Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P3N5, δ-P3N5 and PN2

Non-metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN₆ octahedra frameworks being particularly attractive. In this study, the phosphorus–nitrogen system was studied up to 137 GPa in laser-heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single-crystal X-ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ-P₃N₅ and PN₂ were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN₆ units. The two compounds are ultra-incompressible, having a bulk modulus of K₀=322 GPa for δ-P₃N₅ and 339 GPa for PN₂. Upon decompression below 7 GPa, δ-P₃N₅ undergoes a transformation into a novel α′-P₃N₅ solid, stable at ambient conditions, that has a unique structure type based on PN₄ tetrahedra. The formation of α′-P₃N₅ underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure.     

Novel stereocontrolled addition of allylmetal reagents to alpha-imino esters: efficient synthesis of chiral tetrahydroquinoline derivatives

To prepare in multigram scale new antagonists of the glycine binding site associated to the NMDA receptor, an efficient distereoselective route was set up. The addition of suitable allyltin reagents to chiral N-aryl alpha-imino esters (R-(+)-tert-butyl lactate used as chiral auxiliary), gave the corresponding alpha amino acid-type derivative in high chemical yield and optical purity. This allylation reaction represents a novel example of efficient long-range stereodifferentiation process. In the last part of the synthesis, a regioselective Heck-type cyclization reaction enabled preparation of the target tetrasubstituted exocycle and trisubtituted endocycle double bond derivatives.     

Influence of Cyclodextrins on the Kinetics of Oxidation of Amino Acids and BSA by Hydrazyl Radicals

The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin.     

Stability in the Rotating Bénard Problem and Its Optimal Lyapunov Functions

Stability analysis of the rotating Bénard problem gives a spectral instability threshold of the purely conducting solution that can be expressed as a critical Rayleigh number R ² depending on the Taylor number T ². The definition of a functional which can be used to prove Lyapunov stability up to the threshold of spectral instability (optimal Lyapunov function) is an important step forward both, for a proof of nonlinear stability and for the investigation of the basin of attraction of the equilibrium. In previous works a Lyapunov function was found, but its optimality could be proven only for small T ². In this work we describe the reason why this happens, and provide a weaker definition of Lyapunov function which allows to prove that, for the linearized system, the spectral instability threshold is also the Lyapunov stability threshold for every value of T ².     

The microscopic investigation of structures of moving flux lines by neutron and muon techniques

We have used a variety of microscopic techniques to reveal the structure and motion of flux line arrangements, when the flux lines in low T _c type II superconductors are caused to move by a transport current. Using small-angle neutron scattering by the flux line lattice (FLL), we are able to demonstrate directly the alignment by motion of the nearest-neighbor FLL direction. This tends to be parallel to the direction of flux line motion, as had been suspected from two-dimensional simulations. We also see the destruction of the ordered FLL by plastic flow and the bending of flux lines. Another technique that our collaboration has employed is the direct measurement of flux line motion, using the ultra-high-resolution spectroscopy of the neutron spin-echo technique to observe the energy change of neutrons diffracted by moving flux lines. The muon spin rotation (μSR) technique gives the distribution of values of magnetic field within the FLL. We have recently succeeded in performing μSR measurements while the FLL is moving. Such measurements give complementary information about the local speed and orientation of the FLL motion. We conclude by discussing the possible application of this technique to thin film superconductors.     

The ultraviolet spectra of the chloropyridines and chlorinated pyridines possessing a sulfur (-SR), nitrogen (-NR2), or oxygen (-OR) substituent in either the 2 or 4-position: A convenient method for distinguishing such positional isomers

The ultraviolet spectra for a series of 15 chlorinated pyridines which contain a sulfur, nitrogen or an oxygen substituent at either the 2 or 4-position have been examined. A correlation has been established between the position (2 vs 4) of the S, N, or O substituent on the chlorinated pyridines and their ultraviolet spectra. It was found that the chlorinated pyridines with S, N, or O substitution at the 2-position gave ultraviolet spectra whose longest wavelength absorption maxima were enhanced (moved to a greater wavelength and an increased extinction coefficient) when compared to the spectra of the 4-substituted isomers. The difference is great enough so that an easy identification of positional isomers can be made with a relatively high degree of confidence even when only one positional isomer is available. The ultraviolet spectra of all the chlorinated pyridines has been recorded, and it was observed that the number of chlorine atoms, and not their position, was the more significant factor in determining the overall character of the spectra.     

Novel developments for the production of 6APA in the penicillin g fermentation plant by using fiber-entrapped penicillin amidase

The production of 6APA by enzymatic hydrolysis of penicillin G can be integrated with the production of penicillin G. The penicillin G solutions obtained during the extraction from the fermented broth can be directly hydrolyzed to 6APA and phenyl acetic acid. The 6APA is then recovered while the phenyl acetic acid can also be recovered and recycled to the fermentation plant. Some of the results obtained by the research work performed by SNAM Progetti in their Microbiological Laboratories with the advice of Biochem Design are presented and analyzed. The economic potential of the integrated process is discussed.