Chemistry Student-Faculty Research: Dr. Petia Bobadova

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Design of Carborane-Containing Conducting Polymers for Solar Cell Applications

Design of Fluorescent Dyes with Enhanced Photoluminescent Characteristics


Our research group uses computer modeling to design and develop novel materials with industrial and medical applications. Theoretical models and calculations are able to answer questions that cannot be answered by experiment only. It is possible to explain the properties of different materials and get insights of the reasons for their unique behavior. Thus, it is possible to predict and design new materials with enhanced desired characteristics and propose their synthesis and practical applications.

We currently focus our research on three projects:

Design of Carborane-Containing Conducting Polymers for Solar Cell Applications

High demand for inexpensive and renewable energy resources has stimulated the design of efficient, low-cost conductive materials, most notably conductive organic polymers. Conductive polymers have already found important applications in photovoltaics, microelectronics, and medical sensing. These materials are flexible, malleable, elastic and have potential for roll-to-roll high throughput production. Although they have a lower cost of production than traditional silicon semiconductive materials, conductive polymers are susceptible to photodegredation after prolonged exposure to UV light and heat resulting in a short lifespan.

Fortunately, the most intriguing advantage of conductive polymers is the fact that their properties can be engineered with the use of different substituents on the polymer chain. Recent experiments demonstrated that the incorporation of substituents containing carboranyl groups dramatically increases its chemical, electrochemical and thermal stability, while keeping the conducting properties intact.

We model computationally a series polypyrroles and polythiophenes containing carborane-cage substituent groups, connected to the polymer backbone via variety of aliphatic and substituted or non-substituted aromatic spacers. We study the effect of different substituents and spacers on the conductivity of the polymer. This allows us to finely tune the properties of the material and suggest only the best candidates for actual experimental synthesis. The major advantage of computer modeling is the fact that vast variety of combinations of different substituents and spacers can be investigated in detail without the need of expensive synthesis of the real polymer. Thus, new, not even yet synthesized polymers can be examined and their properties predicted. Once the successful combinations of spacers and substituents are determined, the most promising candidates can be synthesized in the laboratory.

For the successful implementation of this project, we have established an active collaboration with the group of Prof. M. Graca H. Vicente from Louisiana State University (http://chemistry.lsu.edu/site/People/Faculty/Graca%20Vicente/item1107.html) The two groups work synergetically: our group generates candidates for polymers with enhanced conductive ability, and Dr. Vicente’s group performs the actual synthesis of the best candidates.

Design of Fluorescent Dyes with Enhanced Photoluminescent Characteristics

Borondipyrromethene (BODIPY) is a class of fluorescent dyes with exciting applications in fluorescence imaging, molecule sensors, biomedical indicators and photoelectric materials. Due to their favorable photophysical and optoelectronic properties that include high photostability, high extinction coefficients and high fluorescence quantum yields, BODIPYs have attracted special interest in drug discovery, biomedical imaging] and optical sensing.

Recently, a new class of reactions has been discovered for the synthesis of benzo-appended BODIPYs with enhanced photoluminescent characteristics. The synthesis has raised several puzzling questions. First, the use of different substituents results in dramatically different reactivities. Also, two synthetic routes have been proposed, showing different product yields. We model computationally the mechanisms of these reactions, following the two synthetic routes. We examine all intermediates and transition states in detail, linking step-by-step the reactants to the products. We use a series of different ligands and substituents and study their effect on the reaction energetic, aiming to explain why the reaction yield changes dramatically when different subsitutents are used. Our ultimate goal is to understand the reaction mechanism in detail. These insights will help us design and propose for synthesis new BODIPY’s with greater stability and higher yields, while keeping their excellent photoluminescent properties intact.

We work in close synergetic collaboration with the group of Prof. M. Graca H. Vicente from Louisiana State University who performs the synthesis of the series of BODIPYs (http://chemistry.lsu.edu/site/People/Faculty/Graca%20Vicente/item1107.html).

Past research students:

Elizabeth Horn
Gennie Stehn
Joseph Varberg
Stephanie Maschek
James Riddel
Ethan Harak
Michael Cottam
Bridgette Pretz
James Thode
Melissa Hopfiger
Robert Finley
Roxanne Burger
Marie Storer
Jonathan Zinser
Quynh Do

Current research students:

Deanna Mason
 

Undergraduate Research Awards

Spring 2011: Rockhurst Outstanding Research Seminar student: Joseph Varberg project: “Using Computer Modeling to Design Novel Conducting Polymers” featured at the Council on Undergraduate Research website (http://www.cur.org/urwevents.html#Rockhurst).
Spring 2010: Rockhurst Outstanding Research Seminar student: Elizabeth Horn project: “Computer Modeling of Carbon Nanotubes”

Undergraduate Research Students Presentations at Regional and National Conferences

  1. P. Bobadova, “Computational Insights into the Reaction Mechanisms of the Synthesis of B-O Functionalized BODIPYs via Different Experimental Methods”, Theory and Application of Computational Chemistry - TACC 2016, Seattle WA, September 2016.
  2. R. Burger and P. Bobadova, “Computational Modeling of the Functionalization of a Fluorescent Dye”, Rockhurst University Festival of Student Achievements, Kansas City, MO, April 2016
  3. P. Bobadova, “Computational Insights into the Reaction Mechanism of B-O BODIPY Functionalization via Different Experimental Methods”, 2015 ACS Midwest Regional Meeting, St. Joseph, MO, October 2015 (invited talk, Advances in Computational Chemistry Symposium).
  4. P. Bobadova, “Using Computational Chemistry to Study the Reaction Mechanism of B-O BODIPY Functionalization via Different Experimental Methods”, Louisiana State University, Baton Rouge, LA, October 2015 (invited talk).
  5. P. Bobadova, “Modeling the Reaction Mechanism of BODIPY Synthesis”-Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria, July 2014 (invited talk).
  6. M. Storer, J. Zinser, E. Hao, L. Jiao, and P. Bobadova-Parvanova, “Computational Study of the Photochemical Properties of AzaBODIPYs and Fused AzaBODIPYs”, 28th Annual Organic Chemistry Day, University of Missouri, Columbia, MO, April 2015 (poster).
  7. M. Hopfinger, A. L. Nguyen, M. G. H. Vicente, and P. Bobadova-Parvanova, “Computational Insights into the Reaction Mechanism of the Synthesis of Dimethoxy-substituted BODIPY”, 247th National Meeting of the American Chemical Society, Dallas, Texas, March 2014 (poster).
  8. P. Bobadova-Parvanova, “Using Computational Modeling to Design the Conductive Ability of Thermally Stable Conjugated Polymers”, 2013 ACS Midwest Regional Meeting, Springfield, Missouri, October 2014 (invited talk, Symposium on Current Trends in Polymer Science).
  9. B. Pretz, E. Harak, M. G. H. Vicente, and P. Bobadova-Parvanova, “Computational Study of the Band Gaps of a Series of Carborane-Containing Polythiophenes: Comparison with Polypyrroles”, 47th Midwest Regional ACS Meeting, Omaha, NE, October 2012 (poster).
  10. E. Harak, J. Varberg, M. G. H. Vicente, and P. Bobadova-Parvanova, “Molecular Engineering of Carboranylpyrroles: Application of Electronic Structure Calculations to Design Thermally-Resistant Conducting Polymers”, 2012 World Renewable Energy Forum, Denver, CO, May 2012 (poster).
  11. E. Harak, J. Varberg, M. G. H. Vicente, and P. Bobadova-Parvanova, “Band Gap Engineering of Carborane-Containing Conducting Polymers: A Computational Study”, 46th Midwest and 39th Great Lakes Joint Regional ACS Meeting, St. Louis, MO, October 2011 (poster). 
  12. J. Varberg, M. G. H. Vicente, and P. Bobadova-Parvanova, “Using First-Principle Calculations to Design Novel Carborane-Containing Conducting Polymers”, 241st ACS Annual National Meeting, Anaheim, CA, April 2011 (poster). 
  13. S. Maschek, T. Uppal, M. G. H. Vicente, and P. Bobadova-Parvanova, “Computational Insights on the Synthesis of Benzo-fused BODIPYs”, 241st ACS Annual National Meeting, Anaheim, CA, April 2011 (poster). 
  14. J. Varberg, M. G. H. Vicente, and P. Bobadova-Parvanova, “Computational Study of Novel Carborane-Containing Conjugated Polypyrroles”, 45th ACS Midwest Regional Meeting, Wichita, KS, October 2010 (oral presentation). 
  15. E. Horn, K. Morokuma, and P. Bobadova-Parvanova, “Computer Modeling of Large Materials: How to Select the Correct Model”, National Conference on Undergraduate Research, Missoula, MT, April 2010 (poster). 
  16. E. Horn, V. Parvanov, K. Morokuma, and P. Bobadova-Parvanova, “Selecting the Correct ONIOM Model for Computational Studies of Carbon Nanotubes”, ACS Midwest Regional Meeting, Iowa City, IA, October 2009 (poster).

Recent Publications

  1. Book chapter. N. Zhao, P. Bobadova-Parvanova, and M. Graca H. Vicente, Chapter title: “Carborane-functionalized conducting polymers based on polypyrrole and polythiophene", Chapter in “Boron Chemistry in Organometallics, Catalysis, Materials, and Medicine”, Narayan Hosmane and Robert Eagling, Eds., Imperial College Press/World Scientific Publishing, 2017, in press.
  2. N. Zhao, B. Fabre, P. Bobadova-Parvanova, F. R. Fronczek, and M. Graça H. Vicente “Synthesis and Electropolymerization of a series of 2,2'-(ortho-Carboranyl)bisthiophenes”, J. Organometallic Chemistry, 2017, 828, 157.
  3. A. L. Nguyen, M. Wang, P. Bobadova-Parvanova, Q. Do, Z. Zhou, F. R. Fronczek, K. Smith, and M. Graça H. Vicente “Synthesis and properties of B-cyano-BODIPYs”, Journal of Porphyrins and Phthalocyanines, 2016, 20, 1409.
  4. A. L. Nguyen, P. Bobadova-Parvanova, M. Hopfinger, F. R. Fronczek, K. M. Smith, and M. G. H. Vicente, “Synthetic Routes to 4,4-Dialkoxy-BODIPYs: an Experimental and Computational Study”, Inorg. Chem. 2015, 54, 3228.
  5. J. H. Gibbs, L. T. Robins, Z. Zhou, P. Bobadova-Parvanova, M. Cottam, G. T. McCandless, F. R. Fronczek, and M. G. H. Vicente, “Spectrosco[y, Computational Modeling and Cytotoxicity of a Series of meso-phenyl and meso-thienyl-BODIPYs”, Bioorganic & Medicinal Chemistry, 2013, 21, 5770.
  6. T. Uppal, X. Hu, F. R. Fronczek, S. Maschek, P. Bobadova-Parvanova, and M. G. H. Vicente, “Synthesis, Computational Studies, Spectroscopic Properties and Biological Investigations of Benzo-appended BODIPYs“, Chemistry: A European Journal, 2012, 18, 3893.
  7. Book chapter. D. G. Musaev, P. Bobadova-Parvanova, K. Morokuma, “Principles of Dinitrogen Hydrogenation: Computational Insights”, Chapter 4 in “Computational Modelling of Homogenous and Enzymatic Catalysis”, K. Morokuma and D. G. Musaev, Eds, Wiley-VCH, 2008. http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527318437.html