A comprehensive review on metal based active sites and their interaction with O3 during heterogeneous catalytic ozonation process: Types, regulation and authentication.

Heterogeneous catalytic ozonation (HCO) was a promising water purification technology. Designing novel metal-based catalysts and exploring their structural-activity relationship continued to be a hot topic in HCO. Herein, we reviewed the recent development of metal-based catalysts (including monometallic and polymetallic catalysts) in HCO. Regulation of metal based active sites (surface hydroxyl groups, Lewis acid sites, metal redox cycle and surface defect) and their key roles in activating O3 were explored. Advantage and disadvantage of conventional characterization techniques on monitoring metal active sites were claimed. In situ electrochemical characterization and DFT simulation were recommended as supplement to reveal the metal active species. Though the ambiguous interfacial behaviors of O3 at these active sites, the existence of interfacial electron migration was beyond doubt. The reported metal-based catalysts mainly served as electron donator for O3, which resulted in the accumulation of oxidized metal and reduced their activity. Design of polymetallic catalysts could accelerate the interfacial electron migration, but they still faced with the dilemma of sluggish Me(n+m)+/Men+ redox cycle. Alternative strategies like coupling active metal species with mesoporous silicon materials, regulating surface hydrophobic/hydrophilic properties, polaring surface electron distribution, coupling HCO process with photocatalysis and H2O2 were proposed for future research.

Synthesis, conjugating capacity and biocompatibility evaluation of a novel amphiphilic polynorbornene.

Polynorbornenes, prepared by the 'living' and 'controlled' ring-opening metathesis polymerization (ROMP) method, have emerged as a stimuli-sensitive new class of polymer carriers. Herein, we reported a novel amphiphilic diblock polynorbornene, PNCHO-b-PNTEG, containing active benzaldehyde units, which exhibited good conjugating capacity to amino-containing molecules (e.g., doxorubicin (DOX)) via the pH-sensitive Schiff base linkage. The copolymer and its conjugate with DOX, DOX-PNCHO-b-PNTEG, were adequately analyzed by various techniques including 1H NMR, 13C NMR, gel permeation chromatography, etc. Especially, the formed conjugate of DOX-PNCHO-b-PNTEG could self-assemble into near-spherical micelles with the diameter of 81 ± 10 nm, and exhibit acid-triggered DOX release behavior, and the release rate could be adjusted by changing the environmental pH value. The excellent biological safety of PNCHO-b-PNTEG was further demonstrated by the results from both in vitro toxicity evaluation to murine fibroblast cells (L-929 cells) and in vivo evaluation of acute developmental toxicity and cell death in zebrafish embryos. Hence, the present polynorbornene-based PNCHO-b-PNTEG possesses great potential application as a biocompatible polymeric carrier and could be employed to fabricate various pH-sensitive conjugates.