Modeling and Designing Particle-Regulated Amyloid-like Assembly of Synthetic Polypeptides in Aqueous Solution.

In cells, actin and tubulin polymerization is regulated by nucleation factors, which promote the nucleation and subsequent growth of protein filaments in a controlled manner. Mimicking this natural mechanism to control the supramolecular polymerization of macromolecular monomers by artificially created nucleation factors remains a largely unmet challenge. Biological nucleation factors act as molecular scaffolds to boost the local concentrations of protein monomers and facilitate the required conformational changes to accelerate the nucleation and subsequent polymerization. An accelerated assembly of synthetic poly(l-glutamic acid) into amyloid fibrils catalyzed by cationic silica nanoparticle clusters (NPCs) as artificial nucleation factors is demonstrated here and modeled as supramolecular polymerization with a surface-induced heterogeneous nucleation pathway. Kinetic studies of fibril growth coupled with mechanistic analysis demonstrate that the artificial nucleators predictably accelerate the supramolecular polymerization process by orders of magnitude (e.g., shortening the assembly time by more than 10 times) when compared to the uncatalyzed reaction, under otherwise identical conditions. Amyloid-like fibrillation was supported by a variety of standard characterization methods. Nucleation followed a Michaelis-Menten-like scheme for the cationic silica NPCs, while the corresponding anionic or neutral nanoparticles had no effect on fibrillation. This approach shows the effectiveness of charge-charge interactions and surface functionalities in facilitating the conformational change of macromolecular monomers and controlling the rates of nucleation for fibril growth. Molecular design approaches like these inspire the development of novel materials via biomimetic supramolecular polymerizations.

Graphene nanofiber composites for enhanced neuronal differentiation of human mesenchymal stem cells.

Aim: To differentiate mesenchymal stem cells into functional dopaminergic neurons using an electrospun polycaprolactone (PCL) and graphene (G) nanocomposite. Methods: A one-step approach was used to electrospin the PCL nanocomposite, with varying G concentrations, followed by evaluating their biocompatibility and neuronal differentiation. Results: PCL with exiguous graphene demonstrated an ideal nanotopography with an unprecedented combination of guidance stimuli and substrate cues, aiding the enhanced differentiation of mesenchymal stem cells into dopaminergic neurons. These newly differentiated neurons were seen to exhibit unique neuronal arborization, enhanced intracellular Ca2+ influx and dopamine secretion. Conclusion: Having cost-effective fabrication and room-temperature storage, the PCL-G nanocomposites could pave the way for enhanced neuronal differentiation, thereby opening a new horizon for an array of applications in neural regenerative medicine.

New Antimony Selenide/Nickel Oxide Photocathode Boosts the Efficiency of Graphene Quantum-Dot Co-Sensitized Solar Cells.

A novel assembly of a photocathode and a photoanode is investigated to explore their complementary effects in enhancing the photovoltaic performance of a quantum-dot solar cell (QDSC). While p-type nickel oxide (NiO) has been used previously, antimony selenide (Sb2Se3) has not been used in a QDSC, especially as a component of a counter electrode (CE) architecture that doubles as the photocathode. Here, near-infrared (NIR) light-absorbing Sb2Se3 nanoparticles (NPs) coated over electrodeposited NiO nanofibers on a carbon (C) fabric substrate was employed as the highly efficient photocathode. Quasi-spherical Sb2Se3 NPs, with a band gap of 1.13 eV, upon illumination, release photoexcited electrons in addition to other charge carriers at the CE to further enhance the reduction of the oxidized polysulfide. The p-type conducting behavior of Sb2Se3, coupled with a work function at 4.63 eV, also facilitates electron injection to polysulfide. The effect of graphene quantum dots (GQDs) as co-sensitizers as well as electron conduits is also investigated in which a TiO2/CdS/GQDs photoanode structure in combination with a C-fabric CE delivered a power-conversion efficiency (PCE) of 5.28%, which is a vast improvement over the 4.23% that is obtained by using a TiO2/CdS photoanode (without GQDs) with the same CE. GQDs, due to a superior conductance, impact efficiency more than Sb2Se3 NPs do. The best PCE of a TiO2/CdS/GQDs-nS2-/Sn2--Sb2Se3/NiO/C-fabric cell is 5.96% (0.11 cm2 area), which, when replicated on a smaller area of 0.06 cm2, is seen to increase dramatically to 7.19%. The cell is also tested for 6 h of continuous irradiance. The rationalization for the channelized photogenerated electron movement, which augments the cell performance, is furnished in detail in these studies.