Advances in Metal‐Free Heterocycle‐Based Columnar Liquid Crystals

Liquid crystals are ordered soft materials formed by self‐organized molecules and can potentially be used as new functional materials for electron‐, ion‐ or molecular‐transport; optical; and bio‐active materials. In particular, the columnar liquid crystals are promising candidates used in various optical and electronic devices. For this purpose, design and synthesis of unconventional materials are essential. In this review, we have summarized several approaches for the synthesis of columnar liquid crystals composed of various heterocyclic systems. We also outline their liquid crystalline and other relevant properties, and their suitability for applications in diverse fields.     

Defect‐Engineered Metal–Organic Frameworks

Defect engineering in metal–organic frameworks (MOFs) is an exciting concept for tailoring material properties, which opens up novel opportunities not only in sorption and catalysis, but also in controlling more challenging physical characteristics such as band gap as well as magnetic and electrical/conductive properties. It is challenging to structurally characterize the inherent or intentionally created defects of various types, and there have so far been few efforts to comprehensively discuss these issues. Based on selected reports spanning the last decades, this Review closes that gap by providing both a concise overview of defects in MOFs, or more broadly coordination network compounds (CNCs), including their classification and characterization, together with the (potential) applications of defective CNCs/MOFs. Moreover, we will highlight important aspects of “defect‐engineering” concepts applied for CNCs, also in comparison with relevant solid materials such as zeolites or COFs. Finally, we discuss the future potential of defect‐engineered CNCs.     

Non‐Brownian Particle‐Based Materials with Microscale and Nanoscale Hierarchy

Colloidal crystals are interesting materials owing to their customizable photonic properties, high surface area, and analogy to chemical structures. The flexibility of these materials has been greatly enhanced through mixing particles with varying sizes, compositions, and surface charges. In this way, distinctive patterns or analogies to chemical stoichiometries are produced; however, to date, this body of research is limited to particles with nanoscale dimensions. A simple method is now presented for bottom‐up assembly of non‐Brownian particle mixtures to create a new class of hierarchically‐ordered materials that mimic those found in nature (both in pore distribution as well as stoichiometry). Additionally, these crystals serve as a template to create particle‐based inverted crystalline structures with customizable properties.     

Nanofibrillar Stimulus‐Responsive Cholesteric Microgels with Catalytic Properties

We report composite stimulus‐responsive cholesteric catalytically active microgels derived from filamentous supramolecular building blocks: cellulose nanocrystals (CNCs). The variation in the microgel dimensions and pitch in response to the change in ambient conditions was governed by the polymer component. The cholesteric morphology of the microgels resulted from the self‐organization of CNCs in spherical confinement. The microgels exhibited excellent structural integrity and functioned as microreactors in catalytic hydrolysis reactions and in the synthesis of metal nanoparticles. Because of these collective properties, the reported microgels show much promise for application in the design of functional responsive materials.     

纤维素纳米晶的空间受限自组装: 从胶体液晶到功能材料

作为最有前途的生物衍生材料之一, 纤维素纳米晶体(CNCs)具有来源广泛、 生物相容性好和可形成光子结构等优点, 在能源、 生物医学和光子材料领域具有重要的应用价值. 本文总结了CNCs的制备、 CNCs形成的胆甾型胶体液晶及CNCs衍生的光子材料的研究进展, 重点评述了CNCs在液滴和毛细管中的自组装和基于CNCs空间受限组装的功能材料研究进展, 并讨论了空间受限CNCs自组装研究面临的挑战和未来的发展方向.     

Functional Liquid‐Crystalline Assemblies: Self‐Organized Soft Materials

In the 21st century, soft materials will become more important as functional materials because of their dynamic nature. Although soft materials are not as highly durable as hard materials, such as metals, ceramics, and engineering plastics, they can respond well to stimuli and the environment. The introduction of order into soft materials induces new dynamic functions. Liquid crystals are ordered soft materials consisting of self‐organized molecules and can potentially be used as new functional materials for electron, ion, or molecular transporting, sensory, catalytic, optical, and bio‐active materials. For this functionalization, unconventional materials design is required. Herein, we describe new approaches to the functionalization of liquid crystals and show how the design of liquid crystals formed by supramolecular assembly and nano‐segregation leads to the formation of a variety of new self‐organized functional materials.     

Chemical modification of cellulose nanocrystals and their application in thermoplastic starch (TPS) and poly(3‐hydroxybutyrate) (P3HB) nanocomposites

The effect of sulfated (original), carboxylated (oxidized), and Jeffamines M2005‐grafted cellulose nanocrystals (CNCs) on the barrier and mechanical properties of thermoplastic starch (TPS) and poly(3‐hydroxybutyrate) (P(3HB)) matrices was investigated. CNCs were first oxidized via a catalytic reaction using NaClO as an oxidant and then grafted with an amine‐terminated ethylene oxide (EO)/propylene oxide (PO) copolymer (Jeffamine) by an amine‐acid coupling reaction. A degree of oxidation (DO) of 0.108 (mol/mol of anhydroglucose) was attempted for the carboxylated CNCs, whereas a degree of substitution (DS) of 0.04 (mol/mol of anhydroglucose) was determined for the M2005‐grafted CNCs. These values indicated satisfactory reactive process, with yields of 68% and 47.3% for the carboxylation and peptide coupling reactions, respectively. Fourier‐transform infrared spectroscopy (FTIR) analysis showed bands at 1643 cm^?1 and 1550 cm^?1 in the spectrum of M2005‐grafted CNCs, which qualitatively indicated the amide bond formation. In addition, the morphology and the zeta potential of modified CNCs ensured their homogeneity, stability, and surface degree of charge. In spite of a decrease in the solubility in water of the modified crystals, the procedure of chemical modification used avoided any variation in their crystalline structure and thermal stability. Then, the incorporation of sulfated, oxidized, or M2005‐grafted CNCs in matrices of TPS and P(3HB) allowed to produce reinforced nanocomposite films, with excellent barrier properties. Therefore, the chemical compatibility between CNCs and the polymer matrices is essential to produce attractive nanocomposites with improved mechanical properties for industrial applications.     

Liquid crystal templating of nanomaterials with nature's toolbox

Naturally occurring biomolecules are sustainable and green precursors for the development of new materials. Within this family of natural materials, cellulose nanocrystals (CNCs) have emerged as one of the most promising materials because of their outstanding physico-chemical properties and the possibility to produce them in large quantities. One key trait of CNCs is their ability to self-assemble into a chiral nematic liquid crystalline phase. In this review, we discuss how templating can be used to transfer the three-dimensional structure of liquid crystalline CNC phases onto solid materials. This is followed by examples that illustrate the fascinating properties and potential applications that arise from the resulting nanostructured materials such as sensing and catalysis. We then summarize efforts to use the liquid crystalline phase of a selection of other biopolymers for templating. While nanocrystalline chitin, having very similar properties to CNCs, has been successfully employed to make a variety of new materials, efforts to template liquid crystal phases of other biomolecules have been met with limited success. However, we discuss virus nanoparticles and collagen as examples to highlight further possibilities for materials research.     

All‐in‐One Cellulose Nanocrystals for 3D Printing of Nanocomposite Hydrogels

Cellulose nanocrystals (CNCs) with >2000 photoactive groups on each can act as highly efficient initiators for radical polymerizations, cross‐linkers, as well as covalently embedded nanofillers for nanocomposite hydrogels. This is achieved by a simple and reliable method for surface modification of CNCs with a photoactive bis(acyl)phosphane oxide derivative. Shape‐persistent and free‐standing 3D structured objects were printed with a mono‐functional methacrylate, showing a superior swelling capacity and improved mechanical properties.     

2,4-二氰基-3-二乙基氨基-9,9-二乙基芴基星状蓝色发光化合物的合成与性质

本文设计合成了两个新的星状分子1和2,它们分别含有一个三苯胺和苯环的核,并都以三个2,4-二氰基-3-二乙氨基-9,9-二乙基芴为端基。光学性质研究表明,这两个具有D-A结构的化合物都显示出分子内电荷转移的性质。化合物1在强极性溶剂中表现出了双荧光发射特性。这两个化合物还显示出中等强度的荧光和高的热稳定性,这预示了它们在蓝色荧光材料方面的应用潜力。