Preparation of Constrained Unnatural Aromatic Amino Acids via Unsaturated Diketopiperazine Intermediate

Unnatural aromatic amino acids are useful tools in drug discovery, since their insertion in bioactive peptide sequences can change the side chains spatial orientation, the backbone conformation and above all, their bioactivity. In this communication, we propose a straightforward method to synthesize 2′,6′‐dimethyl‐tyrosine and 2′,6′‐dimehylphenyl‐alanine derivatives as handling building blocks for peptide synthesis via unsaturated diketopiperazine (DKP) intermediate.     

Characterization of some causality conditions through the continuity of the Lorentzian distance

A classical result in Lorentzian geometry states that a strongly causal spacetime is globally hyperbolic if and only if the Lorentzian distance is finite valued for every metric choice in the conformal class. It is proved here that a non-total imprisoning spacetime is globally hyperbolic if and only if for every metric choice in the conformal class the Lorentzian distance is continuous. Moreover, it is proved that a non-total imprisoning spacetime is causally simple if and only if for every metric choice in the conformal class the Lorentzian distance is continuous wherever it vanishes. Finally, a strongly causal spacetime is causally continuous if and only if there is at least one metric in the conformal class such that the Lorentzian distance is continuous wherever it vanishes.     

Non-equilibrium vibrational kinetics and ‘hot atom'' models in the recombination of hydrogen atoms on surfaces

Non-equilibrium vibrational kinetics as recently developed for adlayers is applied to experimental data on H-atom recombination and abstraction at solid surfaces. This model allows one to fit vibrational and translational energy distribution functions of the excited diatoms leaving the surface. Eley–Rideal and Langmuir–Hinshelwood mechanisms involving vibrationally excited adatoms are presented together with a criterion for establishing their relative contribution to the total reaction rate. Analogies of this multilevel ‘hot atom' (HA) model with recently employed two and three levels HA kinetic schemes are presented and discussed.     

Laser Nitriding of Iron,Stainless Steel,and Plain Carbon Steel Investigated by Mössbauer Spectroscopy

Nitriding is a common method for improving the hardness, mechanical properties, wear and corrosion resistance of metals. Laser nitriding of metals is an efficient process, where the irradiation of surfaces in air or nitrogen atmospheres with short laser pulses leads to a fast take-up of nitrogen into the irradiated surfaces. This process has been extensively investigated for pure iron, but usually, no tools or functional parts are made of pure iron. Mainly steel or cast iron is used as a base material. Therefore, when looking for technical applicability, also the influence of alloying elements on the laser nitriding process is of great interest. Besides the pure iron various carbon steels and an austenitic stainless steel were studied in laser nitriding experiments in order to investigate the influence of the material itself. Here, the process is investigated via Conversion Electron and X-ray Mössbauer Spectroscopy (CEMS and CXMS), Resonant Nuclear Reaction Analysis (RNRA), and X-Ray Diffraction (XRD). It appears that carbon steels are even better suited for the laser nitriding process than pure iron, and the laser nitriding also works efficiently for the stainless steel which is normally difficult to be nitrided.     

Electrochemistry and electrochemiluminescence of [Ru(II)-tris(bathophenanthroline-disulfonate)]4- in aprotic conditions and aqueous buffers

In this work, the electrochemical and ECL properties of tris[1,10-phenanthrolinediyl-4,7-di(benzenesulfonate)]Ru(II) ([Ru(BPS)3]4-) have been addressed in both strictly aprotic conditions and aqueous buffers. A combined theoretical and experimental approach is presented to focus thermodynamics and kinetic effects of electro-generated species possessing highly negative charge. The complex, prepared as the sodium salt by using a newly developed procedure, was subsequently converted to the tetrabutylammonium salt by ion exchange, thus making it soluble in organic media and allowing, for the first time, its thorough electrochemical investigation in ultra-dry aprotic media. The electrochemically induced luminescence (ECL) of Na 4[Ru(BPS)3] in phosphate buffer, using the co-reactant method (tripropylamine), was investigated as a function of the electrode material and halide addition, and ECL intensities six times higher than that of [Ru(bpy)3]2+ were found. In addition, the ECL behavior of this promising dye for biomolecule recognition was investigated in aprotic media and, for the first time, the direct radical anion-radical cation annihilation ECL was obtained.     

How Does CuII Convert into CuI? An Unexpected Ring‐Mediated Single‐Electron Reduction

Cu(x)O (x=1,2) nanomaterials with tailored composition and properties-a hot topic in sustainable technologies-may be fabricated from molecular sources through bottom-up processes that involve unexpected changes in the metal oxidation state and open intriguing challenges on the copper redox chemistry. How copper(II) sources may lead to copper(I) species in spite of the absence of any explicit reducing agent, and even in the presence of oxygen, is one such question-to date unanswered. Herein, we study copper "reduction without reductants" within one molecule and reveal that the actual reducing agent is abstracted atomic hydrogen. By investigating the fragmentation of a copper(II) precursor for copper oxide nanostructures by combined ESI-MS with multiple collisional experiments (ESI/MS(n)) and theoretical calculations, we highlight a copper-promoted C-H bond activation, leading to reduction of the metal center and formation of a Cu(I)-C-NCCN six-membered ring. Such a novel ring system is the structural motif for a new family of cyclic copper(I) adducts, which show a bonding scheme, herein reported for the first time, that may shed unprecedented light on copper chemistry. Beyond the relevance for the preparation of copper oxide nanostructures, the hydrogen-abstraction/proton-delivery/electron-gain mechanism of copper(II) reduction disclosed herein appears to be a general property of copper and might help to understand its redox reactivity.     

Mild and reversible dehydration of primary amides with PdCl2 in aqueous acetonitrile

[reaction: see text] A new, mild, and reversible method to convert primary amides to nitriles in good yields using PdCl2 in aqueous acetonitrile is described.