This paper describes the heterogenization of single-site transition-metal catalysts in metal-organic frameworks (MOFs) via cation exchange. A variety of cationic complexes of Pd, Fe, Ir, Rh, and Ru have been incorporated into ZJU-28, and the new materials have been characterized by optical microscopy, inductively coupled plasma optical emission spectroscopy, and powder X-ray diffraction. MOF-supported [Rh(dppe)(COD)]BF4 catalyzes the hydrogenation of 1-octene to n-octane. The activity of this supported catalyst compares favorably to its homogeneous counterpart, and it can be recycled at least four times. Overall, this work provides a new and general approach for supporting transition-metal catalysts in MOFs.
Nanoscale metal organic frameworks offer unique advantages for the development of materials for solar energy conversion systems, supercapacitors, batteries and fuel cells.
We recently reported that two artemisinin-derived dimers (dimer primary alcohol 606 and dimer sulfone 4-carbamate 832-4) are significantly more potent in inhibiting human cytomegalovirus (CMV) replication than artemisinin-derived monomers. In our continued evaluation of the activities of artemisinins in CMV inhibition, twelve artemisinin-derived dimers and five artemisinin-derived monomers were used. Dimers as a group were found to be potent inhibitors of CMV replication. Comparison of CMV inhibition and the slope parameter of dimers and monomers suggest that dimers are distinct in their anti-CMV activities. A deoxy dimer (574), lacking the endoperoxide bridge, did not have any effect on CMV replication, suggesting a role for the endoperoxide bridge in CMV inhibition. Differences in anti-CMV activity were observed among three structural analogs of dimer sulfone 4-carbamate 832-4 indicating that the exact placement and oxidation state of the sulfur atom may contribute to its anti-CMV activity. Of all tested dimers, artemisinin-derived diphenyl phosphate dimer 838 proved to be the most potent inhibitor of CMV replication, with a selectivity index of approximately 1500, compared to our previously reported dimer sulfone 4-carbamate 832-4 with a selectivity index of about 900. Diphenyl phosphate dimer 838 was highly active against a Ganciclovir-resistant CMV strain and was also the most active dimer in inhibition of cancer cell growth. Thus, diphenyl phosphate dimer 838 may represent a lead for development of a highly potent and safe anti-CMV compound.
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