Jovica BadjicAssociate Professor
Jovica Badjic received his diploma in Chemistry (1994) from University of Belgrade (Serbia). He obtained Ph.D. in Organic Chemistry (2001) from Iowa State University. From 2001 to 2004 he was a postdoctoral research fellow in the group of J Fraser Stoddart at UCLA where he was awarded Chancellor's award for outstanding research accomplishments in postdoctoral work. He joined the faculty at the Ohio State University in 2004 and was promoted to associate professor in 2010.
The entrapment of molecules (guests) inside cavitands (hosts with an enforced cavity) allows for controlling the guest’s local environment and its chemical characteristics. One can thus use encapsulation for stabilizing fleeting intermediates, accelerating chemical reactions, and modulating conformational dynamics of entrapped compounds. Despite many advances in this rapidly expanding field of organic chemistry there remains numerous challenges. One can entrap a substrate(s) and promote its conversion into product(s) though such procedures often come with a limited synthetic utility and scope. Furthermore, there is a need for developing hosts functionalized at the inner space (catalysts) for investigating encapsulation catalysis. At last, we envision a great potential of completing the encapsulation chemistry in aqueous solvents (environmentally friendly and cheap). Our research program is accordingly focused on (a) developing the efficient syntheses and (b) examining the mechanism of action of modular cavitands – baskets with functionalized entrance and/or inner space for promoting chemical transformations (NSF support). In addition, we are interested in using baskets as working models for learning about the mitigation of harmful substances (DTRA-DoD support). Finally, our interest is in developing stimuli-responsive cavitands/assemblies capable of controlling the rate by which useful compounds are delivered to their immediate environment.
The activation energy (DG‡) corresponding to the process of a guest entering/departing a cavitand is called constrictive binding. How does one go about controlling the constrictive binding? Well, we realized that using the process of gating allows for modulating the rate by which guest molecules enter/exit the host. Typically, the gating constitutes conformational change in the molecular framework of a host that regulates the in/out trafficking of guests. We designed a series of hosts containing a cavitand-like platform and aromatic appendages at the rim for quantitatively examining the process of gating (see Figure above). The results of our studies indicate that increasing the lifetime (1/kout) of encapsulation-based complexes can indeed be achieved and controlled via gating though its effect on modulating the outcome of chemical reactions is still unknown. We hypothesize that this relationship can be examined by studying the interdependence between: the host’s conformational dynamics, the encapsulation kinetics and the rates/outcome of chemical reactions occurring in confined spaces. Our current research interest is therefore oriented toward characterizing the action and catalytic behavior of gated supramolecular catalysts using both experimental and computational methods of chemistry. For more detailed information about our research, we suggest you to consider reading our publications (see a list of selected references below).
We are interested in accepting new graduate students. Our research program has been financially supported by National Science Foundation and Department of Defense (DTRA).
Yian Ruan, Hashem A. Taha, Ryan J. Yoder, Maslak Veselin, Hadad M. and Jovica, The Prospect of Selective Recognition of Nerve Agents with Modular Basket-like Hosts. A Structure-Activity Study of the Entrapment of a Series of Organophosphonates in Aqueous Media, Journal of Physical Chemistry B, 2013, in press.
Hermann Keith, Sardini Stephen, Yian Ruan, Ryan J. Yoder, Mrinal Chakraborty, Shubham Vyas, Hadad M. and Jovica, Method for the Preparation of Derivatives of Heptiptycene: Toward Dual-Cavity Baskets, Journal of Organic Chemistry, 2013, in press.
Wang, Stojanovic Sandra, Turner A Daniel, Young Tanya, Hadad M. and Jovica, The Entrapment of Chiral Guests with Gated Baskets. Can a Kinetic Discrimination of Enantiomers be Governed via Gating? Chemistry A European Journal, 2013, 19, in press.
, Rieth , Taha A. , Wang , Hadad M. and Jovica, An Acid-Catalyzed Cyclialkylation that Provides Rapid Access to a Twisted Molecular Basket. Chemistry A European Journal, 2012, 18, 8301-8305.
Stojanovic, Sandra; Turner, Daniel; Flood Amar, Hadad, Christopher M.; Badjic, Jovica D. A Stereodynamic and Redox-Switchable Encapsulation-Complex Containing a Copper Ion Held by a tris-Quinolinyl Basket. Chemical Communications, 2012, 48, 4429-4431.
Wang, Bao-Yu; Turner, Daniel; Zujovic, Teodora, Hadad, Christopher M.; Badjic, Jovica D. Design, Preparation, and Study of Catalytic Gated Baskets. The Journal of Organic Chemistry, 2012, 77, 2675-2688.
, Rieth , Taha A. , Wang , Hadad M. and Jovica, On the Mechanism of Action of Gated Molecular Baskets: The Synchronicity of the Revolving Motion of Gates and in/out Trafficking of Guests. Beilstein Journal of Organic Chemistry (Supremolacular Chemistry II) 2012, 8, 90–99.
Badjic, Jovica D., Stojanovic Sandra, Ruan Yian, Kinetically and Thermodynamically Controlled Syntheses of Covalent Molecular Capsules. Advances in Physical Organic Chemistry, 2011, 45, 1-35.
Wang, Bao-Yu; Turner, Daniel; Zujovic, Teodora, Hadad, Christopher M.; Badjic, Jovica D. The Role of Chirality in Directing the Formation of Cup-Shaped Porphyrins and the Coordination Characteristics of such Hosts. Chemistry A European Journal, 2011, 17, 8870-8881.
Stojanovic, Sandra; Turner, Daniel; Hadad, Christopher M.; Badjic, Jovica D. Controlling Dynamic Stereoisomerism in Transition-Metal Folded Baskets. Chemical Science, 2011, 2, 752.
Rieth, Stephen; Badjic, Jovica D. The Effect of the Dynamics of Revolving Gates on the Kinetics of Molecular Encapsulation – The Activity/Selectivity Relationship Chemistry A European Journal , 2011, 17, 2562.
Rieth, Stephen; Keith Hermann; Bao-Yu Wang; Badjic, Jovica D. Controlling the Dynamics of Molecular Encapsulation and Gating. Chemical Society Reviews, 2011, 40, 1609.
Xiaoguang; Wang; Rieth, Stephen; Sandra, Stojanovic; Hadad, Christopher M.; Badjic, Jovica D. Molecular Recognition of a Transition State. Angewandte Chemie, International Edition 2010, 49, 4816-4819.
Rieth, Stephen; Bao, Xiaoguang; Wang, Bao-Yu; Hadad, Christopher M.; Badjic, Jovica D. Gated Molecular Recognition and Dynamic Discrimination of Guests. Journal of the American Chemical Society 2010, 132, 773-773.
Rieth, Stephen; Wang, Bao-Yu; Bao, Xiaoguang; Badjic, Jovica D. Four-State Switching Characteristics of a Gated Molecular Basket. Organic Letters 2009, 11, 2495-2498.
Wang, Bao-Yu; Rieth, Stephen; Badjic, Jovica D. Tuning the Rate of Molecular Translocation. Journal of the American Chemical Society 2009, 131, 7250-7252.
Wang, Bao-Yu; Bao, Xiaoguang; Yan, Zhiqing; Maslak, Veselin; Hadad, Christopher M.; Badjic, Jovica D. A 3-fold "Butterfly Valve" in Command of the Encapsulation's Kinetic Stability. Molecular Baskets at Work. Journal of the American Chemical Society 2008, 130, 15127-15133.
A few selected references from earlier work:
Badjic, Jovica D.; Ronconi, Celia M.; Stoddart, J. Fraser; Balzani, Vincenzo; Silvi, Serena; Credi, Alberto. Operating molecular elevators. Journal of the American Chemical Society 2006, 128, 1489-1499.
Badjic, Jovica D.; Nelson, Alshakim; Cantrill, Stuart J.; Turnbull, W. Bruce; Stoddart, J. Fraser. Multivalency and cooperativity in supramolecular chemistry. Accounts of Chemical Research 2005, 38, 723-732.
Badjic, Jovica D.; Cantrill, Stuart J.; Grubbs, Robert H.; Guidry, Erin N.; Orenes, Raul; Stoddart, J. Fraser. The exclusivity of multivalency in dynamic covalent processes. Angewandte Chemie, International Edition 2004, 43, 3273-3278.