Christopher J. Barrett

Photomobile Polymer Materials : Towards Light-Driven Plastic Motors

As light is a good energy source that can be controlled remotely, instantly, and precisely, light-driven soft actuators could play an important role for novel applications in wideranging industrial and medical fields. Liquid-crystalline elastomers (LCEs) are unique materials having both properties of liquid crystals (LCs) and elastomers, and a large deformation can be generated in LCEs, such as reversible contraction and expansion, and even bending, by incorporating photochromic molecules, such as an azobenzene, with the aid of photochemical reactions of these chromophores. Herein we demonstrate new sophisticated motions of LCEs and their composite materials: a plastic motor driven only by light. If materials absorb light and change their shape or volume, they can convert light energy directly into mechanical work (the photomechanical effect) and could be very efficient as a single-step energy conversion. Furthermore, these photomobile materials would be widely applicable because they can be controlled remotely just by manipulating the irradiation conditions. LCEs show an anisotropic order of mesogens with a cooperative effect, which leads them to undergo an anisotropic contraction along the alignment direction of mesogens when heated above their LC-isotropic(I) phase transition temperatures (TLC-I) and an expansion by lowering the temperature below TLC-I. [1, 13–18] The expansion and contraction is due to the microscopic change in alignment of mesogens, followed by the significant macroscopic change in order through the cooperative movement of mesogens and polymer segments. It is well known that when azobenzene derivatives are incorporated into LCs, the LC-I phase transition can be induced isothermally by irradiation with UV light to cause trans–cis photoisomerization, and the I-LC reverse-phase transition by irradiation with visible light to cause cis–trans back-isomerization. This photoinduced phase transition (or photoinduced reduction of LC order) has led successfully to a reversible deformation of LCEs containing azobenzene chromophores just by changing the wavelength of actinic light. Although the photoinduced deformation of LCEs previously reported is large and interesting, it is limited to contraction/expansion and bending, preventing them from being used for actual applications. Herein we report potentially applicable rotational motions of azobenzene-containing LCEs and their composite materials, including a first lightdriven plastic motor with laminated films composed of an LCE film and a flexible polyethylene (PE) sheet. The LCE films were prepared by photopolymerization of a mixture of an LC monomer containing an azobenzene moiety (molecule 1 shown in Scheme 1) and an LC diacrylate with an azobenzene moiety (2 in Scheme 1) with a ratio of 20/ 80 mol/mol, containing 2 mol% of a photoinitiator in a glass cell coated with rubbed polyimide alignment layers. The photopolymerization was conducted at a temperature at which the mixture exhibited a smectic phase. The glasstransition temperature of the LCE films is at about room temperature, allowing the LCE films to work at room temperature in air, as the films are flexible enough at this temperature. We prepared a continuous ring of the LCE film by connecting both ends of the film. The azobenzene mesogens were aligned along the circular direction of the ring. Upon exposure to UV light from the downside right and visible light from the upside right simultaneously (Figure 1), the ring

Photo-mechanical effects in azobenzene-containing soft materials

The change in shape inducible in some photo-reversible molecules using light can effect powerful changes to a variety of properties of a host material. The most ubiquitous natural molecule for reversible shape change is the rhodopsin-retinal protein system that enables vision, and this is perhaps the quintessential reversible photo-switch. Perhaps the best artificial mimic of this strong photo-switching effect however, for reversibility, speed, and simplicity of incorporation, is azobenzene. This review focuses on the study and application of reversible changes in shape that can be achieved with various systems incorporating azobenzene. This photo-mechanical effect can be defined as the reversible change in shape inducible in some molecules by the adsorption of light, which results in a significant macroscopic mechanical deformation of the host material. Thus, it does not include simple thermal expansion effects, nor does it include reversible but non-mechanical photo-switching or photo-chemistry, nor any of the wide range of optical and electro-optical switching effects for which good reviews exist elsewhere.

Photomobile polymer materials—various three-dimensional movements

The composition of a crosslinked azobenzene liquid-crystalline polymer and a flexible polymer film can provide a variety of simple devices that can walk in one direction like an ‘inchworm’ and move like a ‘robotic arm’ induced by light.

All-optical patterning of azo polymer films

Thin films of polymers containing non-linear optical chromophores based on azobenzene have been shown to respond mechanically to low power light interference, resulting in a transfer of an arbitrary optical pattern to surface relief in a single step, often well below the usual glass transition temperature. The timescale for this process is seconds to minutes, and the resulting surface relief patterns can display a depth of features similar to that of the original film thickness. A series of mechanisms has been proposed to describe the origin of this effect, but none are currently able to rationalize the diverse set of surface patterns observed to be formed with various combinations of circularly and linearly polarized inscription lasers.

Using light to control physical properties of polymers and surfaces with azobenzene chromophores

Azobenzene chromophores can be switched between two geometric isomers using visible light. This photoisomerization is rapid, reversible, and of high quantum yield, and the wavelengths effecting the transformation can be tuned synthetically with substituent groups to the chromphores. Upon isomerization, there can be significant changes to the optical, geometric, mechanical, and chemical properties of azobenzene molecules, and these photo-switchable properties can often be transferred to large host systems into which azobenzene is incorporated. This review describes polymers and surfaces that have been prepared recently that incorporate azobenzene groups, and some of the interesting physical and chemical properties that can be switched reversibly as a result.

Recent twists in photoactuation and photoalignment control

The design of functional and stimuli-responsive materials is among the key goals of modern materials science. The structure and properties of such materials can be controlled via various stimuli, among which light is often times the most attractive choice. Light is ubiquitous and a gentle energy source and its properties can be optimized for a specific target remotely, with high spatial and temporal resolution. Light-control over molecular alignment has in recent years attracted particular interest, for potential applications such as reconfigurable photonic elements and optical-to-mechanical energy conversion. Herein, we bring forward some recent examples and emerging trends in this exciting field of research, focusing on liquid crystals, liquid-crystalline polymers and photochromic organic crystals, which we believe serve to highlight the immense potential of light-responsive materials to a wide variety of current and future high-tech applications in photonics, energy harvesting and conversion.

Temperature modeling of laser-irradiated azo-polymer thin films

Azobenzene polymer thin films exhibit reversible surface mass transport when irradiated with a light intensity and/or polarization gradient, although the exact mechanism remains unknown. In order to address the role of thermal effects in the surface relief grating formation process peculiar to azo polymers, a cellular automaton simulation was developed to model heat flow in thin films undergoing laser irradiation. Typical irradiation intensities of 50 mW/cm2 resulted in film temperature rises on the order of 5 K, confirmed experimentally. The temperature gradient between the light maxima and minima was found, however, to stabilize at only 10(-4) K within 2 micros. These results indicate that thermal effects play a negligible role during inscription, for films of any thickness. Experiments monitoring surface relief grating formation on substrates of different thermal conductivity confirm that inscription is insensitive to film temperature. Further simulations suggest that high-intensity pulsed irradiation leads to destructive temperatures and sample ablation, not to reversible optical mass transport.

Preparation and characterization of polyelectrolyte-coated gold nanoparticles.

Gold nanoparticles of 5 nm diameter, stabilized by 4-(dimethylamino)pyridine (DMAP), were coated with poly(sodium 4-styrene sulfonate) (PSS) via electrostatic self-assembly. The suspension stability, monitored by the gold surface plasmon band (SPB), was studied by varying the pH, the PSS chain length, and PSS concentration. Enhanced stability is obtained at pH 10 (above the pKa of DMAP) when the polymer chain length matches or exceeds the particle circumference. Solid state 13C NMR was used to determine the presence of DMAP and polymers after subsequent deposition of weak and strong polycations: poly(allylamine hydrochloride) (PAH) and poly(diallyldimethylammonium chloride) (PDADMAC). At pH 10, DMAP remains associated with the nanoparticle after the first PSS layer has been formed. When PAH or PDADMAC are subsequently added at pH 4.5, DMAP is expelled, the suspensions remain stable, and zeta potential values indicate complete charge reversal. In the case of PDADMAC, however, the first layer of PSS is not fully retained. When PDADMAC is added at pH 10, DMAP and the first PSS layer are retained but lower zeta potentials and a higher SPB shift indicate a degraded stability. For PAH addition at pH 9.5, both DMAP and PSS are expelled and the suspension becomes unstable. These differences in stability of the multilayer components and the nanoparticle suspension are rationalized in terms of chain flexibility, polymer charge density, and the ability of the polymer functional groups to directly interact with the gold surface.

Photomechanical properties of azobenzene liquid-crystalline elastomers

We prepared homogeneously aligned azobenzene liquid-crystalline elastomer (LCE) films with low T g and explored their photomechanical properties. Upon irradiation with UV light, the films bent toward a light source at room temperature. The mechanical force generated upon exposure to UV light was evaluated by thermomechanical analysis. It was found that the mechanical force generated by photo-irradiation increased with an increase in the cross-linking density. In particular, an LCE film containing 80 mol% azobenzene cross-linker produced a force of over 1 MPa by photo-irradiation, which enabled the film to lift an object 20 times heavier than itself. The degree of contraction by photo-irradiation increased with an increase in temperature and light intensity. Bending could be brought about by more than 5000 times with periodic irradiation. Furthermore, it was found that the LCE films exhibited bending and unbending behaviour by irradiation with sunlight.

Ion distribution in multilayers of weak polyelectrolytes : A neutron reflectometry study

Neutron reflectometry was used to determine the distribution of salt ions and water in thin poly(acrylic acid) and poly(allylamine hydrochloride) polyelectrolyte multilayers assembled with and without salt. Increasing salt concentration reverses the exclusion of water from the substrate region, eventually leading to an asymmetric segregation of water near the substrate at high salt concentration. The counterions were found to localize near the substrate in films that were either assembled with salt or were exposed to salt solutions. In addition, the capping layer of the film was found to greatly influence the counterion distribution in the multilayer.