101. Initial excited-state dynamics of an N-alkylated indanylidene-pyrroline (NAIP) rhodopsin analog.
- Author
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Schapiro I, Fusi S, Olivucci M, Andruniów T, Sasidharanpillai S, and Loppnow GR
- Subjects
- Alkylation, Models, Molecular, Molecular Conformation, Spectrum Analysis, Raman, Stereoisomerism, Indans chemistry, Pyrroles chemistry, Rhodopsin chemistry
- Abstract
N-Alkylated indanylidene-pyrroline-based molecular switches mimic different aspects of the light-induced retinal chromophore isomerization in rhodopsin: the vertebrate dim-light visual pigment. In particular, they display a similar ultrashort excited-state lifetime, subpicosecond photoproduct appearance time, and photoproduct vibrational coherence. To better understand the early light-induced dynamics of such systems, we measured and modeled the resonance Raman spectra of the Z-isomer of the N-methyl-4-(5'-methoxy-2',2'-dimethyl-indan-1'-ylidene)-5-methyl-2,3-dihydro-2H-pyrrolium (NAIP) switch in methanol solution. It is shown that the data, complemented with a <70 fs excited-state trajectory computation, demonstrate initial excited-state structural dynamics dominated by double-bond expansion and single-bond contraction stretches. This mode subsequently couples with the five-membered ring inversion and double-bond torsion. These results are discussed in the context of the mechanism of the excited-state photoisomerization of NAIP switches in solution and the 11-cis retinal in rhodopsin.
- Published
- 2014
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