Remarkable electrokinetic features of charge-stratified soft nanoparticles: mobility reversal in monovalent aqueous electrolyte.

The electrokinetic behavior of G6.5 carboxylate-terminated poly(amidoamine) (PAMAM) starburst dendrimers (8 ± 1 nm diameter) is investigated over a broad range of pH values (3-9) and NaNO3 concentrations (c(∞ )= 2-200 mM). The dependence of nanodendrimer electrophoretic mobility µ on pH and c(∞) is marked by an unconventional decrease of the point of zero mobility (PZM) from 5.4 to 5.5 to 3.8 upon increase in salt concentration, with PZM defined as the pH value at which a reversal of the mobility sign is reached. The existence of a common intersection point is further evidenced for series of mobility versus pH curves measured at different NaNO3 concentrations. Using soft particle electrokinetic theory, this remarkable behavior is shown to originate from the zwitterionic functionality of the PAMAM-COOH particles. The dependence of PZM on c(∞) results from the coupling between electroosmotic flow and dendrimeric interphase defined by a nonuniform distribution of amine and carboxylic functional groups. In turn, µ reflects the sign and distribution of particle charges located within an electrokinetically active region, the dimension of which is determined by the Debye length, varied here in the range 0.7-6.8 nm. In agreement with theory, the electrokinetics of smaller G4.5 PAMAM-COOH nanoparticles (5 ± 0.5 nm diameter) further confirms that the PZM is shifted to higher pH with decreasing dendrimer size. Depending on pH, a mobility extremum is obtained under conditions where the Debye length and the particle radius are comparable. This results from changes in particle structure compactness following salt- and pH-mediated modulations of intraparticle Coulombic interactions. The findings solidly evidence the possible occurrence of particle mobility reversal in monovalent salt solution suggested by recent molecular dynamic simulations and anticipated from earlier mean-field electrokinetic theory.

Co-culture of the fungus Fusarium tricinctum with Streptomyces lividans induces production of cryptic naphthoquinone dimers.

Co-cultivation of the endophytic fungus Fusarium tricinctum with Streptomyces lividans on solid rice medium led to the production of four new naphthoquinone dimers, fusatricinones A-D (1-4), and a new lateropyrone derivative, dihydrolateropyrone (5), that were not detected in axenic fungal controls. In addition, four known cryptic compounds, zearalenone (7), (-)-citreoisocoumarin (8), macrocarpon C (9) and 7-hydroxy-2-(2-hydroxypropyl)-5-methylchromone (10), that were likewise undetectable in extracts from fungal controls, were obtained from the co-culture extracts. The known antibiotically active compound lateropyrone (6), the depsipeptides enniatins B (11), B1 (12) and A1 (13), and the lipopeptide fusaristatin A (14), that were present in axenic fungal controls and in co-culture extracts, were upregulated in the latter. The structures of the new compounds were elucidated by 1D and 2D NMR spectra as well as by HRESIMS data. The relative and absolute configuration of dihydrolateropyrone (5) was elucidated by TDDFT-ECD calculations.