In Silico Stark Effect: Determination of Excited-State Polarizabilities of Squaraine Dyes.

The static electric polarizabilities (α) of a quadrupolar squaraine dye are investigated in silico, either as the excess polarizability, i.e., the change from the ground to the lowest excited state, Δα, or as those of the two states separately, depending on the approach. The polarizabilities are worked out by making use of the energy and dipole moment Taylor expansions as a function of the electric field (E), in which α is represented by the quadratic and linear terms, respectively, and also by means of the linear response approach. Dipoles and energies are computed at a few values of the electric field, with different strategies that consider the geometry of the molecule either frozen in the ground state or relaxed at each E value. From a physical standpoint, the most appropriate approach to describing the molecular polarizability depends on the processes in which the molecule is involved: for example, fluorescence methods provide information about relaxed excited states, and absorption methods are used to determine the polarizability changes of excited states frozen in the ground-state conformation. We show that the excited-state polarizability does not strongly differ from the ground-state polarizability when the field is applied along the main axis of the squaraine. In contrast, remarkable differences are found when the field is applied perpendicular to the molecular plane due to a large geometrical distortion of the molecular backbone.

Far- and near-field properties of gold nanoshells studied by photoacoustic and surface-enhanced Raman spectroscopies.

Gold nanoshells, with a silica core and different core and shell dimensions, have been extensively investigated. Optical far-field properties, namely extinction and absorption, have been separately determined by means of spectrophotometry and photoacoustic spectroscopy, respectively, in the 440-900 nm range. The enhancement factor for surface-enhanced Raman scattering, which is related to near-field effects, has been measured from 568 to 920 nm. The absorption contribution to extinction decreases as the overall diameter increases. Moreover, absorption and scattering display different spectral distributions, the latter being red shifted. The Surface Enhanced Raman Scattering enhancement profile, measured using thiobenzoic acid as a Raman probe, is further shifted to the red. The latter result suggests that the enhancement is dominated by the presence of hot spots, which are possibly related to the surface roughness of gold nanoshell particles.

Wavelength dispersion of the local field intensity in silver-gold nanocages.

This study provides a combined theoretical and experimental analysis of the far-field (extinction) and of the near-field (SERS enhancement) spectral distribution in hollow nanoparticles, that is, silver-gold nanocages (NCs). Chitosan protected NCs have been synthesized by a galvanic replacement-based procedure: their morphological properties and chemical composition have been characterized by TEM, STEM and ICP. NCs were then functionalized with a thiolated organic dye prior to carrying out SERS measurements. Finite Element Method simulations of a single NC have shown that the field enhancement at the excitation wavelength follows the same spectral dependence as the extinction spectrum and, consequently, the SERS enhancement profile, as a function of the excitation wavelength, peaks at higher energy with respect to extinction. The simulated extinction is remarkably narrower than the experimental spectrum of NCs in solution, indicating that the colloidal sample is substantially polydispersed. However, a simple qualitative model that we have developed would suggest that the SERS enhancement profile is blue-shifted with respect to the extinction in the presence of polydispersivity as well. In addition, NC dimers have been simulated: both their extinction and near field-spectra shift to the red when the size of the gap is reduced analogous to what happens with dimers of filled spherical nanoparticles (NPs). In addition, simulations also revealed that a NC dimer is only slightly more efficient in amplifying the field with respect to the isolated NC, and this behavior is peculiar to NCs. In fact, filled spherical NP dimers exhibit a remarkably stronger field enhancement with respect to the isolated NP. By means of Wavelength Scanned SERS, we measured the spectral distribution of the local field in a dispersion of NCs. We observed experimentally that the local field is distributed in the same spectral region as the extinction and that the absolute value of the SERS enhancement factor maintains a low value throughout the range explored (568-800 nm). We propose that the observed correlation between the SERS profile and the extinction is accidental and originates from the limited increase in amplification provided by NC aggregates with respect to isolated NCs.

Growth and optical properties of silver nanostructures obtained on connected anodic aluminum oxide templates.

Ag nanostructures are grown by AC electrodeposition on anodic alumina oxide (AAO) connected membranes acting as templates. Depending on the thickness of the template and on the voltage applied during the growth process, different Ag nanostructures with different optical properties are obtained. When AAO membranes about 1 µm thick are used, the Ag nanostructures consist in Ag nanorods, at the bottom of the pores, and Ag nanotubes departing from the nanorods and filling the pores almost for the whole length. When AAO membranes about 3 µm thick are used, the nanostructures are Ag spheroids, at the bottom of the pores, and Ag nanowires that do not reach the upper part of the alumina pores. The samples are characterized by angle resolved x-ray photoelectron spectroscopy, scanning electron microscopy and UV-vis and Raman spectroscopies. A simple NaOH etching procedure, followed by sonication in ethanol, allows one to obtain an exposed ordered array of Ag nanorods, suitable for surface-enhanced Raman spectroscopy, while in the other case (3 µm thick AAO membranes) the sample can be used in localized surface plasmon resonance sensing.

Safe core-satellite magneto-plasmonic nanostructures for efficient targeting and photothermal treatment of tumor cells.

Magneto-plasmonic nanostructures functionalized with cell targeting units are of great interest for nanobiotechnology applications. Photothermal treatment of cells targeted with antibody functionalized nanostructures and followed by magnetic isolation, allows killing selected cells and hence is one of the applications of great interest. The magneto-plasmonic nanostructures reported herein were synthesized using naked gold and magnetite nanoparticles obtained through a green approach based on laser ablation of bulk materials in water. These particles do not need purifications steps for biocompatibility and are functionalized with a SERRS (surface enhanced resonance Raman scattering) active molecule for detection and with an antibody for targeting prostate tumor cells. Quantitative results for the cell targeting and selection efficiency show an overall accuracy of 94% at picomolar concentrations. The photothermal treatment efficiently kills targeted and magneto-selected cells producing a viability below 5% after 3 min of irradiation, compared with almost 100% viability of incubated and irradiated, but non targeted cells.

Nonlinear infrared and optical responses of a Holstein-Peirls-Hubbard dimer.

A simple model based on the Holstein-Peierls-Hubbard Hamiltonian has been used to calculate the nonlinear responses at infrared and optical frequencies. The model is applied to a molecular ion radical dimer in order to account for the contribution to the nonlinear responses arising from the intermolecular charge transfer excitations and from their coupling to both intramolecular and intermolecular phonons. A similar calculation has been performed on a model quadrupolar conjugated molecule characterized by intramolecular charge transfer excitations. The calculations are performed according to a collective electronic oscillator scheme by solving the Liouville equation for the bielectronic density matrix. Such a choice allows us to retain the ability, inherent in the Hubbard type models, to fully account for the on-site electron correlation effects. Calculated spectra are reported for one-photon and two-photon absorption (the latter in the form of the imaginary part of the Kerr susceptibility) and for third harmonic generation. Narrow resonances are observed in the infrared, related mostly to the coupling with intramolecular modes. The off-resonant contribution to the nonlinear susceptibility arising from the electron-phonon interactions appears to be marginal (in the order of 1%) in all cases.

[Catecholamine behavior, adrenoreceptor density of intact cells and sensitivity to catecholamines in a patient with orthostatic hypotension]. / Katecholaminverhalten, Adrenorezeptorendichte an intakten Zellen und Katecholaminempfindlichkeit bei einer Patinetin mit orthostatischer Hypotonie.

We evaluated sympathetic nervous system function in a patient with primary orthostatic hypotension. Plasma catecholamine levels--except for dopamine levels--and urinary catecholamine excretion were decreased, alpha-adrenoreceptor responsiveness to noradrenaline and beta-adrenoreceptor responsiveness to isoproterenol were increased according to increased beta-2-adrenoreceptor density on intact polymorphonuclear leukocytes. Alpha-2-adrenoreceptor density on intact platelets and adrenaline-induced platelet aggregation in vitro, however, were unchanged. We evolved a therapeutic regimen with fludrocortisone, propranolol, and dihydroergotamine that allowed the patient to resume nearly a regular degree of mobility.