Topological liquid crystal superstructures as structured light lasers.

Liquid crystals (LCs) form an extremely rich range of self-assembled topological structures with artificially or naturally created topological defects. Some of the main applications of LCs are various optical and photonic devices, where compared to their solid-state counterparts, soft photonic systems are fundamentally different in terms of unique properties such as self-assembly, self-healing, large tunability, sensitivity to external stimuli, and biocompatibility. Here we show that complex tunable microlasers emitting structured light can be generated from self-assembled topological LC superstructures containing topological defects inserted into a thin Fabry-Pérot microcavity. The topology and geometry of the LC superstructure determine the structuring of the emitted light by providing complex three-dimensionally varying optical axis and order parameter singularities, also affecting the topology of the light polarization. The microlaser can be switched between modes by an electric field, and its wavelength can be tuned with temperature. The proposed soft matter microlaser approach opens directions in soft matter photonics research, where structured light with specifically tailored intensity and polarization fields could be designed and implemented.

Self-shaping liquid crystal droplets by balancing bulk elasticity and interfacial tension.

The shape diversity and controlled reconfigurability of closed surfaces and filamentous structures, universally found in cellular colonies and living tissues, are challenging to reproduce. Here, we demonstrate a method for the self-shaping of liquid crystal (LC) droplets into anisotropic and three-dimensional superstructures, such as LC fibers, LC helices, and differently shaped LC vesicles. The method is based on two surfactants: one dissolved in the LC dispersed phase and the other in the aqueous continuous phase. We use thermal stimuli to tune the bulk LC elasticity and interfacial energy, thereby transforming an emulsion of polydispersed, spherical nematic droplets into numerous, uniform-diameter fibers with multiple branches and vice versa. Furthermore, when the nematic LC is cooled to the smectic-A LC phase, we produce monodispersed microdroplets with a tunable diameter dictated by the cooling rate. Utilizing this temperature-controlled self-shaping of LCs, we demonstrate life-like smectic LC vesicle structures analogous to the biomembranes in living systems. Our experimental findings are supported by a theoretical model of equilibrium interface shapes. The shape transformation is induced by negative interfacial energy, which promotes a spontaneous increase of the interfacial area at a fixed LC volume. The method was successfully applied to many different LC materials and phases, demonstrating a universal mechanism for shape transformation in complex fluids.

Amyloid Fibrils of Stefin B Show Anisotropic Properties.

Human stefin B, a member of the cystatin family of cysteine protease inhibitors, tends to form amyloid fibrils under relatively mild conditions, which is why it is used as a model protein to study amyloid fibrillation. Here, we show for the first time that bundles of amyloid fibrils, i.e., helically twisted ribbons, formed by human stefin B exhibit birefringence. This physical property is commonly observed in amyloid fibrils when stained with Congo red. However, we show that the fibrils arrange in regular anisotropic arrays and no staining is required. They share this property with anisotropic protein crystals, structured protein arrays such as tubulin and myosin, and other anisotropic elongated materials, such as textile fibres and liquid crystals. In certain macroscopic arrangements of amyloid fibrils, not only birefringence is observed, but also enhanced emission of intrinsic fluorescence, implying a possibility to detect amyloid fibrils with no labels by using optical microscopy. In our case, no enhancement of intrinsic tyrosine fluorescence was observed at 303 nm; instead, an additional fluorescence emission peak appeared at 425 to 430 nm. We believe that both phenomena, birefringence and fluorescence emission in the deep blue, should be further explored with this and other amyloidogenic proteins. This may allow the development of label-free detection methods for amyloid fibrils of different origins.

Nematic Liquid-Crystal Necklace Structure Made by Microfluidics System.

We report a necklace structure made of liquid crystal dispersed in poly(vinyl alcohol) (PVA) aqueous solution, which is fabricated by a microfluidic device. In the necklace structure, liquid crystal droplets that are tens of micrometers in diameter are connected by microtethers, which are birefringent, are not penetrating the droplets, and can be elastically stretched by applying external force. The necklace structure was analyzed by fluorescent confocal microscopy, and the tethers were made of liquid crystal and PVA composite. The elastic constant of the tether was determined by using laser tweezers to stretch the tether. The Whispering Gallery Modes circulating inside individual droplets in the necklace structure were also observed.

Self-assembled toron-like structures in inverse nematic gels.

A novel form of nematic gel (N-gel) wherein bright flower-like domains (BFDs) rich in gelator fibres are embedded in a matrix of liquid crystal (LC) molecules has been reported. These gels which we denote as inverse N-gels are unlike typical N-gels in which the LC is encapsulated within an aggregated network of gelator molecules. The self-organization of the helical gelator fibres within the BFDs leads to the creation of localized toron-like structures that are topologically protected due to their skyrmion director profile. Optical and confocal microscopy have been used to deduce the LC director configuration, in order to understand possible intermolecular interactions that can lead to the formation of the twisted structures and the inverse N-gels.

Surfaces Affect Screening Reliability in Formulation Development of Biologics.

PURPOSE: The ability to predict an antibody's propensity for aggregation is particularly important during product development to ensure the quality and safety of therapeutic antibodies. We demonstrate the role of container surfaces on the aggregation process of three mAbs under elevated temperature and long-term storage conditions in the absence of mechanical stress. METHODS: A systematic study of aggregation is performed for different proteins, vial material, storage temperature, and presence of surfactant. We use size exclusion chromatography and micro-flow imaging to determine the bulk concentration of aggregates, which we combine with optical and atomic force microscopy of vial surfaces to determine the effect of solid-liquid interfaces on the bulk aggregate concentration under different conditions. RESULTS: We show that protein particles under elevated temperature conditions adhere to the vial surfaces, causing a substantial underestimation of aggregation propensity as determined by common methods used in development of biologics. Under actual long-term storage conditions at 5°C, aggregate particles do not adhere to the surface, causing an increase in bulk concentration of particles, which cannot be predicted from elevated temperature screening tests by common methods alone. We also identify specific protein - surface interactions which promote oligomer formation in the nanometre range. CONCLUSIONS: Special care should be taken when interpreting size exclusion and particle count data from stability studies if different temperatures and vial types are involved. We propose a novel combination of methods to characterise vial surfaces and bulk solution for a full understanding of protein aggregation processes in a sample.

Improving the Chemical Selectivity of an Electronic Nose to TNT, DNT and RDX Using Machine Learning.

We used a 16-channel e-nose demonstrator based on micro-capacitive sensors with functionalized surfaces to measure the response of 30 different sensors to the vapours from 11 different substances, including the explosives 1,3,5-trinitro-1,3,5-triazinane (RDX), 1-methyl-2,4-dinitrobenzene (DNT) and 2-methyl-1,3,5-trinitrobenzene (TNT). A classification model was developed using the Random Forest machine-learning algorithm and trained the models on a set of signals, where the concentration and flow of a selected single vapour were varied independently. It is demonstrated that our classification models are successful in recognizing the signal pattern of different sets of substances. An excellent accuracy of 96% was achieved for identifying the explosives from among the other substances. These experiments clearly demonstrate that the silane monolayers used in our sensors as receptor layers are particularly well suited to selecting and recognizing TNT and similar types of explosives from among other substances.

Nanoparticles Can Wrap Epithelial Cell Membranes and Relocate Them Across the Epithelial Cell Layer.

Although the link between the inhalation of nanoparticles and cardiovascular disease is well established, the causal pathway between nanoparticle exposure and increased activity of blood coagulation factors remains unexplained. To initiate coagulation tissue factor bearing epithelial cell membranes should be exposed to blood, on the other side of the less than a micrometre thin air-blood barrier. For the inhaled nanoparticles to promote coagulation, they need to bind lung epithelial-cell membrane parts and relocate them into the blood. To assess this hypothesis, we use advanced microscopy and spectroscopy techniques to show that the nanoparticles wrap themselves with epithelial-cell membranes, leading to the membrane's disruption. The membrane-wrapped nanoparticles are then observed to freely diffuse across the damaged epithelial cell layer relocating epithelial cell membrane parts over the epithelial layer. Proteomic analysis of the protein content in the nanoparticles wraps/corona finally reveals the presence of the coagulation-initiating factors, supporting the proposed causal link between the inhalation of nanoparticles and cardiovascular disease.

Remote and autonomous temperature measurement based on 3D liquid crystal microlasers.

We demonstrate non-contact temperature measurement with one tenth of a kelvin precision at distances of several meters using omnidirectional laser emission from dye-doped cholesteric liquid crystal droplets freely floating in a fluid medium. Upon the excitation with a pulsed laser the liquid crystal droplet emits laser light due to 3D Bragg lasing in all directions. The spectral position of the lasing is highly dependent on temperature, which enables remote and contact-less temperature measurement with high precision. Both laser excitation and collection of light emitted by microlasers is performed through a wide telescope aperture optics at a distance of up to several meters. The optical excitation volume, where the droplets are excited and emitting the laser light is of the order of ten cubic millimeters. The measurement is performed with ten second accumulation time, when several droplets pass through the excitation volume due to their motion. The time of measurement could easily be shortened to less than a second by increasing the rate of the excitation laser. Since the method is based solely on measuring the spectral position of a single and strong laser line, it is quite insensitive to scattering, absorption and background signals, such as autofluorescence. This enables a wide use in science and industry, with a detection range exceeding tens of meters.

Geometric stabilisation of topological defects on micro-helices and grooved rods in nematic liquid crystals.

We demonstrate how the geometric shape of a rod in a nematic liquid crystal can stabilise a large number of oppositely charged topological defects. A rod is of the same shape as a sphere, both having genus g = 0, which means that the sum of all topological charges of defects on a rod has to be -1 according to the Gauss-Bonnet theorem. If the rod is straight, it usually shows only one hyperbolic hedgehog or a Saturn ring defect with negative unit charge. Multiple unit charges can be stabilised either by friction or large length, which screens the pair-interaction of unit charges. Here we show that the curved shape of helical colloids or the grooved surface of a straight rod create energy barriers between neighbouring defects and prevent their annihilation. The experiments also clearly support the Gauss-Bonnet theorem and show that topological defects on helices or grooved rods always appear in an odd number of unit topological charges with a total topological charge of -1.

Knot theory realizations in nematic colloids.

Nematic braids are reconfigurable knots and links formed by the disclination loops that entangle colloidal particles dispersed in a nematic liquid crystal. We focus on entangled nematic disclinations in thin twisted nematic layers stabilized by 2D arrays of colloidal particles that can be controlled with laser tweezers. We take the experimentally assembled structures and demonstrate the correspondence of the knot invariants, constructed graphs, and surfaces associated with the disclination loop to the physically observable features specific to the geometry at hand. The nematic nature of the medium adds additional topological parameters to the conventional results of knot theory, which couple with the knot topology and introduce order into the phase diagram of possible structures. The crystalline order allows the simplified construction of the Jones polynomial and medial graphs, and the steps in the construction algorithm are mirrored in the physics of liquid crystals.

Magnetic-field tuning of whispering gallery mode lasing from ferromagnetic nematic liquid crystal microdroplets.

We report magnetic field tuning of the structure and Whispering Gallery Mode lasing from ferromagnetic nematic liquid crystal micro-droplets. Microlasers were prepared by dispersing a nematic liquid crystal, containing magnetic nanoparticles and fluorescent dye, in a glycerol-lecithin matrix. The droplets exhibit radial director structure, which shows elastic distortion at a very low external magnetic field. The fluorescent dye doped ferromagnetic nematic droplets show Whispering Gallery Mode lasing, which is tunable by the external magnetic field. The tuning of the WGM lasing modes is linear in magnetic field with a wavelength-shift of the order of 1 nm/100 mT. Depending on the lasing geometry, the WGMs are red- or blue-shifted.

Chemical Selectivity and Sensitivity of a 16-Channel Electronic Nose for Trace Vapour Detection.

Good chemical selectivity of sensors for detecting vapour traces of targeted molecules is vital to reliable detection systems for explosives and other harmful materials. We present the design, construction and measurements of the electronic response of a 16 channel electronic nose based on 16 differential microcapacitors, which were surface-functionalized by different silanes. The e-nose detects less than 1 molecule of TNT out of 10+12 N2 molecules in a carrier gas in 1 s. Differently silanized sensors give different responses to different molecules. Electronic responses are presented for TNT, RDX, DNT, H2S, HCN, FeS, NH3, propane, methanol, acetone, ethanol, methane, toluene and water. We consider the number density of these molecules and find that silane surfaces show extreme affinity for attracting molecules of TNT, DNT and RDX. The probability to bind these molecules and form a surface-adsorbate is typically 10+7 times larger than the probability to bind water molecules, for example. We present a matrix of responses of differently functionalized microcapacitors and we propose that chemical selectivity of multichannel e-nose could be enhanced by using artificial intelligence deep learning methods.

Liquid microlenses and waveguides from bulk nematic birefringent profiles.

We demonstrate polarization-selective microlensing and waveguiding of laser beams by birefringent profiles in bulk nematic fluids using numerical modelling. Specifically, we show that radial escaped nematic director profiles with negative birefringence focus and guide light with radial polarization, whereas the opposite - azimuthal - polarization passes through unaffected. A converging lens is realized in a nematic with negative birefringence, and a diverging lens in a positive birefringence material. Tuning of such single-liquid lenses by an external low-frequency electric field and by adjusting the profile and intensity of the beam itself is demonstrated, combining external control with intrinsic self-adaptive focusing. Escaped radial profiles of birefringence are shown to act as single-liquid waveguides with a single distinct eigenmode and low attenuation. Finally, this work is an approach towards creating liquid photonic elements for all-soft matter photonics.

Lasing properties of polymerized chiral nematic Bragg onion microlasers.

Dye doped photocurable cholesteric liquid crystal was used to produce solid Bragg onion omnidirectional lasers. The lasers were produced by dispersing and polymerizing chiral nematic LC with parallel surface anchoring of LC molecules at the interface, extracted and transferred into another medium. Lasing characteristics were studied in carrier medium with different refractive index. The lasing in spherical cholesteric liquid crystal was attributed to two mechanisms, photonic bandedge lasing and lasing of whispering-gallery modes. The latter can be suppressed by using a higher index carrier fluid to prevent total internal reflection on the interface of the spheres. Pulse-to-pulse stability and threshold characteristics were also studied and compared to non-polymerized lasers. The polymerization process greatly increases the lasing stability.

Electric field generation of Skyrmion-like structures in a nematic liquid crystal.

Skyrmions are particle-like topological objects that are increasingly drawing attention in condensed matter physics, where they are connected to inversion symmetry breaking and chirality. Here we report the generation of stable Skyrmion-like structures in a thin nematic liquid crystal film on chemically patterned patchy surfaces. Using the interplay of material elasticity and surface boundary conditions, we use a strong electric field to quench the nematic liquid crystal from a fully aligned phase to vortex-like nematic liquid crystal structures, centered on patterned patches, which carry two different sorts of topological defects. Numerical calculations reveal that these are Skyrmion-like structures, seeded from the surface boojum topological defects and swirling towards the second confining surface. These observations, supported by numerical methods, demonstrate the possibility to generate, manipulate and study Skyrmion-like objects in nematic liquid crystals on patterned surfaces.

Nanosecond control and optical pulse shaping by stimulated emission depletion in a liquid crystal.

We study anisotropic Stimulated Emission Depletion (STED) from dye molecules, which are collectively ordered in a host liquid crystal. Due to the ordering of fluorescent emitters, the STED efficiency depends on the polarization of the depletion beam and time-delay of the STED pulse. The depletion efficiency is highest at lower temperatures in the highly ordered smectic-A phase and deteriorates in the higher temperature nematic and isotropic phases. We demonstrate by temporal tuning of STED that it is possible to generate an arbitrary sequence of nanosecond fluorescent pulses with variable width and variable delay. Our results show that the STED mechanism in principle allows for very fast (GHz) and efficient control of light by light, which could in the future be used for all-optical control of the flow of light in photonic microdevices based on liquid crystals. Using STED anisotropy and time-control, new modalities of STED imaging in liquid crystals could be developed.

Ultrafast all-optical response of a nematic liquid crystal.

Liquid crystals are superior optical materials for large area displays, but it is considered that their collective and slow-millisecond response makes them useless for ultrafast optical applications. In contrast to that, we here demonstrate an ultrafast optical response of a nematic liquid crystal, which is induced by an intense femtosecond optical impulse. We show that the refractive index of the nematic liquid crystal pentyl-cyanobiphenyl can be modulated at a time scale as fast as 500 fs via a coherently excited optical Kerr effect. The change in the refractive index is in the order of 10-4 at a fluence of 4 mJ/cm2 and is strongly polarization dependent. This unprecedented result opens new ways towards ultrafast all-optical modulation in liquid crystal-based devices.

In situ laser-imprinted surface realignment of a nematic liquid crystal.

We present a new method for the in-plane realignment of nematic liquid crystals in already fully assembled cells with uni-directionally rubbed polyimide as an aligning layer. We use nematic liquid crystals (NLCs) with a relatively high nematic-isotropic transition temperature and we focus the IR laser beam of the laser tweezers selectively onto one or the other of the inner interfaces. The heat generated by the IR absorption locally melts the liquid crystal and creates an isotropic island with well-defined molecular anchoring at the nematic-isotropic interface. By scanning the laser beam along a pre-defined line, the moving isotropic-nematic interface leaves behind a well oriented LC domain, with LC molecules aligned at 45° to the rubbing direction. If we in addition move the sample with respect to this scanning line, we would be able to selectively realign micro-domains of the liquid crystal with respect to the original alignment induced by the PI rubbing. The realignment can be performed independently on each LC-glass interface, thereby producing predefined domains with customized and controllable alignment within an otherwise uniformly aligned cell.

Stabilisation of 2D colloidal assemblies by polymerisation of liquid crystalline matrices for photonic applications.

Colloidal crystals in anisotropic matrices are extremely stable and versatile, but disassemble as soon as the anisotropy of the matrix disappears. We present an approach to first custom-assemble colloidal structures and subsequently stabilize them through photo-polymerisation of the liquid crystalline matrix. The resulting 2D colloidal assemblies are stable at high temperatures and can even be obtained as free-standing films without a decrease in the degree of organization. This approach could be used to stabilize and extract recently proposed soft-matter photonic microcircuits based on liquid crystal optical microresonators, microlasers and microfibers, and opens up routes towards real soft matter photonic devices that are stable over extended time and temperatures.