New insights in polydopamine formation via surface adsorption

Polydopamine is a biomimetic self-adherent polymer, which can be easily deposited on a wide variety of materials. Despite the rapidly increasing interest in polydopamine-based coatings, the polymerization mechanism and the key intermediate species formed during the deposition process are still controversial. Herein, we report a systematic investigation of polydopamine formation on halloysite nanotubes; the negative charge and high surface area of halloysite nanotubes favour the capture of intermediates that are involved in polydopamine formation and decelerate the kinetics of the process, to unravel the various polymerization steps. Data from X-ray photoelectron and solid-state nuclear magnetic resonance spectroscopies demonstrate that in the initial stage of polydopamine deposition, oxidative coupling reaction of the dopaminechrome molecules is the main reaction pathway that leads to formation of polycatecholamine oligomers as an intermediate and the post cyclization of the linear oligomers occurs subsequently. Furthermore, Tris molecules are incorporated into the initially formed oligomers.

Subnanometric Cu Clusters on Atomically Fe-doped MoO2 for Furfural Upgrading to Aviation Biofuels

Single cluster catalysts (SCCs) are considered as versatile boosters in heterogeneous catalysis due to their modifiable single cluster sites and supports. In this work, we report subnanometric Cu clusters dispersed on Fe-doped MoO2 support for biomass-derived furfural upgrading. Systematical characterizations suggest uniform Cu clusters (composing four Cu atoms in average) are homogeneously immobilized on the atomically Fe-doped ultrafine MoO2 nanocrystals (Cu4/Fe0.3Mo0.7O2@C). The atomic doping of Fe into MoO2 leads to significantly modified electronic structure and consequently charge redistribution inside the supported Cu clusters. The as-prepared Cu4/Fe0.3Mo0.7O2@C shows superior catalytic performance in the oxidative coupling of furfural with C3~C10 primary/secondary alcohols to produce C8~C15 aldehydes/ketones (aviation biofuel intermediates), outperforming the conventionally prepared counterparts. DFT calculations and control experiments are further carried out to interpret the structural and compositional merits of Cu4/Fe0.3Mo0.7O2@C in the oxidative coupling reaction, and elucidate the reaction pathway and related intermediates.

New Spectrophotometric Methods for Estimation of Diosmin in Pharmaceutical Formulations Using Batch and FIA Systems

A new attempt is made to determine diosmin (DIO) in its pure form and in dietary supplements by using spectrophotometric flow injection analysis (FIA) assay method conjugated with batch method. The analysis was achieved depending on the oxidative coupling reaction with N, N-dimethyl-p-phenylenediamine (DMPD) to form a green dye which is measured at wavelength of 677 nm. The tested methods were found to be economical, delicate, precise and sturdy. The validation variables of the batch and FIA methods gave linearity in the determination range of DIO (1-35) μg/mL and (5-120) μg/mL demonstrated calibration graphs with linearity coefficient values of r2 =0.9989 and r2 =0.9991, respectively. Limits of quantitation (LOQ) values were found to be (0.8463 and 1.022) μg/mL, while limits of detection (LOD) were (0.2539 and 0.3067) µg/mL for the two methods, respectively. The precision for the developed methods denoted by relative standard deviation (RSD %), were 0.386 and 0.55 %, while the accuracy based on recovery values (Rec %) were 100.273 and 100.24, respectively. The relative error (RE %) was less than 1% for the batch method and (1.1%) for the FIA method. The values of these parameters were observed to fall within the specified accepted limits; therefore, the tested methods seem to be adequate for the analysis of DIO in pharmaceutical preparations.