A simple,efficient, regioselective and one-pot preparation of N-hydroxy- and N–O-protected hydroxyindoles via cycloaddition of nitrosoarenes with alkynes. Synthetic scope,applications and novel by-products

The thermal reaction between nitrosoarenes and alkynes under alkylating conditions produces N-alkoxyindoles as the major products in moderate to good yields and excellent regioselectivity. Various electrophiles are used affording different N–O-protected hydroxyindoles in a multi-component fashion. Privileged acetylenic substrates used in reactions with substituted nitrosoarenes are arylalkynes or propiolates. Potentially bioactive compounds and other classes of highly functionalizable indole products were prepared. Reactions between o-carbomethoxy-nitrosoarenes and arylacetylenes provided tricyclic compounds containing an acylaziridine indoline skeleton.     

A fast-neutron coincidence collar using liquid scintillators for fresh fuel verification

Journal of Radioanalytical and Nuclear Chemistry - The IAEA has developed a liquid scintillator-based system for the non-destructive assay of 235U in fresh fuel assemblies. The fast neutron...     

A damage constitutive model for sliding friction coupled to wear

Several new constitutive models are formulated for the planar interface of a soft body sliding on a rigid soil, describing stick-slip phenomena due to friction, and wear due to abrasion. Attention is focused on damage at the interface, by neglecting any interaction with damage of body and any propagation of damage inside the body. Models are formulated in the general framework of the Thermodynamics of the irreversible processes and account for suitable defined internal variables of phenomenological type, namely gap, isotropic friction hardening and wear. The main feature of the new presented models is that the formulation of the wear process at the interface is obtained in the contest of Damage Mechanics, and it is based on the formal analogy between abrasion of a soft body and ductile damage of an elastic-plastic material. By following this approach, a scalar wear field, an effective stress and appropriate state and dissipation potentials are defined, able to describe a tangential isotropic wear process due to stick-slip and to hardening mechanism. Both cases of linear and nonlinear friction hardening are formulated; moreover, wearable and no-wearable bodies are considered. Numerical results relevant to one-dimensional problems are illustrated for monotonic, forward-backward and cyclic displacement time-histories, showing evolution for stress, gap and wear. Results furnished by different models are compared and discussed.     

Unconventional stereoselective one-pot synthesis of Knoevenagel-type indoles via in situ condensation of iminium salts with active methylene reagents

A simple one-pot procedure for the stereoselective synthesis of Knoevenagel-type indoles is described. The method is based on the in situ reaction of indole iminium salts (four of them are fully characterized) with acyclic symmetrical and unsymmetrical active methylene reagents in the presence of triethylamine. In general, the overall yields are moderate to good. Some of relevant reaction parameters and steric effects affecting stereoselectivity are discussed.     

Potassium Exchanged Layered Zirconium Phosphate as Base Catalyst for the Desilylation of Phenol Silyl Ethers

Layered zirconium hydrogen phosphonate exchanged with the potassium ion was found to be an efficient heterogeneous catalyst for the hydrolysis of sterically hindered phenolic silyl ethers.     

Modified Guanines as Constituents of Smart Ligands for Nucleic Acid Quadruplexes

Repetitive guanine‐rich nucleic acid sequences play a crucial role in maintaining genome stability and the cell life cycle and represent potential targets for regulatory drugs. Recently, it has been demonstrated that guanine‐based ligands with a porphyrin core can be used as markers of G‐quadruplex assemblies in cell tissues. Herein, model systems of guanine‐based ligands are explored by DFT methods. The energies of formation of modified guanine tetrads and those of modified tetrads stacked on the top of natural guanine tetrads have been calculated. The interaction energy has been decomposed into contributions from hydrogen bonding, stacking, and ion coordination and a twist–rise potential energy scan has been performed to find the individual local minima. Energy decomposition analysis reveals the impact of various substituents (F, Cl, Br, I, Me, NMe₂) on individual energy terms. In addition, cooperative reinforcement in forming the modified and stacked tetrads, as well as the frontier orbitals participating in the hydrogen‐bonding framework involving the HOMO–LUMO gap between the occupied σ_HOMO on the proton‐accepting C=O and =N? groups and unoccupied σ_LUMO on the N?H groups, has been studied. The investigated systems are demonstrated to have a potential in ligand development, mainly due to stacking enhancement compared with natural guanine, which is used as a reference.