Two-color sum-frequency generation spectroscopy (2C-SFG) is used to probe the molecular and electronic properties of an adsorbed layer of the green fluorescent protein mutant 2 (GFPmut2) on a platinum (111) substrate. First, the spectroscopic measurements, performed under different polarization combinations, and atomic force microscopy (AFM) show that the GFPmut2 proteins form a fairly ordered monolayer on the platinum surface. Next, the nonlinear spectroscopic data provide evidence of particular coupling phenomena between the GFPmut2 vibrational and electronic properties. This is revealed by the occurrence of two doubly resonant sum-frequency generation processes for molecules having both their Raman and infrared transition moments in a direction perpendicular to the sample plane. Finally, our 2C-SFG analysis reveals two electronic transitions corresponding to the absorption and fluorescence energy levels which are related to two different GFPmut2 conformations: the B (anionic) and I forms, respectively. Their observation and wavelength positions attest the keeping of the GFPmut2 electronic properties upon adsorption on the metallic surface.
Absolute vibrational spectra of the electrochemical H/Pt and H/Pt(100) interfaces in the underand overpotential ranges are measured by ir-vis sum frequency generation. The vibrational signature of the underpotential-deposited hydrogen is structure sensitive and is related to its bonding configuration and to the water molecules located in the double layer region. A new hydrogen adspecies, presumed to be the intermediate for the hydrogen evolution reaction, shows up in the overpotential range, with a similar vibrational fingerprint on both surfaces. PACS numbers: 68.45.v, 42.65. Ky, 82.45.+z Hydrogen-surface interaction is of importance in various technological fields such as heterogeneous catalysis where hydrogen is involved as reactant, intermediate,
Infrared multiple-photon dissociation (IRMPD) spectroscopy was used to determine the gas-phase structures of deprotonated Pb(2+)/amino acid (Aa) complexes with and without a solvent molecule present. Five amino acid complexes with side chains containing only carbon and hydrogen (Ala, Val, Leu, Ile, Pro) and one with a basic side chain (Lys) were compared. These experiments demonstrated that all [Pb(Aa-H)](+) complexes have Pb(2+) covalently bound between the amine nitrogen and carbonyl oxygen. The nonhydrated complexes containing Ala, Val, Leu, Ile, and Pro are amine-deprotonated, whereas the one containing Lys is deprotonated at its carboxylic acid. The difference is attributed to the polar and basic side chain of lysine, which helps stabilize Pb(2+). IRMPD spectroscopy was also performed on the monohydrated analogues of the [Pb(Aa-H)](+) complexes. The [Pb(Aa-H)H(2)O](+) complexes, where Aa = Ala, Val, Leu, and Ile, exhibited two N-H stretches as well as a carboxylic acid O-H and a PbO-H stretch. Hence, their structures are monohydrated versions of the amine-deprotonated [Pb(Aa-H)](+) complexes where a proton transfer has occurred from the lead-bound water to the deprotonated amine. The IRMPD spectrum and calculations suggest that [Pb(Pro-H)H(2)O](+) has a hydrated carboxylate salt structure. The structure of [Pb(Lys-H)H(2)O](+) was also carboxyl-deprotonated, but Pb(2+) is bound to the carbonyl oxygen and the amine nitrogen, with one of the protons belonging to the water transferred to the basic side chain. This results in an intramolecular hydrogen bond that does not absorb in the region of the spectrum probed in these experiments. The IRMPD spectra and structural characterizations were confirmed and aided by infrared spectra calculated at the B3LYP/6-31+G(d,p) level of theory and 298 K enthalpies and Gibbs energies using the MP2(full)/6-311++G(2d,2p) method on the B3LYP geometries.
We show that sum-frequency generation spectroscopy performed in the total internal
reflection configuration (TIR–SFG) combined with a dense gold nanoparticles monolayer
allows us to study, with an excellent signal to noise ratio and high signal to background
ratio, the conformation of adsorbed molecules. Dodecanethiol (DDT) was used as probe
molecules in order to assess the potentialities of the approach. An enhancement of more
than one order of magnitude of the SFG signals arising from the adsorbed species is
observed with the TIR geometry compared to the external reflection one while
the SFG non-resonant contribution remains the same for both configurations.
Although further work is required to fully understand the origin of the SFG process
on nanoparticles, our work opens new possibilities for studying nanostructures.
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