Biomedical subjects

Roberto Cingolani

Publications and source records attributed to Roberto Cingolani.

At least 19 recordsLinked to original sources

PubMed2006

Heterodimers based on CoPt3-Au nanocrystals with tunable domain size.

We describe an approach to synthesize colloidal nanocrystal heterodimers composed of CoPt(3) and Au. The growth is based on the nucleation of gold domains on preformed CoPt(3) nanocrystals. It is a highly versatile methodology which allows us to tune independently the size of the two domains in each dimer by varying several reaction parameters. The statistical analysis of the distribution of the domain sizes in the dimers and the compositional mapping achieved by dark field imaging and energy dispersive spectroscopy confirm that the two domains in each dimer are indeed made of CoPt(3) and Au, respectively. Structural characterization by high-resolution transmission electron microscopy shows that the two domains, both having cubic fcc Bravais lattice, can share a common {111}, {100}, or {110} facet, depending on the size of the initial CoPt(3) seeds. The magnetization measurements evidence a ferromagnetic CoPt(3) phase with a relatively low anisotropy as a consequence of their disordered crystalline structure, regardless of the presence of a Au tip. We believe that this prototype of nanocrystal dimer, which can be manipulated under air, can find several applications in nanoscience, as the Au section can be exploited as the preferential anchor point for various molecules, while the CoPt(3) domain can be used for magnetic detection.

Journal Article↗

PubMed2006

Optical gain from the open form of a photochromic molecule in the solid state.

This work presents evidence for line-narrowing from the UV photoexcited open form of the photochromic molecule, indolinospiropyran (1',3'-dihydro-1',3',3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2,2'-(2H)-indole]) in the solid state. The line-narrowing is attributable to amplified spontaneous emission induced by optical gain and assisted by the waveguiding within the organic film. Optical gain throughout a band as large as 28 nm, with a maximum gain coefficient of 5.6 cm(-1), is observed in the merocyanine emission region (660-730 nm). These results open the way to the realization of hybrid devices based on the coupling between photochromic behavior and stimulated emission from conjugated molecules, such as lasing optical memories, and lasers gated by optical molecular switches.

Letter↗

PubMed2006

Photocontrolled variations in the wetting capability of photochromic polymers enhanced by surface nanostructuring.

The wetting characteristics of surfaces of polymers doped with photochromic spiropyran molecules can be tuned when irradiated with laser beams of properly chosen photon energy. The hydrophilicity is enhanced upon UV laser irradiation since the embedded nonpolar spiropyran molecules convert to their polar merocyanine isomers. The process is reversed upon green laser irradiation. Structuring of the photochromic polymeric surfaces with soft lithography enhances significantly the hydrophobicity of the system, indicating that the water droplets on the patterned features interact with air that is trapped in the microcavities, thus creating superhydrophobic air-water contact areas. Furthermore, the light-induced wettability variations of the structured surfaces are enhanced by a factor of 3 compared to those on the flat surfaces. This significant enhancement is attributed to the photoinduced reversible volume changes to the imprinted gratings, which additionally contribute to the wettability changes due to the light-induced photochromic interconversions.

Journal Article↗

PubMed2006

Multiple wurtzite twinning in CdTe nanocrystals induced by methylphosphonic acid.

Branching in semiconductor nanocrystals, which leads to tetrapods and to more complex architectures, is the subject of intensive investigation. Here we support the model according to which branching in CdTe nanocrystals is driven by the formation of multiple wurtzite twins. This is in contrast to previous models for this material. We found that twinning, as well as anisotropic growth, can be triggered by the presence of suitable molecules, such as for instance methylphosphonic acid. In the case of CdTe nanocrystals, we designed a robust growth scheme in which the variation of a single parameter (the concentration of methylphosphonic acid in solution) leads to the controlled formation of nanocrystals with shapes ranging from spheres to anisotropic structures with varying level of branching, as both twinning and anisotropic growth are progressively favored. We believe that these concepts can be extended to other nanocrystal systems.

Journal Article↗

PubMed2006

Two dimensional patterning of fluorescent proteins in hydrogels.

This work describes the successful micropatterning of hybrid systems consisting of hydrogel-dispersed optically active and controllable proteins on solid surfaces without degradation of the photophysical properties of the light-emitting biomolecules. It demonstrates the preservation of the luminescence properties of proteins entrapped into isolated microstructures of poly(acrylamide) gel. This way we can exploit both the structural and function-preserving properties of the hydrogels and the functionality of light-emitting proteins. We believe that this approach can open the way to the realization of nanopatterned optical memories based on photochromic biomolecules.

Animals↗

PubMed2006

Confinement effects on optical phonons in polar tetrapod nanocrystals detected by resonant inelastic light scattering.

We investigated CdTe nanocrystal tetrapods of different sizes by resonant inelastic light scattering at room temperature and under cryogenic conditions. We observe a strongly resonant behavior of the phonon scattering with the excitonic structure of the tetrapods. Under resonant conditions we detect a set of phonon modes that can be understood as confined longitudinal-optical phonons, surface-optical phonons, and transverse-optical phonons in a nanowire picture.

Journal Article↗

PubMed2006

Colloidal synthesis and characterization of tetrapod-shaped magnetic nanocrystals.

Tetrapod-shaped maghemite nanocrystals are synthesized by manipulating the decomposition of iron pentacarbonyl in a ternary surfactant mixture under mild thermal conditions. Adjustment of the reaction parameters allows for the systematic tuning of both the width and the length of the tetrapod arms, which grow preferentially along the 111 easy axis direction. Such degree of control leads to modulation of the magnetic behavior of the nanocrystals, which evolves systematically as their surface magnetization phase and shape anisotropy are progressively increased.

Anisotropy↗

PubMed2005

X-ray excited visible luminescence spectroscopy of organic materials using a portable optical spectrometer.

The use of a portable video telescope, mounted externally to a beamline endstation, to obtain synchrotron-radiation-excited visible luminescence, is described. Real-time video monitoring permits simple and quick alignment, and allows a visual record of the luminescence experiment. The telescope is fibre-optic-coupled to an optical spectrometer. Examples are given of X-ray excited optical spectroscopy from organic materials for light-emitting-diode applications.

Equipment Design↗

PubMed2005

Conformation of microcontact-printed proteins by atomic force microscopy molecular sizing.

We investigated the structural changes occurring in proteins patterned via microcontact printing. This was done by molecular sizing using atomic force microscopy to observe the structure of printed individual metalloprotein molecules in the unlabeled and untreated states. We observed that the size of the printed proteins were more than 2-fold smaller than the native shape, which indicates that some deformations take place upon the contact-assisted adsorption on silanized silicon dioxide. This can be attributed to simultaneously occurring effects, and particularly to the sandwiching between surfaces of very different hydrophilic/hydrophobic properties during contact lithography.

Adsorption↗

PubMed2005

First-principles modeling of unpassivated and surfactant-passivated bulk facets of wurtzite CdSe: a model system for studying the anisotropic growth of CdSe nanocrystals.

Equilibrium geometries, surface energies, and surfactant binding energies are calculated for selected bulk facets of wurtzite CdSe with a first-principles approach. Passivation of the surface Cd atoms with alkyl phosphonic acids or amines lowers the surface energy of all facets, except for the polar 000 facet. On the nonpolar facets, the most stable configuration corresponds to full coverage of surface Cd atoms with surfactants, while on the polar 0001 facet it corresponds only to a partial coverage. In addition, the passivated surface energies of the nonpolar facets are in general lower than the passivated polar 0001 facet. Therefore, the polar facets are less stable and less efficiently passivated than the nonpolar facets, and this can rationalize the observed anisotropic growth mechanism of wurtzite nanocrystals in the presence of suitable surfactants.

Journal Article↗

PubMed2005

Emission properties of printed organic semiconductor lasers.

We investigated the emission properties of a distributed-feedback resonator based on an organic semiconductor patterned by a novel printing technology. We observed the peak splitting of the photonic bandstructure of the periodic grating and extracted the effective refractive index of the outcoupled guided modes. The laser works at the second diffraction order, exhibiting narrow single-mode emission at 637 nm, with a threshold as low as 37 microJ/cm2. The results suggest that direct printing is a promising fabrication technique for optically confined integrated optoelectronics.

Journal Article↗

PubMed2005

Microfluidic motion for a direct investigation of the structural dynamics of glass-forming liquids.

Glass-forming liquids, polymer solutions, and biofluids have additional inertial and elastic macroscopic degrees of freedom that are related to the elasticity of the molecular coils and affect the determination of the structural dynamical parameters. In this work, we propose a new approach for the direct evaluation of the fundamental material parameters (viscosity, fragility, glass transition temperature) of a viscoelastic liquid in a capillary flow inside a microfluidic device. The proposed technique substantially reduces the complexity of the theoretical analysis and provides an evaluation of the most relevant functional parameters of the fluid dynamics. Moreover, the approach allows the investigation of localization phenomena in geometrical confined systems, such as those required in miniaturized devices.

Microfluidic Analytical Techniques↗

PubMed2005

Selective growth of PbSe on one or both tips of colloidal semiconductor nanorods.

PbSe nanocrystals with rock-salt structure are grown on the tips of colloidal CdS and CdSe nanorods. The facets of wurtzite rods provide a substrate with various degrees of reactivity for the growth of PbSe. The presence of dangling Cd bonds may explain subtle differences between nonequivalent facets resulting in the selective nucleation of PbSe only on one of the two tips of each CdS rod. This approach has the potential to facilitate the fabrication of heterostructures with tailored optical and electronic properties.

Adsorption↗

PubMed2005

Multilevel, room-temperature nanoimprint lithography for conjugated polymer-based photonics.

We demonstrate the multilevel patterning of organic light-emitting polymers by room-temperature nanoimprint lithography (RT-NIL), which is impossible to obtain by conventional hot embossing. In particular, we realize one- and two-dimensional photonic crystals with 500 nm periodic features and investigate the changes in the optical properties (luminescence and quantum yield) of the organic active layer. An increase of the quantum yield by 2.4% for the patterned film with respect to the untextured one and the enhancement of the output light emitted at a particular angle (Theta = 69 degrees) are observed for gratings whose Bragg periodicity matched the emission wavelength of the polymer. The employment of RT-NIL to pattern polymer semiconductors without degradation of their optical properties represents a strategic route for the realization of novel nanopatterned optoelectronic devices.

Journal Article↗

PubMed2004

Self-assembled monolayers of cobalt(II)- (4-tert-butylphenyl)-porphyrins: the influence of the electronic dipole on scanning tunneling microscopy images.

Self-assembled monolayers (SAMs) of cobalt(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin, a promising material for optical, photoelectrochemical, and chemical sensor applications, were prepared on Au(111) via axial ligation to 4-aminothiophenol, and studied by several surface science techniques. Scanning tunneling microscopy (STM) and spectroscopy (STS) measurements showed the apparent topology of the Au(111) herringbone structure reconstruction, but with bias-dependent contrast images and asymmetric I/V characteristics. Photoelectron spectroscopy confirmed the presence of metalloporphyrins on the surface, whereas near-edge X-ray absorption (NEXAFS) measurements revealed that the porphyrin ring was tilted by about 70 degrees with respect to the surface plane. The above effects are ascribed to the presence of oriented molecular dipole layers between the metal and the organic material as confirmed by a comparison with first-principles density-functional theory calculations. The measured bias-dependent STM profiles have been reproduced by a simple monodimensional tunneling model.

Journal Article↗

PubMed2004

Rapid soft lithography by bottom-up enhanced capillarity.

The growing demand for new solutions to pursue the trend of micro- and nanoelectronics predicted by Moore's law is stimulating the development of new high-resolution, low-cost lithographies. Here we demonstrate that several bottom-up approaches can be used to increase the throughput of soft lithography by exploiting the enhanced hydrophilicity, the low viscosity, and the fragility of the employed materials. In particular, the customized functionalization of the involved surfaces to improve the wettability to polymer fluids and the dramatic decrease of the viscosity of polymer compounds as the temperature is increased, together with the good thermal stability of the functionalized surfaces, allow a faster filling of elastomeric channels, up to almost an order of magnitude with respect to conventional microfluidics.

Journal Article↗

PubMed2003

Solid-state supramolecular organization, established directly from powder diffraction data, and photoluminescence efficiency of rigid-core oligothiophene-S,S-dioxides.

The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene-4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO.

Journal Article↗

PubMed2003

A protein-based three terminal electronic device.

Because of their natural functional characteristics, involving inter- and intramolecular electron transfer, metalloproteins are good candidates for biomolecular nanoelectronics. In particular, blue copper proteins, such as azurin, can bind gold via a disulfide site present on its surface and they have a natural electron transfer activity that can be exploited for the realization of molecular switches whose conduction state can be controlled by tuning their redox state through an external voltage source. We report on the implementation of a prototype of protein transistor operating in air and in the solid state, based on this class of proteins. The three terminal devices exhibit various functions depending on the relative source-drain and gate-drain voltages bias, opening a way to the implementation of a new generation of logic architectures.

Azurin↗