Nature-Inspired Emerging Chiral Liquid Crystal Nanostructures: From Molecular Self-Assembly to DNA Mesophase and Nanocolloids

Liquid crystals (LCs) are omnipresent in living matter, whose chirality is an elegant and distinct feature in certain plant tissues, the cuticles of crabs, beetles, arthropods, and beyond. Taking inspiration from nature, researchers have recently devoted extensive efforts toward developing chiral liquid crystalline materials with self-organized nanostructures and exploring their potential applications in diverse fields ranging from dynamic photonics to energy and safety issues. In this review, an account on the state of the art of emerging chiral liquid crystalline nanostructured materials and their technological applications is provided. First, an overview on the significance of chiral liquid crystalline architectures in various living systems is given. Then, the recent significant progress in different chiral liquid crystalline systems including thermotropic LCs (cholesteric LCs, cubic blue phases, achiral bent-core LCs, etc.) and lyotropic LCs (DNA LCs, nanocellulose LCs, and graphene oxide LCs) is showcased. The review concludes with a perspective on the future scope, opportunities, and challenges in these truly advanced functional soft materials and their promising applications.     

Graphene Oxide Liquid Crystals: Discovery,Evolution and Applications

The discovery and relevant research progress in graphene oxide liquid crystals (GOLCs), the latest class of 2D nanomaterials exhibiting colloidal liquid crystallinity arising from the intrinsic disc‐like shape anisotropy, is highlighted. GOLC has conferred a versatile platform for the development of novel properties and applications based on the facile controllability of molecular scale alignment. The first part of this review offers a brief introduction to LCs, including the theoretical background. Particular attention has been paid to the different types of LC phases that have been reported thus far, such as nematic, lamellar and chiral phases. Several key parameters governing the ultimate stability of GOLC behavior, including pH and ionic strength of aqueous dispersions are highlighted. In a relatively short span of time since its discovery, GOLCs have proved their remarkable potential in a broad spectrum of applications, including highly oriented wet‐spun fibers, self‐assembled nanocomposites, and architectures for energy storage devices. The second part of this review is devoted to an exclusive overview of the relevant applications. Finally, an outlook is provided into this newly emerging research field, where two well established scientific communities for carbon nanomaterials and liquid crystals are ideally merged.     

Laser manipulation in liquid crystals: an approach to microfluidics and micromachines

Laser trapping of particles in three dimensions can occur as a result of the refraction of strongly focused light through micrometre-sized particles. The use of this effect to produce laser tweezers is extremely common in fields such as biology, but it is only relatively recently that the technique has been applied to liquid crystals (LCs). The possibilities are exciting: droplets of LCs can be trapped, moved and rotated in an isotropic fluid medium, or both particles and defects can be trapped and manipulated within a liquid crystalline medium. This paper considers both the possibilities. The mechanism of transfer of optical angular momentum from circularly polarized light to small droplets of nematic LCs is described. Further, it is shown that droplets of chiral LCs can be made to rotate when illuminated with linearly polarized light and possible mechanisms are discussed. The trapping and manipulation of micrometre-sized particles in an aligned LC medium is used to provide a measure of local shear viscosity coefficients and a unique test of theory at low Ericksen number in LCs.     

A Dual Modulated Homochiral Helical Nanofilament Phase with Local Columnar Ordering Formed by Bent Core Liquid Crystals: Effects of Molecular Chirality

Helical nanofilament (HNF) phases form as a result of an intralayer mismatch between top and bottom molecular halves in bent‐core liquid crystals (BC‐LCs) that is relieved by local saddle‐splay geometry. HNFs are immensely attractive for photovoltaic and chiral separation applications and as templates for the chiral spatial assembly of guest molecules. Here, the synthesis and characterization of two unichiral BC‐LCs and one racemic mixture with tris‐biphenyl‐diester cores featuring chiral (R,R) and (S,S) or racemic 2‐octyloxy aliphatic side chains are presented. In comparison to the achiral compound with linear side chains forming an intralayer modulated HNF phase (HNF_mod), synchrotron small angle X‐ray diffraction indicates that the unichiral derivatives form a dual modulated HNF phase with intra‐ as well as interlayer modulations (HNF_mod2) suggesting a columnar local structure of the nanofilaments. Transmission electron microscopy and circular dichroism spectropolarimetry confirm that the unichiral materials exclusively form homochiral HNFs with a twist sense‐matching secondary twist. A contact preparation provides the first example of two identical chiral liquid crystal phases only differing in their handedness that do not mix and form an achiral liquid crystal phase with an entirely different structure in the contact zone.     

Liquid-Crystal-Mediated Geometric Phase: From Transmissive to Broadband Reflective Planar Optics

Planar optical elements that can manipulate the multidimensional physical parameters of light efficiently and compactly are highly sought after in modern optics and nanophotonics. In recent years, the geometric phase, induced by the photonic spin–orbit interaction, has attracted extensive attention for planar optics due to its powerful beam shaping capability. The geometric phase can usually be generated via inhomogeneous anisotropic materials, among which liquid crystals (LCs) have been a focus. Their pronounced optical properties and controllable and stimuli-responsive self-assembly behavior introduce new possibilities for LCs beyond traditional panel displays. Recent advances in LC-mediated geometric phase planar optics are briefly reviewed. First, several recently developed photopatterning techniques are presented, enabling the accurate fabrication of complicated LC microstructures. Subsequently, nematic LC-based transmissive planar optical elements and chiral LC-based broadband reflective elements are reviewed systematically. Versatile functionalities are revealed, from conventional beam steering and focusing, to advanced structuring. Combining the geometric phase with structured LC materials offers a satisfactory platform for planar optics with desired functionalities and drastically extends exceptional applications of ordered soft matter. Some prospects on this rapidly advancing field are also provided.     

Tunable Diffraction Gratings from Biosourced Lyotropic Liquid Crystals

Diffraction gratings are important for modern optical components, such as optical multiplexers and signal processors. Although liquid crystal (LC) gratings based on thermotropic LCs have been extensively explored, they often require expensive molecules and complicated manufacturing processes. Lyotropic LCs, which can be broadly obtained from both synthetic and natural sources, have not yet been applied in optical gratings. Herein, a facile grating fabrication method using a biosourced lyotropic LC formed by cellulose nanocrystals (CNCs), a material extracted from plants, is reported. Hydrogel sheets with vertically aligned uniform periodic structures are obtained by fixing the highly oriented chiral nematic LC of CNCs in polymer networks under the cooperative effects of gravity on phase separation and a magnetic field on LC orientation. The hydrogel generates up to sixth-order diffraction spots and shows linear polarization selectivity, with tunable grating periodicity controlled through LC concentration regulation. This synthesis strategy can be broadly applied to various grating materials and opens up a new area of optical materials from lyotropic LCs.     

Photonic Multishells Composed of Cholesteric Liquid Crystals Designed by Controlled Phase Separation in Emulsion Drops

Cholesteric liquid crystals (CLCs), also known as chiral nematic LCs, show a photonic stopband, which is promising for various optical applications. In particular, CLCs confined in microcompartments are useful for sensing, lasing, and optical barcoding at the microscale. The integration of distinct CLCs into single microstructures can provide advanced functionality. In this work, CLC multishells with multiple stopbands are created by liquid–liquid phase separation (LLPS) in a simple yet highly controlled manner. A homogeneous ternary mixture of LC, hydrophilic liquid, and co-solvent is microfluidically emulsified to form uniform oil-in-water drops, which undergo LLPS to form onion-like drops composed of alternating CLC-rich and CLC-depleted layers. The multiplicity is controlled from one to five by adjusting the initial composition of the ternary mixture, which dictates the number of consecutive steps of LLPS. Interestingly, the concentration of the chiral dopant becomes reduced from the outermost to the innermost CLC drop due to uneven partitioning during LLPS, which results in multiple stopbands. Therefore, the photonic multishells show multiple structural colors. In addition, dye-doped multishells provide band-edge lasing at two different wavelengths. This new class of photonic multishells will provide new opportunities for advanced optical applications.     

液晶分子在受限条件下的液晶相行为（Ⅱ）某些化学受限环境对液晶相行为的影响

综述了液晶分子在与聚合物嵌段、碳纳米管（CNT）和多面低聚倍半硅氧烷（POSS）等通过共价键形成的化学受限环境下的液晶相行为。聚合物嵌段微区的受限作用使侧链液晶嵌段共聚物的液晶有序度减小,相变温度降低。由于碳纳米管的受限作用,液晶聚合物接枝CNTs的有序结构被破坏,液晶性丧失。POSS以共价键的方式引入到液晶分子中,明显提高了液晶相的稳定性。但是当POSS含量高于某临界值后使液晶分子表现出单向性液晶相行为,甚至使其丧失液晶性。     

基于甲壳素的手性分离材料

甲壳素是一种丰富的可再生资源,将甲壳素在碱性条件下脱去乙酰基得到壳聚糖,甲壳素和壳聚糖分子骨架有大量的手性碳原子存在,且含有较多的羟基、乙酰氨基或氨基活性官能团,容易进行化学改性得到有较好手性识别能力的衍生物,且它们能以膜、纤维、凝胶及微球等不同形式出现,可作为各种手性分离介质。概述了近年来甲壳素衍生物作为手性分离介质的重要研究进展,主要包括甲壳素及其衍生物的色谱手性固定相、手性分离膜、分子印迹聚合物。重点介绍了这些手性分离介质的结构、制备及性能,并展望了甲壳素衍生物手性分离介质的研究前景。     

Light‐Driven Chiral Molecular Switches or Motors in Liquid Crystals

The ability to tune molecular self‐organization with an external stimulus is a main driving force in the bottom‐up nanofabrication of molecular devices. Light‐driven chiral molecular switches or motors in liquid crystals that are capable of self‐organizing into optically tunable helical superstructures undoubtedly represent a striking example, owing to their unique property of selective light reflection and which may lead to applications in the future. In this review, we focus on different classes of light‐driven chiral molecular switches or motors in liquid crystal media for the induction and manipulation of photoresponsive cholesteric liquid crystal systems and their consequent applications. Moreover, the change of helical twisting powers of chiral dopants and their capability of helix inversion in the induced cholesteric phases are highlighted and discussed in the light of their molecular geometric changes.     

Optically Rewritable Transparent Liquid Crystal Displays Enabled by Light‐Driven Chiral Fluorescent Molecular Switches

Functional soft materials exhibiting distinct functionalities in response to a specific stimulus are highly desirable towards the fabrication of advanced devices with superior dynamic performances. Herein, two novel light‐driven chiral fluorescent molecular switches have been designed and synthesized that are able to exhibit unprecedented reversible Z/E photoisomerization behavior along with tunable fluorescence intensity in both isotropic and anisotropic media. Cholesteric liquid crystals fabricated using these new fluorescent molecular switches as chiral dopants exhibit reversible reflection color tuning spanning the visible and infrared region of the spectrum. Transparent display devices have been fabricated using both low chirality and high chirality cholesteric films that operate either exclusively in fluorescent mode or in both fluorescent and reflection mode, respectively. The dual mode display device employing short pitch cholesteric film is able to function on demand under all ambient light conditions including daylight and darkness with fast response and high resolution. Moreover, the proof‐of‐concept for a “remote‐writing board” using cholesteric films containing one of the light‐driven chiral fluorescent molecular switches with ease of fabrication and operation is disclosed herein. Such optically rewritable transparent display devices enabled by light‐driven chiral fluorescent molecular switches pave a new way for developing novel display technology under different lighting conditions.     

Plasmonic Chirality and Circular Dichroism in Bioassembled and Nonbiological Systems: Theoretical Background and Recent Progress

Nature is chiral, thus chirality is a key concept required to understand a multitude of systems in physics, chemistry, and biology. The field of optics offers valuable tools to probe the chirality of nanosystems, including the measurement of circular dichroism, the differential interaction strength between matter and circularly polarized light with opposite helicity. Simultaneously, the use of plasmonic systems with giant light-interaction cross-sections opens new paths to investigate and manipulate systems on the nanoscale. Consequently, the interest in chiral plasmonic and hybrid systems has continually grown in recent years, due to their potential applications in biosensing, polarization-encoded optical communication, polarization-selective chemical reactions, and materials with polarization-dependent light–matter interaction. Experimentally, chiral properties of nanostructures can be either created artificially using modern fabrication techniques involving inorganic materials, or borrowed from nature using bioassembly or biomolecular templating. Herein, the recent progress in the field of plasmonic chirality is summarized, with a focus on both the theoretical background and the experimental advances in the study of chirality in various systems, including molecular-plasmonic assemblies, chiral plasmonic nanostructures, chiral assemblies of interacting plasmonic nanoparticles, and chiral metal metasurfaces and metamaterials. The growth prospects of this field are also discussed.     

Supramolecular Helices: Chirality Transfer from Conjugated Molecules to Structures

Different scales of chirality endow a material with many excellent properties and potential applications. In this review, using π‐conjugated molecules as functional building blocks, recent progress on supramolecular helices inspired by biological helicity is summarized. First, induced chirality on conjugated polymers and small molecules is introduced. Molecular chirality can be amplified to nanostructures, superstructures, and even macroscopic structures by a self‐assembly process. Then, the principles for tuning the helicity of supramolecular chirality, as well as formation of helical heterojunctions, are summarized. Finally, the potential applications of chiral structures in chiral sensing and organic electronic devices are critically reviewed. Due to recent progress in chiral structures, an interdisciplinary area called “chiral electronics” is expected to gain wide popularity in the near future.     

基于葡萄糖的星型胆甾相液晶化合物的合成及相行为

以葡萄糖为手性中心,6-（4-（苯甲酸基）苯）己二酸单酯（M1）、6-（4-（4-烷氧基苯甲酸基）苯）己二酸单酯（M2～M3）为侧臂,采用N,N′-二环己基碳化二亚胺（DCC）/4-二甲氨基吡啶（DMAP）成酯法,合成了星型化合物（GM1～GM3）。通过红外光谱（FT-IR）、核磁共振（1H-NMR）、偏光显微镜（PO...     

Engineering the Future of Silk Materials through Advanced Manufacturing

Silk is a natural fiber renowned for its outstanding mechanical properties that have enabled the manufacturing of ultralight and ultrastrong textiles. Recent advances in silk processing and manufacturing have underpinned a re‐interpretation of silk from textiles to technological materials. Here, it is argued that silk materials—optimized by selective pressure to work in the environment at the biotic–abiotic interface—can be harnessed by human micro‐ and nanomanufacturing technology to impart new functionalities and opportunities. A critical overview of recent progress in silk technology is presented with emphasis on high‐tech applications enabled by recent innovations in multilevel modifications, multiscale manufacturing, and multimodal characterization of silk materials. These advances have enabled successful demonstrations of silk materials across several disciplines, including tissue engineering, drug delivery, implantable medical devices, and biodissolvable/degradable devices.     

Influence of zinc oxide nanorods on an orientationally ordered fluid comprising soft-bent dimers

Bent-core liquid crystals (LCs) introduced a whole new dimension to the science of LCs. Besides re-emphasizing the importance of the shape of the molecule, they brought in phases with symmetry, not known earlier. Another sub-class of systems that is emerging is that of soft-bent molecules. In contrast with the bent-core molecules, here the bend is achieved through the parity of the aliphatic linker that connects two monomers. They hold the unique advantage that a simple variation of temperature can favour different conformer states and thus govern the self-assembled structure. A highlight of the power of this route is seen in terms of the discovery of a new type of nematic, viz., twist–bend nematic. Investigations on not only this phase but also the regular nematic that often precedes it have received significant attention in the last few years. Here we present results on the regular nematic phase of a binary mixture comprising such a soft-bent dimer, known in the literature as CB7CB, by incorporating zinc oxide nanorods (NRs) into the system. The NRs with an aspect ratio of \({\sim }\)7.2, not very different from that of LCs, further accentuate the importance of shape and shape anisotropy of the entities. Specifically, we observe that the nematic–isotropic transition temperature increases by \({\sim }\)1.9 K even for a low concentration of 4% NRs. While the dielectric anisotropy decreases, birefringence shows a substantial increase, adding to the complexity of the influence. Upon addition of minute amount of NRs (1%), while the splay elastic constant gets enhanced, its bend counterpart not only gets reduced but retains the convex-shaped thermal profile seen for the parent mixture.     

Anisotropy of building blocks and their assembly into complex structures

A revolution in novel nanoparticles and colloidal building blocks has been enabled by recent breakthroughs in particle synthesis. These new particles are poised to become the 'atoms' and 'molecules' of tomorrow's materials if they can be successfully assembled into useful structures. Here, we discuss the recent progress made in the synthesis of nanocrystals and colloidal particles and draw analogies between these new particulate building blocks and better-studied molecules and supramolecular objects. We argue for a conceptual framework for these new building blocks based on anisotropy attributes and discuss the prognosis for future progress in exploiting anisotropy for materials design and assembly.     

Chiral expressions at metal surfaces

The manifestation of chirality at surfaces has attracted much attention in recent years. In this review, some of main features of chiral endowments by complex organic molecules at defined metal surfaces are reviewed. Detailed surface spectroscopic data have enabled a hierarchy of chiral expressions to be delineated, from point group chirality expressed by local chiral motifs, to space group chirality in which these motifs act as building blocks which self-assemble into organised chiral structures, to deeper propagation of chirality into the metal leading to chiral reconstructions. Chiral endowments by both chiral and achiral molecules is discussed alongside the implications for progressing chirality from the local to the global level.     

MgO-C耐火材料对钢水的增碳作用及机理的研究进展

总结了近年未国内外关于耐火材料对钢水性能的影响的研究成果，重点讨论了MgO—C耐火材料对钢水增碳的影响因素及其机理等方面研究所取得的进展。系统地研究耐火材料对钢火的影响，并利用研究结果设计制备新型耐火材料进而提高钢水性能将成为耐火材料研究发展的新趋势。     

Using localized surface plasmon resonances to probe the nanoscopic origins of adsorbate-driven ordering transitions of liquid crystals in contact with chemically functionalized gold nanodots

We report that localized surface plasmon resonances (LSPRs) of gold nanodots immersed under liquid crystals (LCs) can be used to characterize adsorbate-induced ordering transitions of the LCs on the surfaces of the nanodots. The nanoscopic changes in ordering of the LCs, as measured by LSPR, were shown to give rise to macroscopic ordering transitions of the LCs that were observed by polarized light microscopy. The results reported herein suggest that (i) LCs may be useful for enhancing the sensitivity of LSPR-based detection of binding events and (ii) that LSPR measurements of gold nanodots provide a means to characterize the nanoscopic origins of macroscopic, adsorbate-induced LC ordering transitions.