Temperature induced structural changes in even-odd nylons with long polymethylene segments

Structural transitions of nylons 8 9 and 12 9 heating and cooling processes were investigated using calorimetric, spectroscopic during and real time X-ray diffraction data. These even-odd nylons had three polymorphic forms related to structures where hydrogen bonds were established in two planar directions. Heating processes showed a first structural transition at low temperature where the two strong reflections related to the packing mode of the low temperature structure (form I) disappeared instead of moving together and merging into a single reflection, as observed for conventional even-even nylons. The high temperature structure corresponded to a typical pseudohexagonal packing (form III) attained after the named Brill transition temperature. Structural transitions were not completely reversible since an intermediate structure (form II) became clearly predominant at room temperature in subsequent cooling processes. A single spherulitic morphology with negative birefringence and a flat-on edge-on lamellar disposition was obtained when the two studied polyamides crystallized from the melt state. Kinetic analyses indicated that both nylons crystallized according to a single regime and a thermal nucleation. Results also pointed out a secondary nucleation constant for nylon 12 9 higher than that for nylon 8 9, suggesting greater difficulty in crystallizing when the amide content decreased. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2494–2506Peer ReviewedPostprint (author's final draft

Physics of Polymorphic Transitions in CeRuSn

We report a detailed study of the polymorphic transitions in ternary stannide CeRuSn on high quality single crystals through a combination of X-ray diffraction experiments conducted at 300, 275 and 120 K, and measurements of the thermal expansion, magnetization, and resistivity, along main crystallographic axes. In addition, the transition was followed as a function of pressure up to 0.8 GPa. The present X-ray diffraction data show that the room temperature polymorph consists of the lattice doubled along the c axis with respect to the CeCoAl-type structure consistent with previous reports. Upon cooling, the compound undergoes two successive transitions, first to a quintuple (290 K) and than to a triple CeCoAl superstructure at 225 K. The transitions are accompanied by a tremendous volume change due to a strong shrinking of the lattice along the c axis, which is clearly observed in thermal expansion. We advance arguments that the volume collapse originates from an increasing number of crystallographically inequivalent Ce sites and the change of ratio between the short and long Ce-Ru bonds. The observed properties of the polymorphic transition in CeRuSn are reminiscent of the transition in elementary Cerium, suggesting that similar physics, i.e., a Kondo influenced transition and strong lattice vibrations might be the driving forces

Reflections on God and Evil in the Krishna Bhakti Theology of Caitanya

The story that forms the short prologue at the start of Valmiki’s Rāmāyana expresses something of how the bhakta deals with tragic loss and senseless violence. In the briefest of words, the story goes something like this: As Valmiki is performing his morning ablutions in the Tamasa River, he witnesses two cranes sweetly cooing at one another lovingly on a branch in a nearby tree. Suddenly, a hunter comes along and shoots an arrow through the chest of the male crane, who immediately drops to the ground. The female, herself alighting on the ground, sees her beloved mate writhing in agony with his mortal wound, and thus she begins to weep, drowning herself in the tears of her sorrow. Valmiki, upon seeing this senseless killing, in his anger curses the hunter from that day on to wander all the days of his life homelessly. Who can mortally wound such an innocent loving creature? What kind of person does this? What kind of senseless act is this? Where is God in all this? Questions such as these are easily elicited from those who hear this story. We shall return to this story following a brief sketch of the relationship between God and evil in a bhakti theology

Functional plasticity of antibacterial EndoU toxins.

Bacteria use several different secretion systems to deliver toxic EndoU ribonucleases into neighboring cells. Here, we present the first structure of a prokaryotic EndoU toxin in complex with its cognate immunity protein. The contact-dependent growth inhibition toxin CdiA-CTSTECO31 from Escherichia coli STEC_O31 adopts the eukaryotic EndoU fold and shares greatest structural homology with the nuclease domain of coronavirus Nsp15. The toxin contains a canonical His-His-Lys catalytic triad in the same arrangement as eukaryotic EndoU domains, but lacks the uridylate-specific ribonuclease activity that characterizes the superfamily. Comparative sequence analysis indicates that bacterial EndoU domains segregate into at least three major clades based on structural variations in the N-terminal subdomain. Representative EndoU nucleases from clades I and II degrade tRNA molecules with little specificity. In contrast, CdiA-CTSTECO31 and other clade III toxins are specific anticodon nucleases that cleave tRNAGlu between nucleotides C37 and m2 A38. These findings suggest that the EndoU fold is a versatile scaffold for the evolution of novel substrate specificities. Such functional plasticity may account for the widespread use of EndoU effectors by diverse inter-bacterial toxin delivery systems

Structure of Equilenin at 100 K: an estrone-related steroid

The structure of the estrone-related steroid, Equilenin, C18H18O2 (systematic name 3-hy-droxy-13-methyl-11,12,13,14,15,16-hexa-hydro-cyclo-penta-[a]phen-anthren-17-one), has been determined at 100 K. The crystals are ortho-rhom-bic, P212121, and the absolute structure of the mol-ecule in the crystal has been determined by resonant scattering [Flack parameter = -0.05 (4)]. The C atoms of the A and B rings are almost coplanar, with an r.m.s. deviation from planarity of 0.0104 Å. The C ring has a sofa conformation, while the D ring has an envelope conformation with the methine C atom as the flap. The keto O atom and the methyl group are translated 0.78 and 0.79 Å, respectively, from the equivalent positions on 17β-estrone. In the crystal, mol-ecules are linked by O-H⋯O hydrogen bonds, forming chains parallel to the c-axis direction

XAS Study of the High Pressure Behaviour of Quartzlike Compounds

EXAFS spectroscopy experiments have been carried out on quartz-like GaAsO4 and AlAsO4 at high pressure and room temperature. It has been shown that these materials exhibit two structural phase transitions; the first transition to a high pressure crystalline form occurs at 9 GPa and is reversible upon decompression, whereas the second transition occurs at higher pressures and is irreversible. In GaAsO4, EXAFS measurements agree with the predicted transition from four- to six-fold coordination of oxygen atoms around the cations, but the two local coordination transformations are not dissociated; in fact, both As and Ga atoms exhibit a coordination change at the onset of the first phase transition, the rate of transformation being significantly higher for Ga atoms. In both cases, the average bond length increases very rapidly with pressure thus yielding the first compression stage after the transition. In the second stage, the average bond lengths increase slowly, ultimately reaching six-fold coordination above 28 GPa and 24 GPa for As and Ga respectively. The behaviour of the As K-edge EXAFS is the same for both compounds, and enables us to link the behaviour of Ga and Al atoms. The local transformations are well described and a direct link with phosphate berlinites seems timely.Comment: 5 pages, 3 figures, LaTeX2e, J. de Physique (in press