Dynamic Spirals of Nanoparticles in Light-Responsive Polygonal Fields Orlova, Tetiana; Plamont, Remi; Depauw, Alexis; Katsonis, Nathalie
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10.1002/smll.201902419
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Publication date: 2019
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Orlova, T., Plamont, R., Depauw, A., & Katsonis, N. (2019). Dynamic Spirals of Nanoparticles in Light-Responsive Polygonal Fields. Small, 15(39), [1902419]. https://doi.org/10.1002/smll.201902419
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Dynamic Spirals of Nanoparticles in Light-Responsive Polygonal Fields Tetiana Orlova, Rémi Plamont, Alexis Depauw, and Nathalie Katsonis*
Dr. T. Orlova, Dr. R. Plamont, Dr. A. Depauw, Prof. Dr. N. Katsonis
Bio-inspired and Smart Materials, MESA+ Institute for Nanotechnology, University of Twente, 7500 AE Enschede, The Netherlands
E-mail: n.h.katsonis@utwente.nl
Keywords: chirality, smart materials, molecular switches, nanoparticles, self-assembly
Nanoparticles tend to aggregate once integrated into soft matter and consequently, self-assembling nanoparticles into large-scale, regular, well-defined and ultimately chiral patterns remains an ongoing challenge towards the design and realization of organized superstructures of nanoparticles. The patterns of nanoparticles that have been reported in liquid crystals so far are all static, and this lack of responsiveness extends to assemblies of nanoparticles formed in topological singularities and other localized structures of anisotropic matter. Here, we show that gold nanoparticles form spiral superstructures in polygonal fields of cholesteric liquid crystals. Moreover, when cholesteric liquid crystals that incorporate molecular photo-switches in their composition, we show that the period of the nanoparticulate spirals follows the light-induced reorganization of the cholesteric liquid crystals. These experimental findings evidence that chiral liquid crystals can be used as chiral and dynamic templates for soft photonic nanomaterials. Controlling the geometry of these spirals of nanoparticles will ultimately allow modulating the plasmonic signature hybrid and chiral systems and materials.
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Promoting the self-assembly of nano-objects into larger, functional, dynamic materials in which the size-related properties of these nano-objects can be preserved, enhanced and eventually controlled has become a contemporary field of investigations.1-6 Living systems
offer compelling evidence that multiscale, sophisticated and stimuli-responsive architectures can be built simply by letting their smallest parts self-organize, as dictated by their intrinsic properties. In particular, the templating of micro- and nano-inclusions to form hybrid materials is a well-known strategy employed by nature,7,8 that has inspired the realization of
hybrid optical materials.9-12
In designing and realization of soft and responsive nanomaterials, taking advantage of the long-range order of liquid crystals is a valuable approach to achieve templated self-assembly.16 In particular, the supramolecular helices found in cholesteric liquid crystals are
excellent candidates for the templated self-assembly of nano-objects because they combine long range ordering with mobility at the molecular level.17,18 They also display a rich range of
helix-based textures that can be used as templates: oily streaks, fingerprints, grids, fan-shaped focal conics, Grandjean steps and many more.19 While dispersions of micro- and
nanoparticles in chiral liquid crystals have been described,20 most investigations of
self-assembled patterns are restricted to colloidal particles or to the formation of two-dimensional architectures from particle-like structures.21 Once incorporated in liquid crystals,
nanoparticles form aggregates that fail to mirror any liquid-crystalline organization,22-32
except for one series of investigations templating the self-assembly of metallic nanoparticles with cholesteric fingerprints.33,34 In a few examples, the shape,22-24 orientation22-24- or the
pattern geometry32 of larger aggregates were found to be dependent from a liquid crystalline
environment, while bulk liquid crystals doped with nanoparticles are known to reorient under an electric field35 and light.36
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As an alternative to bulk systems, localized topological structures have been used as energetic traps for nanoparticles, in a variety of chiral and non-chiral liquid crystals, ranging from nematic25,26 to cholesteric droplets,27,37 blue phases,28,29 smectic films,38,39 liquid crystal
colloids30 and liquid crystals in toroidal geometries.35 Arrays of topological structures
carrying trapped nanoparticles were reorganized by driving each of the topological elements individually,40 but precise control over such topological structures in dynamic liquid crystals
remains unaccounted for.27,41,42 The hybrid liquid-crystalline materials reported so far have
shown limited possibilities for structural switching by an external stimulus. By contrast, we demonstrate dynamic spirals of gold nanoparticles, that are formed by the templating effect of polygonal fields of light-responsive liquid crystals. We show that the period of these dynamic spirals of nanoparticles can be tuned by irradiation with light.
Our system features the polygonal field that is formed by chiral nematic liquid crystals when their planar alignment is promoted in the bulk, whereas they orient perpendicularly at the free interface with air, so that their helix-based organization transforms into a polygonal texture near the interface. In two dimensions, microscopy images show fields of polygons, and in three dimensions, this geometry corresponds to patterns of double spirals that lie on surface of convex cones.43 Polygonal patterns are known to behave as multiwavelength micro-mirrors,44
in which the intrinsic helical organization of polygonal fields determines the spatial intensity distribution of the reflected light depending on its wavelength, as seen in biological materials such as the chitin-based cuticle of beetles10,55 and helicoidal cell-wall architecture in fruits.46
Polygonal patterns in soft matter also show potential as materials for trapping nanoparticles and living cells.47
Three glass-forming cyclic siloxane liquid crystals were designed and synthesized to be used as templates for nanoparticles (Figure 1a).48 These materials can be stabilized by simple
thermal quenching below the glass transition temperature, which allows performing structural investigations by scanning electron microscopy (SEM).
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As a photo-switchable dopant we use a derivative of isosorbide acid (Sorb, Figure 1b) that undergoes a thermally irreversible E-Z isomerization under irradiation with UV light.31
Moreover, the overlap between the absorption spectra before and after UV irradiation (Fig. 1b) does not allow reversing the Z–E isomerization by irradiation with light.49 As a general
note, the choice of artificial molecular switches is always limited by solubility effects in liquid crystals. In spite of its poor switchable performances, Sorb was chosen as a photo-switch for this system because it is soluble up to ~3.5 wt%,31 in siloxane-based liquid crystals and up to
10 mol% in other cholesteric liquid crystals.49 In addition, Sorb is known to induce large
changes in the liquid crystal helix under illumination.31,49 Typically, a large shift in selective
reflection was demonstrated for silicon blue doped with Sorb, only after a few minutes of light illumination at λ = 365 nm.31 Notably, no significant photo-induced dimerization is
observed for the typical irradiation conditions that we use, and traces of dimers can be found only after significantly longer exposure times.31
The octanethiol-functionalized gold nanoparticles were mixed with the liquid crystals at a concentration of 1 wt% (Figure 1c). The preparation of the hybrid light-responsive materials was optimized to promote the self-assembly of gold nanoparticles in the polygonal texture (Figure 2a,b).
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Figure 1. Chemical structures and properties of the components. a) Cyclic siloxanes CLC15,
CLC35, and CLC50. b) Photo-switchable chiral dopant used in this study (Sorb). c) Thiol-covered gold nanoparticles and associated image obtained by transmission electron microscopy.
The nanoparticles were first incorporated in the siloxane with the highest glass transition temperature (CLC50). From the hybrid liquid crystal, a polygonal texture was formed after ~30 min of heating at 120°C, which is a typical annealing temperature for cyclic siloxanes.33,34 However the polygonal pattern started collapsing after two hours, and
eventually disappeared entirely. This temperature-induced collapse is a consequence of distortions that penetrate deeper into to bulk of the liquid crystal as annealing proceeds, which leads to the continuous inclination of the helical axis, until this axis eventually becomes nearly parallel to the surface, and consequently the polygonal texture disappears. At lower temperatures, the polygonal field remains stable for up to 16 hours, which is close to the annealing time that is typically necessary for nanoparticles to organize in liquid crystals.33,34
However, only large aggregates of nanoparticles were formed at the end of the process (Figure S1a,b), likely because CLC50 is very viscous at temperatures that are so much below
Compound x λR, nm Transition temperature, °C CLC15 0.15 640 G 15 N* 084 I CLC35 0.35 460 G 26 N* 141 I CLC50 0.50 422 G 38 N* 176 I a) b) c) Ø 2 - 4 nm H3CO O O O O H H O O H3CO H3CO O O O O H H O O OCH3 UV light 365 nm O O O O H H O O H3CO OCH3 UV light 365 nm Au S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S X240,000 10 nm O Me Si MeSi O MeSiO Si Me O SiMe O R R R R R R= O O H H H H O O O 1-x x +
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the temperature where it becomes an isotropic fluid. The viscosity limits the mobility of the nanoparticles and thus prevents their self-assembly.
Figure 2. Self-assembly of nanoparticles in polygonal textures. a - b) Polarized optical
micrographs of the same polygonal field formed by the cholesteric liquid crystal CLC15, respectively in transmission and in reflection mode. c) Double spiral in a polygonal field of cholesteric liquid crystal (CLC15 40% + CLC35 60%), which is more stable against the electron beam compared to CLC15 because the mixture has a higher glass transition temperature. Each double spiral corresponds to a single polygon. These patterns are in the absence of any metallic nanoparticles. d) Spirals of gold nanoparticles in polygonal fields of non-photoresponsive cholesteric liquid crystal CLC15.
b)
a)
d)
c)
0.87 kV X15,000 2 µm 1 kV X15,050 2 µm 0.86 kV X15,000 2 µm 25 µm 25 µm S SS SS S S S S S S S S S SS S S Au7
Next we used a liquid crystal with a longer helical pitch (CLC35), because the ratio between the bulk free energy and the surface energy theoretically depends on the helical pitch.43 The
stability of the polygonal pattern was indeed improved, and long chains of nanoparticles were found to be occasionally nested in the periodic modulation of the polygonal texture (Figure S1c,d). We thus concluded that a liquid crystal with an even longer helical pitch would lead to the formation of well-defined patterns of nanoparticles.
When using a long-pitch liquid crystal with a low isotropic temperature transition (CLC15), we found that the nanoparticles self-assemble on a large scale by truly mimicking the organization of the polygonal field in which they form spiral patterns. We found large-scale patterns of nanoparticles nested in a network of double spirals, which we evidence by using SEM with a detection mode involving high efficiency secondary electrons that allows localizing the nanoparticles and visualizing the polygonal pattern with the same measurement (Figure 2c). Mostly the pattern involved ensembles of ~20 nanoparticles, although larger aggregates were observed occasionally (Figure S2). The nanoparticles patterns are characterized by a well-defined organization that spreads over hundreds of micrometers – evidence for such a long-range order is unprecedented (Figure 2d). We note that besides featuring double spirals on a scale of ~10−20 µm2, larger circle-like structures of ~30−40 µm2
are also formed (Figure S3). The coexistence of these patterns in the same large-scale organization of nanoparticles adds to the richness of the system, with future perspectives to switch between different structural elements under irradiation with light.
In terms of mechanism, we hypothesize that the octanethiol-covered nanoparticles, which promote perpendicular anchoring of liquid crystal molecules, are capable to nucleate point topological defects, thus generating elastic forces that lead to the nanoparticles self-assembly into chains.50 These chains preferably locate close to the energetically favorable regions,
which correspond to areas where the liquid crystal molecules are preferentially oriented parallel to the hybrid film surface, while perpendicular boundary conditions dominate at the
8
vicinity of the siloxane-air interface.33 The nanoparticle network of double spirals is formed
by following these locations in the polygonal texture.
The polygonal patterns respond to irradiation with light – provided that irradiation occurs at higher temperatures, where the liquid crystals are not in their glassy state. The photo-isomerization of the molecular switch decreases its molecular anisotropy and thus its helical twisting power, and consequently, the tightness of the helix-based hybrid material is increased (Figure 1b).31,49 The light-induced pitch modification of the liquid crystal (Figure 3a) has
consequences on the geometry of the spirals of gold nanoparticles. The double spiral patterns of nanoparticles follow the light-induced transformations of the polygonal field (Figure 3b-g) and namely, irradiating the nanoparticle-doped photo-responsive films modifies the distance between the spiral arms, as the periodic modulation in these double spirals is directly related to the period of the cholesteric helix. The narrowing of the double-spiral nanoparticle patterns is not always very visible in the SEM images because they correspond to 2D-projections of 3D-cones, and thus the decrease in the period of the fingerprint spirals is observable in two dimensions only when the polygonal field is composed by uniform cones, that all have the same size and height. Besides, the chains of nanoparticles become thicker as the UV irradiation times increase (Figure 3f). We attribute the thickening of the network lines to the necessity to heat the samples out of the glassy state during exposure to light, which increases the mobility of the nanoparticles in the template.
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Figure 3. Light-induced structural modifications. a) Position of the selective reflection band
for planar films of Sorb-doped cholesteric liquid crystal CLC15, and in the presence of gold nanoparticles. Insets: optical microscopic images. The center of the selective reflection band
λR is determined from the Lorentz fit of each absorption spectrum. b - g) SEM micrographs of nanoparticle patterns in the photoactive cholesteric liquid crystal (CLC15 + Sorb 0.6 wt%) exposed to UV light for b) 0 s, c) 15 s, d) 30 s, e) 120 s, f) 240 s, g) 600 s.
c) b) d) f) e) g) 0.85 kV X15,000 2 µm 0.85 kV X15,000 2 µm 0.85 kV X15,000 2 µm 0.86 kV X15,010 2 µm 0.87 kV X15,000 2 µm 0.85 kV X15,000 2 µm
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Extending this templating approach to non-spherical or larger nanoparticles is likely to support new developments towards soft photonic nanomaterials with optical characteristics that are controlled from the molecular level upwards, as the characteristics of the surface plasmon resonance depend both on the size and on shape of nanoparticles.51 In particular,
larger nanoparticles with an intense plasmon band are more likely to influence the optical properties of the system. Moreover, Achieving uniform polygonal fields, combined with the use of liquid crystals that undergo large pitch changes under illumination, is expected to maximize the amplitude of light-induced reorganizations. We envision that the light-induced structural changes can be further amplified by choosing other artificial molecular switches to drive the response to light, such as chiral azobenzenes or hydrazones typically, provided that these switches are sufficiently soluble in the liquid crystal host, and that they do not photo-degrade in a liquid crystalline environment. Finally, using lyotropic liquid crystals as templates for bigger nanoparticles would broaden the field further, as the size of the defect cores that hold the nanoparticles in the vicinity of the interfacial zone reaches several dozens of nanometers in these materials,52 whereas it is ∼10 nm only in thermotropic liquid crystals.53
Further studies on the development of dynamic spirals of nanoparticles will be aimed both at understanding the multistep mechanism of nanoparticles self-assembly in polygonal fields, and in improving the characteristic properties of these polygonal templates, such as realizing a uniform field of photo-controllable polygons, for a wide range of helical pitches.
In conclusion, we demonstrate a chiral and tunable platform that directs the self-assembly of gold nanoparticles into well-defined double spirals that lie on convex cones, in polygonal fields of cholesteric liquid crystals. The distance between the spiral arms of the patterns of nanoparticles can be controlled by light, because the periodic modulation in the double spirals directly relates to the period of the cholesteric helix. The system features the possibility to reconfigure a long-range network of nanoparticles with light, by dynamic amplification of chirality across increasing length scales. Moreover, this hybrid system demonstrates a true
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nanoparticle self-assembly in chiral soft matter – meaning that the nanoparticles follow the periodic helical modulation of the ordered cholesteric arrangement, instead of being trapped in topological defects or other regions of molecular disorder. Such a bio-inspired templating approach holds potential for the future of reconfigurable hybrid materials because there is no conceptual restriction to extend it to a large variety of nano-objects, including platelets,54
plant viruses55 and other nanocontainers.56 Directing the self-assembly of metallic
nanoparticles with chiral liquid crystals will give rise to periodically structured hybrid materials that comply with the definition of metamaterials, with potential applications to light-based technologies.
Experimental Section
Materials: The cholesteric liquid crystal siloxanes CLC15, CLC35, and CLC50 were
synthesized by Synthon.Before use, we performed an additional purification procedure that involves dissolution in acetone under sonication, filtration of the clear solution on paper and precipitation by addition of methanol, centrifugation of the cloudy precipitate for 5 min at 5000 rpm, and removal of the solvents mixture. The procedure was repeated a few times, and traces of solvents were eventually removed under vacuum to yield a sticky oil.
The photo-switchable chiral dopant Sorb (2,5-bis(4-methoxycinnamoyl)-1,4;3,6-dianhydro-D-sorbitol) was synthesized by following a reported protocol.49 Gold nanoparticles of 2−4 nm in
diameter and functionalized with octanethiol were purchased from Sigma-Aldrich. All components are soluble in toluene.
Doping of liquid crystal siloxanes: The siloxanes were heated up to 75 − 120 °C depending on
the temperature of their phase transition to the isotropic state. Then, the photo-switchable chiral dopant was added (Section S4). Next, an appropriate volume of gold nanoparticles in suspension was added, as well as 3 mL of toluene. The thus prepared solution was sonicated
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for 1 hour in the ultrasonic bath, and then placed in a flask at 140 °C until all the toluene was evaporated. The procedure yielded a hybrid, cholesteric liquid crystal.
Planar photo-responsive films: Planar cells of the nominal thickness of 15 µm were
purchased from E.H.C. All cells were filled at 65−75 °C, kept for 20 min at this temperature to reach thermodynamic equilibrium, and slowly cooled down to room temperature.
Hybrid photo-responsive materials: Two clean glass substrates and a flask containing the
siloxane were heated up to 65−75 °C. Two pieces of 6 µm Mylar spacer were placed on the first glass substrate at a distance of about 2.5 cm. A drop of cholesteric mixture was placed in the center. The second glass substrate was placed on top of the droplet. When irradiation was required, the cell was exposed to UV light at 65−75°C, i.e. in the mesoscopic state of chiral liquid crystal. The cell was kept on a hot plate for a few minutes under mechanical pressure created by a metal cylinder that was preheated to the same temperature. The color optical reflection appearing from the cell indicated the planar liquid crystal arrangement introduced by shearing. The cell was then placed on a metal plate at 4 °C, down to the glassy state. CLC15-based cell was additionally transferred to the freezer at − 22−25 °C to prevent the liquid crystal from sticking on the glass slide, when opening the sample. After four hours in the freezer, the top glass of the cell was removed. The resulting hybrid film was then annealed, and a polygonal field was formed to satisfy the perpendicular boundary conditions at the free interface with air.
Our first SEM observations of the annealed films based on CLC15 revealed that the nanoparticles locate preferably well below the open surface, in the bulk of the cholesteric layer. The absence of nanoparticles at the free interface likely stems from the fact that, at the stage of cell preparation, the nanoparticles avoid the interface with the glass substrate, because of the perpendicular anchoring conditions promoted by the thiol coating.50 We thus
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before annealing. After annealing, the patterns of nanoparticles were thus located at the air interface instead of being buried in the bulk.
UV light source: UV illumination was performed using a Hönle bluepoint LED lamp
(λ = 365 nm). An LED lamp was used for irradiation based on its proven ability to induce significant changes to cholesteric liquid crystals, even with short exposure times.31,49 All cells
were placed at ≈6 cm from the exit pupil of the optical fiber. The intensity of the UV lamp was set at 80% level from the maximum intensity measured as 170 mW cm-2. UV irradiation
of the photo-responsive siloxanes was carried out at 65−75 °C to ensure that the material is in the mesoscopic liquid crystalline state.
Structural characterization: The liquid crystal textures were imaged with an Olympus BX-51
polarized optical microscope. The UV-visible spectra were acquired using an Ocean Optics USB2000+ spectrometer. SEM images were taken by using a HE-SE2 detector at low accelerating voltage of the electron beam, to avoid damaging the films. The films were not coated with any metallic layer, because heating during the coating deposition destroyed the polygonal texture.
Supporting Information
Supporting Information is available from the Wiley Online Library or from the author.
Acknowledgements
We thank Mark A. Smithers from the MESA+ NanoLab for assistance with the SEM and TEM measurements. The authors acknowledge funding support from the European Research Council (Consolidator Grant Morpheus 30968307) and from the Netherlands Organization for Scientific Research (NWO Projectruimte Grant 13PR3105).
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Received: ((will be filled in by the editorial staff)) Revised: ((will be filled in by the editorial staff)) Published online: ((will be filled in by the editorial staff))
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18
The long range organization of nanoparticles is templated effectively by double spirals
that lie on the convex cones of polygonal fields of chiral liquid crystals. Moreover, the distance between the spiral arms of nanoparticles can be controlled by light. This approach towards dynamic, long-range and self-assembled patterns of metallic nanoparticles features chiral amplification across length-scales and holds perspective for advanced hybrid nanomaterials.
Light-responsive spirals of nanoparticles
T. Orlova, R. Plamont, A. Depauw, N. Katsonis*
Dynamic Spirals of Nanoparticles in Light-Responsive Polygonal Fields S SSS S S S S S S S S S S S SS S UV 1 µm 1 µm Au
