Kristin Bowman-James


Kristin Bowman-James
  • Distinguished Professor
  • Director Kansas NSF EPSCoR

Contact Info

Phone:
3114 GL (ISB)
Lawrence
1567 Irving Hill Rd
Lawrence, KS 66045

Education

Ph.D., Temple University, 1974
B.S., Temple University, 1968
Postdoctoral Research Fellow, The Ohio State University,
1974-1975

Specialization

Supramolecular and Traditional Coordination Chemistry

Research

Bowman-James Research Group Poster

Research in the Bowman-James group involves the strategic design of organized molecular frameworks as selective receptors for anions as well as potential ligands for transition metal ions. Our interest in these areas stems from potential environmental and biological applications in sensing, separations, catalysis, and biomimetic chemistry. We also seek to examine the similarities (and differences) between supramolecular anion coordination chemistry and transition metal coordination chemistry.

 

Transition metals, anions, dative bond, hydrogen bond model

Hence, we frequently explore the same ligands as frameworks for coordinating both anions and transition metals as shown in the figure for one of our amide-based macrocyclic ligands. One basic similarity between hydrogen bond and transition metal coordination is the donation of an electron pair. For anion coordination the electrons are donated from the anion to the ligand, while in transition metal chemistry, the donation is from the ligand to the metal ion (see ChemDraw diagram).

Examples of different fluoride-containing complexes illustrate the wide range of anion binding ligands that we designed.

Fluoride, bifluoride, hydrated fluoride model

Our research especially targets anions of environmental relevance. We focus on current day challenges including remediation, such as nuclear waste site clean-up, as well as ways to address the looming depletion of the world’s available phosphorus reserves. As a result, we have explored the capture of small oxo anions, halides, and larger carboxylates and polyphosphates. Anions of interest range in shape, from monoatomic to complex polyatomic anions; and charge, from -1 to -12. One goal has been to design anion ligands capable of binding sulfate for nuclear remediation efforts at waste sites such as the National Laboratory at Hanford, in Washington state. While seemingly innocuous, sulfate’s physical properties, e.g., lack of solubility in borosilicate glass and caustic nature, are detrimental to separations efforts. Newer hosts include a urea macrocycle that binds sulfate selectively and a new ion pair host design as shown below.

Sulfate in urea macrocycle, K2C03 in ion-pair urea-crown ether chelate

A newer project, targeting growing concern about world-wide phosphorus reserves, involves phosphorus anions, particularly those of agricultural and environmental relevance. Phosphorus plays crucial roles in the well-being and growth of plants, with significant impacts on global food sources. We are using some of our macrocyclic hosts to bind phytate, an inositol hexaphosphate anion that is prominent in soils and in plant metabolism, but for which not much structural information is known. Since this polyphosphate anion contains almost 30% phosphorus by weight, and is the most prevalent organophosphate in soils, it could be a significant source of readily available phosphorus. This interesting anion is known as an anti-nutrient because of its affinity for metal ion nutrients, rendering them insoluble and ineffective. It also can possess an incredible maximum -12 charge for such a small anion. We have succeeded in obtaining important structural information by using our macrocyclic hosts to sequester phytate followed by elucidating their crystalline structures using single crystal X-ray crystallographic techniques. The structure is shown below, and is only one of a number of structures we have now obtained, providing significant new information about this intriguing anion.

amide-based macrocycle sandwich with phytate

 

Selected Publications

J. Lohrman, S. Pramanik, S. Kaur, H. Telikepalli, V. W. Day, K. Bowman-James, Hydrophilic and hydrophobic carboxamide pincers as anion hosts, Org. Biomol. Chem. 2021, 8516-8520DOI: https://doi.org/10.1039/D1OB01605A

Q.-Q. Wang, V. W. Day, K. Bowman-James, Chemistry and Structure of a Host Guest Relationship: The Power of NMR and X-ray Diffraction in Tandem, J. Am. Chem. Soc.  2013135(1), 392-399. DOI: 10.1021/ja3096762

B. A. Moyer, R. Custelcean, B. P. Hay, J. L. Sessler, K. Bowman-James, V. W. Day, S.-O. Kang, A Case for Molecular Recognition in Nuclear Separations: Sulfate Separation from Nuclear Wastes,  Inorg. Chem., 2013, 52(7), 3473-3490. DOI: 10.1021/ic3016832

Q.-Q. Wang, V.W. Day, K. Bowman-James, Hexagonal Molecular “Palladawheel,” Chem. Commun. 2013, 49(73), 8042-8044. DOI: 10.1039/C3CC44714F

Q.-Q. Wang, R. A. Begum, V.W. Day, K. Bowman-James, Chemical Mustard Containment Using Simple Palladium Pincer Complexes: The Influence of Molecular Walls, J. Am. Chem. Soc. 2013135(45), 17193-17199. DOI: 10.1021/ja408770u

Q.Q. Wang, V. W. D.; K. Bowman-James, Macrocyclic Influences in CO2 Uptake and Stabilization, Org. Lett   201416, 3982-3985. DOI: 10.1021/ol501812u

C. Jia, Q.-Q, Wang, R.A. Begum, V. W. Day, and K. Bowman-James, Chelate effects in sulfate binding by amide/urea-based ligands, Org. & Biomolec. Chem. 201513(15), 6953-6957.  Selected for cover art.  DOI: 10.1039/C5OB00618J

J.  Lohrman, H. Telikepalli, T. S.  Johnson, T. A. Jackson, V. W. Day, and K. Bowman-James,  Pyrazinetetracarboxamide: A Duplex Ligand for Palladium(II), Inorg. Chem. 2016, 55 (11), 5098-5100. DOI: 10.1021/acs.inorgchem.6b00594

S.-O. Kang, T. S. Johnson, V. W. Day, and K. Bowman-James, Pyridine-2,6-dicarboxamide pincer-based macrocycle: a versatile ligand for oxoanions, oxometallates, and transition metals, J. Supramolec. Chem. 2018, 30(4), 305-314. DOI: 10.1080/10610278.2017.1361534.

J. Lohrman, E. A. Vázquez-Montelongo, S. Pramanik, V. W. Day, M. A. Hix, K. Bowman-James, G. A. Cisneros, Characterizing Hydrogen-Bond Interactions in Pyrazinetetracarboxamide Complexes: Insights from Experimental and Quantum Topological Analyses,  Inorg. Chem.  201857, 9775-9778.  DOI: 10.1021/acs.inorgchem.8b00627

M. Reinmuth, S. Pramanik, J. T. Douglas, V. W. Day, K. Bowman-James, Structural Impact of Chelation on Phytate, a Highly Phosphorylated Biomolecule, Eur J. Inorg. Chem. 2019, (Iss. 14), 1870-1874. DOI10.1002/ejic.201900091, Phosphorus 2019 category. Invited for cover page and cover profile.

K. Bowman-James, Supramolecular cages trap pesky anions, Science 2019365, 124-125.

S. Pramanik, V. W. Day, K. Bowman-James, Supramolecular traps for highly phosphorylated inositol sources of phosphorus, Chem. Commun. 202056, 3269-3272.  DOI: 10.1039/c9cc09321d

S. Kaur, V. W. Day, K. Bowman-James, Urea-Based Macrocycle Selective for Sulfate and Structurally Sensitive to Water, Cryst. Growth & Des. 202020, 4212-4216. DOI: 10.1021/acs.cgd.0c00411

S. Kaur, S. Pramanik, V. W. Day, K. Bowman-James, Snapshots of “crystalline” salt-water solutions of inositol hexaphosphate conformers, Dalton Trans. 202150, 480-484. DOI: 10.1039/d0dt03775c

S. Kaur, P. Kumarj R. Gupta, K. Bowman-James, Pincers based on dicarboxamide and dithiocarboxamide functional groups in Pincer Compounds, 2018, 295-325.

Supramolecular Chemistry of Anions, A. Bianchi, K. Bowman-James, E. García-España, Eds. Wiley-VCH: New York, 1997, 461 pp.

Adv. Inorg. Chem., From the Template Effect to Spontaneous Intermolecular Organization, A Celebration of Daryle Busch's First 50 years of Leadership Teaching, Research and Service.  R. van Eldik and K. Bowman-James, Eds.   (Proceedings held in Philadelphia, Pennsylvania, 2004.) 200759, 320 pp.

Anion Coordination Chemistry, K. Bowman-James, A. Bianchi, E. García-España, Eds., Wiley-Interscience,  2012, 560 pp.

Awards & Honors

American Academy of Arts and Sciences Fellow

2021

American Chemical Society Award in Inorganic Chemistry

2021

University of Kansas Leading Light Award

2011

American Chemical Society Fellow

2010

University Distinguished Professor

2007

Temple University Gallery of Success

2004

St. Louis Section Midwest Award of the American Chemical Society

2003

University of Kansas Higuchi Award - Dolph Simons Award for Research in the Biomedical Sciences

2002

ACS Women Chemists Committee Regional Award for Diversity

2002

Iota Sigma Pi Award for Professional Excellence

2002