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Panoramic portrait of primary molecular events preceding excited state proton transfer in water.

ABSTRACT: Photochemistry powers numerous processes from luminescence and human vision, to light harvesting. However, the elucidation of multidimensional photochemical reaction coordinates on molecular timescales remains challenging. We developed wavelength-tunable femtosecond stimulated Raman spectroscopy to simultaneously achieve pre-resonance enhancement for transient reactant and product species of the widely used photoacid pyranine undergoing excited-state proton transfer (ESPT) reaction in solution. In the low-frequency region, the 280 cm^-1 ring deformation mode following 400 nm photoexcitation exhibits pronounced intensity oscillations on the sub-picosecond timescale due to anharmonic vibrational coupling to the 180 cm^-1 hydrogen-bond stretching mode only in ESPT-capable solvents, indicating a primary event of functional relevance. This leads to the contact ion pair formation on the 3 ps timescale before diffusion-controlled separation. The intermolecular 180 cm^-1 mode also reveals vibrational cooling time constants, ?500 fs and 45 ps in both H₂O and D₂O, which differ from ESPT time constants of ?3/8 and 90/250 ps in H₂O/D₂O, respectively. Spectral results using H₂¹⁸O further substantiate the functional role of the intermolecular 180 cm^-1 mode in modulating the distance between proton donor and acceptor and forming the transient ion pair. The direct observation of molecular structural evolution across a wide spectral region during photochemical reactions enriches our fundamental understanding of potential energy surface and holds the key to advancing energy and biological sciences with exceptional atomic and temporal precision.

SUBMITTER: Liu W

PROVIDER: S-EPMC6021748 | biostudies-literature | 2016 Aug

REPOSITORIES: biostudies-literature

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Panoramic portrait of primary molecular events preceding excited state proton transfer in water.

Liu Weimin W Wang Yanli Y Tang Longteng L Oscar Breland G BG Zhu Liangdong L Fang Chong C

Chemical science 20160512 8

Photochemistry powers numerous processes from luminescence and human vision, to light harvesting. However, the elucidation of multidimensional photochemical reaction coordinates on molecular timescales remains challenging. We developed wavelength-tunable femtosecond stimulated Raman spectroscopy to simultaneously achieve pre-resonance enhancement for transient reactant and product species of the widely used photoacid pyranine undergoing excited-state proton transfer (ESPT) reaction in solution. ...[more]

PMID: 30034688

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Project description:Fluorescent probes that exhibit solvatochromic or excited-state proton-transfer (ESPT) properties are essential tools for the study of complex biological or chemical systems. Herein, the synthesis and characterization of a novel fluorophore that reveals both features, 5-isocyanonaphthalene-1-ol (ICOL), are reported. Various solvatochromic methods, such as Lippert-Mataga and Bilot-Kawski, together with time-dependent density functional theory (TD-DFT) and time-resolved emission spectroscopy (TRES), were applied to gain insights into its excited-state behavior. To make comparisons, the octyloxy derivative of ICOL, 5-isocyano-1-(octyloxy)naphthalene (ICON), was also prepared. We found that internal charge transfer (ICT) takes place between the isocyano and -OH groups of ICOL, and we determined the values of the dipole moments for the ground and excited states of both ICOL and ICON. Furthermore, in the emission spectra of ICOL, a second band at higher wavelengths (green emission) in solvents of higher polarities (dual emission), in addition to the band present at lower wavelengths (blue emission), were observed. The extent of this dual emission increases in the order of 2-propanol < methanol < N,N-dimethylformamide (DMF) < dimethyl sulfoxide (DMSO). The presence of the dual fluorescence of ICOL in these solvents can be ascribed to ESPT. For ICOL, we also determined ground- and excited-state pKa values of 8.4 ± 0.3 and 0.9 ± 0.7, respectively, which indicates a considerable increase in acidity upon excitation. The TRES experiments showed that the excited-state lifetimes of the ICOL and ICON spanned from 10.1 ns to 5.0 ns and from 5.7 ns to 3.8 ns, respectively. In addition, we demonstrated that ICOL can be used as an effective indicator of not only the critical micelle concentration (cmc) of ionic (sodium lauryl sulfate (SLS)) and nonionic surfactants (Tween 80), but also other micellar parameters, such as partition coefficients, as well as to map the microenvironments in the cavities of biomacromolecules (e.g., BSA). It is also pointed out that fluorescence quenching by pyridine can effectively be utilized for the determination of the fractions of ICOL molecules that reside at the water-micelle interface and in the interior spaces of micelles.

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Panoramic portrait of primary molecular events preceding excited state proton transfer in water.

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Panoramic portrait of primary molecular events preceding excited state proton transfer in water.

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