Light-Harvesting in Biophotonic Optofluidic Microcavities via Whispering-Gallery Modes.

Phycobiliproteins are a class of light-harvesting fluorescent proteins existing in cyanobacteria and microalgae, which harvest light and convert it into electricity. Owing to recent demands on environmental-friendly and renewable apparatuses, phycobiliproteins have attracted substantial interest in bioenergy and sustainable devices. However, converting energy from biological materials remains challenging to date. Herein, we report a novel scheme to enhance biological light-harvesting through light-matter interactions at the biointerface of whispering-gallery modes (WGMs), where phycobiliproteins were employed as the active gain material. By exploiting microdroplets as a carrier for light-harvesting biomaterials, strong local electric field enhancement and photon confinement at the cavity interface resulted in significantly enhanced bio-photoelectricity. A threshold-like behavior was discovered in photocurrent enhancement and the WGM modulated fluorescence. Systematic studies of biologically produced photoelectricity and optical mode resonance were carried out to illustrate the impact of the cavity quality factor, structural geometry, and refractive indices. Finally, a biomimetic system was investigated by exploiting cascade energy transfer in phycobiliprotein assembly composed of three light-harvesting proteins. The key findings not only highlight the critical role of optical cavity in light-harvesting but also offer deep insights into light energy coupling in biomaterials.

Mechanical adaptability of artificial muscles from nanoscale molecular action.

The motion of artificial molecular machines has been amplified into the shape transformation of polymer materials that have been compared to muscles, where mechanically active molecules work together to produce a contraction. In spite of this progress, harnessing cooperative molecular motion remains a challenge in this field. Here, we show how the light-induced action of artificial molecular switches modifies not only the shape but also, simultaneously, the stiffness of soft materials. The heterogeneous design of these materials features inclusions of free liquid crystal in a liquid crystal polymer network. When the magnitude of the intrinsic interfacial tension is modified by the action of the switches, photo-stiffening is observed, in analogy with the mechanical response of activated muscle fibers, and in contrast to melting mechanisms reported so far. Mechanoadaptive materials that are capable of active tuning of rigidity will likely contribute to a bottom-up approach towards human-friendly and soft robotics.

Light-Directed Liquid Manipulation in Flexible Bilayer Microtubes.

Flexible microfluidic systems have potential in wearable and implantable medical applications. Directional liquid transportation in these systems typically requires mechanical pumps, gas tanks, and magnetic actuators. Herein, an alternative strategy is presented for light-directed liquid manipulation in flexible bilayer microtubes, which are composed of a commercially available supporting layer and the photodeformable layer of a newly designed azobenzene-containing linear liquid crystal copolymer. Upon moderate visible light irradiation, various liquid slugs confined in the flexible microtubes are driven in the preset direction over a long distance due to photodeformation-induced asymmetric capillary forces. Several light-driven prototypes of parallel array, closed-loop channel, and multiple micropump are established by the flexible bilayer microtubes to achieve liquid manipulation. Furthermore, an example of a wearable device attached to a finger for light-directed liquid motion is demonstrated in different gestures. These unique photocontrollable flexible microtubes offer a novel concept of wearable microfluidics.

Self-reporting and self-regulating liquid crystals.

Liquid crystals (LCs) are anisotropic fluids that combine the long-range order of crystals with the mobility of liquids1,2. This combination of properties has been widely used to create reconfigurable materials that optically report information about their environment, such as changes in electric fields (smart-phone displays) 3 , temperature (thermometers) 4 or mechanical shear 5 , and the arrival of chemical and biological stimuli (sensors)6,7. An unmet need exists, however, for responsive materials that not only report their environment but also transform it through self-regulated chemical interactions. Here we show that a range of stimuli can trigger pulsatile (transient) or continuous release of microcargo (aqueous microdroplets or solid microparticles and their chemical contents) that is trapped initially within LCs. The resulting LC materials self-report and self-regulate their chemical response to targeted physical, chemical and biological events in ways that can be preprogrammed through an interplay of elastic, electrical double-layer, buoyant and shear forces in diverse geometries (such as wells, films and emulsion droplets). These LC materials can carry out complex functions that go beyond the capabilities of conventional materials used for controlled microcargo release, such as optically reporting a stimulus (for example, mechanical shear stresses generated by motile bacteria) and then responding in a self-regulated manner via a feedback loop (for example, to release the minimum amount of biocidal agent required to cause bacterial cell death).

Continuous Isotropic-Nematic Transition in Amyloid Fibril Suspensions Driven by Thermophoresis.

The isotropic and nematic (I + N) coexistence for rod-like colloids is a signature of the first-order thermodynamics nature of this phase transition. However, in the case of amyloid fibrils, the biphasic region is too small to be experimentally detected, due to their extremely high aspect ratio. Herein, we study the thermophoretic behaviour of fluorescently labelled ß-lactoglobulin amyloid fibrils by inducing a temperature gradient across a microfluidic channel. We discover that fibrils accumulate towards the hot side of the channel at the temperature range studied, thus presenting a negative Soret coefficient. By exploiting this thermophoretic behaviour, we show that it becomes possible to induce a continuous I-N transition with the I and N phases at the extremities of the channel, starting from an initially single N phase, by generating an appropriate concentration gradient along the width of the microchannel. Accordingly, we introduce a new methodology to control liquid crystal phase transitions in anisotropic colloidal suspensions. Because the induced order-order transitions are achieved under stationary conditions, this may have important implications in both applied colloidal science, such as in separation and fractionation of colloids, as well as in fundamental soft condensed matter, by widening the accessibility of target regions in the phase diagrams.

Light Responsive Microstructured Surfaces of Liquid Crystalline Network with Shape Memory and Tunable Wetting Behaviors.

Using adaptive soft materials to fabricate microstructured surfaces renders them with tunable topographic feature and thus controllable physical properties. Here, light responsive microstructured surfaces are reported with shape memory and tunable wetting behaviors; the surfaces are covered with micropillar arrays and constructed by lightly crosslinked azo-containing liquid crystalline network (LCN). UV light irradiation induces 25% contraction in length of the micropillars along their long axes and, as a consequence, the variations of topographic feature and wetting behavior of the surfaces. In addition, the LCNs exhibit shape memory properties, which can freeze the temporary topographic feature of microstructured surfaces (formed under UV irradiation and relatively high temperature) and enable application of their functionalities at mild conditions. This light responsiveness makes it feasible to remotely and precisely tune the local regions of microstructured surfaces, which should broaden the applications of adaptive surfaces in regulating the wetting, optical, and adhesion properties in selected regions.

Lipid Liquid-Crystal Phase Change Induced through near-Infrared Irradiation of Entrained Graphene Particles.

Lipid packing is intimately related to the geometry of the lipids and the forces that drive self-assembly. Here, the photothermal response of a cubic liquid-crystalline phase formed using phytantriol in the presence of low concentrations of pristine graphene was evaluated. Small-angle X-ray scattering showed the reversible phase changes from cubic to hexagonal to micellar due to localized heating through irradiation with near-infrared (NIR) light and back to cubic after cooling.

Surface modification of alignment layer by ultraviolet irradiation to dramatically improve the detection limit of liquid-crystal-based immunoassay for the cancer biomarker CA125.

Liquid crystal (LC)-based biosensing has attracted much attention in recent years. We focus on improving the detection limit of LC-based immunoassay techniques by surface modification of the surfactant alignment layer consisting of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (DMOAP). The cancer biomarker CA125 was detected with an array of anti-CA125 antibodies immobilized on the ultraviolet (UV)-modified DMOAP monolayer. Compared with a pristine counterpart, UV irradiation enhanced the binding affinity of the CA125 antibody and reproducibility of immunodetection in which a detection limit of 0.01 ng∕ml for the cancer biomarker CA125 was achieved. Additionally, the optical texture observed under a crossed polarized microscope was correlated with the analyte concentration. In a proof-of-concept experiment using CA125-spiked human serum as the analyte, specific binding between the CA125 antigen and the anti-CA125 antibody resulted in a distinct and concentration-dependent optical response despite the high background caused by nonspecific binding of other biomolecules in the human serum. Results from this study indicate that UVmodification of the alignment layer, as well as detection with LCs of large birefringence, contributes to the enhanced performance of the label-free LC-based immunodetection, which may be considered a promising alternative to conventional label-based methods.

Geometrically unrestricted, topologically constrained control of liquid crystal defects using simultaneous holonomic magnetic and holographic optical manipulation.

Despite the recent progress in physical control and manipulation of various condensed matter, atomic, and particle systems, including individual atoms and photons, our ability to control topological defects remains limited. Recently, controlled generation, spatial translation, and stretching of topological point and line defects have been achieved using laser tweezers and liquid crystals as model defect-hosting systems. However, many modes of manipulation remain hindered by limitations inherent to optical trapping. To overcome some of these limitations, we integrate holographic optical tweezers with a magnetic manipulation system, which enables fully holonomic manipulation of defects by means of optically and magnetically controllable colloids used as "handles" to transfer forces and torques to various liquid crystal defects. These colloidal handles are magnetically rotated around determined axes and are optically translated along three-dimensional pathways while mechanically attached to defects, which, combined with inducing spatially localized nematic-isotropic phase transitions, allow for geometrically unrestricted control of defects, including previously unrealized modes of noncontact manipulation, such as the twisting of disclination clusters. These manipulation capabilities may allow for probing topological constraints and the nature of defects in unprecedented ways, providing the foundation for a tabletop laboratory to expand our understanding of the role defects play in fields ranging from subatomic particle physics to early-universe cosmology.

Lehmann rotation of the cholesteric helix in droplets oriented by an electric field.

We study the Lehmann rotation of the cholesteric helix in droplets of the liquid crystal N-(p-methoxybenzilidene)-p-butylaniline doped with a small amount of the chiral molecule R811 when they are subjected to a temperature gradient. We show that the helix rotates much faster when it is parallel to the temperature gradient than when it is perpendicular to it. The first configuration is obtained by submitting the droplets to an ac electric field parallel to the temperature gradient, whereas the second one is observed at zero field. We show that the rotation velocity of the helix strongly depends on the droplet radius, even when the helix is parallel to the temperature gradient. This observation supports the idea that the Leslie thermomechanical coupling cannot explain alone the Lehmann effect.

Rheology of nematic liquid crystals with highly polar molecules.

We report experimental studies on the rheology of a few nematic liquid crystals with highly polar molecules (CCH-7, PCH-7, CB-7). The selected molecules have the same alkyl chain (-C(7)H(15)) and cyano (-CN) end group. In the core part of the molecule, CCH-7 has two cyclohexane rings, PCH-7 has one cyclohexane and one aromatic ring, and CB-7 has two aromatic rings. Two viscosities were measured as a function of temperature, namely, η(2) (director parallel to the shear direction) and η(1) (director perpendicular to the shear direction). The orientation of the director was studied using small angle light scattering techniques. η(2) was measured in presheared sample, whereas the electrorheological technique was used to measure η(1). We show that both viscosities of the liquid crystals depend on the number of aromatic rings and Kirkwood correlation factor. The temperature dependent viscosities can be understood based on the intramolecular π-electron conjugation and intermolecular association of highly polar molecules.

Discontinuous anchoring transition and photothermal switching in composites of liquid crystals and conducting polymer nanofibers.

We prepared nanocomposites of a nematic liquid crystal and nanofibers of a conducting polymer (polyaniline). All the nanocomposites exhibit a discontinuous surface anchoring transition from planar to homeotropic in the nematic phase on a perfluoropolymer coated surface with a thermal hysteresis (≈ 5.3 °C). We observe a relatively large bistable conductivity and demonstrate a light driven switching of conductivity and dielectric constant in dye doped nanocomposites in the thermal hysteresis (bistable) region. The experimental results have been explained based on the reorientation of the nanofibers driven by the anchoring transition of the nematic liquid crystal. We show a significant enhancement of the bistable temperature range (≈ 13 °C) by an appropriate choice of compound in the binary system.

Electrically tunable infrared filter based on the liquid crystal Fabry-Perot structure for spectral imaging detection.

An electrically tunable infrared (IR) filter based on the liquid crystal (LC) Fabry-Perot (FP) key structure, which works in the wavelength range from 5.5 to 12 µm, is designed and fabricated successfully. Both planar reflective mirrors with a very high reflectivity of ∼95%, which are shaped by depositing a layer of aluminum (Al) film over one side of a double-sided polished zinc selenide wafer, are coupled into a dual-mirror FP cavity. The LC materials are filled into the FP cavity with a thickness of ∼7.5 µm for constructing the LC-FP filter, which is a typical type of sandwich architecture. The top and bottom mirrors of the FP cavity are further coated by an alignment layer with a thickness of ∼100 nm over Al film. The formed alignment layer is rubbed strongly to shape relatively deep V-grooves to anchor LC molecules effectively. Common optical tests show some particular properties; for instance, the existing three transmission peaks in the measured wavelength range, the minimum full width at half-maximum being ∼120 nm, and the maximum adjustment extent of the imaging wavelength being ∼500 nm through applying the voltage driving signal with a root mean square (RMS) value ranging from 0 to ∼19.8 V. The experiment results are consistent with the simulation, according to our model setup. The spectral images obtained in the long-wavelength IR range, through the LC-FP device driven by the voltage signal with a different RMS value, demonstrates the prospect of the realization of smart spectral imaging and further integrating the LC-FP filter with IR focal plane arrays. The developed LC-FP filters show some advantages, such as electrically tunable imaging wavelength, very high structural and photoelectronic response stability, small size and low power consumption, and a very high filling factor of more than 95% compared with common MEMS-FP spectral imaging approaches.

Stabilization of cholesteric blue phases using polymerized nanoparticles.

This study explores the roles of UV-polymerizable silicon-based nanoparticles in polymer-stabilized blue phase (PSBP) liquid crystals. Our analysis reveals that the polymerized polymer leads to widening of the temperature range of the blue phase and stabilization of the reflection wavelength against temperature variations. A polymer morphology study of PSBP reveals the polydomain nature of the blue phase. In practical application, the advantage of the low-surface-energy property of the UV-polymerizable silicon-based nanoparticles leads to a significant reduction in switching voltage from 140 to 40 V.

Highly sensitive and selective glucose sensor based on ultraviolet-treated nematic liquid crystals.

Glucose is an extremely important biomolecule, and the ability to sense it has played a significant role in facilitating the understanding of many biological processes. Here, we report a novel glucose sensor based on ultraviolet (UV)-treated nematic liquid crystals. Submerging UV-treated 4-cyano-4'-pentylbiphenyl (5CB) in a glucose solution (while carefully adjusting its pH to 7.5 with NaOH and HCl) triggered an optical response, from dark to bright, observed with a polarized microscope. Notably, 5CB was located inside a glucose oxidase (GOx)-modified gold grid. We exploited this pH-driven phenomenon to design a new glucose sensor. This device could detect as little as 1 pM analyte, which is 3 orders of magnitude lower than the detection limit of the most sensitive glucose sensor currently available. It also exhibits high selectivity due to GOx modification. Thus, this is a promising technique for glucose detection, not only for clinical diagnostics, but also for sensing low levels of glucose in a biological environment (e.g., single cells and bacterial cultures).

Electric-field-induced patterns and their temperature dependence in a bent-core liquid crystal.

Two kinds of electroconvection patterns in an ether-bridged bent-core nematic liquid crystal material (BCN), which appear in different frequency ranges, are examined and compared. One is a longitudinal pattern with the stripes parallel to the orientation of the BCN and with a periodicity of approximately the cell thickness, occurring in the high-frequency range of several hundreds Hz; the other one is oblique stripes, which results in a zigzag pattern, and appears in the low-frequency range of several tens Hz. In addition, within an intermediate-frequency range, transformations from oblique to longitudinal and then to normal stripes occur at increased ac voltages. In particular, we investigated the temperature behavior of longitudinal and oblique stripes: When the temperature T increases and approaches the clearing temperature Tc, the contrast of the domains is enhanced and the frequency range of existence becomes wider, while the onset voltages increase only moderately instead of diverging, thus suggesting an isotropic mechanism of pattern formation.

Light-induced pitch transitions in photosensitive cholesteric liquid crystals: effects of anchoring energy.

We experimentally study how the cholesteric pitch P depends on the equilibrium pitch P0 in planar liquid crystal (LC) cells with both strong and semistrong anchoring conditions. The cholesteric phase was induced by dissolution in the nematic LC of the right-handed chiral dopant 7-dehydrocholesterol (7-DHC, provitamin D3) which transforms to left-handed tachysterol under the action of uv irradiation at the wavelength of 254 nm. By using the model of photoreaction kinetics we obtain the dependencies of isomer concentrations and, therefore, of the equilibrium pitch on the uv irradiation dose. The cholesteric pitch was measured as a function of irradiation time using the polarimetry method. In this method, the pitch is estimated from the experimental data on the irradiation time dependence of the ellipticity of light transmitted through the LC cells. It is found that the resulting dependence of the twist parameter 2D/P (D is the cell thickness) on the free twisting number parameter 2D/P0 shows jumplike behavior and agrees well with the known theoretical results for the anchoring potential of Rapini-Papoular form.

Laser-induced instabilities in liquid crystal cells with a photosensitive substrate.

Liquid crystal layers sandwiched between a reference plate and a photosensitive substrate were investigated. We focused on the reverse geometry, where the cell was illuminated by a laser beam from the reference side. In planar cells both static and dynamic instabilities occurred, depending on the angle between the laser polarization and the director orientation on the reference plate. In cells where the molecules were aligned along the normal of the reference plate, a dynamic pattern was observed at all angles of polarization. A simple model based on a photoinduced surface torque accounts for the findings. Light scattering studies revealed some basic properties of the instabilities.

Micro- and nanofibers and liquid crystals for light-scattering shutters: simulation of electro-optical properties.

This work demonstrates the feasibility of using polymeric micro- and nanofiber-composed films and liquid crystals as electrically switchable scattering light shutters. We present a concept of electro-optic device based on an innovative combination of two mature technologies: optics of nematic liquid crystals and electrospinning of nanofibers. These devices have electric and optical characteristics far superior to other comparable methods. The simulation presented shows results that are highly consistent with those of experiments and that explain the working mechanism of the devices.

Birefringence-induced wavelength mismatch between the polarization rotation and resonant modes in magnetophotonic structures containing nematic layers.

The present work is devoted to the study of spectral characteristics of normal incident light transmitted by a multilayered structure composed of an alternated sequence of nematic and magnetic layers presenting a central magneto-optical defect. Using the Berreman 4 × 4 matrix formalism, we numerically obtain the transmission spectrum and the polarization rotation angle of the system as a function of the nematic optical axis direction. Our results reveal the emergence of a shift between the wavelengths of the resonant mode and polarization rotation angle, which strongly depends on the birefringence of the nematic layers. In particular, we show the existence of distinct regimes for the wavelength mismatch between the transmission of resonant modes and the maximum polarization rotation angle, which are governed by the ordinary and extraordinary refractive indices of nematic layers. The mechanism behind such shift is discussed under the light of propagation eigenmodes for a medium presenting circular and linear birefringence. The effects associated with the defect thickness are also analyzed.