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UV–Visible Lysine–Glutamate Dimer Excitations in Protein Charge Transfer Spectra: TDDFT Descriptions Using an Optimally Tuned CAM-B3LYP Functional
journal contribution
posted on 2019-12-12, 12:39 authored by Imon Mandal, Sutanuka Manna, Ravindra VenkatramaniRecent reports of distinctive UV–vis absorption
profiles
for monomeric proteins rich in charged amino acids that span 250–800
nm have opened up a new label-free optical spectral window for probing
biomolecular structure and interactions. Combined experimental-computational
studies have revealed that such broad absorption profiles of these
proteins arise from photoexcited charge transfer (CT) transitions
in spatially proximal charged amino acids such as lysine (Lys) and
glutamate (Glu). Here, using time-dependent density functional theory
(TDDFT) with an optimally tuned CAM-B3LYP functional, we refine the
computed UV–vis spectra for Lys-Glu dimers within protein folds
and quantify the percentage CT character of the constituent transitions.
The optimally tuned functionals are derived through a careful analysis
of the CAM-B3LYP parameter space for Lys-Glu dimers as a function
of amino-acid conformation and side chain separation. Our studies
reveal that the tuned Lys-Glu dimer spectrum spans 150–650
nm and possesses 5 specific types of CT excitations with diverse and
large spatial charge separation length scales of 2–10 Å.
These include inter-/intra-residue peptide backbone to peptide backbone
(BB-CT) excitations spanning 160–210 nm, inter-/intra-residue
peptide backbone to side chain (BS-CT) excitations spanning 160–260
nm, and side chain to side chain (SS-CT) excitations, which show the
broadest absorption range spanning 260–650 nm.
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side chain separationOptimally Tuned CAM-B 3LYP Functionalside chainabsorptionoptimallypercentage CT characteracidProtein Charge Transfer SpectraLys-Glu dimersCAM-B 3LYP parameter spaceÅ.Lys-Glu dimer spectrumphotoexcited charge transferSS-CTtransitionBS-CTpeptideproteinUVprofileexcitationTDDFTnmcharge separation length scalesBB-CT
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