Arginine mimetics using α-guanidino acids: introduction of functional groups and stereochemistry adjacent to recognition guanidiniums in peptides

Arginine residues are broadly employed for specific biomolecular recognition, including in protein-protein, protein-DNA, and protein-RNA interactions. Arginine recognition commonly exploits the potential for bidentate electrostatic and hydrogen-bonding interactions. However, in arginine residues, the guanidinium functional group is located at the terminus of a flexible hydrocarbon side chain, which lacks the functionality to contribute to specific arginine-mediated recognition and may entropically disfavor binding. In order to enhance the potential for specificity and affinity in arginine-mediated molecular recognition, we have developed an approach to the synthesis of peptides that incorporates an α-guanidino acid as a novel arginine mimetic. α-Guanidino acids, derived from α-amino acids, with guanidinylation of the amino group, were incorporated stereospecifically into peptides on solid phase via coupling of an Fmoc amino acid to diaminopropionic acid (Dap), Fmoc deprotection, guanidinylation of the amine on solid phase, and deprotection, generating a peptide containing an α-functionalized arginine mimetic. This approach was examined by incorporating arginine mimetics into ligands for the Src, Grb, and Crk SH3 domains at the site of the key recognition arginine. Protein binding was examined for peptides containing guanidino acids derived from Gly, L-Val, L-Phe, L-Trp, D-Val, D-Phe, and D-Trp. We demonstrate that paralogue specificity and target site affinity may be modulated with the use of α-guanidino acid-derived arginine mimetics, generating peptides that exhibit enhanced Src specificity by selection against Grb and peptides that reverse the specificity of the native peptide ligand, with enhancements in Src target specificity of up to 15-fold (1.6 kcal mol(-1)).     

Effect of substrate temperature on microstructure and optical properties of nanocrystalline alumina thin films

Aluminum oxide (Al₂O₃) thin films were deposited on silicon (100) and quartz substrates by pulsed laser deposition (PLD) at an optimized oxygen partial pressure of 3.0×10^?3 mbar in the substrate temperatures range 300–973 K. The films were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy, spectroscopic ellipsometry, UV–visible spectroscopy and nanoindentation. The X-ray diffraction studies showed that the films deposited at low substrate temperatures (300–673 K) were amorphous Al₂O₃, whereas those deposited at higher temperatures (≥773 K) were polycrystalline cubic γ-Al₂O₃. The transmission electron microscopy studies of the film prepared at 673 K, showed diffuse ring pattern indicating the amorphous nature of Al₂O₃. The surface morphology of the films was examined by atomic force microscopy showing dense and uniform nanostructures with increased surface roughness from 0.3 to 2.3 nm with increasing substrate temperature. The optical studies were carried out by ellipsometry in the energy range 1.5–5.5 eV and revealed that the refractive index increased from 1.69 to 1.75 (λ=632.8 nm) with increasing substrate temperature. The UV–visible spectroscopy analysis indicated higher transmittance (>80%) for all the films. Nanoindentation studies revealed the hardness values of 20.8 and 24.7 GPa for the films prepared at 300 K and 973 K respectively.     

Transient analysis of energy storage in a thermally stratified water tank

A one-dimensional transient heat conduction model to describe the decay of the thermocline in a stratified water tank is presented. The problem is formulated as an initial boundary value problem and the resulting governing equations in the fluid and in the storage wall are solved numerically to obtain the temperature profiles in the wall and the fluid. The formulation considers the axial conduction of heat, both in the fluid and in the solid wall. The mixing parameters introduced in the boundary conditions at the top and bottom of the tank in the fluid region account for mixing due to inlet and outlet streams with the stored fluid. The model is applicable to the storage of both hot and chilled water. The model is validated with experimental data from the literature. The parameters that influence the operation of a stratified thermal energy storage for both heat and cool storage are examined. © 1998 John Wiley & Sons, Ltd.     

Advanced Pd-based nanomaterials for electro-catalytic oxygen reduction in fuel cells: A review

Devising cost-effective and high-performance nanocatalysts for the inherently slow oxygen reduction reaction (ORR) represents a critical hurdle in the commercial improvement of fuel cells for energy conversion. Recently, considerable attempts have concentrated on exploring Pd-based nanocatalysts with advanced stability to utilize as substitutes for Pt. In this review, we first describe ORR mechanisms and summarize research conducted with Pd electro-catalysts, including single and alloyed Pd nanostructures on different substrates. The application of Pd catalysts as cathode nanomaterials in proton exchange membrane fuel cells (PEMFCs), direct methanol fuel cells (DMFCs), and anion exchange membrane fuel cells (AEMFCs) is also reviewed. The insights into the connections between catalytic performance, structure, and preparation process are addressed. In particular, approaches for fabricating efficient Pd electro-catalysts, such as increasing the number of reactive centers and modifying nanoparticle-support interactions, are discussed. Challenges and prospects for upcoming investigations in developing desirable ORR nanocatalysts are highlighted.