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Draft:Robert D. Hancock

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Robert D. Hancock was born in Fort Beaufort South Arica on May 27 1944. He is a South African - American Inorganic Chemist, who is currently a Professor in the Department of Chemistry and Biochemistry at the University of North Carolina Wilmington.

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Education and Career.

Hancock attended high school at St. Andrews College in Grahamstown South Africa and obtained his B.Sc. (Hons) degree at Rhodes University there followed by a Ph.D in Inorganic Chemistry at the University of Cape Town in 1969. He spent a post-doctoral year at Oxford University in 1972 working with Francis Rossotti and Courtenay Phillips. He worked at the National Institute of Metallurgy in Johannesburg from 1970 to 1980, researching ligand design for applications in hydrometallurgy. In 1980 he moved to the University of the Witwatersrand, where he became the Professor of Inorganic Chemistry. In 1994 he moved to the United States and spent some time at Texas A&M University working with Professor A. E. Martell. In 2002 he was appointed as the de Loach Distinguished Professor of Chemistry in the Department of Chemistry of the University of North Carolina Wilmington, where he continues today as a professor after his ten-year term as a Distinguished Professor finished.

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Research Interests.

Hancock’s research career spanning over fifty years has focused almost entirely on ligand design for the selective complexation of metal ions in aqueous solution. His first finding was the effect of chelate ring size on metal ion selectivity: 5-membered chelate rings favor large metal ions (ionic radius ≥ 0.9 Å) while 6-membered chelate rings favor small metal ions (ionic radius < 0.9 Å).[1][2][3][4] This observation accounts for the selectivity patterns displayed by tetra-aza macrocycles, which are not explicable at all in terms of the idea that hole-sizes in the macrocycles account for the observed metal ion selectivities. His second significant idea was that of archetypal ligands: thus log K1 for all nitrogen donor ligands such as polyamines or polypyridyls relate directly to log K1 for NH3, the archetypal nitrogen donor ligand, while log K1 for all negatively charged oxygen donor ligands such as oxalate or citrate relate directly to that of the archetypal OH- ligand.[5][6] The effect of the neutral oxygen donor, in the form of alcoholic, ethereal, or amide donors, on log K1 for ligands was found to be that neutral oxygen donors raise log K1 for large metal ions and depress log K1 for small metal ions. [7][8] The crown ethers and cryptands are thus extreme examples of the effect of neutral oxygen donors on metal ion selectivity, and again hole sizes play only a small part in their selectivity patterns. Recently he has focused on the design of ligands to act as fluorescent sensors[9] and on f-block chemistry.[10][9] The amide donor ligand DOTAM first synthesized and designed by Hancock and coworkers[7] is currently in wide use in theragnostic applications. He is the author of 260 peer-reviewed papers and a book co-authored with A. E. Martell: “Metal Complexes in Aqueous Solutions”, Plenum, 1996.

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Personal Life.

Hancock married Roslyn B. van der Riet in Port Elizabeth South Africa, in 1969 and has two sons. He currently lives with his wife in Wilmington North Carolina.




References

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  1. ^ Thom, Vivienne J.; Fox, Christine C.; Boeyens, Jan C. A.; Hancock, Robert D. (1984). "Molecular Mechanics and Crystallographic Study of Hole Sizes in Nitrogen donor Tetraaza Macrocycles". Journal of the American Chemical Society. 106 (20): 5947–5955 – via American Chemical Society.
  2. ^ Hancock, Robert D. (1992). "Chelate Ring Size and Metal Ion Selection. The Basis of Selectivity for Metal Ions in Open-Chained Ligands and Macrocyles". Journal of Chemical Education. 69 (8): 615–621 – via American Chemical Society.
  3. ^ Hancock, Robert D. (1990). "Molecular Mechanics Calculations and Metal Ion Recognition". Accounts of Chemical Research. 23 (8): 253–257 – via American Chemical Society.
  4. ^ Thom, Vivienne J.; Hosken, Gladys D.; Hancock, Robert D. (1985). "Anomalous Metal Ion Size Selectivity of Tetra-aza Macrocycles". Inorganic Chemistry. 24 (21): 3378–3381 – via American Chemical Society.
  5. ^ Hancock, Robert D. (1991). "Some Correlations Involving the Stability of Complexes of Transuranium Metal Ions and Ligands with Negatively Charged Oxygen Donors". Inorganica Chemica Acta. 182 (2): 229–232 – via Elsevier Science Direct.
  6. ^ Hancock, Robert D. (1989). "Ligand Design for Selective Complexation of Metal Ions in Aqueous Solution". Chemical Reviews. 89 (8): 1875–1914 – via American Chemical Society.
  7. ^ a b Hancock, Robert D.; Mamuela, Hulisani; de Sousa, Alvaro S. (1996). "Macrocyclic Ligands with Pendant Amide and Alcoholic Oxygen Donor Groups". Coordination Chemistry Reviews. 148 (-): 315–347 – via Elsevier Science Direct.
  8. ^ Mamuela, Hulisani; Hancock, Robert D. (1995). "The Amide Oxygen as a Donor Group. Metal Complexing Properties of tetra-N-acetamide substituted Cyclen - A Crystallographic, NMR, Molecular Mechanics, and Thermodynamic Study". Journal of American Chemical Society. 117 (25): 6698–6707 – via American Chemical Society.
  9. ^ a b Hancock, Robert D. (2013). "The pyridyl group in ligand design for selective metal ion complexation and sensing". Chemical Society Reviews. 42 (4): 1500–1524 – via Royal Society of Chemistry.
  10. ^ Hancock, Robert D.; Nikolayenko, Igor V.; Jones, S. Bart; Lee, Hee-Seung; Skerkis, Rachel E.; Littmann, Galen C.; Grimmer, Craig D. (2025). "The Weakly Basic Nitrogen Donor in TPTZ Generates Selectivity Against More Covalently Binding Metal Ions, Resulting in a Remarkable Stability Sequence along the Lanthanide Series". Inorganic Chemistry. 64 (42): 20887–20895 – via National Library of Medicine.