Cocatalysis in Cationic Polymerization

Problems concerned with the principles of cocatalysis and coinitiation as a part of cationic polymerization are discussed. When the established concept of different reactive particles, i.e., contact and separated ion-pairs or free ions, is applied to cationic initiation and propagation centers, then common features for one general process can be drawn even in so diverse cases as “pseudocationic” polymerization, solvent “cocatalysis,” polymerization during condensation and induced by co-monomer addition. A special case of activation by solvent is “cocatalysis” by water.

The model for these cases was found during the interpretation of waves observed on styrene polymerization curves. The formation of ion-pairs proceeds spontaneously. The activation and deactivation of these ion-pairs is effected via coordination of suitable molecules with the former, i.e., by equilibrium shifts     

How To Reach Intense Luminescence for Compounds Capable of Excited‐State Intramolecular Proton Transfer?

Photoinduced intramolecular direct arylation allows structurally unique compounds containing phenanthro[9′,10′:4,5]imidazo[1,2‐f]phenanthridine and imidazo[1,2‐f]phenanthridine skeletons, which mediate excited‐state intramolecular proton transfer (ESIPT), to be efficiently synthesized. The developed polycyclic aromatics demonstrate that the combination of five‐membered ring structures with a rigid arrangement between a proton donor and a proton acceptor provides a means for attaining large fluorescence quantum yields, exceeding 0.5, even in protic solvents. Steady‐state and time‐resolved UV/Vis spectroscopy reveals that, upon photoexcitation, the prepared protic heteroaromatics undergo ESIPT, converting them efficiently into their excited‐state keto tautomers, which have lifetimes ranging from about 5 to 10 ns. The rigidity of their structures, which suppresses nonradiative decay pathways, is believed to be the underlying reason for the nanosecond lifetimes of these singlet excited states and the observed high fluorescence quantum yields. Hydrogen bonding with protic solvents does not interfere with the excited‐state dynamics and, as a result, there is no difference between the occurrences of ESIPT processes in MeOH versus cyclohexane. Acidic media has a more dramatic effect on suppressing ESIPT by protonating the proton acceptor. As a result, in the presence of an acid, a larger proportion of the fluorescence of ESIPT‐capable compounds originates from their enol excited states.     

Synthesis of 2-alkenyl-3-hydroxyquinolin-4(1H)-ones as promising antimicrobial and fluorescent agents

2-Alkenyl-3-hydroxyquinolin-4(1H)-ones were prepared by the rearrangement of anthranilic acid esters synthesized by two alternative methods. The prepared derivatives were screened for their antimicrobial activities against representative Gram-positive and Gram-negative bacteria, displaying notable minimum inhibitory concentration values against specific strains. The emission spectra of the target quinolines exhibited two well-separated emission bands, and the maximum excitation wavelengths of the selected compounds were detected at relatively high values.     

Absorption of ammonia in the melt of ammonium nitrate

The paper deals with the absorption of ammonia in a model fertilizer of ammonium nitrate. Volumetric overall mass transfer coefficient quantitatively characterizing the process was estimated on the basis of experimental data and kinetics modeling. The volumetric overall mass transfer coefficient depends on the temperature, content of water in the fertilizer and hydrodynamic conditions. Different hydrodynamic conditions were simulated by different speeds of the propeller stirrer. The empirical equation describing the volumetric overall mass transfer coefficient was proposed.