Increased temperature and high pressure are applied to beta-lactoglobulin fibrils in the autoclave, resulting in the acquisition of a composite material comprised of partially disassembled amyloid fibrils and carbon dots. Confirmation of the preservation of the beta-sheet motif attributed to amyloids in the hydrothermally treated fibrils is obtained through wide-angle X-ray scattering and ThT assay. Z-scan analysis reveals a two-photon absorption (2PA) enhancement in the low-lying transition band (La) of tyrosine, while quantum chemical calculations demonstrate a correlation between the yield of 2PA and the interspace distance between aromatic residues. Overall, the intrinsic optical properties of amyloid fibrils treated in a subcritical water environment are found to be linked with the pi-conjugation of tyrosine units and their through-space coupling. The resulting composite material is employed as a coating for a commercial ultraviolet light-emitting diode lamp, showcasing the potential utility of sustainable biomaterials with improved optical properties for photonics applications. By subjecting beta-lactoglobulin fibrils to elevated temperature and pressure in autoclave, partially disassembled fibrils are generated. The study reveals a correlation between fluorescence and two-photon absorption and the spacing of aromatic residues, shedding light on the mechanism behind the improved optical properties of amyloid fibrils. Furthermore, the hydrothermally treated beta-lactoglobulin fibrils are utilized to coat ultraviolet light-emitting diode lamps. image (c) 2024 WILEY-VCH GmbH

The concept of combining mixing of solids by milling (a type of mechanochemistry) with aqueous self-assembly provides interesting possibilities for energy efficient production of advanced nanomaterials. Many proteins are outstanding building blocks for self-assembly, a prominent example being the conversion of proteins into protein nanofibrils (PNFs) - a structure related to amyloid fibrils. PNFs have attractive mechanical properties and have a tendency to form ordered materials. They are accordingly of interest as materials for bioplastics and potentially also for more high-tech applications. In this concept article we highlight our effort on valorization of such proteins with hydrophobic organic compounds such an organic dyes and drug molecules, by developing scalable methodology combining mechanochemistry and self-assembly. Compared to more established methodology, mechanochemical methodology is a valuable complement as it allows potential scalable production of hybrids between e. g. proteins and highly hydrophobic compounds - a class of hybrid material that is difficult to access by other means. This may allow for development of sustainable processes for fabrication of advanced protein-based materials derivable from renewable source materials.

A green, though black, sustainable and low-cost carbon material-charcoal produced from wood-is developed for electricity storage. Charcoal electrodes are fabricated by ball-milling charcoal and adding protein nanofibril binders. The charcoal electrode presents a capacitance of 360 F g(-1) and a conductivity of 0.2 S m(-1). A pair of redox peaks is observed in the cyclic voltammetry and assigned to originate from quinone groups. Compared with other wooden electrodes, these charcoal electrodes display better cycling stability with 88% capacity retention after 1000 cycles. Their discharge capacity is 2.5 times that of lignosulfonate/graphite hybrid electrodes.

Gelatin is an excellent gelling agent and is widely employed for hydrogel formation. Because of the poor mechanical properties of gelatin when dry, gelatin-aerogels are comparatively rare. Herein we demonstrate that protein nanofibrils can be employed to improve the mechanical properties of gelatin aerogels, and the materials can moreover be functionalized with a an electrically conductive polyelectrolyte resulting in formation of an elastic electrically conductive aerogel that can be employed as a piezoresistive pressure sensor. The aerogel sensor shows a good linear relationship in a wide pressure range (1.8-300 kPa) with a sensitivity of 1.8 kPa(-1). This work presents a convenient way to produce electrically conductive elastic aerogels from low-cost protein precursors.

A combination of mechanochemistry and aqueous self-assembly is employed to prepare protein nanofibrils (PNFs) functionalized with perylene diimide (PDI) dyes. These materials are then mixed with poly(vinyl alcohol) (PVA) and casted into bioplastic films. The functionalization process not only results in luminescent hybrid materials, but the presence of the dye modifies the physical properties of the PNFs. Films formed from PNFs functionalized with PDIs display anisotropic organization, which enables emission of polarized light. Crucially, the presence of PDI dyes improves the stability of PNF-PVA films in water and moreover the films are processable when wet. By applying water, films can be glued together or self-healed by applying water. Mechanochemical methodology can thus be employed for modifying properties of protein materials. This represents a new highly flexible and novel strategy for tuning both properties and functionality of protein materials.

Many proteins undergoes self-assembly into fibrillar structures known as amyloid fibrils. During the self-assembly process related structures, known as spherulites, can be formed. Herein we report a facile method where the balance between amyloid fibrils and spherulites can be controlled by stirring of the reaction mixture during the initial stages of the self-assembly process. Moreover, we report how this methodology can be used to prepare non-covalently functionalized amyloid fibrils. By stirring the reaction mixture continuously or for a limited time during the lag phase the fibril length, and hence the propensity to form liquid crystalline phases, can be influenced. This phenomena is utilized by preparing films consisting of aligned protein fibrils incorporating the laser dye Nile red. The resulting films display polarized Nile red fluorescence.

Developing sustainable organic electrode materials for energy storage applications is an urgent task. We present a promising candidate based on the use of lignin, the second most abundant biopolymer in nature. This polymer is combined with a conducting polymer, where lignin as a polyanion can behave both as a dopant and surfactant. The synthesis of PEDOT/Lig biocomposites by both oxidative chemical and electrochemical polymerization of EDOT in the presence of lignin sulfonate is presented. The characterization of PEDOT/Lig was performed by UV-Vis-NIR spectroscopy, FTIR infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry and galvanostatic charge-discharge. PEDOT doped with lignin doubles the specific capacitance (170.4 F g(-1)) compared to reference PEDOT electrodes (80.4 F g(-1)). The enhanced energy storage performance is a consequence of the additional pseudocapacitance generated by the quinone moieties in lignin, which give rise to faradaic reactions. Furthermore PEDOT/Lig is a highly stable biocomposite, retaining about 83% of its electroactivity after 1000 charge/discharge cycles. These results illustrate that the redox doping strategy is a facile and straightforward approach to improve the electroactive performance of PEDOT.

Two self-doped conjugated polyelectrolytes, having semiconducting and metallic behaviors, respectively, have been blended from aqueous solutions in order to produce materials with enhanced optical and electrical properties. The intimate blend of two anionic conjugated polyelectrolytes combine the electrical and optical properties of these, and can be tuned by blend stoichiometry. In situ conductance measurements have been done during doping of the blends, while UV vis and EPR spectroelectrochemistry allowed the study of the nature of the involved redox species. We have constructed an accumulation/depletion mode organic electrochemical transistor whose characteristics can be tuned by balancing the stoichiometry of the active material.

Electrical interfaces between biological cells and man-made electrical devices exist in many forms, but it remains a challenge to bridge the different mechanical and chemical environments of electronic conductors (metals, semiconductors) and biosystems. Here we demonstrate soft electrical interfaces, by integrating the metallic polymer PEDOT-S into lipid membranes. By preparing complexes between alkyl-ammonium salts and PEDOT-S we were able to integrate PEDOT-S into both liposomes and in lipid bilayers on solid surfaces. This is a step towards efficient electronic conduction within lipid membranes. We also demonstrate that the PEDOT-S@alkyl-ammonium: lipid hybrid structures created in this work affect ion channels in the membrane of Xenopus oocytes, which shows the possibility to access and control cell membrane structures with conductive polyelectrolytes.

Herein we report on the investigation of self-assembled protein nanofibrils functionalized with metallic organic compounds. We have characterized the electronic behaviour of individual nanowires using conductive atomic force microscopy. In order to follow the self assembly process we have incorporated fluorescent molecules into the protein and used the energy transfer between the internalized dye and the metallic coating to probe the binding of the polyelectrolyte to the fibril.