Multi-Responsive Supercapacitors from Chiral Nematic Cellulose Nanocrystal-Based Activated Carbon Aerogels.

The development of long-lived electrochemical energy storage systems based on renewable materials is integral for the transition toward a more sustainable society. Supercapacitors have garnered considerable interest given their impressive cycling performance, low cost, and safety. Here, the first example of a chiral nematic activated carbon aerogel is shown. Specifically, supercapacitor materials are developed based on cellulose, a non-toxic and biodegradable material. The chiral nematic structure of cellulose nanocrystals (CNCs) is harnessed to obtain free-standing hierarchically ordered activated carbon aerogels. To impart multifunctionality, iron- and cobalt-oxide nanoparticles are incorporated within the CNC matrix. The hierarchical structure remains intact even at nanoparticle concentrations of ≈70 wt%. The aerogels are highly porous, with specific surface areas up to 820 m2 g-1 . A maximum magnetization of 17.8 ± 0.1 emu g-1 with superparamagnetic behavior is obtained, providing a base for actuator applications. These materials are employed as symmetric supercapacitors; owing to the concomitant effect of the hierarchically arranged carbon skeleton and KOH activation, a maximum Cp of 294 F g-1 with a capacitance retention of 93% after 2500 cycles at 50 mV s-1 is achieved. The multifunctionality of the composite aerogels opens new possibilities for the use of biomass-derived materials in energy storage and sensing applications.

Coassembly of Cellulose Nanocrystals and Neutral Polymers in Iridescent Chiral Nematic Films.

Photonic materials based on composite films of cellulose nanocrystals (CNCs) and polymers are promising as they can be renewable and show tunable optical and mechanical properties. However, the influence of polymers on CNC self-assembly is not always well understood, and conflicting results are present in the literature. In this study, we incorporate three neutral, water-soluble polymers-poly(ethylene glycol) (PEG), poly(vinyl pyrrolidone) (PVP), and poly(acrylic acid) (PAA)-with different molecular weights into CNC suspensions at various concentrations prior to obtaining iridescent composite thin films by solvent evaporation. Through spectroscopic, potentiometric, and rheological analyses, we find that PVP physically adsorbs to the surface of CNCs resulting in a bathochromic shift in film color with both increasing concentration and polymer molecular weight. In contrast, PEG induces depletion interactions that result in a decrease in the size of chiral nematic CNC domains, with a negligible change in film color. Finally, PAA hydrogen bonds to the hydroxyl groups of CNCs, resulting in a bathochromic color shift along with interesting rheological and liquid-state properties. This work demonstrates a deeper understanding of CNC-polymer interactions during coassembly and formation of iridescent chiral nematic films, allowing for greater control over optical properties of future CNC-based materials.

Iridescent Cellulose Nanocrystal Films Modified with Hydroxypropyl Cellulose.

The introduction of polymers into a chiral nematic cellulose nanocrystal (CNC) matrix allows for the tuning of optical and mechanical properties, enabling the development of responsive photonic materials. In this study, we explored the incorporation of hydroxypropyl cellulose (HPC) into a CNC film prepared by slow evaporation. In the composite CNC/HPC thin films, the CNCs adopt a chiral nematic structure, which can selectively reflect certain wavelengths of light to yield a colored film. The color could be tuned across the visible spectrum by changing the concentration or molecular weight of the HPC. Importantly, the composite films were more flexible than pure CNC films with up to a ten-fold increase in elasticity and a decrease in stiffness and tensile strength of up to six times and four times, respectively. Surface modification of the films with methacrylate groups increased the hydrophobicity of the films, and therefore, the water stability of these materials was also improved.

Concentric chiral nematic polymeric fibers from cellulose nanocrystals.

Hierarchical biological materials, such as osteons and plant cell walls, are complex structures that are difficult to mimic. Here, we combine liquid crystal systems and polymerization techniques within confined systems to develop complex structures. A single-domain concentric chiral nematic polymeric fiber was obtained by confining cellulose nanocrystals (CNCs) and hydroxyethyl acrylate inside a capillary tube followed by UV-initiated polymerization. The concentric chiral nematic structure continues uniformly throughout the length of the fiber. The pitch of the chiral nematic structure could be controlled by changing the CNC concentration. We tracked the formation of the concentric structure over time and under different conditions with variation of the tube orientation, CNC concentration, CNC type, and capillary tube size. We show that the inner radius of the capillary tube is important and a single-domain structure was only obtained inside small-diameter tubes. At low CNC concentration, the concentric chiral nematic structure did not completely cover the cross-section of the fiber. The highly ordered structure was studied using imaging techniques and X-ray diffraction, and the mechanical properties and structure of the chiral nematic fiber were compared to a pseudo-nematic fiber. CNC polymeric fibers could become a platform for many applications from photonics to complex hierarchical materials.

Bright Surface-Enhanced Raman Scattering with Fluorescence Quenching from Silica Encapsulated J-Aggregate Coated Gold Nanoparticles.

Plexitonic nanoparticles offer variable optical properties through tunable excitations, in addition to electric field enhancements that far exceed molecular resonators. This study demonstrates a way to design an ultrabright surface-enhanced Raman spectroscopy (SERS) signal while simultaneously quenching the fluorescence background through silica encapsulation of the semiconductor-metal composite nanoparticles. Using a multistep approach, a J-aggregate-forming organic dye is assembled on the surface of gold nanoparticles using a cationic linker. Excitonic resonance of the J-aggregate-metal system shows an enhanced SERS signal at an appropriate excitation wavelength. Further encapsulation of the decorated particles in silica shows a significant reduction in the fluorescence signal of the Raman spectra (5× reduction) and an increase in Raman scattering (7× enhancement) when compared to phospholipid encapsulation. This reduction in fluorescence is important for maximizing the useful SERS enhancement from the particle, which shows a signal increase on the order of 104 times greater than J-aggregated dye in solution and 24 times greater than Oxonica S421 SERS tag. The silica layer also serves to promote colloidal stability. The combination of reduced fluorescence background, enhanced SERS intensity, and temporal stability makes these particles highly distinguishable with potential to enable high-throughput applications such as SERS flow cytometry.