Marco Allione

Two-photon-induced blue shift of core and shell optical transitions in colloidal CdSe/CdS quasi-type II quantum rods.

The spectral dependence of the two-photon absorption in CdSe/CdS core/shell nanocrystal heterorods has been studied via two-photon-induced luminescence excitation spectroscopy. We verified that the two-photon absorption in these samples is a purely nonlinear phenomenon, excluding the contribution from multistep linear absorption mediated by defect states. A large absorption cross section was observed for CdSe/CdS core/shell quantum rods, in the range of 10(5) GM (1 GM = 10(-50) cm(4) s phot(-1)), scaling with the total nanocrystal volume and thus independent of the core emission wavelength. In the two-photon luminescence excitation spectra, peaks are strongly blue-shifted with respect to the one-photon absorption peaks, for both core and shell transitions. The experimental results are confirmed by k·p calculations, which attribute the shift to both different parity selection rules that apply to one-photon and two-photon transitions and a low oscillator strength for two-photon transitions close to the ground-state one-photon absorption. In contrast with lead chalcogenide quantum dots, we found no evidence of a breakdown of the optical selection rules, despite the presence of band anisotropy, via the anisotropic hole masses, and the explicitly induced reduction of the electron wave function symmetry via the rod shape of the shell. The anisotropy does lead to an unexpected splitting of the electron P-states in the case of a large CdSe core encapsulated in a thin CdS shell. Hence, tuning of the core and shell dimensions and the concurrent transition from type I to quasi-type II carrier localization enables unprecedented control over the band-edge two-photon absorption.

The structure of DNA by direct imaging.

The DNA helix and its internal structures were directly imaged; characteristic lengths and inner components were measured and reported. The structure of DNA was determined in 1953 by x-ray fiber diffraction. Several attempts have been made to obtain a direct image of DNA with alternative techniques. The direct image is intended to allow a quantitative evaluation of all relevant characteristic lengths present in a molecule. A direct image of DNA, which is different from diffraction in the reciprocal space, is difficult to obtain for two main reasons: the intrinsic very low contrast of the elements that form the molecule and the difficulty of preparing the sample while preserving its pristine shape and size. We show that through a preparation procedure compatible with the DNA physiological conditions, a direct image of a single suspended DNA molecule can be obtained. In the image, all relevant lengths of A-form DNA are measurable. A high-resolution transmission electron microscope that operates at 80 keV with an ultimate resolution of 1.5 Å was used for this experiment. Direct imaging of a single molecule can be used as a method to address biological problems that require knowledge at the single-molecule level, given that the average information obtained by x-ray diffraction of crystals or fibers is not sufficient for detailed structure determination, or when crystals cannot be obtained from biological molecules or are not sufficient in understanding multiple protein configurations.

Microfluidic device for continuous single cells analysis via Raman spectroscopy enhanced by integrated plasmonic nanodimers

In this work a Raman flow cytometer is presented. It consists of a microfluidic device that takes advantages of the basic principles of Raman spectroscopy and flow cytometry. The microfluidic device integrates calibrated microfluidic channels- where the cells can flow one-by-one -, allowing single cell Raman analysis. The microfluidic channel integrates plasmonic nanodimers in a fluidic trapping region. In this way it is possible to perform Enhanced Raman Spectroscopy on single cell. These allow a label-free analysis, providing information about the biochemical content of membrane and cytoplasm of the each cell. Experiments are performed on red blood cells (RBCs), peripheral blood lymphocytes (PBLs) and myelogenous leukemia tumor cells (K562).

Rod-shaped nanostructures based on superparamagnetic nanocrystals as viscosity sensors in liquid

Superparamagnetic nanostructures are becoming increasingly important as tools for biological and medical applications. We report the study of the movement of rod-shaped assemblies of superparamagnetic nanocrystals under the action of a rotating magnetic field. The dynamic was characterized by means of light scattering detection at different frequencies and for different values of the intensity of the applied external field. The possibility to correlate the motion to the viscosity of the medium is used to monitor viscosity changes inside the liquid. We propose this technique as a valuable tool to monitor viscosity at microscale for application in biological studies.

Adiabatic nanofocusing: spectroscopy, transport and imaging investigation of the nano world

Adiabatic compression plays a fundamental role in the realization of localized enhanced electromagnetic field hot spots, it provides the possibility to focus at nanoscale optical excitation. It differs from the well-known lightning rod effect since it is based on the lossless propagation of surface plasmon polaritons (SPPs) up to a nano-sized metal tip where the energy density is largely enhanced. Here we discuss two important applications of adiabatic compression: Raman and hot electron spectroscopy at nanometric resolution. The underlying phenomena are the conversion of SPPs into photons or hot electrons. New scanning probe spectroscopy techniques along with experimental results are discussed. We foresee that these techniques will play a key role in relating the functional and structural properties of matter at the nanoscale.

Photoinduced variable stiffness of spiropyran-based composites

A quantitative demonstration of reversible stiffness upon appropriate light stimulus in a spiropyran-polymeric composite is presented. The polymeric films containing 3% wt. of the photochromic spiropyran were irradiated with alternating ultraviolet and visible light and the storage modulus was measured. A reversible change in modulus of about 7% was observed. The modulus change was attributed to an interaction of the polar merocyanine with the polymeric chains and/or to a variation of effective free volume induced by merocyanine aggregates formed in the polymer upon ultraviolet irradiation. The effect is fully reversed when the merocyanine isomers turn back to the spiropyran state after visible irradiation.

Plasmonic Nanowires for Wide Wavelength Range Molecular Sensing

In this paper, we propose the use of a standing nanowires array, constituted by plasmonic active gold wires grown on iron disks, and partially immersed in a supporting alumina matrix, for surface-enhanced Raman spectroscopy applications. The galvanic process was used to fabricate nanowires in pores of anodized alumina template, making this device cost-effective. This fabrication method allows for the selection of size, diameter, and spatial arrangement of nanowires. The proposed device, thanks to a detailed design analysis, demonstrates a broadband plasmonic enhancement effect useful for many standard excitation wavelengths in the visible and NIR. The trigonal pores arrangement gives an efficiency weakly dependent on polarization. The devices, tested with 633 and 830 nm laser lines, show a significant Raman enhancement factor, up to around 6 × 104, with respect to the flat gold surface, used as a reference for the measurements of the investigated molecules.

Graphene: A Building Foundation for Efficient Plasmonic SERS Device

In this paper graphene over SiO2/Si substrate was used as a building base to fabricate SERS device. A thin film of silver was deposited over graphene and annealed at 250°C. The substrate was examined after chemisorption of two molecules; rhodamine 6G which is a fluorescent dye, and 3-mercaptobenzoic acid, a thiol molecule. SERS enhancement factor for the proposed device is estimated to be 2.1 × 106 with respect to the flat silver substrate deposited over Si. The experimental results were compared in two ways: a) by using electromagnetic field calculation and b) quantum mechanical calculation derived from density function theory. The experimental findings were consistent with the theoretical observations.

Novel Plasmonic Probes and Smart Superhydrophobic Devices, New Tools for Forthcoming Spectroscopies at the Nanoscale

In this work we review novel strategies and new physical effects to achieve compositional and structural recognition at single molecule level. This chapter is divided in two main parts. The first one introduces the strategies currently adopted to investigate matter at few molecules level. Exploiting the capability of surface plasmon polaritons to deliver optical excitation at nanoscale, we introduce a technique relying on a new transport phenomenon with chemical sensitivity and nanometer spatial resolution. The second part describes how micro and nanostructured superhydrofobic textures can concentrate and localize a small number of molecules into a well-defined region, even when only an extremely diluted solution is available. Several applications of these devices as micro- and nano-systems for high-resolution imaging techniques, cell cultures and tissue engineering applications are also discussed.

Fabrication, Mercury Intrusion Porosimetry Characterization and In Vitro Qualitative Analysis of Biocompatibility of Various Porosities Polycaprolactone Scaffolds

In order to develop surfaces with improved cell culture biocompatibility, we optimized a solvent-casting and particulate-leaching fabrication technique to create porous three-dimensional polycaprolactone scaffolds. These biocompatible porous surfaces were realized by means of NaCl particles as porogen; salt leaching by immersion in distilled water created porosity and pore interconnectivity in the material. Scanning electron microscopy and mercury intrusion porosimetry were used for the measurement of porosity, pore size distribution, permeability and compressibility. To evaluate scaffold biocompatibility, fibroblasts were cultured on the porous surfaces and confocal immunofluorescence characterization indicated that they were effective for in vitro cell culture and practical tissue engineering applications.