The π–π stacking interaction between lumiflavin and a number of π-electron-rich molecules has been studied by density functional theory using several new-generation density functionals. Six known lumiflavin-aromatic adducts were used and the models were evaluated by comparing the geometry and energetics with experimental results. The study found that dispersion-corrected and hybrid functionals with larger (>50%) Hartree–Fock exchanges produced superior results in modeling thermodynamic characteristics of these complexes. The functional producing the best energetics for these model systems was used to study the stacking interactions of lumiflavin with biologically relevant aromatic groups. Additionally, the reduction of flavin — in the presence of both a hydride donor and a non-donor π-electronic system was also studied. Weak interactions were observed in the stacked lumiflavin complexes of benzene, phenol, and indole, mimicking phenyl alanine, tryptophan, and tyrosine side chains, respectively, of an enzyme. The stacked complex of naphthalene and flavin showed little change in flavin’s redox potential indicating insignificant effect on the thermodynamics of the hydride transfer reaction. In contrast, the hydride transfer reaction with the hydride donor N-methyl nicotinamide tells a different story, as the transition state was found to be strongly impacted by the stacking interactions. A comparison of performance between the density functional theory (DFT) and the computationally less expensive dispersion-corrected self-consistent density functional tight-binding (SCC-DFTB-D) theory revealed that the latter produces consistent energetics for this hydride transfer reaction and additional DFT-computed perturbative corrections could significantly improve these results.
Written by Sudeep Bhattacharyay
In This Story
- Caitlin Bresnahan
- Clorice Reinhardt
- Thomas Bartholow
- John Rumpel
- Michael North
Departments + Programs
You may also like:
Alum studies Yellowstone geysers
Mara Reed remembers being awed by the geysers in Yellowstone National Park when she visited the park for the first time as a girl. The UW-Eau Claire graduate never guessed that nearly 20 years later her research there would bring her national attention.
Still sharing her kind soul and love of learning
With new passions and plans in graduate school ahead, May 2020 grad Erica Nerbonne continues to show that while chronic illness may slow her down a bit at times, it will never stop her from aiming high and reaching her goals.
Finding his passion and path
Ryan Pelle came to UW-Eau Claire thinking he would someday be a field biologist. Instead, he discovered that his passion is education. After earning his biology degree this month, he plans to return to college for a teaching degree.