Lanthanide metals are found in many common place materials such as hybrid car batteries, magnets, bioprobes, optical materials and smart phones. Actinide metals, especially uranium, represent an alternative source of energy as a component in nuclear fuel. The need to recycle these metals from current materials and spent nuclear fuel, as well as develop more efficient ways to isolate them from raw sources, remains a pressing problem.

The Biros Lab aims to address the separation, isolation and purification of both lanthanide and actinide metals through the use of multidentate organic ligands. We use organic synthesis to prepare these ligands, then characterize the resultant metal ligand complexes with NMR, IR, MS, luminescence and X-Ray crystallography. We also carry out analytical studies to determine the ability of these compounds to extract one lanthanide or actinide metal out of aqueous solution and into an organic solvent.

Students in the Biros Lab will have the opportunity to learn techniques in organic synthesis and inorganic coordination chemistry. Students will also learn carry out analysis using multinuclear NMR, IR, MS, luminescence, X-ray crystallography and separation experiments.

 

Collaborators

Dr. John Bender (GVSU)

Dr. Eric Werner (UTampa)

Dr. Richard Staples (Center for Crystallographic Research, MSU)

The TIM Consortium: A Dispersed REU site in Theoretically Interesting Molecules

Publications (*denotes undergraduate students)

Alan R. Lear,* Jonah Lenters,* Michael G. Patterson,* Richard J. Staples, Eric J. Werner and Shannon M. Biros “Two beta-phosphorylamide compounds as ligands for Sm³⁺, Eu³⁺ and Tb³⁺: X-Ray Crystallography and Luminescence Properties” Molecules – Special Issue on Lanthanide Luminescence, 2020, 25, 2971. doi: 10.3390/molecules25132971    

Eric J. Werner and Shannon M. Biros “Supramolecular ligands for the separation of lanthanides and actindes” Curr. Org. Front. - Special Issue in honor of Julius Rebek’s 75th birthday, 2019, 6, 2067-2094. doi: 10.1039/C9QO00242A

Andrew I. VanderWeide,* Richard J. Staples, Shannon M. Biros. “Crystal structures of two bis-carbamoylmethylphosphine oxide (CMPO) compounds” Acta Cryst., 2019, E75, 991-996. doi: 10.1107/S205698901900820X    

Tomilola J. Ajayi, Moses Ollengo, Lukas le Roux, Michael N. Pillay, Richard J. Staples, Shannon M. Biros, Kasper Wenderich, Bastian Mei, Werner E. van Zyl. “Heterodimetallic Ferrocenyl Dithiophosphonate Complexes of Nickel(II), Zinc(II) and Cadmium(II) as Sensitizers for TiO₂-Based Dye-Sensitized Solar Cells” ChemistrySelect, 2019, 4, 7416-7424. doi: 10.1002/slct.201900622    

Thomas L. Neils, Shannon M. Biros, Richard J. Staples, Brandon G. Wackerle,* Robert B. Harrison.* “Three monomeric compounds containing the dipyrimidine-2-thiolategold(I) anion” Polyhedron, 2018, 157, 474-478; doi: 10.1016/j.poly.2018.10.043    

Michael G. Patterson*, Andrew K. Mulville*, Emily K. Connor*, Alyssa T. Henry*, Michael L. Hudson*, Kirsten Tissue*, Shannon M. Biros, Eric J. Werner. “Lanthanide extraction selectivity of a tripodal carbamoylmethylphosphine oxide ligand system” Dalton Trans. - Special Issue on Metal-containing Soft Materials, 2018, 47, 14318-14326; doi: 10.1039/C8DT02239A

Jimmy Mugemana,* John Bender, Richard J. Staples, Shannon M Biros. "Crystal structure of cis-[1,2-bis(diphenylphosphanyl)ethene-k² P,P']dichloridoplatinum(II) chloroform disolvate: a new polymorph" Acta Cryst., 2018, E74, 998-1001. doi: 10.1107/S2056989018008836    

Shannon M. Biros and KC Russell. "The TIM Consortium: A Dispersed REU Site at Primarily Undergraduate Institutes" in Best Practices for Chemistry REU Programs; Mark A. Griep and Linette M. Watkins, Eds.; American Chemical Society,: Washington, DC, 2018, p 59-71. doi: 10.1021/bk-2018-1295.ch005.

Pablo Ballester and Shannon M. Biros. "CH-pi and pi-pi Interactions as Contributors to the Guest Binding in Reversible Inclusion and Encapsulation Complexes" in The Importance of Pi-Interactions in Crystal Engineering (Frontiers in Crystal Engineering 3) Edward Tiekink and Julio  Zukerman-Schpector, Eds.; John Wiley & Sons; 2012, p 79-105.

Jia Li, Atanu Banerjee, Timothy A. Hasse, Reza Loloee, Shannon M. Biros, Richard J. Staples, Ferman Chavez. “Synthesis and reactivity of a 4His enzyme model complex” RSC Advances, 2017, 7, 50713-50719. 

Erin G. Leach,* Justin R. Shady,* Adam C. Boyden,* Anne-lise Emig,* Alyssa T. Henry,* Emily K. Connor,* Richard J. Staples, Stephanie Schaertel, Eric J. Werner, Shannon M. Biros. “X-ray crystallographic, luminescence and NMR studies of phenacyldiphenylphosphine oxide with the Ln(III) ions Sm, Eu, Gd, Tb and Dy” Dalton Trans., 2017, 46, 15458-15469.  doi: 10.1039/c7dt02678a.

Jia Li, Monika A. Molenda, Shannon M. Biros, Richard J. Staples, Ferman A. Chavez. “Assembly of a mononuclear ferrous site using a bulky aldehyde-imidazole ligand” Inorg. Chim. Acta, 2017, 464, 152-156. doi: 10.1016/j.ica.2017.05.028.

Katherine M. Coburn,* David A. Hardy,* Michael G. Patterson,* Shelby N. McGraw,* Michael T. Peruzzi,* Felix Boucher,* Bethany Beelen,* Hope T. Sartain,* Thomas Neils, Christopher L. Lawrence, Richard J. Staples, Eric J. Werner, Shannon M. Biros. “f-Element coordination and extraction selectivity using a multipodal carbamoylmethylphosphine oxide ligand on a tridentate phosphoryl scaffold” Inorg. Chim. Acta 2016, 449, 96-106; doi: 10.106/j.ica.2016.05.003.

Sean Riley,* Richard J. Staples, Shannon M. Biros, Felix N. Ngassa. “Crystal structure of phenyl 2,4,5-trichlorobenzenesulfonate” Acta Cryst. 2016, E72, 789-792. doi:10.1107/S2056989016007325.

Evan P. Beaumier,* Brennan S. Billow, Amrendra K. Singh, Shannon M. Biros, Aaron L. Odom. “A Complex with Nitrogen Single, Double and Triple Bonds to the Same Chromium Atom: Synthesis, Structure and Reactivity” Chem. Sci. 2016, 7, 2532-2536; doi: 10.1039/C5SC04608D, Edge Article.

Paul T. Morse,* Richard J. Staples, Shannon M. Biros. “Th(IV) complexes with cis-ethylenebis(diphenylphosphine oxide): X-ray structures and NMR solution studies” Polyhedron – Special Issue on Undergraduate Research, 2016, 114, 2-12; doi: 10.1016/j.poly.2015.05.016.

Felix N. Ngassa, Shannon M. Biros, Richard J. Staples. “Crystal structure of N-[(1S,2S)-2-aminocyclohexyl]-2,4,6-trimethylbenzenesulfonamide” Acta Cryst. 2015, E71, 1521-1524.

Tyler A. Cooley,* Sean Riley,* Shannon M. Biros, Richard J. Staples, Felix N. Ngassa. “Crystal structure of 2,4-dinitrophenyl 4-methylbenzene sulfonate: A new polymorph” Acta Cryst. 2015, E71, 1085-1088.

Tsvetelina P. Atanasova,* Sean Riley,* Shannon M. Biros, Richard J. Staples, Felix N. Ngassa. “Crystal structure of 3,5-dimethylphenyl 2-nitrobenzenesulfonate” Acta Cryst. 2015, E71, 1045-1047.

Alyssa A. Kulesza,* Richard J. Staples, Shannon M. Biros. “Crystal structure of bis(3,3-dimethyl-2-oxobutyl)diphenyl phosphonium bromide chloroform solvate (1/1)” Acta Cryst. 2015, E71, o339-o340.

Erin G. Leach,* Alyssa A. Kulesza,* Richard J. Staples, Shannon M. Biros. “Crystal structures of 1-(4-chlorophenyl)-2-(diphenylphosphoryl)ethan-1-one and 1-(diphenylphosphoryl)-3,3-dimethylbutan-2-one” Acta Cryst. 2015, E71, 523-527.

Hope T. Sartain,* Shelby N. McGraw,* Christopher Lawrence, Eric J. Werner, Shannon M. Biros. “A Novel Tripodal CMPO Ligand: Affinity for f-Elements, Computational Investigations and Luminescence Properties” Inorg. Chim. Acta 2015, 426, 126-135.

Hope T. Sartain,* Richard J. Staples, Shannon M. Biros. “Crystal structure of pentakis (ethylenediamine-[kappa]2N,N')lanthanum(III) trichloride-ethylenediamine (1/1) dichloromethane solvate” Acta Cryst. 2014, E70, 424-426.

Nathan H. Murray,* Shannon M. Biros, Robert L. LaDuca. “Crystal structure of [propane-1,3-diyldbis(piperidine-4,1-diyl)]bis[(pyridin-4-yl)methanone]-isophthalic acid (1/1)” Acta Cryst. 2014, E70, 298-300.

Julie A. Stoscup,* Richard J. Staples, Shannon M. Biros. “Crystal Structure of a Samarium(III) nitrate Chain Cross-linked by a bis-Carbamoylmethylphosphine oxide ligand”, Acta Cryst 2014, E70, 188-191.

Laurie A. Witucki, William R. Winchester, Shannon M. Biros. “Investigation of ¹H NMR Chemical Shift in Various Systems: A Set of Advanced 1D ¹H NMR Undergraduate Laboratory Projects”, Chemical Educator, 2014, 19, 471-476.

Shannon M. Biros and Fraser Hof. “Supramolecular Chemistry in Drug Design” in Supramolecular Chemistry: From Molecules to Nanomaterials; Philip A. Gale and Jonathan W. Steed, Eds.; John Wiley & Sons, Ltd: Southern Gate, Chichester, 2012, p 1909-1928.

Pablo Ballester and Shannon M. Biros. "CH-pi and pi-pi Interactions as Contributors to the Guest Binding in Reversible Inclusion and Encapsulation Complexes" in The Importance of Pi-Interactions in Crystal Engineering (Frontiers in Crystal Engineering 3) Edward Tiekink and Julio  Zukerman-Schpector, Eds.; John Wiley & Sons; 2012, p 79-105.

Courtney J. Hastings, Michael D. Pluth, Shannon M. Biros, Robert G. Bergman and Kenneth N. Raymond. “Simultaneously Bound Guests and Chiral Recognition: A Chiral Self-Assembled Supramolecular Host Encapsulates Hydrophobic Guests”, Tetrahedron 2008, 64, 8362-8367.

Shannon M. Biros, Robert M. Yeh and Kenneth N. Raymond. “Design and Formation of a Large, Tetrahedral M₄L₆ Supramolecular Cluster using 1,1’-Binaphthyl Ligands”, Angew. Chem. Int. Ed. 2008, 47, 6062-6064.

Shannon M. Biros, Robert G. Bergman and Kenneth N. Raymond. “The Hydrophobic Effect Drives the Recognition of Hydrocarbons by an Anionic Metal-Ligand Cluster”, J. Am. Chem. Soc., 2007, 129, 12094-12095.

Lionel Moisan, Trevor J. Dale, Naran Gombosuren, Shannon M. Biros, Enrique Mann, Jun-Li Hou, Fernando P. Crisostomo and Julius Rebek, Jr. “Facile Synthesis of Pyridazine-Based a-Helix Mimetics”, Heterocycles, 2007, 73, 661-671.

Shannon M. Biros, Lionel Moisan, Enrique Mann, Alexandre Carella, Dayong Zhai, John C. Reed and Julius Rebek, Jr. “Heterocyclic a-Helix Mimetics for Targeting Protein-Protein Interactions”, Bioorg. Med. Chem. Lett., 2007, 17, 4641-4645.

Shannon M. Biros and Julius Rebek, Jr. “Water-soluble Cavitands and Capsules”, Chem. Soc. Rev., 2007, 36, 93-104. 

Richard J. Hooley, Shannon M. Biros and Julius Rebek, Jr.  “The Use of a Deep, Water-Soluble Cavitand as a Phase-Transfer Catalyst”, Angew. Chem. Int. Ed. 2006, 45, 3517-3519. 

Alasdair M. Barr, Jefferson W. Kinney, Matthew N. Hill, Xiaoying Lu, Shannon M. Biros, Julius Rebek, Jr., Tamas Bartfai. “A Novel, Systemically Active, Selective Galanin Receptor Type-3 Ligand Exhibits Antidepressant-like Activity in Preclinical Tests”, Neurosci. Lett., 2006, 405, 111-115. 

Richard J. Hooley, Shannon M. Biros and Julius Rebek, Jr.  “Normal Hydrocarbons Tumble Rapidly in a Deep, Water-Soluble Cavitand”, Chem. Commun. 2005, 509-510.

Clemens H. Haas, Shannon M. Biros and Julius Rebek, Jr. “Binding Properties of Cavitands in Aqueous Solution – The Effect of Charge on Guest Selectivity”, Chem. Commun. 2005, 6044-6045. 

Shannon M. Biros, Elke C. Ullrich, Fraser Hof, Laurent Trembleau, and Julius Rebek, Jr.  “Kinetically Stable Complexes in Water: The Role of Hydration and Hydrophobicity”, J. Am. Chem. Soc. 2004, 126, 2870-2876. 

Shannon M. Biros,* Brian M. Bridgewater, Adriel Villeges-Estrada, Joseph Tanski, Gerard Parkin.  “Antimony Ethylene Glycolate and Catecholate Compounds: Structural Characterization of Polyesterification Catalysts”, Inorg. Chem., 2002, 41, 4051-4057.