Controlled self‐assembly of bio‐sourced nanocolloids is of high importance for the development of sustainable and low‐cost functional materials but controlling nanocomposite fabrication with both satisfactory optical properties and composition remains challenging. Silk fibroin (SF) and cellulose nanocrystals (CNCs) have independently demonstrated their ability to produce high‐quality photonic materials, in part due to their low absorbance and their transparency in the visible range. While SF is able to replicate inverse structures by high‐resolution nano‐templating, CNCs can spontaneously assemble into cholesteric liquid crystalline structures that are retained upon solvent evaporation, yielding photonic films. In this work, the conditions of successful co‐assembly of regenerated SF, extracted from silkworm silk, with CNCs extracted from cotton, are investigated. Their co‐assembly is investigated for various relative concentration ratios and pH, combining polarized optical microscopy and spectroscopy, SEM, and other characterization techniques (XRD, ATR‐FTIR, TGA). The appearance of photonic properties is observed when CNC and SF are assembled at pH ≥ 4.15, highlighting the importance of suppressing attractive electrostatic interactions between the two species for an organized structure to emerge. Beyond its fundamental motivations for colloidal co‐assembly with structural proteins, this work is relevant to design sustainable optical materials compatible with food packaging coatings and edible coloring pigments.
Incorporating photonic crystals with nanoplasmonic building blocks gives rise to novel optoelectronic properties that promise designing advanced multifunctional materials and electronics. Herein, the free‐standing chiral plasmonic composite films are designed by coassembling anisotropic plasmonic gold nanorods (GNRs) and rod‐like cellulose nanocrystals (CNCs). The effects of surface charge and concentration of the GNRs on the structure and optical properties of the CNC/GNR films are examined within this study. The CNC/GNR hybrid films retain the photonic characteristic of the CNCs host while concomitantly possessing the plasmonic resonance of GNRs. The negatively charged GNRs distribute uniformly in the layered CNCs host, inducing strong electrostatic repulsion among the CNCs and thus promoting the formation of a larger helical pitch than the case without GNRs. The positively charged GNRs decrease the chiroptical activity in the composite films with increasing the concentration of GNR, which is confirmed by the circular dichroism spectra. Notably, the surface plasmon resonances of GNRs enhance the fluorescence emission, which has been demonstrated by surface‐enhanced fluorescence signals in this work. This study sheds light on fabricating functional chiral plasmonic composite films with enhanced chiral plasmonics by utilizing CNCs as a dynamic chiral nematic template and adjusting surface charges.
more » « less- Award ID(s):
- 1654192
- NSF-PAR ID:
- 10461494
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Optical Materials
- Volume:
- 7
- Issue:
- 9
- ISSN:
- 2195-1071
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Photo-induced thiol-ene crosslinking of allyl-functionalized cellulose nanocrystal (CNC)/polymer nanocomposites allows access to films that mimic the water-enhanced mechanical gradient characteristics of the squid beak. These films are prepared by mixing the functionalized CNCs and polymer in a solvent before solution casting and drying. The photocrosslinking agents are then imbibed into the film before UV exposure. Reported herein are studies aimed at better understanding the effect of the film preparation procedure, film thickness and the conditions under which the UV treatment is carried out. It was found that when the film is heated at a temperature higher than its glass transition temperature (Tg) during the UV irradiation step there is a greater enhancement in the mechanical properties of the films, presumably on account of more efficient crosslinking between the CNC fillers. Moreover, composite films that were compression molded (at 90°C) before the imbibing step displayed lower mechanical properties compared to the as-cast films, which is attributed to phase separation of the CNC fillers and polymer matrix during this additional processing step. Finally, the film thickness was also found to be a critical factor that affects the degree of crosslinking. For example, thinner films (50 µm) displayed a higher wet modulus ca. 130 MPa compared to ca. 80 MPa for the thicker films (150 µm). Understanding the processing conditions allows access to a larger range of mechanical properties which is important for the design of new bio-inspired mechanical gradient nanocomposites.more » « less
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