Molecular and electronic structure of zwitterionic diamino-meta-quinonoid molecules

Quantum chemical calculations using molecular orbital (HF, CASSCF) and density functional theory (B3LYP) methods, in conjunction with the 6–311 + + G(d,p) basis set, have been applied to investigate the molecular and electronic structure of two diamino-meta-quinonoid molecules 1a and 2a, each containing a six-membered ring coupled with two exocyclic C = O bonds situated in a meta position, along with two amino substituents (NH₂ and NH-CH₃). It is confirmed that these substituted meta-quinone systems exhibit a zwitterionic structure in which the positively charged N-C-C(H)-C-N subunit, containing the two amino-groups, forms two chemical bonds with the negatively charged O-C-C(H)-C-O subunit. The negative charge amounts to about half of an electron. The charge separation has been approached in terms of geometries, vibrational frequencies, and electronic distribution. The ionization energy for molecule 1a is about 7.8±0.3eV. The quinonoid systems are essentially non-aromatic characterized by the NICS(+1) values of around 1.2 ppm.     

Selective Removal of the Tert-Butoxycarbonyl Group from Secondary Amines: ZnBr2 as the Deprotecting Reagent

ZnBr₂ in dichloromethane is a convenient reagent for mild and selective removal of the tert-butoxycarbonyl group from secondary amines.     

pH‐Responsive Relaxometric Behaviour of Coordination Polymer Nanoparticles Made of a Stable Macrocyclic Gadolinium Chelate

Lanthanide‐containing nanoscale particles have been widely explored for various biomedical purposes, however, they are often prone to metal leaching. Here we have created a new coordination polymer (CP) by applying, for the first time, a stable Gd^III chelate as building block in order to prevent any fortuitous release of free lanthanide(III) ion. The use of the Gd‐DOTA‐4AmP complex as a design element in the CP allows not only for enhanced relaxometric properties (maximum r₁=16.4 mm ^?1 s^?1 at 10 MHz), but also for a pH responsiveness (Δr₁=108 % between pH 4 and 6.5), beyond the values obtained for the low molecular weight Gd‐DOTA‐4AmP itself. The CP can be miniaturised to the nanoscale to form colloids that are stable in physiological saline solution and in cell culture media and does not show cytotoxicity.     

Behaviour of tyres in fire

Journal of Thermal Analysis and Calorimetry - The increasing numbers of used tyres constitute a serious threat to the natural environment. The progress made in recent years in the management of...