Fluorescence Modulation of -Green Fluorescent Protein Chromophores Following Ultrafast Proton Transfer in Solution.

Photophysical and photochemical properties of the green fluorescent protein (GFP) chromophore and derivatives underlie their bioimaging applications. To date, ultrafast spectroscopic tools represent the key for unraveling fluorescence mechanisms toward rational design of this powerful biomimetic framework. To correlate the excited-state intramolecular proton transfer (ESIPT) with chromophore emission properties, we implement experimental and computational tool sets to elucidate real-time electronic and structural dynamics of two archetypal -GFP chromophores (-HBDI and -LHBDI) possessing an intramolecular hydrogen bond to undergo efficient ESIPT, only differing in a bridge-bond constraint.

Excited-State Dynamics of a meta-Dimethylamino Locked GFP Chromophore as a Fluorescence Turn-on Water Sensor.

Strategic incorporation of a meta-dimethylamino (-NMe ) group on the conformationally locked green fluorescent protein (GFP) model chromophore (m-NMe -LpHBDI) has drastically altered molecular electronic properties, counterintuitively enhancing fluorescence of only the neutral and cationic chromophores in aqueous solution. A ~200-fold decrease in fluorescence quantum yield of m-NMe -LpHBDI in alcohols (e.g.

Photoinduced Charge Transfer and Bimetallic Bond Dissociation of a Bi-W Complex in Solution.

Organometallic complexes including metal carbonyls have been widely utilized in academic and industrial settings for purposes ranging from teaching basic catalytic reactions to developing state-of-the-art electronic circuits. Characterization of these materials can be obtained via steady-state measurements; however, the intermediate photochemical events remain unclear, hindering effective and rational molecular engineering methods for new materials. We employed femtosecond transient absorption (fs-TA) and ground-state femtosecond stimulated Raman spectroscopy (FSRS) on triphenylbismuth-tungsten pentacarbonyl complex, a solution precursor for bimetallic oxide thin films.

Discovering a rotational barrier within a charge-transfer state of a photoexcited chromophore in solution.

Methylation occurs in a myriad of systems with protective and regulatory functions. 8-methoxypyrene-1,3,6-trisulfonate (MPTS), a methoxy derivative of a photoacid, serves as a model system to study effects of methylation on the excited state potential energy landscape. A suite of spectroscopic techniques including transient absorption, wavelength-tunable femtosecond stimulated Raman spectroscopy (FSRS), and fluorescence quantum yield measurements via steady-state electronic spectroscopy reveal the energy dissipation pathways of MPTS following photoexcitation.

Ultrafast excited-state proton transfer dynamics in dihalogenated non-fluorescent and fluorescent GFP chromophores.

Green fluorescent protein (GFP) has enabled a myriad of bioimaging advances due to its photophysical and photochemical properties. To deepen the mechanistic understanding of such light-induced processes, novel derivatives of GFP chromophore p-HBDI were engineered by fluorination or bromination of the phenolic moiety into superphotoacids, which efficiently undergo excited-state proton transfer (ESPT) in aqueous solution within the short lifetime of the excited state, as opposed to p-HBDI where efficient ESPT is not observed. In addition, we tuned the excited-state lifetime from picoseconds to nanoseconds by conformational locking of the p-HBDI backbone, essentially transforming the nonfluorescent chromophores into highly fluorescent ones.