A deuterium NMR investigation of polymorphism in benzene pizzanes

The polymorphism of three members of the homologous series hexa(p−alkoxyphenoxymethyl) benzene (benzene pizzanes) with 5, 6 and 7 carbons in the alkoxy chains and several of their deuteriated isotopomers have been investigated by differential scanning calorimetry, polarizing optical microscopy, X−ray diffraction and deuterium NMR spectroscopy. These homologues exhibit several solid phases and a high temperature M phase, which is isomorphic in the three homologues and whose nature is discussed. In the solid phases, the benzene cores of the molecules remain rigid, but the side chains are mobile, as reflected by rapid pi−flips of the benzene rings in the side chains. It is found that there are two types of such benzene rings, differing in the rates of flips. In the M phase the molecules undergo fast overall reorientation and the side chains are even more disordered than in the solid phases. However the X−ray measurements do not provide a clear cut determination as to whether this phase is crystalline or mesomorphic. Mixing of the benzene pizzanes with p−xylene yields lyomesophases, which appear to belong to the Dho clas

Regulated phase transitions of bacterial chromatin: a non-enzymatic pathway for generic DNA protection

The enhanced stress resistance exhibited by starved bacteria represents a central facet of virulence, since nutrient depletion is regularly encountered by pathogens in their natural in vivo and ex vivo environments. Here we explore the notion that the regular stress responses, which are mediated by enzymatically catalyzed chemical transactions and promote endurance during the logarithmic growth phase, can no longer be effectively induced during starvation. We show that survival of bacteria in nutrient-depleted habitats is promoted by a novel strategy: finely tuned and fully reversible intracellular phase transitions. These non-enzymatic transactions, detected and studied in bacteria as well as in defined in vitro systems, result in DNA sequestration and generic protection within tightly packed and highly ordered assemblies. Since this physical mode of defense is uniquely independent of enzymatic activity or de novo protein synthesis, and consequently does not require energy consumption, it promotes virulence by enabling long-term bacterial endurance and enhancing antibiotic resistance in adverse habitats

Local Environment of Sc and Y Dopant Ions in Aluminum Nitride Thin Films

The local environments of Sc and Y in predominantly ⟨002⟩ textured, Al1–xDoxN (Do = Sc, x = 0.25, 0.30 or Y, x = 0.25) sputtered thin films with wurtzite symmetry were investigated using X-ray absorption (XAS) and photoelectron (XPS) spectroscopies. We present evidence from the X-ray absorption fine structure (XAFS) spectra that, when x = 0.25, both Sc3+ and Y3+ ions are able to substitute for Al3+, thereby acquiring four tetrahedrally coordinated nitrogen ligands, i.e., coordination number (CN) of 4. On this basis, the crystal radius of the dopant species in the wurtzite lattice, not available heretofore, could be calculated. By modeling the scandium local environment, extended XAFS (EXAFS) analysis suggests that when x increases from 0.25 to 0.30, CN for a fraction of the Sc ions increases from 4 to 6, signaling octahedral coordination. This change occurs at a dopant concentration significantly lower than the reported maximum concentration of Sc (42 mol % Sc) in wurtzite (Al, Sc)N. XPS spectra provide support for our observation that the local environment of Sc in (Al, Sc)N may include more than one type of coordination