Since our discovery of the catalytic reduction of dinitrogen to ammonia at a single molybdenum center, we have embarked on a variety of studies designed to further understand this complex reaction cycle. These include studies of both individual reaction steps and of ligand variations. An important step in the reaction sequence is exchange of ammonia for dinitrogen in neutral molybdenum(III) compounds. We have found that this exchange reaction is first order in dinitrogen and relatively fast (complete in <1 h) at 1 atm of dinitrogen. Variations of the terphenyl substituents in the triamidoamine ligand demonstrate that the original ligand is not unique in its ability to yield successful catalysts. However, complexes that contain sterically less demanding ligands fail to catalyze formation of ammonia from dinitrogen; it is proposed as a consequence of a base-catalyzed decomposition of a diazenido (Mo N NH) intermediate.
Antimicrobial photodynamic inactivation (aPDI) employing the BODIPY-based photosensitizer 2,6-diiodo-1,3,5,7-tetramethyl-8-(N-methyl-4-pyridyl)-4,4′-difluoro-boradiazaindacene (DIMPy-BODIPY) was explored in an in vitro assay against six species of bacteria (eight total strains), three species of yeast, and three viruses as a complementary approach to their current drug-based or non-existent treatments. Our best results achieved a noteworthy 5–6 log unit reduction in CFU at 0.1 μM for Staphylococcus aureus (ATCC-2913), methicillin-resistant S. aureus (ATCC-44), and vancomycin-resistant Enterococcusfaecium (ATCC-2320), a 4–5 log unit reduction for Acinetobacter baumannii ATCC-19606 (0.25 μM), multidrug resistant A. baumannii ATCC-1605 (0.1 μM), Pseudomonas aeruginosa ATCC-97 (0.5 μM), and Klebsiella pneumoniae ATCC-2146 (1 μM), and a 3 log unit reduction for Mycobacterium smegmatis mc2155 (ATCC-700084). A 5 log unit reduction in CFU was observed for Candida albicans ATCC-90028 (1 μM) and Cryptococcus neoformans ATCC-64538 (0.5 μM), and a 3 log unit reduction was noted for Candida glabrata ATCC-15545 (1 μM). Infectivity was reduced by 6 log units in dengue 1 (0.1 μM), by 5 log units (0.5 μM) in vesicular stomatitis virus, and by 2 log units (5 μM) in human adenovirus-5. Overall, the results demonstrate that DIMPy-BODIPY exhibits antiviral, antibacterial and antifungal photodynamic inactivation at nanomolar concentrations and short illumination times.