Using 15N‐Ammonium to Characterise and Map Potassium Binding Sites in Proteins by NMR Spectroscopy

A variety of enzymes are activated by the binding of potassium ions. The potassium binding sites of these enzymes are very specific, but ammonium ions can often replace potassium ions in vitro because of their similar ionic radii. In these cases, ammonium can be used as a proxy for potassium to characterise potassium binding sites in enzymes: the ¹H,¹⁵N spin‐pair of enzyme‐bound ¹⁵NH₄⁺ can be probed by ¹⁵N‐edited heteronuclear NMR experiments. Here, we demonstrate the use of NMR spectroscopy to characterise binding of ammonium ions to two different enzymes: human histone deacetylase 8 (HDAC8), which is activated allosterically by potassium, and the bacterial Hsp70 homologue DnaK, for which potassium is an integral part of the active site. Ammonium activates both enzymes in a similar way to potassium, thus supporting this non‐invasive approach. Furthermore, we present an approach to map the observed binding site onto the structure of HDAC8. Our method for mapping the binding site is general and does not require chemical shift assignment of the enzyme resonances.     

A Reliable Method for Recycling (RE)‐Ba‐Cu‐O (RE: Sm,Gd, Y) Bulk Superconductors

Single grain (RE)‐Ba‐Cu‐O (RE: Sm, Gd, Y) high‐temperature superconductors are able to generate high magnetic fields. However, the relatively high cost of the raw materials and the low yield of the manufacturing process have impeded the development of practical applications of these materials to date. This article describes a simple, reliable, and economical method of recycling failed bulk (RE)‐Ba‐Cu‐O (RE: Sm, Gd, Y) samples. Sixty‐four failed bulk samples, with diameters up to 31 mm, were recycled with a yield of 90%. The key innovation in this recycling process involves reintroducing the liquid phase into the melt process, which is normally lost during the primary peritectic processing of these materials. This enables the direct re‐growth of failed samples from solid form without the need for re‐grinding into powder. We also demonstrate that the superconducting performance and microstructure of the recycled samples is similar to that of the primary grown samples.     

Soft X‐ray Ptychographic Imaging and Morphological Quantification of Calcium Silicate Hydrates (C–S–H)

Morphological details of calcium silicate hydrate (C–S–H) stemming from the hydration process of Portland cement (PC) phases are crucial for understanding the PC‐based systems but are still only partially known. Here we introduce the first soft X‐ray ptychographic imaging of tricalcium silicate (C₃S) hydration products. The results are compared using both scanning transmission X‐ray and electron transmission microscopy data. The evidence shows that ptychography is a powerful method to visualize the details of outer and inner product C–S–H of fully hydrated C₃S, which have fibrillar and an interglobular structure with average void sizes of 20 nm, respectively. The high‐resolution ptychrography image enables us to perform morphological quantification of C–S–H, and, for the first time, to possibly distinguish the contributions of inner and outer product C–S–H to the small angle scattering of cement paste. The results indicate that the outer product C–S–H is mainly responsible for the q^?3 regime, whereas the inner product C–S–H transitions to a q^?2 regime. Various hypotheses are discussed to explain these regimes.     

Cellular Disulfide Bond Formation in Bioactive Peptides and Proteins

Bioactive peptides play important roles in metabolic regulation and modulation and many are used as therapeutics. These peptides often possess disulfide bonds, which are important for their structure, function and stability. A systematic network of enzymes—a disulfide bond generating enzyme, a disulfide bond donor enzyme and a redox cofactor—that function inside the cell dictates the formation and maintenance of disulfide bonds. The main pathways that catalyze disulfide bond formation in peptides and proteins in prokaryotes and eukaryotes are remarkably similar and share several mechanistic features. This review summarizes the formation of disulfide bonds in peptides and proteins by cellular and recombinant machinery.     

The Polymerization of Metal-Containing Vinylic Monomers of Iron and Tungsten with Metal–Carbon σ Bonds

A series of metal-containing vinylic monomers of the type and was homopolymerized using 2,2-azobisisobutyronitrile (AIBN) as the free-radical initiator. These monomers were also copolymerized with styrene in the presence of AIBN. These compounds represent a class of organometallic polymers in which the metal is bonded to the polymer backbone via a metal–carbon bond. The new compounds were characterized by IR and ¹H NMR spectroscopy as well as scanning electron microscopy, gel permeation chromatography, and thermoanalytical studies (DSC and TGA). The properties of the new organometallic polymers are discussed.     

Mechanical Behavior of MoSi2 Reinforced–Si3N4Matrix Composites

The mechanical behavior of MoSi₂ reinforced–Si₃N₄ matrix composites was investigated as a function of MoSi₂ phase content, MoSi₂ phase size, and amount of MgO densification aid for the Si₃N₄ phase. Coarse-phase MoSi₂-Si₃N₄ composites exhibited higher room-temperature fracture toughness than fine-phase composites, reaching values >8 MP·am^1/2. Composite fracture toughness levels increased at elevated temperature. Fine-phase composites were stronger and more creep resistant than coarse phase composites. Room-temperature strengths >1000 MPa and impression creep rates of ∼10⁻⁸ s⁻¹ at 1200°C were observed. Increased MgO levels generally were deleterious to MoSi₂-Si₃N₄ mechanical properties. Internal stresses due to MoSi₂ and Si₃N₄ thermal expansion coefficient mismatch appeared to contribute to fracture toughening in MoSi₂-Si₃N₄ composites.     

Elastic Properties and Microcracking Behavior of Particulate Titanium Diboride–Silicon Carbide Composites

The spontaneous microcracking of particulate TiB₂–SiC composites is studied as a function of TiB₂ volume fraction. The degree of microcracking was examined by measuring elastic properties from room temperature to 1300°C. The results showed that only one composition contains microcracks. All other compositions did not microcrack regardless of TiB₂ volume fraction. This was attributed to the difference in the sintering aids. In particular, the Al₂O₃ sintering aid needed in these compositions had reacted with SiO₂ to form an amorphous grain boundary phase that allowed residual stresses to relax by viscous flow at moderate to high temperatures. The existence of this amorphous grain boundary phase was directly observed by transmission electron microscopy.