structures.
However, it cannot exhibit helical supramolecular structures.
In most cases, PDI materials with helical supramolecular structure are produced by complexing PDI
with chiral surfactants.29-35 The chiral surfactants often exert steric demands on the possible arrangement
of PDI complex, which promote the construction of helical supramolecular structures. However, to the
best of our knowledge, the helical stacking ISA PDI material without guidance of chiral surfactants has
not been reported yet. Compared to chiral surfactant, non-chiral surfactant can be more commercially
available and conveniently incorporated into PDI systems. It is of great interest to investigate whether it
is possible to develop PDI material with helical supramolecular structure by complexing PDI with non-
chiral surfactants. Moreover, it has been demonstrated that the flexible or rigid linkages have a great
influence on the molecular packing behavior and then finally tune the material structure and properties.
16,36,37
Thus, it should be possible to fabricate ISA PDI compound capable of forming helical
supramolecular structure by the rigid linkage between the PDI core and non-chiral surfactant.
Furthermore, the advantage of the ionic compound, and the strong absorption and high solution
fluorescence quantum yield of the PDI compound can also play important roles in the fluorescence
detection. ATP (adenosine triphosphate), as the primary energy currency, plays an important role in
various physiological and pathological processes of cells. The changes in ATP levels can affect cell
function and reflect the normal state of the cell.38-45 Therefore, the accurate and sensitive detection of
ATP is important for biochemical studies and clinical diagnosis. However, most of the methods of
detecting ATP need multiple operations for detection, such as form copper complex before responding
to ATP.46,47 Therefore, it is necessary to develop the PDI compound to directly detect ATP with high
selectivity.
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In this article, as part of our continuing research in PDI materials, a novel complex with non-chiral
surfactants attached to PDI via a rigid phenylene linkage (PDTA-DHAB) was prepared by ISA method.
Due to the steric requirement of the rigid linkage, the PDTA-DHAB molecules can rotationally stack
and self-assemble into highly ordered helical columns which further pack into a monoclinic crystalline
lattice. During heating, this helical crystalline structure transformed to a lamellar liquid crystalline
structure. Furthermore, the PDTA-DHAB system realize the sensitivity and selectivity detection to ATP
and the changes of the detection solution color can be clearly observed by naked eye in sunlight or in
UV light.
2. Experimental Section
2.1. Instruments
1H NMR spectra were employed on a Bruker 400 HMz NMR spectrometer at room temperature using
tetramethylsilane (TMS) as the internal standard. Pressed KBr disks of samples were employed on FT-
IR measurements, and the FT-IR spectra were obtained on a Perkin-Elmer FTIR-100 spectrometer. UV-
Vis absorption spectra were performed on an Agilent Technologies Cary 300 UV-Vis
spectrophotometer. Fluorescence quantum yield was measured using a Hamamatsu absolute PL
quantum yield spectrometer C11347 Quantaurus_QY. The dynamic light scattering (DLS) experiments
were performed on zetasizer by utilizing Malvern Nano ZS instrument. The absorbance for MTT
analysis was recorded on microplate reader (Thermofisher, USA) at a wavelength of 450 nm.
Thermogravimetric analysis (TGA, TA SDTQ-600 controller) and differential scanning calorimetry
(DSC, TA Q100 controller) were used to study the thermal stability and phase transition of the complex.
Two-dimensional X-ray diffraction (2D XRD) patterns of the oriented sample were recorded by
employing a Bruker D8 Discover diffractometer with a Vantec500 detector. The oriented sample
prepared by mechanical shearing was mounted on the sample stage equipped with a temperature control
unit. The 2D XRD patterns were obtained through a transmission mode, with the X-ray incident beam
aligned perpendicular to the shearing direction.
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2.2. Chemicals
Perylene-3,4,9,10-tetracarboxylic acid dianhydride (PDA), 5-aminoisophthalic acid and
dihexadecyldimethylammonium bromide (DHAB) were bought from HWRK Chem Co. Ltd. The
adenosine triphosphate (ATP), adenosine diphosphate (ADP), adenosine monophosphate (AMP),
glucose, cyclic adenosine monophosphate (cAMP) and guanosine triphosphate (GTP) were purchased
from Beijing Solarbio Science & Technology Co., Ltd. All the other materials were bought from
Jiangtian Chemical Technology Co. Ltd. and used directly without further purification.
2.3. Synthesis
Under nitrogen atmosphere, PDA (1g, 2.55 mmol), 5-aminoisophthalic acid (1.15 g, 6.37 mmol) and
imidazole (20 g) were heated at 130 C for 6 h. Then 100 mL of ethanol was added into the hot mixture
and refluxed for 6 h. The precipitate was filtered and washed with ethanol. After dried under vacuum,
1
PDTA was obtained as deep red powder (yield: 82%). H NMR (D2O, 400 MHz), δ (TMS, ppm): 7.15
(m, 8 H), 8.11 (s, 4 H), 8.43 (s, 2 H). Then, 143.6 mg (0.2 mmol) PDTA was added in 40 mL KOH
aqueous solution with stir for 2 h to get potassium salt (PDTK) at 50 °C. The DHAB solution was
obtained by dissolving 460 mg (0.8 mmol) DHAB in 40 mL mixed solution of water and ethanol (v:v =
2:1) at 50 °C for 2 h. After completely dissolved, PDTK solution was dropwise added into DHAB
solution. The mixture was stirred overnight at room temperature and a charge stoichiometric
precipitated complex was formed. The precipitate was purified by filtrating, washing with mixed water
and ethanol solution to remove any remaining excess surfactants or inorganic salt. The PDTA-DHAB
1
was dried under vacuum and obtained as red powder (yield: 95%). H NMR (CDCl3, 400 MHz), δ
(TMS, ppm): 0.90 (t, 24 H), 1.28 (m, 208 H), 1.66 (m, 16 H), 3.04 (s, 24 H), 3.30 (m, 16 H), 8.05 (m, 8
H), 8.38 (s, 4 H), 8.74 (s, 2 H). FI-IR (KBr, cm-1): 3025, 2955, 2918, 2852, 1664, 1590, 1468, 1347,
1241, 1099, 995, 801, 780, 717.
3. Results and Discussion
3.1. Molecular Design and Synthesis
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The supramolecular organization of PDIs can be modified by the introduction of diverse functional
substituents. A non-chiral surfactants-tethered PDI connected with a flexible alkyl linkage (PDIC-
DOAB) has been reported recently (Fig. S1).28 The complex possesses multiple thermally-induced
phase structures, while exhibits non-helical supramolecular structure. It is interesting to study the
influence of the linkage between PDI and surfactants on the optical property and phase structure. In
order to explore the effect of rigid linkage on the supramolecular structure of the ISA PDI complex, the
phenylene linkage was chosen to connect PDI and non-chiral surfactants in this study. It is expected that
the change of linkage from flexible alkyl to rigid phenylene will endow the complex with novel
supramolecular structure.
In order to introduce phenylene linkage between PDI core and surfactants, compound PDTA was
conveniently synthesized in one step from 5-aminoisophthalic acid and PDA according to the reported
procedure (Fig. S2).42 Then the potassium salt was prepared from a simple treatment of PDTA with
aqueous potassium hydroxide. Adding DHAB aqueous solutions dropwise to PDTK aqueous solution
immediately yielded the charge-stoichiometric precipitates. The formed complex was obtained with
high yield at room temperature, named as PDTA-DHAB. The synthetic procedure in detail is showed in
1
Scheme 1. The target complex was characterized by H NMR and FT-IR measurements, which
confirmed the successful preparation of PDTA-DHAB (Figs. S3-S4).
Scheme 1. Synthesis process and chemical formula of PDTA-DHAB complex.
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3.2. Self-Assembly Behavior in Solution and Film State
It is well known that the PDI derivative exhibits different self-assembly behavior in different polar
solvents. In order to investigate the aggregation behavior, the solubility of PDTA-DHAB was tested in
various solvents. PDTA-DHAB shows high solubility in a wide range of common organic solvents such
as ethanol, tetrahydrofuran and dichloromethane (CH2Cl2), but exhibits poor solubility in toluene. Thus,
the concentration-dependent UV-Vis spectra of PDTA-DHAB were studied in CH2Cl2 and toluene to
investigate the dynamic process of aggregation behaviors, respectively.
In Fig. 1, the spectra of PDTA-DHAB show well-resolved vibronic absorption bands from 450-600
nm in CH2Cl2 solution, which is characteristic of PDI chromophores. The absorption maxima occur at
around 525, 489, and 457 nm, corresponding to the S0−0, S0−1, and S0−2 vibronic transitions, respectively.
Based on the reported literatures,49, 50 the ratio of the absorption intensity of 0–0 and 0–1 transitions (A0–
0/A0–1) can be utilized to analyze the degree of aggregation in solution. As shown in Table S1, the A0–
0/A0–1 ratios of PDTA-DHAB in CH2Cl2 solution are very close to the literature value of 1.635,49
indicating that the complex was in monomeric state throughout the investigated concentration range.
,
Fig. 1. UV-Vis spectra of PDTA-DHAB in CH2Cl2 with different concentration.
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In contrast, PDTA-DHAB shows low solubility in toluene and then will exhibit different self-
assembly behavior. As displayed in Fig. 2, the absorption spectra of PDTA-DHAB exhibit a broad
structured feature from 450 nm to 550 nm in toluene. Compared to the fine vibrational profiles in
CH2Cl2, the spectra become less structured, indicating a predominant aggregated state of PDTA-DHAB
in toluene. There are only two distinct absorption bands at around 530 nm and 500 nm of the spectra,
and the absorption maximum with high concentration now represents for the S0−1 transition instead of
the S0−0. The A0−0/A0−1 ratios reveal that PDTA-DHAB exhibits increased tendency for aggregation
behavior in the all experimental concentrations (Table S1). The blue shift of the absorption maximum in
toluene is characteristic of the formation of aggregated PDTA-DHAB in which the central perylene
units are stacked cofacially.
Fig. 2. UV-Vis spectra of PDTA-DHAB in toluene with different concentration.
To obtain further information about the self-assembly behavior of PDTA-DHAB, UV-Vis
spectroscopy was recorded in solid state at room temperature. The PDTA-DHAB film was prepared by
heating the solution-cast film to 70 °C followed by cooling to ice-water mixture and then annealed at
room temperature for 2 days. As shown in Fig. 3, the solid-state absorption spectrum appears broadened
and the vibronic structure becomes much less defined. Moreover, the spectral feature is similar to that of
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PDI compound with bulky substituent group, which is highly indicative of parallel and rotary packing
arrangement of perylene units.51
Fig. 3. UV-Vis spectrum of PDTA-DHAB in thin film.
3.3. Thermal Properties and Structural Evolution
The complex was subjected to thermal analysis to determine its stability and phase behavior. TGA
result in Fig. S5 reveals that the complex has a comparably good thermal stability. Fig. 4 shows the
DSC diagram of PDTA-DHAB obtained during cooling and subsequent heating at a rate of 10 °C/min.
Two thermal transition processes are clearly observed before the onset of degradation, and the
endothermic peaks during heating progress are at 24 and 48 C, respectively. The DSC trace suggests
three phases: first phase (at lower temperature); second phase (at room temperature); third phase (at
higher temperature). Although DSC experiment is sensitive to heat absorption and release events, it
cannot provide direct information about structural change and molecular packing behavior. Therefore,
2D XRD experiments of the oriented sample were utilized to identify the corresponding structural
evolutions. Since the temperature of the first phase is relatively low, we focus on the second phase and
the third phase in following content.
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Fig. 4. A set of DSC cooling and subsequent heating thermal diagrams of PDTA-DHAB at a rate of 10
°C/min.
3.4. Structure Identification and Molecular Packing Behavior
A 2D XRD pattern for PDTA-DHAB, from a sample sheared at 70 °C followed by cooling to ice-
water mixture and then annealed at room temperature for 2 days, is shown in Fig. 5. The pattern was
taken at room temperature with the X-ray incident beam perpendicular to the shear direction which is
along the meridian. It shows diffractions not only on the equator and meridian but also in the quadrants,
indicating an ordered crystalline phase. In particular, several diffractions between 0.37 and 0.48 nm can
be detected in the high-angle region, which indicates the ordered arrangement of the alkyl chains.52, 53
As indicated in this figure, the a*- and b*- axes are assigned to the equator, and the c*- axis is along the
meridian. On the equator, the locations of the first two strong diffraction arcs in low-angle region can be
identified at 2θ = 2.20° (d = 4.02 nm) and 2.60° (d = 3.40 nm), which can be indexed as (100) and (010),
respectively. When the diffraction arc in the low-angle quadrants (indexed as (-111)) is projected onto
the equator, the location of the diffraction arc on the equator can be identified at 2θ = 3.35° (d = 2.64
nm), which can be assigned to be (-110) according to the triangulation method of building a 2D a*b*
lattice of the unit cell.54-57 Consequently, an oblique lattice of the (hk0) diffractions on the equator
direction can be constructed as: a = 4.02 nm, b =3.40 nm and γ = 92º, and all of the (hk0) diffractions
can be indexed based on this triangle.
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Fig. 5. 2D XRD pattern of sheared PDTA-DHAB recorded at 25 ºC. The shear direction is on the
meridian and the X-ray beam is perpendicular to the shear direction.
On the meridian, there is a pair of strong diffractions with d-spacing of 0.36 nm in the high-angle
region. Seeing that this is the typical spacing of π-π stacking of the PDI cores, this set of culminant arcs
reveals that the PDI cores may stack parallel to each other. However, the diffraction arc (-111) in the
quadrant should not be overlooked. When this diffraction arc is projected onto the meridian, the location
of the extinct diffraction arc on the meridian can be identified at 2θ = 3.05°, which can be assigned to be
the (001). Note that the meridianal arc of 0.36 nm is in fact located on the eighth layer of the diffractions,
and thus should be indexed as the (008), identifying that the structure of PDTA-DHAB possesses a large
c parameter of 2.90 nm. Such a large c parameter is quite remarkable, which indicates that the molecules
are rotationally stacked and helically assembled in the supramolecular column, giving an 8-fold helix
(Fig. 6). This new complex helical column differs from that reported previously for non-helical column
composed of PDIC-DOAB without rigid linkage.28 As pointed out by Würthner,51 the two phenylene
rings at imide positions are not co-planar with the PDI core. Owing to the bulkiness of the phenylene
linkage, a rotation displacement is required for the close π-π stacking of PDTA-DHAB. As a result, a
rotationally stacked and helically supramolecular structure with large c parameter has been detected
from the 2D XRD pattern. Then, these helical columns further pack into a lattice irrespective of the
helical sense, so the circular dichroism spectra of the PDIC-DOAB film showed no Cotton effect at the
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absorption band of the complex. Using the standard refinement procedure,54-57 the unit cell of the
crystalline structure is finally calculated to be a monoclinic one with dimensions of a = 4.02 nm, b
=3.40 nm, c = 2.90 nm, α = β = 90º, γ = 92º. The experimental and calculated d-spacing values and
diffraction angles of the crystal lattice are listed in Table 1. The calculated crystallographic density is
0.91 g/cm3, in agreement with the experimental result of 0.90 g/cm3.
Fig. 6. Model of the helical column in the monoclinic lattice of PDTA-DHAB. For clarity, peripheral
alkyl chains are not shown and the benzene rings are drawn in different colors.
Table 1. Crystallographic parameters of the monoclinic crystalline phase of PDTA-DHAB.
2θ (deg)
d-spacing (nm)
Intensity
exptc
(hkl)
expta
calcdb
expta
calcdb
100
010
-110
200
020
220
-320
440
450
-111
008
2.20
2.60
2.20
2.60
4.02
3.40
2.64
1.99
1.70
1.27
1.09
0.64
0.55
1.94
0.36
4.02
3.40
2.64
2.01
1.70
1.28
1.07
0.64
0.55
1.95
0.36
s
vs
vw
w
3.35
3.35
4.45
4.40
5.20
5.20
m
vw
w
6.95
6.93
8.10
8.26
13.90
16.10
4.55
13.89
16.00
4.53
w
w
w
24.60
24.58
m
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a
b
Experimental values observed in Fig. 5. Calculated values based on the monoclinic unit cell of a =
c
4.02 nm, b =3.40 nm, c = 2.90 nm, α = β = 90º, γ = 92º. The experimental intensities in Fig. 5 are
semiquantitatively estimated via a microdesitometer and classified as very strong (vs), strong (s),
medium (m), weak (w), and very weak (vw).
When the oriented sample was heated to 70 °C, the 2D XRD pattern (Fig. 7a) shows fewer and
diffused diffraction arcs in comparison with Fig. 5, suggesting the formation of liquid crystalline phase.
The original diffractions between 0.37 and 0.48 nm in the quadrants degenerate into a diffuse ring,
indicating that the crystalline ordering of side-chains has been destroyed. Simultaneously, the original
diffraction arc indexed as the (-111) in the low-angle quadrant disappears, indicating that helically
assembled structure was disturbed. However, the three diffractions on the equator are found to possess q
ratio of 1:2:3 with corresponding d-spacings of 3.33, 1.67, and 1.11 nm, respectively. This indicates that
PDTA-DHAB still forms ordered lamellar structure due to the separation between the aromatic PDI core
and peripheral aliphatic chains (Fig. 7b).
Fig. 7. (a) 2D XRD pattern of sheared PDTA-DHAB recorded at 70 ºC. The shear direction is on the
meridian and the X-ray beam is perpendicular to the shear direction. (b) Molecular packing model of
PDTA-DHAB in lamellar liquid crystalline phase.
3.5. The Sensitivity and Selectivity Responses to ATP
Considering the PDTA-DHAB material has many characteristics: self-assembly characteristic, the
presence of ionic bonds, strong absorption (molar absorptivity: 5×104 L•mol-1•cm-1) and moderately
high fluorescence quantum yield in EtOH: H2O (1:1) solution (fluorescent quantum yield: 56%), we
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would like to further study the potential application of PDTA-DHAB as detection sensor. In order to
evaluate the detection ability of PDTA-DHAB toward ATP, the absorption spectroscopy in an aqueous
solution was carried out. As showed in Fig. 8a, the absorption bands at 492 nm and 528 nm of PDTA-
DHAB decrease gradually and a new broad shoulder at 459 nm is appeared with increasing ATP
concentrations. The changes of spectra indicate that ATP can interact with PDTA-DHAB in aqueous
solution and the degree of aggregation has significantly increased in the new system. More interesting,
the color of the solution has also undergone obvious changes that can be observed by the naked eye
before and after the addition of ATP. Notably, there exists liner relationship between absorbance and
ATP concentration in the range of 0-28 μM (R2 = 0.996), indicating that this method is applicable for
quantitative detection of ATP (Fig. S6). Furthermore, the selectivity of PDTA-DHAB to ATP over other
ions or similar chemicals was also studied (Fig. 8b). Only after the addition of ATP, it displays a
significant change in the shape of the spectra. It finds that ADP can also reduce the absorbance intensity
to some extent. The absorption decrease could be because that ADP has two phosphate species, so ADP
will also exhibit a certain electrostatic interaction with PDTA-DHAB as that of ATP. However, no
bathochromic shift or hypsochromic shift can be observed for ADP, while the more serious intensity
decrease and the distinct hypsochromic shift can be detected for ATP. And the addition of other ions did
not cause a significant change in the spectra. These results show that the approach has good selectivity
and can be applied to ATP detection directly in aqueous solution.
Fig. 8. (a) Absorption spectra of PDTA-DHAB (10 μM) in EtOH:H2O (1:1) solution by increasing the
amount of ATP (0-4 equiv.). Inset: images of PDTA-DHAB solution with 0 and 4 equiv. ATP in
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sunlight. (b) Absorption spectra change of PDTA-DHAB (10 μM) upon the addition of various anions
(4 equiv.).
The sensitivity and selectivity of PDTA-DHAB to ATP was further investigated by fluorescence
spectra. With the addition of ATP, the fluorescence intensity of the solution was gradually decreased.
As displayed in Fig. 9a, the solution color under UV light from bright yellow emission to fluorescence
quenching shows remarked change before and after the ATP addition. In addition, no significant
changes in the fluorescence spectra were observed after the addition of other anions only the ATP
exhibits a decrease of the emission intensity (Fig. 9b). And the addition of ATP at the same
concentration will decrease obviously, indicating that ATP can be detected selectively. These results
imply that the PDTA-DHAB system can realize the sensitivity and selectivity responses to ATP.
Fig. 9. (a) Fluorescence spectra of PDTA-DHAB (10 μM) in EtOH:H2O (1:1) solution by increasing the
amount of ATP (0-4 equiv.). Inset: emission images of PDTA-DHAB solution with 0 and 4 equiv. ATP
under UV light. (b) Fluorescence spectra change of PDTA-DHAB (10 μM) upon the addition of various
anions (4 equiv.).
To further study the mechanism of ATP binding to the PDTA-DHAB, the dynamic light scattering
(DLS) experiment were employed (Fig. 10). Before the addition of ATP, the average particle size of the
sample in the EtOH: H2O (1:1) solution was 346 nm. After the addition of ATP, the particle size
increases to 1109 nm. And then the aggregates are further enlarged to 1518 nm after 30 minutes. While
with the addition of other anions (ADP, AMP, Br-) to system, the average particle size of the solution
respectively was 533 nm, 378 nm, 346 nm (Fig. S7). Due to the ATP has three phosphate species, it
shows the stronger electrostatic binding ability with PDTA-DHAB, leading to the maximum particle
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size of the solution system. Furthermore, cytotoxicity study was performed using the MTT method to
evaluate the biocompatibility of the PDTA-DHAB to living cells (Fig. S8). At low concentrations,
PDTA-DHAB has little effect on cell viability. While the concentration at 10 μM, the average of cell
viability decreases to 91%. This result means that PDTA-DHAB has lower cytotoxicity at moderate
concentrations and can be used in biological applications.
Fig. 10. (a) Particle size distribution of PDTA-DHAB (10 μM) in the EtOH: H2O (1:1) solution. (b)
Particle size distribution of PDTA-DHAB (10 μM) upon the addition of ATP (4 equiv.). (c) Particle size
distribution of PDTA-DHAB (10 μM) upon the addition of ATP (4 equiv.) after 30min.
4. Conclusions
In summary, a novel functional material PDTA-DHAB with non-chiral surfactants attached to PDI
core via a phenylene linkage was designed and prepared by ISA method. Different to the reported PDI
complex with flexible linkage, the PDTA-DHAB molecules with rigid linkage can be rotationally
stacked and helically assembled in the supramolecular column. The unit cell of crystalline phase at room
temperature was determined to be monoclinic with dimensions of a = 4.02 nm, b =3.40 nm, c = 2.90 nm,
α = β = 90º, γ = 92º. With increasing temperature, the helical supramolecular structure was destroyed,
and the crystalline phase transformed to a lamellar liquid crystalline phase. In addition, PDTA-DHAB
system can realize the sensitivity and selectivity responses to ATP. The unique supramolecular structure
and the detection of ATP are significant for the field of ionic self-assembly and for the molecular design
of supramolecular electronics.
Conflicts of interest
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There are no conflicts of interest to declare.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant No. 21875157),
Science and Technology Commission of Shanghai Municipality (16JC1400700), the Program for
Changjiang Scholars and Innovative Research Team in University (IRT-16R13), and the Foundation of
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University
(LK1705).
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Table of Contents entry
The novel PDI complex can be self-assembled into helical supramolecular structure. Moreover, the
solution of complex can also realize the visual detection on ATP.
1