Safety assessment by multiphoton fluorescence/second harmonic generation/hyper-Rayleigh scattering tomography of ZnO nanoparticles used in cosmetic products.

Zinc oxide nanoparticles (ZnO NPs) are commonly used as UV filters in commercial sunscreen products. Their penetration into the skin is intensively discussed in the literature. In the present in vivo study, penetration of ZnO NPs (30 nm in size) into human skin was investigated by multiphoton tomography. Based on the non-linear effects of a second harmonic generation and hyper-Rayleigh scattering, the distribution of ZnO NPs in the horny layers of the epidermis, as well as the furrows, wrinkles and orifice of the hair follicles was analyzed. This method permitted distinguishing between the particulate and dissolved forms of Zn. A detection limit of 0.08 fg/µm(3) was estimated. Taking advantage of this sensitivity, it was clearly shown that ZnO NPs penetrate only into the outermost layers of stratum corneum, furrows and into the orifices of the hair follicles and do not reach the viable epidermis.

Mode-selective vibrational redistribution after spectrally selective N-H stretching mode excitation in intermolecular hydrogen bonds.

Mode-selective vibrational redistribution after spectrally selective excitation within the highly structured N-H stretching band of the 7-azaindole dimer was observed by subpicosecond infrared-pump/anti-Stokes Raman-probe spectroscopy. Measurements after relaxation of the N-H stretching vibration indicate ultrafast initial population transfer to vibrations with pronounced N-H bending character. From these modes energy is transferred to modes of frequencies below 1000 cm(-1) on a slower time scale of about 3 ps. Tuning the spectrally narrow infrared excitation to the different substructures of the N-H stretching band influences the distribution of populations between the fingerprint modes. Their relative populations are correlated with the contributions of the modes forming the different coupled combination tones of the N-H stretching band. These results provide experimental support to a Fermi resonance model previously used for simulations of the N-H stretching infrared absorption band shape and insight into relaxation from the initially excited combination bands.

Tuning intramolecular anharmonic vibrational coupling in 4-nitroaniline by solvent-solute interaction.

Applying a combined experimental and theoretical approach we demonstrate that doublets of the nu(s)(NO(2)) band of 4-nitroaniline which have been observed in several environments originate from Fermi resonances. Changes of the line shapes typical for Fermi resonances are reported also for other isotopomers of 4-nitroaniline, however, for each of them in different solvents and solvent mixtures. Simulations of the infrared spectra based on the solvatochromic frequency shifts of the nu(s)(NO(2)) vibration determined experimentally together with calculated cubic couplings with overtones and combination bands account for the experimental findings.