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Article
A General Approach to Construct Photo-Responsive Self-Assembly in Light Inert Amphiphilic System Qiang Zhao, Zhen Lian, Xuedong Gao, Yun Yan, and Jianbin Huang Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.6b02836 • Publication Date (Web): 20 Oct 2016 Downloaded from http://pubs.acs.org on October 31, 2016
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A General Approach to Construct Photo-Responsive Self-Assembly in Light Inert Amphiphilic System
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Qiang Zhao,† Zhen Lian,† Xuedong Gao,† Yun Yan*† and Jianbin Huang*†
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†Beijing National Laboratory for Molecular Sciences (BNLMS), State Key
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Laboratory for Structural Chemistry of Unstable and Stable Species, College of
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Chemistry and Molecular Engineering, Peking University, Beijing 100871, People’s
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Republic of China.
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KEYWORDS: Photo-Responsive, Azobenzene, Cyclodextrin, Self-Assembly,
1 2
10
Host-Guest Interaction
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ABSTRACT
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The ability to modulate the amphiphilic aggregation reversibly with external stimuli,
13
especially by light trigger, is of great importance. It makes great contribution to the
14
development of applications by self-assembly. However, most previously described
15
systems are based on specific molecular design and difficultly applied in light-inert
16
aggregations. Here we develop a general and effective approach to control the
17
morphology of amphiphilic aggregates by light, which is suitable for different
18
assemblies such as micelle, vesicle and helix. Our strategy is to construct a
19
photo-responsive factor into light-inert self-assemblies. Based on the different
20
capabilities to form host-guest inclusion between photo-responsive azobenzene
21
sodium and light-inert molecules with cyclodextrin, the transformation of the
22
corresponding amphiphilic aggregation can be controlled easily and reversibly by 1
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light stimuli. Not only the nanostructure of aggregates, but also the phase behavior
2
such as gel are modulated upon light irradiation by this method.
3
4
INTRODUCTION
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Amphiphilic molecules are able to form various well-defined self-assemblies in
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water, such as micelle,1-3 vesicle,4-6 tube,7-8 helix,9-11 etc., which provide chances to
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many
8
optoelectronics,15,16 homogeneous catalysis.17 Among them, smart materials
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especially for photo-responsive materials have attracted great attention recently,
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which provides promising potential in controlled morphology and function
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transformation.18,19 Compared to other responsive methods, light stimuli offers the
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advantage with easily conducted and no extra chemical additives are needed to induce
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the response. Generally, the most often used method to fabricate a photo-responsive
14
system is to introduce a light responsive group into molecular structures.20-22 Although
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many successful breakthroughs were made with great efforts,23-25 challenges still exist
16
to break the limits in this research field. For examples, synthesis, instead of a general
17
approach, sometimes exhibits time-consuming processes and need specific method to
18
each system. Moreover, the aggregation morphology and other properties of
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amphiphiles would be changed after chemical modifications. In fact, a work was
20
reported
21
(4-phenylazo-phenoxy)-acetate
22
cetyltrimethyl ammonium bromide (CTAB), which constructed a photo-responsive
23
system based on the electrostatic attraction and generated multi-state nanostructures
24
including wormlike micelle, vesicle, lamellar structure, spherical micelle by
25
ultraviolent (UV)/visible (Vis) light irradiation and control.26 However, shortcomings
26
are also obvious in this method that it was hardly applied into the electrostatic
27
repulsion or non-electrostatic systems. Even in the electrostatic attraction systems,27,28
28
conformation variation of the light sensitive group is not always effective in tuning
applications,
by
simple
for
sensors,12,13
example,
mixing
light-responsive with
oppositely
medical
molecule charged
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diagnostics,14
such light-inert
as
sodium surfactant
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the self-assembly structures. Hence, pursuing a simple and general approach to
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construct photo-triggered system, especially in light-inert self-assembly, is an urgent
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and challenging work. To achieve this goal, some requirements should be satisfied so
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that the responsive group is necessary to have general interactions29,30 with
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amphiphilic molecules. Moreover, the structures of aggregates are able to be
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significantly modulated by the change of light responsive group under light
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trigger.31-33
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Cyclodextrin (CD) is a kind of compound which could form host-guest
9
complexes with many molecules, particularly for surfactant, resulting in the
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disassembly of surfactant aggregation.34-36 Considering the fact that CD cannot
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response to light,37 we develop 4-(phenylazo)benzoic acid sodium (Azo) into system
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which can insert into CD cavity based on the stable inclusion. It forms Azo@CD
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photo-responsive factor to couple with light-inert amphiphilic assemblies that
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successfully make a general approach to control the morphology of amphiphilic
15
aggregates by UV or visible light irradiation. The key point of this strategy is that the
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different capability of forming host-guest inclusion with CD which is trans-
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azobenzene > alky chain of amphiphilic molecules > cis- azobenzene.38-41 The
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inclusion of trans- Azo@CD can stably coexist with light-inert amphiphilic
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aggregations under visible light. Upon UV light irradiation, with the formation from
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trans- Azo to cis- Azo, CDs are released into solution and form new inclusions with
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amphiphilic molecules which lead to the disassembly of the light-inert aggregations.
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With the alternative UV/Vis light irradiation, the corresponding light control process
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can be realized many circles in three typical assembly systems of micelle,42,43
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vesicle44-46 and helix47,48 as shown in figure 1.
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Figure 1. Schematic illustrations of construction (a) photo-responsive self-assembly
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by Azo@CD in (b) micelle, (c) vesicle and (d) helix systems.
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Experiment section
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Materials
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SDS (sodium dodecyl sulfate), DEAB (dodecetyl trimethyl ammonium bromide) and
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OTAB (octadecyl trimethyl ammonium bromide) were prepared by recrystallizing
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five times from ethanol/acetone. SL (sodium laurate) and SC (sodium cholate) were
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purchased from Sigma-Aldrich and used as received. β-CD and α-CD were purchased
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from Sinopharm Chemical Reagent Co. with a water content of 14%. D2O (99.9%)
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was purchased from Cambridge Isotope Laboratories, Inc. Aqueous solutions were
13
prepared using Milli-Q water of 18 MΩ. Other reagents were from Beijing Chemical
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Reagents (Beijing, China). All reagents were used as received and the solvents were
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purified according to the general procedures before used. 4
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METHODS
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Sample preparations. The SDS micelle system was mixed by 12 mM SDS and
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Azo@β-CD (6 mM / 6 mM) in aqueous solution. The vesicle system was mixed by
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SDS/DEAB (0.4 mM / 0.6 mM) solution with Azo@β-CD (6 mM / 6 mM). The helix
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solution was mixed by CaCl2/SC (20 mM /20 mM) with Azo@β-CD (10 mM / 10
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mM). Moreover, for α-CD systems, the vesicle system was mixed by SL/OTAB (2.5
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mM / 2.5 mM) with Azo@α-CD (5 mM / 5 mM) in 10 mM borax buffer. The helix
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solution was mixed by CaCl2/SC (20 mM /20 mM) with Azo@α-CD (10 mM / 10
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mM) as described before. All the solutions were then thermostatically incubated at
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25oC for 48 h to allow form stable aggregations. All structures were given in figure S1.
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The UV light was conducted by MODEL FC-100/F Long Wave Ultraviolet (365nm,
12
230VOLTS 50Hz 0.9AMPS). The duration of irradiating time was 4 h for each time.
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Transmission Electron Micrograph (TEM). Samples were observed by a Jeol JEM
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100 CX, 80kV and JEM-2100, 200kV. Drops of samples were put onto 230 mesh
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copper grids coated with formvar film. Excess water was removed by filter paper and
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the samples were allowed to dry in ambient air at RT, before TEM observation. It is
17
noticed that all samples were stained except for the hydrogel systems.
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Spectra Measurements. UV-Vis absorbance measurements were carried out on the
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Pgeneral TU-1810 UV-Vis spectrophotometer. All the spectra measurements were
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conducted at RT. The samples irradiated by UV were exposure under UV light for 4 h.
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Dynamic Light Scattering (DLS). A commercialized spectrometer (Brookhaven
22
Instruments Corporation, Holtsville, NY ) equipped with a 100 mW solid-state laser
23
(GXC-III, CNI, Changchun, China) operating at 532 nm was used to conduct dynamic
24
light scattering experiments. Photon correlation measurements in self-beating mode
25
were carried out at multiple scattering angles by using a BI-TurboCo Digital
26
Correlator. The temperature was held at room temperature.
27
1
28
performed on a Bruker ARX 400 MHz spectrometer with D2O as solvent.
29
Rheological
30
Ca2+/SC-Azo@β-CD and Ca2+/SC-Azo@α-CD were assessed by dynamic rheology
H Nuclear Magnetic Resonance (1H NMR). The 1H NMR experiments were
Measurement.
Rheological
properties
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Ca2+/SC,
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measurements by a Thermo Haake RS300 rheometer with cone and plate geometry
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(35 mm diameter, 0.105 mm cone gap). The temperature was kept at 25°C and a
3
water trap was used to minimize water evaporation from the sample. Frequency
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spectra were conducted in the linear viscoelastic regime of the samples determined
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from dynamic strain sweep measurements. In dynamic rheology measurements,
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hydrogel was deformed with frequency f to give the elastic (or storage) modulus G’
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and viscous (or loss) modulus G”. We started with oscillation frequency sweep tests,
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where the stress was chosen as 1 Pa to be nondestructive to the emulsion structure and
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the frequency was varied exponentially.
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RESULTS AND DISCUSSION
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1. Micelle system
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The photo-responsive factor was fabricated by Azo and β-CD and then added into
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target sodium dodecyl sulfate (SDS) system49. The light-triggered process of SDS
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micelle was tested by dynamic light scattering (DLS) (Figure 2a). The SDS micelle
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was stable by addition of responsive factor of Azo@β-CD. Both SDS and trans- Azo
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could form inclusion with β-CD by host-guest interaction but the ability of trans-Azo
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is superior to SDS. The binding constant of cis-Azo with β-CD is 4.54×102 mol·dm-3,
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and trans-Azo with β-CD is 1.36×102 mol·dm-3.50 In addition, the SDS and DEAB to
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β-CD binding abilities are 3.12×102 mol·dm-3; 1.49×103 mol·dm-3, respectively, which
21
is between trans-Azo and cis-Azo.51-54 Hence, the SDS-Azo@β-CD system was
22
predominated by plenty of SDS micelles. After UV irradiation, the solution scattering
23
is notably decreased and no aggregation was found since azobenzene turns into cis-
24
form upon UV irradiation with a lower binding ability with β-CD than SDS. It results
25
in the formation of SDS@β-CD inclusion that leads to SDS micelles disassembled.7
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In addition, the scattering light recovers triggered by visible light because trans-
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azobenzene reappears by visible light and recaptures β-CD to form stable
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trans-Azo@β-CD inclusion complex in SDS micelle solution. It is worth noticing that
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the photo-stimuli process could be repeated several times by ultraviolent and visible
2
light alternatively (Figure 2b).
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The transition of azobenzene between trans- and cis- form was confirmed by
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UV/Vis and 1H NMR. As Figure S2 depicts, the π-π* absorption of the trans-
5
azobenzene at 346 nm in SDS-Azo@β-CD solution. The absorbance of cis- isomer
6
was observed by UV light irradiation. Meanwhile, 1H NMR tests reveal that the
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protons of trans- azobenzene were dominant in SDS-Azo@β-CD solution under
8
visible light and protons of cis- azobenzene increased after UV light irradiation
9
(Figure S3a). The chemical shift of alkyl group in SDS molecule have moved to a
10
high field upon UV irradiation because of the formation of SDS@β-CD inclusion
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dimer by host-guest interaction when trans- Azo turns into cis- isomer under UV light
12
(Figure S3b), which could leads to the breakup of SDS micelle.
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Figure 2. (a) DLS test for SDS-Azo@β-CD and (b) diameter of SDS-Azo@β-CD
15
after UV and visible light irradiated alternatively. [SDS] = 12 mM, [Azo] = 6 mM,
16
[β-CD]= 6 mM.
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2. Vesicle system
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Vesicle is a fundamental self-assembled model for biological studies because of
20
the bilayer membranes and inner water environment. It has been reported that CD
21
could bind with surfactant and affect the aggregation effectively.50 Hence,
22
cationic-anionic surfactant SDS/dodecetyl trimethyl ammonium bromide (DEAB)
23
vesicles55 was chosen to construct a light-responsive system (Figure S4). The 7
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reversible photo-triggered process of SDS/DEAB-Azo@β-CD was confirmed by DLS
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and transmission electron microscopy (TEM) measurements (Figure 3). In
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SDS/DEAB-Azo@β-CD system, the vesicles existed (Figure 3a) with a DLS peak at
4
150 nm (Figure 3d), indicating that since trans- Azo and β-CD could form stable
5
inclusion by host-guest interaction, most β-CD was inserted by guest molecules in the
6
solution under visible light. Upon UV light irradiation, the vesicles disassembled
7
(Figure 3b) accompanied with the aggregation peak disappearing (Figure 3d). As
8
trans-Azo turns into cis- isomer by UV light, it leads to the formation of SDS@β-CD
9
and DEAB@β-CD host-guest inclusions and results in the vanish of SDS/DEAB
10
vesicles.40,55 As expected, the aggregation could reassemble when exposed by visible
11
light (Figure 3c, 3d). In addition, when the light beam goes across the solution, the
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solutions with obvious light path indicated the existence of aggregations. After
13
irradiation by UV light, the light path disappeared with aggregation broken down
14
(Figure 3, insert).
15 16
Figure 3. TEM images of (a) SDS/DEAB-Azo@β-CD, (b) under UV light and then (c)
17
under visible light irradiation in turn. (d) The process tested by DLS measurement.
18
[SDS] = 0.4 mM, [DEAB] = 0.6 mM, [Azo] = 6 mM, [β-CD]= 6 mM. The insets in
19
panels (a)-(c) show photographs of the sample with a laser beam passing across. 8
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The photo-responsive process was also visualized by 1H NMR measurements.
3
The 1H NMR spectra showed when cis- Azo was dominant in solution under UV
4
irradiation, the peak of alkyl proton in SDS and DEAB shifted to a high field (Figure
5
S5). Since binding ability between cis- Azo and β-CD was less than that between
6
surfactant (SDS, DEAB) and β-CD, SDS@β-CD and DEAB@β-CD channel type
7
dimers were formed by host-guest interaction in solution. In figure S3 and S5, the 1H
8
NMR tests demonstrated that β-CD formed channel type dimers, because H3 and H5
9
of β-CD located at cavity of cyclodextrin and only the guest molecules inserting the
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cavity of CD, a shift of H3 and H5 could be observed. Moreover, compared to free
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β-CD, the peak of H3 and H5 shifted to high field under visible and UV light in the
12
mixed solutions which indicated no free β-CD was released under alternative lights
13
and β-CD always formed inclusive dimer with azobenzene or surfactants by
14
host-guest interaction. Furthermore, the supramolecular complex could lead to the
15
break of SDS/DEAB vesicles which is in agreement with TEM and DLS results.
16
In addition, the ratio of the components of every nano-objects were calculated by
17
integrating the peak area of H NMR (Figure S6). In the SDS-Azo@β-CD system, 93%
18
β-CD formed inclusive dimers with trans- Azo under visible light. After UV light
19
irradiation, 70% β-CD were released and formed SDS@β-CD complex in the solution.
20
On the other hand, in the SDS/DEAB-Azo@β-CD system, 88% β-CD formed
21
inclusive dimers with trans- Azo under visible light. After UV light irradiation, 59%
22
β-CD were released and formed SDS@β-CD complex in the solution.
23 24
3. Helix system
25
Helix is ubiquitous in nature and has exclusive structure that attracted research
26
interest because of their potentials in biological and material application. Our research
27
group previously reported that metal ions/sodium cholate (SC) assembled hierarchical
28
nanostructures and formed super hydrogel in aqueous solution.48,56-58 Ca2+/SC helix
29
system was chosen as a hydrogel model (Figure S7 and insert). It is conducted to 9
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identify the photo-triggered transformation upon addition of Azo@β-CD. TEM and
2
rheology measurements were used to measure the structure and hydrogel properties in
3
Ca2+/SC-Azo@β-CD. Before UV irradiation, the hierarchical nanostructures were
4
dominated in the system (Figure 4a). After UV irradiated, the β-CDs turned to bind
5
with SC and the helical structure disassembled (Figure 4b). It is a reversible process
6
upon visible light irradiation as well (Figure 4c). Moreover, the morphological change
7
of aggregation accompanied with a hydrogel-solution phase transformation (Figure 4a
8
- 4c insert).
9
Dynamic rheology was further performed to investigate the mechanical properties
10
of hydrogel. Nondestructive frequency sweep shows Ca2+/SC-Azo@β-CD hydrogel
11
exhibits typical solid-like rheological behavior with storage modulus G’ (～ 1200 Pa)
12
dominating the loss modulus G” ( ～ 250 Pa) over the investigated oscillating
13
frequency as well as Ca2+/SC hydrogel in Figure 4d. When UV light is turned on, the
14
Ca2+/SC-Azo@β-CD hydrogel shows a liquid-like property which is also a revisable
15
process under visible light. In addition, amplitude sweep (f = 1 Hz) indicates weak
16
dependence of G’ and G” in Ca2+/SC-Azo@β-CD hydrogel on applied stress until the
17
yield stress (～ 150 Pa) achieved in Figure 4e. Upon UV light irradiation, the yield
18
stress (～ 3 Pa) significantly decreased because the SC and β-CD formed inclusion
19
dimer resulting in the deformation of hydrogel. The mechanism of hydrogel could be
20
reversible upon UV/Vis light irradiation alternately. In all, not only nanostructures but
21
also phase behavior of Ca2+/SC hydrogel can be controlled by addition of Azo@β-CD
22
upon UV/Vis light.
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Figure 4. TEM images of (a) Ca2+/SC-Azo@β-CD and Ca2+/SC-Azo@β-CD after (b)
3
UV and (c) visible light irradiated in turn. Insert: photo for each sample. (d)
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Oscillation frequency sweep test and (e) amplitude sweep test for Ca2+/SC,
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Ca2+/SC-Azo@β-CD and the sample after UV and visible light irradiated in turn.
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[CaCl2] = 20 mM, [SC] = 20 mM, [Azo] = 10 mM, [β-CD]= 10 mM.
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4. α-CD system
9
Moreover, this method was available for α-CD as well, exhibiting a general
10
approach for amphiphilic self-assemblies. We utilized Azo@α-CD inclusions to
11
sodium laurate (SL)/octadecyl trimethyl ammonium bromide (OTAB) vesicle59
12
and Ca2+/SC helix systems. In SL/OTAB-Azo@α-CD system, the construction or
13
not of vesicles could be tuned by UV/Vis light which is similar to other vesicle
14
system we described before (Figure S8). The photo-responsive process was
15
confirmed by 2D NMR measurements (Figure S9). NOESY spectrum showed
16
the correlation of Ha and Hb in trans- Azo and H2, H3, H4 in α-CD which
17
indicated that trans- Azo formed inclusion with α-CD in visible light (Figure S9a
18
and S9b). After UV light irradiation, trans- Azo turned into cis- form and the 11
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correlating peaks of azobenzene and α-CD disappeared. Instead, α-CD formed another
2
inclusive dimers with SL and OTAB accompanied with correlation of HA in
3
SL/OTAB and H2, H3, H4 in α-CD (Figure S9a and S9c). The results exhibited α-CD
4
could form different complexes in azobenzene and surfactants mixed solution under
5
visible and UV light, similar to β-CD system. In Ca2+/SC-Azo@α-CD hydrogel, both
6
the nanostructure and gel phase were successfully controlled by UV/Vis light in TEM
7
and rheology measurements (Figure S10). It is revealed that macrocycle such as β-CD
8
and α-CD could form Azo@CD inclusions by host-guest interaction and modulate a
9
light-inert assemblies into photo-responsive system, suggesting that we can design
10
more photo-triggered system in non-photo responsive aggregations.
11
In summary, we proposed a simple and effective approach to construct a general
12
photo-responsive system with Azo@CD and amphiphilic aggregations, which is
13
suitable to be applied in different systems of single surfactant or mixed surfactants for
14
many kinds of assemblies such as micelle, vesicle and helix. In addition, not only
15
nanostructures but also phase behavior such as gel formation can be controlled by this
16
method. Furthermore, this general strategy can be developed to many other kinds of
17
systems, for example, nanoparticles,60 polymer or polymer surfactant assemblies and
18
regulate more phase behaviors closely related to self-assembly, for instance of light
19
controlled formation of aqueous two-phase and emulsion. Besides, we successfully
20
conducted Azo@CD photo-responsive factor with both α-CD and β-CD with efforts.
21
Based on this principle, more responsive factors could be designed by other
22
macrocycle molecules such as cucurbituril. It is also expected that other stimuli
23
factors (T, pH) were going to be developed basing on this strategy. This proposed new
24
method is not only helpful to obtain the better scientific understanding in the field of
25
the light controlled assemblies, but also would open a new vista for construction and
26
application of smart materials.
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ASSOCIATED CONTENT
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Supplementary information. 1H NMR, DLS, TEM and Rheology measurements are
2
listed in supporting information. This material is available free of charge via the
3
Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
5
*Corresponding Author is
[email protected] 6
ACKNOWLEDGMENTS
7
This work is supported by National Natural Science Foundation of China
8
(21422302, 21573011, 21273013), National Basic Research Program of China (973
9
Program, 2013CB933800), and Doctoral Program of Higher Education of China.
10
11
Reference
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Nature 1992, 359, 710-712.
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Israelachvili, J. N.; Mitchell, D. J.; Ninham, B. W., Theory of self-assembly of
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hydrocarbon amphiphiles into micelles and bilayers. J. Chem. Soc., Faraday
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Trans. Ⅱ 1976, 72, 1525-1568.
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Dubertret, B.; Skourides, P.; Norris, D. J.; Noireaux, V.; Brivanlou, A. H.;
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