Qualitatively different thickness dependences have been observed in the glass transition temperature, T g , of polystyrene (PS) films supported by hydrogen-passivated silicon (H-Si). It has been suggested that upon annealing at high temperatures in air, the polymer/substrate interface of these films (i.e., PS/Si), though buried underneath the PS layer, might be oxidized, rendering the films a different polymer/ substrate interface (i.e., PS/SiO x -Si), which may account for the different thickness dependences of the T g observed. In this experiment, we examine if the buried substrate interface of PS/H-Si films can indeed be oxidized by annealing the films at 150 °C in air. Our result shows that a residual film does form on top of the H-Si surface, but it is a bound layer of PS. X-ray photoelectron spectroscopic (XPS) analyses and independence of the residual film on the initial PS thickness evidence that the H-Si substrate buried underneath a PS film is not oxidized by annealing. We discuss a possible explanation to how the different thickness dependences may be observed in the T g of these films.
The measured stresses associated with the growth of oxide on the surface of aluminum are much lower than those calculated from the Pilling‐Bedworth ratio. The magnitude of the stresses in alumina formed anodically on pure aluminum is shown to be dependent on the rate of formation. Some experiments are described which show that, even at low temperatures, the presence of a large ionic flux will permit the deformation of alumina providing a mechanism by which the growth stresses can be relieved.
Understanding peptide self-assembly mechanisms and stability of the formed assemblies is crucial for the development of functional nanomaterials. Herein, we have adopted a rational design approach to demonstrate how a minimal structural modification to a nonassembling ultrashort ionic selfcomplementary tetrapeptide FEFK (Phe4) remarkably enhanced the stability of self-assembly into β-sheet nanofibers and induced hydrogelation. This was achieved by replacing flexible phenylalanine residue (F) by the rigid phenylglycine (Phg), resulting in a constrained analogue PhgEPhgK (Phg4), which positioned aromatic rings in an orientation favorable for aromatic stacking. Phg4 self-assembly into stable β-sheet ladders was facilitated by π-staking of aromatic side chains alongside hydrogen bonding between backbone amides along the nanofiber axis. The contribution of these noncovalent interactions in stabilizing self-assembly was predicted by in silico modeling using molecular dynamics simulations and semiempirical quantum mechanics calculations. In aqueous medium, Phg4 β-sheet nanofibers entangled at a critical gelation concentration ≥20 mg/mL forming a network of nanofibrous hydrogels. Phg4 also demonstrated a unique surface activity in the presence of immiscible oils and was superior to commercial emulsifiers in stabilizing oil-in-water (O/W) emulsions. This was attributed to interfacial adsorption of amphiphilic nanofibrils forming nanofibrilized microspheres. To our knowledge, Phg4 is the shortest ionic self-complementary peptide rationally designed to self-assemble into stable β-sheet nanofibers capable of gelation and emulsification. Our results suggest that ultrashort ionic-complementary constrained peptides or UICPs have significant potential for the development of cost-effective, sustainable, and multifunctional soft bionanomaterials.
The ‘second quantum revolution’ has been the subject of substantial speculation, investment by public and private sectors, and media hype. We investigate some of this hype in the form of three national strategies for quantum technology. In the course of analysing these strategies, we ask: how can we ensure new quantum technologies benefit the societies they are used in and are a part of ? To help clarify this question, we posit a public good test for quantum research requiring diversity in research agendas, social orders, and research-society networks.
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