Chiral Nematic Cellulose Nanocrystal Films for Enhanced Charge Separation and Quantum-Confined Stark Effect.

Efficient charge separation is essential in various optoelectronic systems, yet it continues to pose substantial challenges. Building upon the recent evidence that chiral biomolecules can function as electron spin filters, this study aims to extend the application of chirality-driven charge separation from the molecular level to the mesoscale and supramolecular scale. Utilizing cellulose nanocrystals (CNCs) derived from cellulose, the most abundant biomaterial on Earth, this research leverages their self-assembly into chiral nematic structures and their dielectric properties. A device is introduced featuring a chiral nematic hybrid film composed of CNCs and quantum dots (QDs), decorated with iron oxide nanoparticles. Using the quantum-confined Stark effect (QCSE) to probe charge separation, we reveal significant sensitivity to the circular polarization of light and the chiral nematic structure of the film. This approach achieves effective, long-lasting charge separation, both locally and across length scales exceeding 1 µm, enabling potential applications such as self-assembled devices that combine photovoltaic cells with electric capacitance as well as optical electric-field hybrid biosensors.

Biobased Electronics: Tunable Dielectric and Piezoelectric Cellulose Nanocrystal-Protein Films.

Cellulose has been a go-to material for its dielectric properties from the onset of capacitor development. The demand for an energy storage solution continues to grow, but the supply remains limited and relies too often on fossil and mined materials. This work proposes a fully sustainable and green method with which to produce dielectric thin films made of renewable and degradable materials. Cellulose nanocrystals (CNC) made an excellent matrix for the dispersion of proteins and the fabrication of robust transparent thin films with enhanced dielectric permittivity. A range of proteins sources, additives and concentrations allowed for us to control the dielectric permittivity from εr = 4 to 50. The proteins screened came from animal and plant sources. The films were formed from drying a water suspension of the CNC and proteins through evaporation-induced self-assembly. This yielded nano-layered structures with very high specific surface areas, ideal for energy storage devices. The resulting films were characterized with respect to the electrical, mechanical, piezoelectric, and optical properties to be compared. Electrically conductive (σ = 1.53 × 103 S/m) CNC films were prepared with carbon nanotubes (CNT). The fabricated films were used to make flexible, sustainable, and degradable capacitors by layering protein-based films between CNC-CNT composite films.

Spin-Induced Organization of Cellulose Nanocrystals.

Cellulose nanocrystals (CNCs) are composed of chiral cellulose units, which form chiral nematic liquid crystals in water that, upon drying, self-assemble to more complex spiral chiral sheets. This secondary structure arrangement is found to change with an external magnetic or electric field. Here, we show that one of the basic organization driving forces is electron spin, which is produced as the charge redistributes in the organization process of the chiral building blocks. It is important to stress that the electron spin-exchange interactions supply the original driving force and not the magnetic field per se. The results present the first utilization of the chiral-induced spin selectivity (CISS) effect in sugars, enabling one to regulate the CNC bottom-up fabrication process. Control is demonstrated on the organization order of the CNC by utilizing different magnetization directions of the ferromagnetic surface. The produced spin is probed using a simple Hall device. The measured Hall resistance shows that the CNC sheets' arrangement is affected during the first four hours as long as the CNC is in its wet phase. On introducing the 1,2,3,4-butanetetracarboxylic acid cross-linker into the CNC sheet, the packing density of the CNC helical structure is enhanced, presenting an increase in the Hall resistance and the chiral state.

Cellulose Nanocrystals and Corn Zein Oxygen and Water Vapor Barrier Biocomposite Films.

Cellulose nanocrystals (CNC) are well-suited to the preparation of biocomposite films and packaging material due to its abundance, renewability, biodegradability, and favorable film-forming capacity. In this study, different CNC and corn zein (CZ) composite films were prepared by adding CZ to the CNC suspension prior to drying, in order to change internal structure of resulting films. Films were developed to examine their performance as an alternative water vapor and oxygen-barrier for flexible packaging industry. Water vapor permeability (WVP) and oxygen transmission rate (OTR) of the biocomposite films decreased significantly in a specific ratio between CNC and CZ combined with 1,2,3,4-butane tetracarboxylic acid (BTCA), a nontoxic cross linker. In addition to the improved barrier properties, the incorporation of CZ benefitted the flexibility and thermal stability of the CNC/CZ composite films. The toughness increased by 358%, and Young's modulus decreased by 32% compared with the pristine CNC film. The maximum degradation temperature increased by 26 °C, compared with that of CNC film. These results can be attributed to the incorporation of a hydrophobic protein into the matrix creating hydrophobic interactions among the biocomposite components. SEM and AFM analysis indicated that CZ could significantly affect the CNC arrangement, and the film surface topography, due to the mechanical bundling and physical adsorption effect of CZ to CNC. The presented results indicate that CNC/CZ biocomposite films may find applications in packaging, and in multi-functionalization materials.