SERS in PAH-Os and gold nanoparticle self-assembled multilayers.

We present a detailed structural and surface-enhanced Raman scattering (SERS) study of poly(allylamine) modified with Os(byp)2ClPyCHO (PAH-Os) and gold nanoparticles self-assembled multilayers [PAH-Os+(Au-nanoparticlesPAH-Os)n, n=1 and 5]. Atomic force microscopy and variable-angle spectroscopic ellipsometry measurements indicate that the first nanoparticle layer grows homogenously by partially covering the substrate without clustering. Analyzing the sample thickness and roughness we infer that the growth process advances thereafter by filling with nanoparticles the interstitial spaces between the previously adsorbed nanoparticles. After five immersion steps the multilayers reach a more compact structure. The interaction between plasmons of near-gold nanoparticles provides a new optical absorption around 650 nm which, in addition, allows a more effective SERS process in that spectral region than at the single-plasmon resonance (approximately 530 nm). We compare the electronic resonance Raman and SERS amplification mechanisms in these self-assembled multilayers analyzing Raman resonance scans and Raman intensity micromaps. As a function of nanoparticle coverage we observe large changes in the Raman intensity scans, with maxima that shift from the electronic transitions, to the plasmon resonance, and finally to the coupled-plasmon absorption. The Raman micromaps, on the other hand, evidence huge intensity inhomogeneities which we relate to "hot spots." Numerical discrete dipole approximation calculations including the interaction between gold nanoparticles are presented, providing a qualitative model for the coupled-plasmon absorption and redshifted Raman hot spots in these samples.

Coupling between molecular vibrations and liquid crystalline order parameters.

Specific Raman active modes in two prototype cyanobiphenyl liquid crystals are shown to display a temperature dependent softening proportional to either the nematic or smectic order parameters, while other vibrations (like the C identical withN stretch mode) remain unaltered. This selective coupling between intramolecular vibrations and the liquid crystalline order is related to the intrinsic symmetry of the modes. The method provides a simple, microscopic, noninvasive optical technique with which the liquid crystalline order parameters can be qualitatively mapped out.

Phonon self-energies and phase transitions in a prototype discotic liquid crystal

Specific Raman active vibrations in the discotic liquid crystal nematogen hexakis(6-hexyloxy)triphenylene are shown to be sensitive to either the isotropic<-->columnar or the columnar<-->solid phase transitions. Changes in frequency and/or intensity of vibrations with specific symmetries demonstrate that the method can be used not only to monitor the phase transitions themselves with a microscopic and noninvasive optical technique, but also to gain physical information on the origin of the molecular interactions that produce them.

Photoinduced oxygen dynamics in lyophilized hemoglobin.

Reversible laser induced deoxygenation in the lyophilized phase of hemoglobin is demonstrated by means of resonant Raman scattering, luminescence, and optical transmission. Specific Raman modes, which are both sensitive to the spin states of Fe(II) in the hemes and resonant in the visible, are monitored as a function of time to evaluate the effect of the illuminating laser. These modes act as in-situ markers of the oxygen content of the protein. The reversible photoinduced deoxygenation can be observed through both the Raman spin-markers and the optical transmission experiments. In the former, reversible changes in the intensities of specific Raman modes are observed, while in the latter, the oscillator strength of the two main absorptions of oxyhemoglobin in the visible are seen to vary accordingly. The luminescence in lyophilized hemoglobin is found to have at least two different contributions, (i) a resonant component with the Raman modes and; (ii) a nonresonant contribution, which increases at high input laser powers and eventually masks the Raman signals. The nonresonant contribution is the luminescence of the photoproduct achieved by thermal denaturation of the protein and remains standing as a permanent nonreversible damage in the illuminated spot. Semiempirical electronic calculations of the wavefunction and total energy of the iron porphyrin reveal the underlying physical origin of the laser induced deoxygenation process in the hemes and are also presented.

Universal low-frequency vibrations of proteins from a simple interaction potential.

A pairwise Born potential connecting the heavy atom sites within a prescribed cutoff, and the equation of motion method (EOM), reproduce the existence of a universal singularity in the low-frequency vibrational density of states of typical globular proteins. This is due to quasilocalization of acoustic waves and an analogy with a similar feature found in glasses is stressed. We explain the dependence of this anomaly with the effective dimensionality of the protein. The EOM method allows for the study of even the largest proteins with a simple personal computer.