Regulatory Mechanism of Opposite Charges on Chiral Self-Assembly of Cellulose Nanocrystals.

The charge plays an important role in cellulose nanocrystal (CNC) self-assembly to form liquid crystal structures, which has rarely been systematically explored. In this work, a novel technique combining atomic force microscopy force and atomistic molecular dynamics simulations was addressed for the first time to systematically investigate the differences in the CNC self-assembly caused by external positive and negative charges at the microscopic level, wherein sodium polyacrylate (PAAS) and chitosan oligosaccharides (COS) were used as external positive and negative charge additives, respectively. The results show that although the two additives both make the color of CNC films shift blue and eventually disappear, their regulatory mechanisms are, respectively, related to the extrusion of CNC particles by PAAS and the reduction in CNC surface charge by COS. The two effects both decreased the spacing between CNC particles and further increased the cross angle of CNC stacking arrangement, which finally led to the color variations. Moreover, the disappearance of color was proved to be due to the kinetic arrest of CNC suspensions before forming chiral nematic structure with the addition of PAAS and COS. This work provides an updated theoretical basis for the detailed disclosure of the CNC self-assembly mechanism.

Switchable Circularly Polarized Signals with High Asymmetric Factor Triggered by Dual Photonic Bandgap Structure.

Currently, the smart photonic materials that can switch circularly polarized signals in real-time have attracted extensive attention due to numerous potential applications in information storage and photonics displays. However, the dynamically reversible switching of circularly polarized signals requires precise structural reconfiguration, which is rarely achieved in traditional biomaterials. Herein, a dual photonic bandgap (PBG) structure is constructed based on the optical propagation principle of cellulose-based photonic crystals, enabling the flexible switching of the intensity, wavelength, and direction of circularly polarized luminescence (CPL). By adjusting the fluorescence intensity and the matching degree of chiral structure, the asymmetric factor value of dual PBG structure is up to -1.47, far exceeding other cellulose-based materials. Importantly, it is demonstrated that dual CPL emission can be efficiently induced by two different PBGs, opening a new approach for on-demand switching of single and dual CPL emission. In addition, the dual PBG structure exhibits dual circularly polarized reflected signals under the circular polarizer, which perfectly embodies the applicability of multiple encryptions in QR codes. This work provides new insights into the real-time manipulation of circularly polarized signals by chiral photonic materials.

Chiral Photonic Liquid Crystal Films Derived from Cellulose Nanocrystals.

As a nanoscale renewable resource derived from lignocellulosic materials, cellulose nanocrystals (CNCs) have the features of high purity, high crystallinity, high aspect ratio, high Young's modulus, and large specific surface area. The most interesting trait is that they can form the entire films with bright structural colors through the evaporation-induced self-assembly (EISA) process under certain conditions. Structural color originates from micro-nano structure of CNCs matrixes via the interaction of nanoparticles with light, rather than the absorption and reflection of light from the pigment. CNCs are the new generation of photonic liquid crystal materials of choice due to their simple and convenient preparation processes, environmentally friendly fabrication approaches, and intrinsic chiral nematic structure. Therefore, understanding the forming mechanism of CNCs in nanoarchitectonics is crucial to multiple fields of physics, chemistry, materials science, and engineering application. Herein, a timely summary of the chiral photonic liquid crystal films derived from CNCs is systematically presented. The relationship of CNC, structural color, chiral nematic structure, film performance, and applications of chiral photonic liquid crystal films is discussed. The review article also summarizes the most recent achievements in the field of CNCs-based photonic functional materials along with the faced challenges.

Multidimensional dynamic regulation of cellulose coloration for digital recognition and humidity response.

Structural color is an eye-catching phenomenon in nature, which originates from the synergistic effect of cholesteric structure inside living organisms and light. However, biomimetic design and green construction of dynamically tunable structural color materials have been a great challenge in the field of photonic manufacturing. In this work, the new ability of L-lactic acid (LLA) to multi-dimensionally modulate the cholesteric structures constructed from cellulose nanocrystals (CNC) is revealed for the first time. By studying the molecular-scale hydrogen bonding mechanism, a novel strategy that electrostatic repulsion and hydrogen bonding forces jointly drive the uniform arrangement of cholesteric structures is proposed. Due to the flexible tunability and uniform alignment of the CNC cholesteric structure, different encoded messages were developed in the CNC/LLA (CL) pattern. Under different viewing conditions, the recognition information of different digits will continue to reversibly and rapidly switch until the cholesteric structure is destroyed. In addition, the LLA molecules facilitated the more sensitive response of the CL film to the humidity environment, making it exhibit reversible and tunable structural colors under different humidity. These excellent properties provide more possibilities for the application of CL materials in the fields of multi-dimensional display, anti-counterfeiting encryption, and environmental monitoring.

Novel carboxylated cellulose nanocrystals synthesized by co-oxidation of sodium periodate/Fenton as a green solid emulsifier for oil-in-water Pickering emulsion.

The preparation of carboxylated cellulose nanocrystals (cCNCs) and their stabilization in oil-in-water (O/W) Pickering emulsions hold great potential for application and research value. In this work, a novel integrated oxidation strategy was proposed to prepare needle-like cCNCs by sodium periodate (NaIO4)/Fenton (SF-cCNCs) with considerable yield (58.58 %), plentiful carboxyl groups (1.28 mmol/g), and high crystallinity (83.3 %). The distinctive features of smaller size and high viscosity accelerated the as-prepared SF-cCNCs to be used in stabilizing Pickering emulsion. Moreover, the effects of oil-water ratio (OWR), SF-cCNCs content, pH, and sodium chloride (NaCl) content on the stability of SF-cCNCs-stabilized Pickering emulsions were also investigated systematically. Interestingly, the stability of the as-obtained emulsions was dependent on pH and salt. Afterwards, the rheological behaviors validated that the emulsion viscosity increased rapidly after adding NaCl, which was dominated by the elastic behavior. Finally, the main stabilization mechanism was confirmed to be interfacial adsorption of SF-cCNCs rather than the formation of spatial network structures between droplets. This study reports a synthetic strategy to efficiently prepare SF-cCNCs, endowing the SF-cCNCs stabilized Pickering emulsion with environmentally friendly, long-term stable and highly anti-agglomeration abilities for cosmetics and food products.

Silver-Nanoparticle-Embedded Hybrid Nanopaper with Significant Thermal Conductivity Enhancement.

Nanopapers derived from nanofibrillated cellulose (NFC) are urgently required as attractive substrates for thermal management applications of electronic devices because of their lightweight, easy cutting, cost efficiency, and sustainability. In this paper, we provided a facile fabrication strategy to construct hybrid nanopapers composed of dialdehyde nanofibrillated cellulose (DANFC) and silver nanoparticles (AgNPs), which exhibited a favorable thermal conductivity property. AgNPs were in situ proceeded on the surface of DANFC by the silver mirror reaction inspired by the aldehyde groups. Owing to the intermolecular hydrogen bonds inside the hybrid nanopapers, the DANFC enables the uniform dispersion of AgNPs as well as promotes the formation of the hierarchical structure. It was found that the AgNPs-coated DANFC (DANFC/Ag) hybrid nanopapers could easily form an effective thermally conductive pathway for phonon transfer. As a result, the thermal conductivity (TC) of the obtained DANFC/Ag hybrid nanopapers containing only 1.9 vol % of Ag was 5.35 times higher than that of the pure NFC nanopapers along with a significantly TC enhancement per vol % Ag of 230.0%, which was supposed to benefit from the continuous heat transfer pathway constructed by the connection of AgNPs decorated on the cellulose nanofibers. The DANFC/Ag hybrid nanopapers possess potential applications as thermal management materials in the next-generation portable electronic devices.