Inorganic chemistry is a discipline that spans areas ranging from materials chemistry to organic synthesis and on to biochemistry. The Inorganic Division at the University of North Carolina ranks among the top ten nationally and has been a major strength of the Chemistry Department for many decades. Catalysis is a particularly prominent research area at UNC with ongoing activities involving the synthesis of homogeneous polymerization and alkane funciopnalization catalysts, the design of chiral molecules and metal-organic frameworks for asymmetric catalysis, and the exploitation of transition metal complexes in photocatalytic water splitting and carbon dioxide reduction and for applications in biotechnology.
Inorganic materials chemistry is another strength at UNC, with research activities in nanomedicine, solar fuels and photovoltaics, the design of novel materials using transition metal complexes as building blocks. Organometallic synthesis and reactivity studies are also actively pursued at UNC. Graduate students in the Inorganic Division are exposed to an exciting research environment, and a breadth of synthetic methods and characterization techniques, which together provide an excellent foundation for future careers in industry and academia.
The platinum-containing chemotherapeutic cisplatin is the first-line treatment for many types of cancer, but results in a myriad of disparaging dose-limiting side effects, such as nephrotoxicity and neurotoxicity. Nanomaterials have shown great promise in selectively delivering chemotherapeutics to tumors to reduce these side effects and to increase therapeutic indices. As reported in JACS, the Lin Group has developed a novel nanovector platform based on nanoscale metal-organic frameworks, NMOFs, for delivering chemotherapeutics and imaging contrast agents.
NMOFs are materials crafted from metals and organic bridging ligands, and can be engineered to contain reactive functional groups. In this study, the amino groups incorporated into the NMOFs were used to graft optical imaging contrast agents or platinum-containing chemotherapeutics. These modified NMOFs were coated in silica to reduce premature release of imaging contrast agents or chemotherapeutics before arriving at the tumor sites. Preliminary in vitro tests showed that these NMOFs could effectively cause cell death in human colon cancer cell cultures with an efficacy similar to cisplatin. The Lin Group hopes to further modify this strategy to deliver other cancer drugs and imaging contrast agents.
Gold salts, once thought to be a catalytic wasteland, have shown great promise for the electrophilic activation of carbon-carbon unsaturation. Members of the Gagné Group have capitalized on this reactivity by using allenes to initiatiate cyclization cascades that produce carbocycles and heterocycles, for example, the polyether natural product-like scaffolds shown below.
As reported in Angewandte Chemie, mechanistic analysis of an allene hydroarylation reaction indicates a surprisingly more complex process than originally envisioned, with the catalyst actually resting as a 3-centered, 2-electron intermediate with a weak Au---Au interaction.
Highly Porous and Stable Metal–Organic Frameworks for Uranium Extraction. Michael Carboni, Carter W. Abney, Shubin Liu and Wenbin Lin. Chem. Sci., 2013,4, 2396-2402.
A Sensitized Nb2O5 Photoanode for Hydrogen Production in a Dye-Sensitized Photoelectrosynthesis Cell. Hanlin Luo, Wenjing Song, Paul G. Hoertz, Kenneth Hanson, Rudresh Ghosh, Sylvie Rangan, M. Kyle Brennaman, Javier J. Concepcion, Robert A. Binstead, Robert Allen Bartynski, Rene Lopez, and Thomas J. Meyer. Chem. Mater., 2013, 25 (2), pp 122–131.
Tunable Energy Transfer Rates via Control of Primary, Secondary, and Tertiary Structure of a Coiled Coil Peptide Scaffold. Dale J. Wilger, Stephanie E. Bettis, Christopher K. Materese, Maria Minakova, Garegin A. Papoian, John M. Papanikolas, and Marcey L. Waters. Inorg. Chem., 2012, 51 (21), pp 11324–11338.
Photoinduced Electron Transfer in a Chromophore–Catalyst Assembly Anchored to TiO2. Dennis L. Ashford, Wenjing Song, Javier J. Concepcion, Christopher R. K. Glasson, M. Kyle Brennaman, Michael R. Norris, Zhen Fang, Joseph L. Templeton, and Thomas J. Meyer. J. Am. Chem. Soc., 2012, 134 (46), pp 19189–19198.
Synthesis of p-Xylene from Ethylene. Thomas W. Lyons, Damien Guironnet, Michael Findlater, and Maurice Brookhart. J. Am. Chem. Soc., 2012, 134 (38), pp 15708–15711.
A High Connectivity Metal–Organic Framework with Exceptional Hydrogen and Methane Uptake Capacities. Demin Liu, Haohan Wu, Shunzhi Wang, Zhigang Xie, Jing Li and Wenbin Lin . Analytical and Bioanalytical Chemistry, January 2012, Volume 402, Issue 3, pp 1065-1072.
Zr- and Hf-based Nanoscale Metal–Organic Frameworks as Contrast Agents for Computed Tomography. Kathryn deKrafft, William Boyle, Laurel Burk, Otto Zhou, and Wenbin Lin. J. Mater. Chem., 2012,22, 18139-18144.
Cavity-Induced Enantioselectivity Reversal in a Chiral Metal–Organic Framework Brønsted Acid Catalyst. Min Zheng, Yan Liu, Cheng Wang, Shubin Liu and Wenbin Lin. Chem. Sci., 2012,3, 2623-2627.
A Chiral Porous Metal–Organic Framework for Highly Sensitive and Enantioselective Fluorescence Sensing of Amino Alcohols. Marcela M. Wanderley, Cheng Wang, Chuan-De Wu, and Wenbin Lin. J. Am. Chem. Soc., 2012, 134 (22), pp 9050–9053.
Pt Nanoparticles@Photoactive Metal–Organic Frameworks: Efficient Hydrogen Evolution via Synergistic Photoexcitation and Electron Injection. Cheng Wang, Kathryn E. deKrafft, and Wenbin Lin. J. Am. Chem. Soc., 2012, 134 (17), pp 7211–7214.