Light-Triggered Enhancement of Fluorescence Efficiency in Organic Cages.

The fluorescence efficiency of excited molecules can be enhanced by many external factors. Here, we showcase a surprising phenomenon whereby light is used as a gating source to increase the fluorescence efficiency of organic cages composed of biphenyl subunits. We show that the enhancement of fluorescence is not due to structural changes or ground-state events. Cryo-fluorescence measurements and kinetic studies suggest a restriction of the phenyl-based structures in the excited state, leading to increased fluorescence, which is also supported by time-resolved measurements. Through computational calculations, we propose that the planarization of the biphenyl units within the cages contributes to emission enhancement. This phenomenon offers insights into the design of optoelectronic structures with improved fluorescence properties.

Proton Transport Across Collagen Fibrils and Scaffolds: The Role of Hydroxyproline.

Collagen is one of the most studied proteins due to its fundamental role in creating fibrillar structures and supporting tissues in our bodies. Accordingly, collagen is also one of the most used proteins for making tissue-engineered scaffolds for various types of tissues. To date, the high abundance of hydroxyproline (Hyp) within collagen is commonly ascribed to the structure and stability of collagen. Here, we hypothesize a new role for the presence of Hyp within collagen, which is to support proton transport (PT) across collagen fibrils. For this purpose, we explore here three different collagen-based hydrogels: the first is prepared by the self-assembly of natural collagen fibrils, and the second and third are based on covalently linking between collagen via either a self-coupling method or with an additional cross-linker. Following the formation of the hydrogel, we introduce here a two-step reaction, involving (1) attaching methanesulfonyl to the -OH group of Hyp, followed by (2) removing the methanesulfonyl, thus reverting Hyp to proline (Pro). We explore the PT efficiency at each step of the reaction using electrical measurements and show that adding the methanesulfonyl group vastly enhances PT, while reverting Hyp to Pro significantly reduces PT efficiency (compared with the initial point) with different efficiencies for the various collagen-based hydrogels. The role of Hyp in supporting the PT can assist in our understanding of the physiological roles of collagen. Furthermore, the capacity to modulate conductivity across collagen is very important to the use of collagen in regenerative medicine.

Molecular-Doped Protein-Based Elastomers as a Versatile Platform for Energy-Transfer Studies and Emissive Down-Converting Polymers for Light-Emitting Applications.

Much effort is being employed for designing "green" environmental emissive materials that are capable of color-tuning, i.e., down-converting the emission, and white-light generation (WLG). Here, we introduce a protein-based elastomer that can noncovalently bind a variety of chromophores while preventing their aggregation. Such binding capabilities are unique to the albumin-based materials that we use here in a process we refer to as "molecular doping". In the first part of this study, we explore the energy transfer across five different chromophores within the protein matrix, where the closely packed chromophore organization enables high energy-transfer efficiencies among them. In the second part, we show the easy control of blue, green, and red chromophores within the biopolymer, resulting in tunable emission properties of the film and WLG. The highly affordable chosen protein and the straightforward molecular doping strategy make our protein elastomers an attractive choice for an emissive material, as either a scaffold for investigating energy transfer in proteins or possible integration in light-emitting applications.

Robust Biosensor Based on Carbon Nanotubes/Protein Hybrid Electrolyte Gated Transistors.

Semiconducting single walled carbon nanotubes (SWCNTs) are promising materials for biosensing applications with electrolyte-gated transistors (EGT). However, to be employed in EGT devices, SWCNTs often require lengthy solution-processing fabrication techniques. Here, we introduce a simple solution-based method that allows fabricating EGT devices from stable dispersions of SWCNTs/bovine serum albumin (BSA) hybrids in water. The dispersion is then deposited on a substrate allowing the formation of a SWCNTs random network as the semiconducting channel. We demonstrate that this methodology allows the fabrication of EGT devices with electric performances that allow their use in biosensing applications. We demonstrate their application for the detection of cortisol in solution, upon gate electrode functionalization with anti-cortisol antibodies. This is a robust and cost-effective methodology that sets the ground for a SWCNT/BSA-based biosensing platform that allows overcoming many limitations of standard SWCNTs biosensor fabrications.