Controlling the Photonic Properties of Cholesteric Cellulose Nanocrystal Films with Magnets

The self‐assembly of cellulose nanocrystals is a powerful method for the fabrication of biosourced photonic films with a chiral optical response. While various techniques have been exploited to tune the optical properties of such systems, the presence of external fields has yet to be reported to significantly modify their optical properties. In this work, by using small commercial magnets (≈ 0.5–1.2 T) the orientation of the cholesteric domains is enabled to tune in suspension as they assemble into films. A detailed analysis of these films shows an unprecedented control of their angular response. This simple and yet powerful technique unlocks new possibilities in designing the visual appearance of such iridescent films, ranging from metallic to pixelated or matt textures, paving the way for the development of truly sustainable photonic pigments in coatings, cosmetics, and security labeling.     

Uncovering the Circular Polarization Potential of Chiral Photonic Cellulose Films for Photonic Applications

Circularly polarized light (CPL) is central to photonic technologies. A key challenge lies in developing a general route for generation of CPL with tailored chiroptical activity using low‐cost raw materials suitable for scale‐up. This study presents that cellulose films with photonic bandgaps (PBG) and left‐handed helical sense have an intrinsic ability for circular polarization leading to PBG‐based CPL with extraordinary | g | values, well‐defiend handedness, and tailorable wavelength by the PBG change. Using such cellulose films, incident light ranging from near‐UV to near‐IR can be transformed to passive L‐CPL and R‐CPL with viewing‐side‐dependent handedness and | g | values up to 0.87, and spontaneous emission transformed to R‐CPL emission with | g | values up to 0.68. Unprecedented evidence is presented with theoretical underpinning that the PBG effect can stimulate the R‐CPL emission. The potential of cellulose‐based CPL films for polarization‐based encryption is illustrated. The evaporation‐induced self‐assembly coupled with nanoscale mesogens of cellulose nanocrystals opens new venues for technological advances and enables a versatile strategy for rational design and scalable manufacturing of organic and inorganic CPL films for photonic applications.     

Retrieving the Coassembly Pathway of Composite Cellulose Nanocrystal Photonic Films from their Angular Optical Response

Aqueous suspensions of cellulose nanocrystals (CNCs) are known to self-assemble into a chiral nematic liquid crystalline phase, leading to solid-state nanostructured colored films upon solvent evaporation, even in the presence of templating agents. The angular optical response of these structures, and therefore their visual appearance, are completely determined by the spatial arrangement of the CNCs when the drying suspension undergoes a transition from a flowing and liquid crystalline state to a kinetically arrested state. Here, it is demonstrated how the angular response of the final film allows for retrieval of key physical properties and the chemical composition of the suspension at the onset of the kinetic arrest, thus capturing a snapshot of the past. To illustrate this methodology, a dynamically evolving sol–gel coassembly process is investigated by adding various amounts of organosilica precursor, namely, 1,2-bis(trimethoxysilyl)ethane. The influence of organosilica condensation on the kinetic arrest can be tracked and thus explains the angular response of the resulting films. The a posteriori and in situ approach is general; it can be applied to a variety of additives in CNC-based films and it allows access to key rheological information of the suspension without using any dedicated rheological technique.     

纤维素纳米晶手性向列液晶在颜色防伪中的应用

目的介绍纤维素纳米晶(Cellulose Nanocrystal,CNC)手性向列液晶的形成原理与特征,以及该结构的调控方法,包括螺距和折射率的调控,最后总结纤维素纳米晶及其衍生材料在颜色防伪中的应用。方法归纳CNC手性向列液晶的形成机理方法,如硫酸水解结合蒸发诱导自主装法以及以CNC为手性模板与其他溶液共混制备法。最后总结国内外CNC手性向列液晶在颜色防伪中的研究现状,并简要讨论纤维素纳米晶在颜色防伪的未来发展趋势。结论纤维素纳米晶,具有绿色环保、来源丰富、合成工艺简单等特点,在一定条件下能形成手性向列液晶结构,具有独特的光学性质并呈现出结构色,可应用于颜色防伪。     

Perovskite-Nanocrystal-Doped Cellulose Nanocrystal Ligands for Electrospun Nanofibers with Excellent Stability

Because of their exceptional physical and thermal properties, cellulose nanocrystals (CNCs) are a highly promising bio-based material for reinforcing fillers. Studies have revealed that some functional groups from CNCs can be used as a capping ligand to coordinate with metal nanoparticles or semiconductor quantum dots during the fabrication of novel complex materials. Therefore, through CNCs ligand encapsulation and electrospinning, perovskite-NC-embedded nanofibers with exceptional optical and thermal stability are demonstrated. The results indicate that, after continuous irradiation or heat cycling, the relative photoluminescence (PL) emission intensity of the CNCs-capped perovskite-NC-embedded nanofibers is maintained at ≈90%. However, the relative PL emission intensity of both ligand-free and long-alkyl-ligand-doped perovskite-NC-embedded nanofibers decrease to almost 0%. These results are attributable to the formation of specific clusters of perovskite NCs along with the CNCs structure and thermal property improvement of polymers. CNCs-doped luminous complex materials offer a promising avenue for stability-demanding optoelectronic devices and other novel optical applications.     

Transparent and Flexible Cellulose Nanocrystal/Reduced Graphene Oxide Film for Proximity Sensing

The rapid development of touch screens as well as photoelectric sensors has stimulated the fabrication of reliable, convenient, and human‐friendly devices. Other than sensors that detect physical touch or are based on pressure sensing, proximity sensors offer controlled sensibility without physical contact. In this work we present a transparent and eco‐friendly sensor made through layer‐by‐layer spraying of modified graphene oxide filled cellulose nanocrystals on lithographic patterns of interdigitated electrodes on polymer substrates, which help to realize the precise location of approaching objects. Stable and reproducible signals generated by keeping the finger in close proximity to the sensor can be controlled by humidity, temperature, and the distance and number of sprayed layers. The chemical modification and reduction of the graphene oxide/cellulose crystal composite and its excellent nanostructure enable the development of proximity sensors with faster response and higher sensitivity, the integration of which resolves nearly all of the technological issues imposed on optoelectronic sensing devices.     

Sustainable,Insoluble, and Photonic Cellulose Nanocrystal Patches for Calcium Ion Sensing in Sweat

Self-assembly of cellulose nanocrystals (CNCs) is invaluable for the development of sustainable optics and photonics. However, the functional failure of CNC-derived materials in humid or liquid environments inevitably impairs their development in biomedicine, membrane separation, environmental monitoring, and wearable devices. Here, a facile and robust method to fabricate insoluble hydrogels in a self-assembled CNC–polyvinyl alcohol (PVA) system is reported. Due to the reconstruction of inter- or intra-molecular hydrogen bond interactions, thermal dehydration makes an optimized CNC/PVA photonic film form a stable hydrogel network in an aqueous solution rather than dissolve. Notably, the resulting hydrogel exhibits superb mechanical performance (stress up to 3.3 Mpa and tough up to 0.73 MJ m⁻³) and reversible conversion between dry and wet states, enabling it convenient for specific functionalization. Sodium alginate (SA) can be adsorbed into the CNC photonic structure by swelling dry CNC/PVA film in a SA solution. The prepared hydrogel showcases the comprehensive properties of freezing resistance (−20°C), strong adhesion, satisfactory biocompatibility, and highly sensitive and selective Ca²⁺ sensing. The material could act as a portable wearable patch on the skin for the continuous analysis of calcium trends during different physical exercises, facilitating their development in precision nutrition and health monitoring.     

Flexible and Responsive Chiral Nematic Cellulose Nanocrystal/Poly(ethylene glycol) Composite Films with Uniform and Tunable Structural Color

The fabrication of responsive photonic structures from cellulose nanocrystals (CNCs) that can operate in the entire visible spectrum is challenging due to the requirements of precise periodic modulation of the pitch size of the self‐assembled multilayer structures at the length scale within the wavelength of the visible light. The surface charge density of CNCs is an important factor in controlling the pitch size of the chiral nematic structure of the dried solid CNC films. The assembly of poly(ethylene glycol) (PEG) together with CNCs into smaller chiral nematic domains results in solid films with uniform helical structure upon slow drying. Large, flexible, and flat photonic composite films with uniform structure colors from blue to red are prepared by changing the composition of CNCs and PEG. The CNC/PEG(80/20) composite film demonstrates a reversible and smooth structural color change between green and transparent in response to an increase and decrease of relative humidity between 50% and 100% owing to the reversible swelling and dehydration of the chiral nematic structure. The composite also shows excellent mechanical and thermal properties, complementing the multifunctional property profile.     

载银纳米纤维素/聚乙烯醇复合膜的制备及性能研究

目的制备一种具有良好力学性能和抑菌性能的新型抗菌聚乙烯醇复合膜。方法通过酸水解微晶纤维素制备纳米纤维素,经高碘酸钠氧化获得醛基纳米纤维素,加入银氨溶液原位合成载银纳米纤维素(Ag-DCNC)。以聚乙烯醇(PVA)为成膜基底,加入Ag-DCNC共混流延制备载银纳米纤维素/聚乙烯醇复合膜。结果 Ag-DCNC体积分数为3%时,复合膜的拉伸强度比纯PVA膜提高了8.8%。Ag-DCNC体积分数为5%的复合膜对大肠杆菌和金黄色葡萄球菌均具有较好的抑菌效果。结论载银纳米纤维素/聚乙烯醇复合膜具有较好的力学强度,对2种细菌均有良好的杀菌效果。该材料不但具有良好的性能,而且合成工艺简单,可以作为一种很有前途的抑菌膜用于包装行业。     

羊毛与纤维素共混膜的性能

以自制的离子液体[Amim]Cl(1-烯丙基-3-甲基咪唑氯盐)为溶剂,分别制得纤维素与羊毛溶液,将二者以不同比例共混后在玻璃板上刮膜。用FT-IR、DSC、SEM、XRD和TG等对共混膜的结构与性能进行了分析和测试。结果表明:羊毛和纤维素相容性较好,存在着强烈的相互作用力。纤维素含量较高的共混膜透光率较大,随着纤维素含量的增多,复合膜的物理机械性能和热稳定性得到改善,当角蛋白/纤维素比例为4∶6时,共混膜的强力、断裂伸长率及热稳定性较为优异。     

Visual Appearance of Chiral Nematic Cellulose‐Based Photonic Films: Angular and Polarization Independent Color Response with a Twist

Hydroxypropyl cellulose (HPC) is a biocompatible cellulose derivative capable of self‐assembling into a lyotropic chiral nematic phase in aqueous solution. This liquid crystalline phase reflects right‐handed circular polarized light of a specific color as a function of the HPC weight fraction. Here, it is demonstrated that, by introducing a crosslinking agent, it is possible to drastically alter the visual appearance of the HPC mesophase in terms of the reflected color, the scattering distribution, and the polarization response, resulting in an exceptional matte appearance in solid‐state films. By exploiting the interplay between order and disorder, a robust and simple methodology toward the preparation of polarization and angular independent color is developed, which constitutes an important step toward the development of real‐world photonic colorants.