title: Mimic of the green fluorescent protein β-barrel: photophysics and dynamics of confined chromophores defined by a rigid porous scaffold.
abstract: Chromophores with a benzylidene imidazolidinone core define the emission profile of commonly used biomarkers such as the green fluorescent protein (GFP) and its analogues. In this communication, artificially engineered porous scaffolds have been shown to mimic the protein β-barrel structure, maintaining green fluorescence response and conformational rigidity of GFP-like chromophores. In particular, we demonstrated that the emission maximum in our artificial scaffolds is similar to those observed in the spectra of the natural GFP-based systems. To correlate the fluorescence response with a structure and perform a comprehensive analysis of the prepared photoluminescent scaffolds, (13)C cross-polarization magic angle spinning solid-state (CP-MAS) NMR spectroscopy, powder and single-crystal X-ray diffraction, and time-resolved fluorescence spectroscopy were employed. Quadrupolar spin-echo solid-state (2)H NMR spectroscopy, in combination with theoretical calculations, was implemented to probe low-frequency vibrational dynamics of the confined chromophores, demonstrating conformational restrictions imposed on the coordinatively trapped chromophores. Because of possible tunability of the introduced scaffolds, these studies could foreshadow utilization of the presented approach toward directing a fluorescence response in artificial GFP mimics, modulating a protein microenvironment, and controlling nonradiative pathways through chromophore dynamics.
authors: Department of Chemistry and Biochemistry, University of South Carolina , Columbia, South Carolina 29208, United States.
authors: Derek E
authors: DE
authors: Williams
authors: Ekaterina A
authors: EA
authors: Dolgopolova
authors: Perry J
authors: PJ
authors: Pellechia
authors: Andrei
authors: A
authors: Palukoshka
authors: Thomas J
authors: TJ
authors: Wilson
authors: Rui
authors: R
authors: Tan
authors: Josef M
authors: JM
authors: Maier
authors: Andrew B
authors: AB
authors: Greytak
authors: Mark D
authors: MD
authors: Smith
authors: Jeanette A
authors: JA
authors: Krause
authors: Natalia B
authors: NB
authors: Shustova
mesh_terms: D049452:Green Fluorescent Proteins / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D016062:Porosity; D011487:Protein Conformation
chemical_list: D049452:Green Fluorescent Proteins