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Biaxial nematic liquid crystals are fascinating systems sometimes referred to as the Higgs boson of soft matter because of experimental observation challenges. Here we describe unexpected states of matter that feature biaxial orientational order of colloidal supercritical fluids and gases formed by sparse rodlike particles. Colloidal rods with perpendicular surface boundary conditions exhibit a strong biaxial symmetry breaking when doped into conventional chiral nematic fluids. Minimization of free energy prompts these particles to orient perpendicular to the local molecular director and the helical axis, thereby imparting biaxiality on the hybrid molecular-colloidal system. The ensuing phase diagram features colloidal gas and liquid and supercritical colloidal fluid states with long-range biaxial orientational symmetry, as supported by analytical and numerical modeling at all hierarchical levels of ordering. Unlike for nonchiral hybrid systems, dispersions in chiral nematic hosts display biaxial orientational order at vanishing colloid volume fractions, promising both technological and fundamental research utility., Competing Interests: Competing interests The authors declare no competing interests., (© 2024. The Author(s).)

We explore the potential of nanocrystals (a term used equivalently to nanoparticles) as building blocks for nanomaterials, and the current advances and open challenges for fundamental science developments and applications. Nanocrystal assemblies are inherently multiscale, and the generation of revolutionary material properties requires a precise understanding of the relationship between structure and function, the former being determined by classical effects and the latter often by quantum effects. With an emphasis on theory and computation, we discuss challenges that hamper current assembly strategies and to what extent nanocrystal assemblies represent thermodynamic equilibrium or kinetically trapped metastable states. We also examine dynamic effects and optimization of assembly protocols. Finally, we discuss promising material functions and examples of their realization with nanocrystal assemblies.

Many living and artificial systems show similar emergent behavior and collective motions on different scales, starting from swarms of bacteria to synthetic active particles, herds of mammals, and crowds of people. What all these systems often have in common is that new collective properties like flocking emerge from interactions between individual self-propelled or driven units. Such systems are naturally out-of-equilibrium and propel at the expense of consumed energy. Mimicking nature by making self-propelled or externally driven particles and studying their individual and collective motility may allow for deeper understanding of physical underpinnings behind collective motion of large groups of interacting objects or beings. Here, using a soft matter system of colloids immersed into a liquid crystal, we show that resulting so-called nematoelastic multipoles can be set into a bidirectional locomotion by external oscillating electric fields. Out-of-equilibrium elastic interactions between such colloidal objects lead to collective flock-like behaviors emerging from time-varying elasticity-mediated interactions between externally driven propelling particles. Repulsive elastic interactions in the equilibrium state can be turned into attractive interactions in the out-of-equilibrium state under applied external electric fields. We probe this behavior at different number densities of colloidal particles and show that particles in dense dispersions collectively select the same direction of a coherent motion due to elastic interactions between near neighbors. In our experimentally implemented design, their motion is highly ordered and without clustering or jamming often present in other colloidal transport systems, which is promising for technological and fundamental-science applications, like nano-cargo transport, out-of-equilibrium assembly, and microrobotics., Competing Interests: Competing interests statement:The authors declare no competing interest.

Photoswitching of photoluminescence has sparked tremendous research interests for super-resolution imaging, high-security-level anti-counterfeiting, and other high-tech applications. However, the excitation of photoluminescence is usually ready to trigger the photoswitching process, making the photoluminescence readout unreliable. Herein, we report a new photoswitch by the marriage of spiropyran with platinum(II) coordination complex. Viable photoluminescence can be achieved upon excitation by 480 nm visible light while the photoswitching can be easily triggered by 365 nm UV light. The feasible photoswitching may be benefited from the formed liquid crystalline (LC) phase of the designed photoswitch as a crystalline spiropyran is normally unable to implement photoswitching. Compared to the counterparts, this LC photoswitch can show distinct and reliable apparent colors and emission colors before and after photoswitching, which may promise the utility in high-security-level anti-counterfeiting and other advanced information technologies., (© 2024 Wiley‐VCH GmbH.)

Polymer stabilized cholesteric liquid crystals (PSCLCs) are electrically reconfigurable reflective elements. Prior studies have hypothesized and indirectly confirmed that the electro-optic response of these composites is associated with the electrically mediated distortion of the stabilizing polymer network. The proposed mechanism is based on the retention of structural chirality in the polymer stabilizing network, which upon deformation is spatially distorted, which accordingly affects the pitch of the surrounding low molar-mass liquid crystal host. Here, we utilize fluorescent confocal polarized microscopy to directly assess the electro-optic response of PSCLCs. By utilizing dual fluorescent probes, sequential imaging experiments confirm that the periodicity of the polymer stabilizing network matches that of the low molar-mass liquid crystal host. Further, we isolate distinct ion-polymer interactions that manifest in certain photopolymerization conditions.

In this paper, we demonstrate that exciton/exciton annihilation in the 2D perovskite (PEA) 2 PbI 4 (PEPI)─a major loss mechanism in solar cells and light-emitting diodes, can be controlled through coupling of excitons with cavity polaritons. We study the excited state dynamics using time-resolved transient absorption spectroscopy and show that the system can be tuned through a strong coupling regime by varying the cavity width through the PEPI layer thickness. Remarkably, strong coupling occurs even when the cavity quality factor remains poor, providing easy optical access. We demonstrate that the observed derivative-like transient absorption spectra can be modeled using a time-dependent Rabi splitting that occurs because of transient bleaching of the excitonic states. When PEPI is strongly coupled to the cavity, the exciton/exciton annihilation rate is suppressed by 1 order of magnitude. A model that relies on the partly photonic character of polaritons explains the results as a function of detuning.

Magnetic monopoles, despite their ongoing experimental search as elementary particles, have inspired the discovery of analogous excitations in condensed matter systems. In chiral condensed matter systems, emergent monopoles are responsible for the onset of transitions between topologically distinct states and phases, such as in the case of transitions from helical and conical phase to A-phase comprising periodic arrays of skyrmions. By combining numerical modeling and optical characterizations, we describe how different geometrical configurations of skyrmions terminating at monopoles can be realized in liquid crystals and liquid crystal ferromagnets. We demonstrate how these complex structures can be effectively manipulated by external magnetic and electric fields. Furthermore, we discuss how our findings may hint at similar dynamics in other physical systems and their potential applications.

Topological solitons are currently under investigation for their exotic properties, especially in nonlinear physics, optics, and material sciences. However, challenges of robust generation and limited stability over time have hindered their practical uses. To address this issue, an approach is developed to form structured arrays of solitons in films of polymerizable liquid crystals. Their complex molecular architecture is preserved by in situ photopolymerization forming a stable liquid crystal network. Most excitingly, their properties are advanced to include responsiveness functions. When thermally actuated, these topological solitons mediate the reconfiguration of surface topographies. Complex shape changes occur depending on the intrinsic complex spatial distribution of the director, which may even lead to full shape inversion and topographical changes as high as ≈40% of the initial thickness. Conversely, the shape changes provide information on the initial director profile, which is consistent with the mathematical model. The soliton-containing polymer coatings are applicable in multiple domains, ranging from tunable optics to haptics, and from shape-coupled sensing systems to temperature-coupled heat management., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Being key components of the building envelope, glazing products with tunable optical properties are in great demand because of their potential for boosting energy efficiency and privacy features while enabling the main function of allowing natural light indoors. However, windows and skylights with electric switching of haze and transparency are rare and often require high voltages or electric currents, as well as not fully meet the stringent technical requirements for glazing applications. Here, by introducing a predesigned gel material we describe an approach dubbed "Haze-Switch" that involves low-voltage tuning of the haze coefficient in a broad range of 2-90% while maintaining high visible-range optical transmittance. The approach is based on a nanocellulose fiber gel network infiltrated by a nematic liquid crystal, which can be switched between polydomain and monodomain spatial patterns of optical axis via a dielectric coupling between the nematic domains and the applied external electric field. By utilizing a nanocellulose network of nanofibers ∼10 nm in diameter we achieve <10 V dielectric switching and <2% haze in the clear state, as needed for applications in window products. We characterize physical properties relevant to window and smart glass technologies, like the color rendering index, haze coefficient, and switching times, demonstrating that our material and envisaged products can meet the stringent requirements of the glass industry, including applications such as privacy windows, skylights, sunroofs, and daylighting.

Recent years have witnessed the major advances of nanolights with extensive exploration of nano-luminescent materials like carbon dots (CDs). However, solvent-free processing of these materials remains a formidable challenge, impeding endeavors to develop advanced manufacturing techniques. Herein, in response to this challenge, liquid crystallization is demonstrated as a versatile and robust approach by deliberately anchoring flexible alkyl chains on the CDs surface. Alkyl chain grafting on the CDs surface is observed to substantially depress the common aggregation-caused quenching effect, and results in a shift of self-assembly structure from the crystalline phase to smectic liquid crystalline phase. The liquid-crystalline phase-transition temperature is ready to adjust by varying the alkyl chain length, endowing low-temperature (<50 °C) melt-processing capabilities. Consequently, the first case of direct ink writing (DIW) with liquid crystal (LC) carbon dots is demonstrated, giving rise to highly emissive objects with blue, green and red fluorescence, respectively. Another unexpected finding is that DIW with the LC inks dramatically outperforms DIW with isotropic inks, further highlighting the significance of the LC processing. The approach reported herein not only exhibits a fundamental advance by imparting LC functions to CDs, but also promises technological utility in DIW-based advanced manufacturing., (© 2023 Wiley-VCH GmbH.)

Being ubiquitous, solitons have particle-like properties, exhibiting behaviour often associated with atoms. Bound solitons emulate dynamics of molecules, though solitonic analogues of polymeric materials have not been considered yet. Here we experimentally create and model soliton polymers, which we call "polyskyrmionomers", built of atom-like individual solitons characterized by the topological invariant representing the skyrmion number. With the help of nonlinear optical imaging and numerical modelling based on minimizing the free energy, we reveal how topological point defects bind the solitonic quasi-atoms into polyskyrmionomers, featuring linear, branched, and other macromolecule-resembling architectures, as well as allowing for encoding data by spatial distributions of the skyrmion number. Application of oscillating electric fields activates diverse modes of locomotion and internal vibrations of these self-assembled soliton structures, which depend on symmetry of the solitonic macromolecules. Our findings suggest new designs of soliton meta matter, with a potential for the use in fundamental research and technology., (© 2023. The Author(s).)

Self-assembly of colloidal particles into predefined structures is a promising way to design inexpensive manmade materials with advanced macroscopic properties. Doping of nematic liquid crystals (LCs) with nanoparticles has a series of advantages in addressing these grand scientific and engineering challenges. It also provides a very rich soft matter platform for the discovery of unique condensed matter phases. The LC host naturally allows the realization of diverse anisotropic interparticle interactions, enriched by the spontaneous alignment of anisotropic particles due to the boundary conditions of the LC director. Here we demonstrate theoretically and experimentally that the ability of LC media to host topological defect lines can be used as a tool to probe the behavior of individual nanoparticles as well as effective interactions between them. LC defect lines irreversibly trap nanoparticles enabling controlled particle movement along the defect line with the use of a laser tweezer. Minimization of Landau-de Gennes free energy reveals a sensitivity of the ensuing effective nanoparticle interaction to the shape of the particle, surface anchoring strength, and temperature, which determine not only the strength of the interaction but also its repulsive or attractive character. Theoretical results are supported qualitatively by experimental observations. This work may pave the way toward designing controlled linear assemblies as well as one-dimensional crystals of nanoparticles such as gold nanorods or quantum dots with tunable interparticle spacing.

Liquid crystals are widely known for their technological uses in displays, electro-optics, photonics and nonlinear optics, but these applications typically rely on defining and switching non-topological spatial patterns of the optical axis. Here, we demonstrate how a liquid crystal's optical axis patterns with singular vortex lines can robustly steer beams of light. External stimuli, including an electric field and light itself, allow us to reconfigure these unusual light-matter interactions. Periodic arrays of vortices obtained by photo-patterning enable the vortex-mediated fission of optical solitons, yielding their lightning-like propagation patterns. Predesigned patterns and spatial trajectories of vortex lines in high-birefringence liquid crystals can steer light into closed loops or even knots. Our vortex lattices might find technological uses in beam steering, telecommunications, virtual reality implementations and anticounterfeiting, as well as possibly offering a model system for probing the interaction of light with defects, including the theoretically predicted, imagination-capturing light-steering action of cosmic strings, elusive defects in cosmology., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Colloidal systems are abundant in technology, in biomedical settings, and in our daily life. The so-called "colloidal atoms" paradigm exploits interparticle interactions to self-assemble colloidal analogs of atomic and molecular crystals, liquid crystal glasses, and other types of condensed matter from nanometer- or micrometer-sized colloidal building blocks. Nematic colloids, which comprise colloidal particles dispersed within an anisotropic nematic fluid host medium, provide a particularly rich variety of physical behaviors at the mesoscale, not only matching but even exceeding the diversity of structural and phase behavior in conventional atomic and molecular systems. This feature article, using primarily examples of works from our own group, highlights recent developments in the design, fabrication, and self-assembly of nematic colloidal particles, including the capabilities of preprogramming their behavior by controlling the particle's surface boundary conditions for liquid crystal molecules at the colloidal surfaces as well as by defining the shape and topology of the colloidal particles. Recent progress in defining particle-induced defects, elastic multipoles, self-assembly, and dynamics is discussed along with open issues and challenges within this research field.

Topological solitons have knotted continuous field configurations embedded in a uniform background, and occur in cosmology, biology, and electromagnetism. However, real-time observation of their morphogenesis and dynamics is still challenging because their size and timescale are enormously large or tiny. Liquid crystal (LC) structures are promising candidates for a model-system to study the morphogenesis of topological solitons, enabling direct visualization due to the proper size and timescale. Here, a new way is found to rationalize the real-time observation of the generation and transformation of topological solitons using cholesteric LCs confined in patterned substrates. The experimental demonstration shows the topologically protected structures arise via the transformation of topological defects. Numerical modeling based on minimization of free energy closely reconstructs the experimental findings. The fundamental insights obtained from the direct observations pose new theoretical challenges in understanding the morphogenesis of different types of topological solitons within a broad range of scales., (© 2022 Wiley-VCH GmbH.)

Biological functionality is often enabled by a fascinating variety of physical phenomena that emerge from orientational order of building blocks, a defining property of nematic liquid crystals that is also pervasive in nature. Out-of-equilibrium, "living" analogs of these technological materials are found in biological embodiments ranging from myelin sheath of neurons to extracellular matrices of bacterial biofilms and cuticles of beetles. However, physical underpinnings behind manifestations of orientational order in biological systems often remain unexplored. For example, while nematiclike birefringent domains of biofilms are found in many bacterial systems, the physics behind their formation is rarely known. Here, using cellulose-synthesizing Acetobacter xylinum bacteria, we reveal how biological activity leads to orientational ordering in fluid and gel analogs of these soft matter systems, both in water and on solid agar, with a topological defect found between the domains. Furthermore, the nutrient feeding direction plays a role like that of rubbing of confining surfaces in conventional liquid crystals, turning polydomain organization within the biofilms into a birefringent monocrystal-like order of both the extracellular matrix and the rod-like bacteria within it. We probe evolution of scalar orientational order parameters of cellulose nanofibers and bacteria associated with fluid-gel and isotropic-nematic transformations, showing how highly ordered active nematic fluids and gels evolve with time during biological-activity-driven, disorder-order transformation. With fluid and soft-gel nematics observed in a certain range of biological activity, this mesophase-exhibiting system is dubbed "biotropic," analogously to thermotropic nematics that exhibit solely orientational order within a temperature range, promising technological and fundamental-science applications.

Arising in many branches of physics, Hopf solitons are three-dimensional particle-like field distortions with nontrivial topology described by the Hopf map. Despite their recent discovery in colloids and liquid crystals, the requirement of applied fields or confinement for stability impedes their utility in technological applications. Here we demonstrate stable Hopf solitons in a liquid crystal material without these requirements as a result of enhanced stability by tuning anisotropy of parameters that describe energetic costs of different gradient components in the molecular alignment field. Nevertheless, electric fields allow for inter-transformation of Hopf solitons between different geometric embodiments, as well as for their three-dimensional hopping-like dynamics in response to electric pulses. Numerical modelling reproduces both the equilibrium structure and topology-preserving out-of-equilibrium evolution of the soliton during switching and motions. Our findings may enable myriads of solitonic condensed matter phases and active matter systems, as well as their technological applications., (© 2022. The Author(s).)

One of the many functions of reduction-oxidation (redox) cofactors is to mediate electron transfer in biological enzymes catalyzing redox-based chemical transformation reactions. There are numerous examples of enzymes that utilize redox cofactors to form electron transfer relays to connect catalytic sites to external electron donors and acceptors. The compositions of relays are diverse and tune transfer thermodynamics and kinetics towards the chemical reactivity of the enzyme. Diversity in relay design is exemplified among different members of hydrogenases, enzymes which catalyze reversible H 2 activation, which also couple to diverse types of donor and acceptor molecules. The [FeFe]-hydrogenase I from Clostridium acetobutylicum (CaI) is a member of a large family of structurally related enzymes where interfacial electron transfer is mediated by a terminal, non-canonical, His-coordinated, [4Fe-4S] cluster. The function of His coordination was examined by comparing the biophysical properties and reactivity to a Cys substituted variant of CaI. This demonstrated that His coordination strongly affected the distal [4Fe-4S] cluster spin state, spin pairing, and spatial orientations of molecular orbitals, with a minor effect on reduction potential. The deviations in these properties by substituting His for Cys in CaI, correlated with pronounced changes in electron transfer and reactivity with the native electron donor-acceptor ferredoxin. The results demonstrate that differential coordination of the surface localized [4Fe-4S]His cluster in CaI is utilized to control intermolecular and intramolecular electron transfer where His coordination creates a physical and electronic environment that enables facile electron exchange between electron carrier molecules and the iron-sulfur cluster relay for coupling to reversible H 2 activation at the catalytic site., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Colloidal particles in liquid crystals tend to induce topological defects and distortions of the molecular alignment within the surrounding anisotropic host medium, which results in elasticity-mediated interactions not accessible to their counterparts within isotropic fluid hosts. Such particle-induced coronae of perturbed nematic order are highly responsive to external electric fields, even when the uniformly aligned host medium away from particles exhibits no response to fields below the realignment threshold. Here we harness the nonreciprocal nature of these facile electric responses to demonstrate colloidal locomotion. Oscillations of the electric field prompt repetitive deformations of the corona of dipolar elastic distortions around the colloidal inclusions, which upon appropriately designed electric driving synchronize the displacement directions. We observe the colloid-hedgehog dipole accompanied by an umbilical defect in the tilt directionality field ( c -field), along with the texture of elastic distortions that evolves with a change in the applied voltage. The temporal out-of-equilibrium evolution of the director and c -field distortions around particles when the voltage is turned on and off is not invariant upon reversal of time, prompting lateral translations and interactions that markedly differ from those accessible to these colloids under equilibrium conditions. Our findings may lead to both technological and fundamental science applications of nematic colloids as both model reconfigurable colloidal systems and as mesostructured materials with predesigned temporal evolution of structure and composition.

Evaporative self-assembly of noble metal nanoparticles into ordered structures holds great promise for fabricating optical and plasmonic devices by virtue of its low cost, high efficiency, and ease of operation. However, poor control of Marangoni flows is one of the challenges accounting for realizing a well-defined assembly. Herein, based on the theoretical analysis of the influence of evaporative intensity on the assembly, two simple but reliable flow-field-confinement platforms are designed to control the evaporative microflows and to work concurrently with depletion forces to enable the regulated self-assembly of gold nanorods. Orientationally ordered assemblies are realized by the designed strong unidirectional microflow in a capillary, and a device-scale assembly of monolayer membrane is obtained by the created weak convection in homemade glass cells. Morphologically diversified superstructure assemblies, such as spherulite-like, boundary-twisted, chiral spiral assemblies, and merging membranes with a π-twisted domain wall, are obtained due to the spontaneous symmetry breaking or in the presence of defects, such as surface steps and screw dislocations. Optical anisotropy and polarization-dependent behaviors of these assemblies are further revealed, implying the potential applications in plasmonic coupling devices and optoelectronic components. An understanding of the entropy-driven assembly behaviors and control of evaporative microflows to guide the self-assembly of gold nanorods provides insights into the general bottom-up approach that is helpful for constructing complex yet robust nanosuperstructures.

Dispersing inorganic colloidal nanoparticles within nematic liquid crystals provides a versatile platform both for forming new soft matter phases and for predefining physical behavior through mesoscale molecular-colloidal self-organization. However, owing to formation of particle-induced singular defects and complex elasticity-mediated interactions, this approach has been implemented mainly just for colloidal nanorods and nanoplatelets, limiting its potential technological utility. Here, orientationally ordered nematic colloidal dispersions are reported of pentagonal gold bipyramids that exhibit narrow but controlled polarization-dependent surface plasmon resonance spectra and facile electric switching. Bipyramids tend to orient with their C 5 rotation symmetry axes along the nematic director, exhibiting spatially homogeneous density within aligned samples. Topological solitons, like heliknotons, allow for spatial reorganization of these nanoparticles according to elastic free energy density within their micrometer-scale structures. With the nanoparticle orientations slaved to the nematic director and being switched by low voltages ≈1 V within a fraction of a second, these plasmonic composite materials are of interest for technological uses like color filters and plasmonic polarizers, as well as may lead to the development of unusual nematic phases, like pentatic liquid crystals., (© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The organization of nanocolloidal liquid crystals in constrained geometries has fundamental and practical importance, since under confinement, liquid crystals contain stable topological defects that can serve as templates for nanoparticle organization. Three-dimensional confinement of cholesteric (Ch) liquid crystals formed by cellulose nanocrystals (CNCs) have been extensively studied; however, their two-dimensional confinement remains under-investigated. Here, we report the results of systematic experimental studies of two-dimensional confinement of Ch-CNC liquid crystal in cylindrical capillaries with varying inner diameters. Confinement resulted in phase separation of the Ch-CNC liquid crystal into a Ch shell formed by concentric CNC pseudolayers with the helicoidal axis perpendicular to the inner surface of the capillary walls, and a micrometer-diameter isotropic core thread running parallel to the long axis of the capillary. The morphology of the confined Ch-CNC liquid crystal varied when progressively increasing the degree confinement. Finally, we show that phase separation of the Ch-CNC liquid crystal into a Ch shell and an isotropic core is preserved in flexible capillary tubing, suggesting the applicability of this system for the fabrication of flexible optical waveguides.

Colloidal rods immersed in a thermotropic liquid-crystalline solvent are at the basis of so-called hybrid liquid crystals, which are characterized by tunable nematic fluidity with symmetries ranging from conventional uniaxial nematic or antinematic to orthorhombic [Mundoor et al., Science 360, 768 (2018)SCIEAS0036-807510.1126/science.aap9359]. We provide a theoretical analysis of the elastic moduli of such systems by considering interactions between the individual rods with the embedding solvent through surface-anchoring forces, as well as steric and electrostatic interactions between the rods themselves. For uniaxial systems, the presence of colloidal rods generates a marked increase of the splay elasticity, which we found to be in quantitative agreement with experimental measurements. For orthorhombic hybrid liquid crystals, we provide estimates of all 12 elastic moduli and show that only a small subset of those elastic constants play a relevant role in describing the nematoelastic properties. The complexity and possibilities related to identifying the elastic moduli in experiments are briefly discussed.

One of the grand current research challenges is to improve the energy efficiency of residential and commercial buildings, which cumulatively consume more than 40% of the energy generated globally. In addition to improving the comfort of the inhabitants and mitigating the growing energy consumption problem, new building materials and technologies could provide a safe strategy for geoengineering to mitigate global climate change. Herein, recent progress in developing such advanced materials from nanocellulose, which is often derived from wood or even dirty feedstocks like waste, is reviewed. By using chemical and bacteria-enabled processing, nanocellulose can be used to fabricate broadband photonic reflectors, thermally super-insulating aerogels, solar gain regulators, and low-emissivity coatings, with potential applications in windows, roofs, walls, and other components of buildings envelopes. These material developments draw inspiration from advanced energy management found in nature, such as the nanoporous photonic structures that evolved in cuticles of beetles. Fabrication of such materials takes advantage of mesoscale liquid crystalline self-assembly, which allows for pre-designed control of cellulose nanoparticle orientations at the mesoscale. With the potential fully realized, such materials could one day transform the current energy-lossy buildings into energy plants on Earth and possibly even enable extraterrestrial habitats., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Emulsions comprising isotropic fluid drops within a nematic host are of interest for applications ranging from biodetection to smart windows, which rely on changes of molecular alignment structures around the drops in response to chemical, thermal, electric, and other stimuli. We show that absorption or desorption of trace amounts of common surfactants can drive continuous transformations of elastic multipoles induced by the droplets within the uniformly aligned nematic host. Out-of-equilibrium dynamics of director structures emerge from a controlled self-assembly or desorption of different surfactants at the drop-nematic interfaces, with ensuing forward and reverse transformations between elastic dipoles, quadrupoles, octupoles, and hexadecapoles. We characterize intertransformations of droplet-induced surface and bulk defects, probe elastic pair interactions, and discuss emergent prospects for fundamental science and applications of the reconfigurable nematic emulsions., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Chemical organization in reaction-diffusion systems offers a strategy for the generation of materials with ordered morphologies and structural hierarchy. Periodic structures are formed by either molecules or nanoparticles. On the premise of new directing factors and materials, an emerging frontier is the design of systems in which the precipitation partners are nanoparticles and molecules. We show that solvent evaporation from a suspension of cellulose nanocrystals (CNCs) and l-(+)-tartaric acid [l-(+)-TA] causes phase separation and precipitation, which, being coupled with a reaction/diffusion, results in rhythmic alternation of CNC-rich and l-(+)-TA-rich rings. The CNC-rich regions have a cholesteric structure, while the l-(+)-TA-rich bands are formed by radially aligned elongated bundles. The moving edge of the pattern propagates with a finite constant velocity, which enables control of periodicity by varying film preparation conditions. This work expands knowledge about self-organizing reaction-diffusion systems and offers a strategy for the design of self-organizing materials., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Control of physical behaviors of nematic colloids and colloidal crystals has been demonstrated by tuning particle shape, topology, chirality and surface charging. However, the capability of altering physical behaviors of such soft matter systems by changing particle shape and the ensuing responses to external stimuli has remained elusive. We fabricated genus-one nematic elastomeric colloidal ring-shaped particles and various microstructures using two-photon photopolymerization. Nematic ordering within both the nano-printed particle and the surrounding medium leads to anisotropic responses and actuation when heated. With the thermal control, elastomeric microstructures are capable of changing from genus-one to genus-zero surface topology. Using these particles as building blocks, we investigated elastomeric colloidal crystals immersed within a liquid crystal fluid, which exhibit crystallographic symmetry transformations. Our findings may lead to colloidal crystals responsive to a large variety of external stimuli, including electric fields and light. Pre-designed response of elastomeric nematic colloids, including changes of colloidal surface topology and lattice symmetry, are of interest for both fundamental research and applications.

Fundamental relationships are believed to exist between the symmetries of building blocks and the condensed matter phases that they form 1 . For example, constituent molecular and colloidal rods and disks impart their uniaxial symmetry onto nematic liquid crystals, such as those used in displays 1,2 . Low-symmetry organizations could form in mixtures of rods and disks 3-5 , but entropy tends to phase-separate them at the molecular and colloidal scales, whereas strong elasticity-mediated interactions drive the formation of chains and crystals in nematic colloids 6-11 . To have a structure with few or no symmetry operations apart from trivial ones has so far been demonstrated to be a property of solids alone 1 , but not of their fully fluid condensed matter counterparts, even though such symmetries have been considered theoretically 12-15 and observed in magnetic colloids 16 . Here we show that dispersing highly anisotropic charged colloidal disks in a nematic host composed of molecular rods provides a platform for observing many low-symmetry phases. Depending on the temperature, concentration and surface charge of the disks, we find nematic, smectic and columnar organizations with symmetries ranging from uniaxial 1,2 to orthorhombic 17-21 and monoclinic 12-15 . With increasing temperature, we observe unusual transitions from less- to more-ordered states and re-entrant 22 phases. Most importantly, we demonstrate the presence of reconfigurable monoclinic colloidal nematic order, as well as the possibility of thermal and magnetic control of low-symmetry self-assembly 2,23,24 . Our experimental findings are supported by theoretical modelling of the colloidal interactions between disks in the nematic host and may provide a route towards realizing many low-symmetry condensed matter phases in systems with building blocks of dissimilar shapes and sizes, as well as their technological applications.

The physical behavior of anisotropic charged colloids is determined by their material dielectric anisotropy, affecting colloidal self-assembly, biological function, and even out-of-equilibrium behavior. However, little is known about anisotropic electrostatic screening, which underlies all electrostatic effective interactions in such soft or biological materials. In this work, we demonstrate anisotropic electrostatic screening for charged colloidal particles in a nematic electrolyte. We show that material anisotropy behaves markedly different from particle anisotropy. The electrostatic potential and pair interactions decay with an anisotropic Debye screening length, contrasting the constant screening length for isotropic electrolytes. Charged dumpling-shaped near-spherical colloidal particles in a nematic medium are used as an experimental model system to explore the effects of anisotropic screening, demonstrating competing anisotropic elastic and electrostatic effective pair interactions for colloidal surface charges tunable from neutral to high, yielding particle-separated metastable states. Generally, our work contributes to the understanding of electrostatic screening in nematic anisotropic media., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Lyotropic myelin figures (MFs), i.e., long cylindrical structures formed by certain surfactants, owe their name to their resemblance to the biological membrane that covers nerve fibers. Herein, we used a strong bilayer-forming zwitterionic phospholipid stained by the Nile Red dye to study lamellar mesophases. Polarized optical microscopy and fluorescence confocal microscopy allowed us to investigate the morphology of myelin structures and determine the orientational order of amphiphilic molecules. The cross-sectional views reveal significant differences in the configurations of MFs within the liquid crystalline cell, as well as the details of a spontaneous and stimulated formation of branched lipid tubes. Our results provide insights into small-scale morphology and out-of-equilibrium structural changes in the multilamellar structures.

Luminescent liquid crystals (LLCs) attract considerable attention because of their broad applications in displays, chemosensors, and anti-counterfeiting. However, it remains challenging to achieve a high luminescence efficiency in LCs because of the common aggregation-caused quenching effect. Herein, we demonstrate a facile approach to designing LLCs with a high quantum yield up to 88% by deliberately tuning the aggregation behavior of platinum(II) complexes with alkoxy chains (C n H 2 n +1 O-). LLCs in hexagonal columnar and rectangular columnar phases are achieved when n = 12 and 16, respectively, as revealed by one-dimensional wide-angle X-ray diffraction and small-angle X-ray scattering. These LLCs are able to not only exhibit strong emission at elevated temperatures but also show attractive reversible vapochromism upon alternative CH 2 Cl 2 and EtOH fuming, which imparts added functions and promises technological utility.

Doping of nematic liquid crystals with colloidal nanoparticles presents a rich soft matter platform for controlling material properties and discovering diverse condensed matter phases. We describe nematic nanocolloids that simultaneously exhibit strong electrostatic monopole and dipole moments and yield competing long-range anisotropic interactions. Combined with interactions due to orientational elasticity and order parameter gradients of the nematic host medium, they lead to diverse forms of self-assembly both in the bulk of an aligned liquid crystal and when one-dimensionally confined by singular topological defect lines. Such nanocolloids exhibit facile responses to electric fields. We demonstrate electric reconfigurations of nanocolloidal pair-interactions and discuss how our findings may lead to realizing ferroelectric and dielectric molecular-colloidal fluids with different point group symmetries.

Assembly of plasmonic nanomaterials into a low refractive index medium, such as an aerogel, holds a great promise for optical metamaterials, optical sensors, and photothermal energy converters. However, conventional plasmonic aerogels are opaque and optically isotropic composites, impeding them from being used as low-loss or polarization-dependent optical materials. Here we demonstrate a plasmonic-cellulose nanofiber composite aerogel that comprises of well-dispersed gold nanorods within a cellulose nanofiber network. The cellulose aerogel host is highly transparent owing to the small scattering cross-section of the nanofibers and forms a nematic liquid crystalline medium with strong optical birefringence. We find that the longitudinal surface plasmon resonance peak of gold nanorods shows a dramatic shift when probed for the cellulose aerogel compared with the wet gels. Simulations reveal the shift of surface plasmon resonance peak with gel drying can be attributed to the change of the effective refractive index of the gels. This composite material may provide a platform for three- dimensional plasmonic devices ranging from optical sensors to metamaterials.

Humankind has been obsessed with knots in religion, culture and daily life for millennia, while physicists like Gauss, Kelvin and Maxwell already involved them in models centuries ago. Nowadays, colloidal particles can be fabricated to have shapes of knots and links with arbitrary complexity. In liquid crystals, closed loops of singular vortex lines can be knotted by using colloidal particles and laser tweezers, as well as by confining nematic fluids into micrometer-sized droplets with complex topology. Knotted and linked colloidal particles induce knots and links of singular defects, which can be interlinked (or not) with colloidal particle knots, revealing the diversity of interactions between topologies of knotted fields and topologically nontrivial surfaces of colloidal objects. Even more diverse knotted structures emerge in nonsingular molecular alignment and magnetization fields in liquid crystals and colloidal ferromagnets. The topological solitons include hopfions, skyrmions, heliknotons, torons and other spatially localized continuous structures, which are classified based on homotopy theory, characterized by integer-valued topological invariants and often contain knotted or linked preimages, nonsingular regions of space corresponding to single points of the order parameter space. A zoo of topological solitons in liquid crystals, colloids and ferromagnets promises new breeds of information displays and a plethora of data storage, electro-optic and photonic applications. Their particle-like collective dynamics echoes coherent motions in active matter, ranging from crowds of people to schools of fish. This review discusses the state of the art in the field, as well as highlights recent developments and open questions in physics of knotted soft matter. We systematically overview knotted field configurations, the allowed transformations between them, their physical stability and how one can use one form of knotted fields to model, create and imprint other forms. The large variety of symmetries accessible to liquid crystals and colloids offer insights into stability, transformation and emergent dynamics of fully nonsingular and singular knotted fields of fundamental and applied importance. The common thread of this review is the ability to experimentally visualize these knots in real space. The review concludes with a discussion of how the studies of knots in liquid crystals and colloids can offer insights into topologically related structures in other branches of physics, with answers to many open questions, as well as how these experimentally observable knots hold a strong potential for providing new inspirations to the mathematical knot theory.

We experimentally and numerically show that chirality can play a major role in the nonlinear optical response of soft birefringent materials, by studying the nonlinear propagation of laser beams in frustrated cholesteric liquid crystal samples. Such beams exhibit a periodic nonlinear response associated with a bouncing pattern for the optical fields, as well as a self-focusing effect enhanced by the chirality of the birefringent material. Our results open new possible designs of nonlinear optical devices with low power consumption and tunable interactions with localized topological solitons.

Three-dimensional topological solitons attract a great deal of interest in fields ranging from particle physics to cosmology, but remain experimentally elusive in solid-state magnets. Here we numerically predict magnetic heliknotons, an embodiment of such nonzero-Hopf-index solitons localized in all spatial dimensions while embedded in a helical or conical background of chiral magnets. We describe conditions under which heliknotons emerge as metastable or ground-state localized nonsingular structures with fascinating knots of magnetization field in widely studied materials. We demonstrate magnetic control of three-dimensional spatial positions of such solitons, as well as show how they interact to form moleculelike clusters and possibly even crystalline phases comprising three-dimensional lattices of such solitons with both orientational and positional order. Finally, we discuss both fundamental importance and potential technological utility of magnetic heliknotons.

Improving building energy performance requires the development of new highly insulative materials. An affordable retrofitting solution comprising a thin film could improve the resistance to heat flow in both residential and commercial buildings and reduce overall energy consumption. Here, we propose cellulose aerogel films formed from pellicles produced by the bacteria Gluconacetobacter hansenii as insulation materials. We studied the impact of the density and nanostructure on the aerogels' thermal properties. A thermal conductivity as low as 13 mW/(K·m) was measured for native pellicle-based aerogels that were dried as-is with minimal post-treatment. The use of waste from the beer brewing industry as a solution to grow the pellicle maintained the cellulose yield obtained with standard Hestrin-Schramm media, making our product more affordable and sustainable. In the future, our work can be extended through further diversification of food wastes as the substrate sources, facilitating higher potential production and larger applications.

Chiral condensed matter systems, such as liquid crystals and magnets, exhibit a host of spatially localized topological structures that emerge from the medium's tendency to twist and its competition with confinement and field coupling effects. We show that the strength of perpendicular surface boundary conditions can be used to control the structure and topology of solitonic and other localized field configurations. By combining numerical modeling and three-dimensional imaging of the director field, we reveal structural stability diagrams and intertransformation of twisted walls and fingers, torons, and skyrmions and their crystalline organizations upon changing boundary conditions. Our findings provide a recipe for controllably realizing skyrmions, torons, and hybrid solitonic structures possessing features of both of them, which will aid in fundamental explorations and technological uses of such topological solitons. Moreover, we discuss how other material parameters can be used to determine soliton stability and how similar principles can be systematically applied to other liquid crystal solitons and solitons in other material systems.

Malleability of metals is an example of how the dynamics of defects like dislocations induced by external stresses alters material properties and enables technological applications. However, these defects move merely to comply with the mechanical forces applied on macroscopic scales, whereas the molecular and atomic building blocks behave like rigid particles. Here, we demonstrate how motions of crystallites and the defects between them can arise within the soft matter medium in an oscillating electric field applied to a chiral liquid crystal with polycrystalline quasi-hexagonal arrangements of self-assembled topological solitons called "torons." Periodic oscillations of electric field applied perpendicular to the plane of hexagonal lattices prompt repetitive shear-like deformations of the solitons, which synchronize the electrically powered self-shearing directions. The temporal evolution of deformations upon turning voltage on and off is not invariant upon reversal of time, prompting lateral translations of the crystallites of torons within quasi-hexagonal periodically deformed lattices. We probe how these motions depend on voltage and frequency of oscillating field applied in an experimental geometry resembling that of liquid crystal displays. We study the interrelations between synchronized deformations of the soft solitonic particles and their arrays, and the ensuing dynamics and giant number fluctuations mediated by motions of crystallites, five-seven defects pairs, and grain boundaries in the orderly organizations of solitons. We discuss how our findings may lead to technological and fundamental science applications of dynamic self-assemblies of topologically protected but highly deformable particle-like solitons., Competing Interests: The authors declare no competing interest.

Topological solitons are non-singular but topologically nontrivial structures in fields, which have fundamental significance across various areas of physics, similar to singular defects. Production and observation of singular and solitonic topological structures remain a complex undertaking in most branches of science - but in soft matter physics, they can be realized within the director field of a liquid crystal. Additionally, it has been shown that confining liquid crystals to spherical shells using microfluidics resulted in a versatile experimental platform for the dynamical study of topological transformations between director configurations. In this work, we demonstrate the triggered formation of topological solitons, cholesteric fingers, singular defect lines and related structures in liquid crystal shells. We show that to accommodate these objects, shells must possess a Janus nature, featuring both twisted and untwisted domains. We report the formation of linear and axisymmetric objects, which we identify as cholesteric fingers and skyrmions or elementary torons, respectively. We then take advantage of the sensitivity of shells to numerous external stimuli to induce dynamical transitions between various types of structures, allowing for a richer phenomenology than traditional liquid crystal cells with solid flat walls. Using gradually more refined experimental techniques, we induce the targeted transformation of cholesteric twist walls and fingers into skyrmions and elementary torons. We capture the different stages of these director transformations using numerical simulations. Finally, we uncover an experimental mechanism to nucleate arrays of axisymmetric structures on shells, thereby creating a system of potential interest for tackling crystallography studies on curved spaces.

Light provides a powerful means of controlling physical behavior of materials but is rarely used to power and guide active matter systems. We demonstrate optical control of liquid crystalline topological solitons dubbed "skyrmions", which recently emerged as highly reconfigurable inanimate active particles capable of exhibiting emergent collective behaviors like schooling. Because of a chiral nematic liquid crystal's natural tendency to twist and its facile response to electric fields and light, it serves as a testbed for dynamic control of skyrmions and other active particles. Using ambient-intensity unstructured light, we demonstrate large-scale multifaceted reconfigurations and unjamming of collective skyrmion motions powered by oscillating electric fields and guided by optically-induced obstacles and patterned illumination.

We study the plasmon-enhanced fluorescence of a single semiconducting quantum dot near the apex of a colloidal gold pyramid spatially localized by the elastic forces of the liquid crystal host. The gold pyramid particles were manipulated within the liquid crystal medium by laser tweezers, enabling the self-assembly of a semiconducting quantum dot dispersed in the medium near the apex of the gold pyramid, allowing us to probe the plasmon-exciton interactions. We demonstrate the effect of plasmon coupling on the fluorescence lifetime and the blinking properties of the quantum dot. Our results demonstrate that topological defects around colloidal particles in liquid crystal combined with laser tweezers provide a platform for plasmon exciton interaction studies and potentially could be extended to the scale of composite materials for nanophotonic applications.

Colloidal interactions in nematic liquid crystals can be described as interactions between elastic multipoles that depend on particle shape, topology, chirality, boundary conditions and induced topological defects. Here, we describe a nematic colloidal system consisting of mesostructures of gold capable of inducing elastic multipoles of different order. Elastic monopoles are formed by relatively large asymmetric mesoflower particles, for which gravity and elastic torque balancing yields monopole-type interactions. High-order multipoles are instead formed by smaller mesoflowers with a myriad of shapes corresponding to multipoles of different orders, consistent with our computer simulations based on free energy minimization. We reveal unexpected many-body interactions in this colloidal system, ranging from de-mixing of elastic monopoles to a zoo of unusual colloidal crystals formed by high-order multipoles like hexadecapoles. Our findings show that gold mesoflowers may serve as a designer toolkit for engineering colloidal interaction and self-assembly, potentially exceeding that in atomic and molecular systems.

The actuation and levitation of air-suspended objects by a magnetic field, due to its noncontact and holonomic manipulation modes, are important technological capabilities for device applications. However, owing to a higher density of conventional ferromagnets or nanoparticle-containing polymers and strong magnetic fields required for actuation, fabricating lightweight materials with a sensitive magnetic response for weight critical applications is challenging. Here, we report ultralight aerogel-based magnets (aero-magnets) comprising assembled ferromagnetic nanomaterials with highly magnetic anisotropy where the magnetic domains can be programmed by external predesigned fields. To demonstrate the breadth of manufacturing methods for this breed of aero-magnet composites, both silica/nanocellulose aerogel hosts and ferromagnetic nanorod/nanoplatelet guests have been explored. Single and double domains with out-of-plane magnetization are programmed into the aero-magnets and characterized by magnetic force microscopy. The levitation and actuation of the aero-magnets are realized while exposed to a small external magnetic field of 11 mT and introduced to a switching circuit. Furthermore, the elastic moduli of the aero-magnets are estimated by dynamic magnetic responses of the ferromagnetic nanoparticles tightly tethered in the aerogel hosts under rapid cyclic fields. These programmable aero-magnets could serve as monolithic magnetic actuator units in the fields of tiny robots and aerospace components.

Optical properties can be programmed on mesoscopic scales by patterning host materials while ordering their nanoparticle inclusions. While liquid crystals are often used to define the ordering of nanoparticles dispersed within them, this approach is typically limited to liquid crystals confined in classic geometries. In this work, the orientational order that liquid crystalline colloidal hosts impose on anisotropic nanoparticle inclusions is combined with an additive manufacturing method that enables engineered, macroscopic three-dimensional (3D) patterns of co-aligned gold nanorods and cellulose nanocrystals. These gels exhibit polarization-dependent plasmonic properties that emerge from the unique interaction between the host medium's anisotropic optical properties defined by orientationally ordered cellulose nanocrystals, from the liquid crystal's gold nanorod inclusions, and from the complexity of spatial patterns accessed with 3D printing. The gels' optical properties that are defined by the interplay of these effects are tuned by controlling the gels' order, which is tuned by adjusting the gels' cellulose nanocrystal concentrations. Lithe optical responsiveness of these composite gels to polarized radiation may enable unique technological applications like polarization-sensitive optical elements., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Coexistence of order and fluidity in soft matter often mimics that in biology, allowing for complex dynamics and applications-like displays. In active soft matter, emergent order can arise because of such dynamics. Powered by local energy conversion, this behavior resembles motions in living systems, like schooling of fish. Similar dynamics at cellular levels drive biological processes and generate macroscopic work. Inanimate particles capable of such emergent behavior could power nanomachines, but most active systems have biological origins. Here we show that thousands-to-millions of topological solitons, dubbed "skyrmions", while each converting macroscopically-supplied electric energy, exhibit collective motions along spontaneously-chosen directions uncorrelated with the direction of electric field. Within these "schools" of skyrmions, we uncover polar ordering, reconfigurable multi-skyrmion clustering and large-scale cohesion mediated by out-of-equilibrium elastic interactions. Remarkably, this behavior arises under conditions similar to those in liquid crystal displays and may enable dynamic materials with strong emergent electro-optic responses.

Topological solitons, such as skyrmions, arise in field theories of systems ranging from Bose-Einstein condensates to optics, particle physics, and cosmology, but they are rarely accessible experimentally. Chiral nematic liquid crystals provide a platform to study skyrmions because of their natural tendency to form twisted structures arising from the lack of mirror symmetry at the molecular level. However, large-scale dynamic control and technological utility of skyrmions remain limited. Combining experiments and numerical modeling of chiral liquid crystals with optically controlled helical pitch, we demonstrate that low-intensity, unstructured light can control stability, dimensions, interactions, spatial patterning, self-assembly, and dynamics of these topological solitons.

Starting with Gauss and Kelvin, knots in fields were postulated to behave like particles, but experimentally they were found only as transient features or required complex boundary conditions to exist and could not self-assemble into three-dimensional crystals. We introduce energetically stable, micrometer-sized knots in helical fields of chiral liquid crystals. While spatially localized and freely diffusing in all directions, they resemble colloidal particles and atoms, self-assembling into crystalline lattices with open and closed structures. These knots are robust and topologically distinct from the host medium, though they can be morphed and reconfigured by weak stimuli under conditions such as those in displays. A combination of energy-minimizing numerical modeling and optical imaging uncovers the internal structure and topology of individual helical field knots and the various hierarchical crystalline organizations that they form., (Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Differing from isotropic fluids, liquid crystals exhibit highly anisotropic interactions with surfaces, which define boundary conditions for the alignment of constituent rod-like molecules at interfaces with colloidal inclusions and confining substrates. We show that surface alignment of the nematic molecules can be controlled by harnessing the competing aligning effects of surface functionalization and electric field arising from surface charging and bulk counterions. The control of ionic content in the bulk and at surfaces allows for tuning orientations of shape-anisotropic particles like platelets within an aligned nematic host and for changing the orientation of director relative to confining substrates. The ensuing anisotropic elastic and electrostatic interactions enable colloidal crystals with reconfigurable symmetries and orientations of inclusions.