Laser synthesis of ligand-free bimetallic nanoparticles for plasmonic applications.

A picosecond laser ablation approach has been developed for the synthesis of ligand-free AuAg bimetallic NPs where the relative amount of Ag is controlled in situ through a laser shielding effect. Various measurements, such as optical spectroscopy, transmission electron microscopy combined with energy dispersive X-ray spectroscopy and inductively coupled plasma optical emission spectrometry, revealed the generation of homogenous 15 nm average size bimetallic NPs with different compositions and tunable localized surface plasmon resonance. Furthermore, ligand-free metallic nanoparticles with respect to chemically synthesized nanoparticles display outstanding properties, i.e. featureless Raman background spectrum, which is a basic requirement in many plasmonic applications such as Surface Enhanced Raman Spectroscopy. Various molecules were chemisorbed on the nanoparticle and SERS investigations were carried out, by varying the laser wavelength. The SERS enhancement factor for AuAg bimetallic NPs shows an enhancement factor of about 5.7 × 10(5) with respect to the flat AuAg surface.

Neurons sense nanoscale roughness with nanometer sensitivity.

The interaction between cells and nanostructured materials is attracting increasing interest, because of the possibility to open up novel concepts for the design of smart nanobiomaterials with active biological functionalities. In this frame we investigated the response of human neuroblastoma cell line (SH-SY5Y) to gold surfaces with different levels of nanoroughness. To achieve a precise control of the nanoroughness with nanometer resolution, we exploited a wet chemistry approach based on spontaneous galvanic displacement reaction. We demonstrated that neurons sense and actively respond to the surface nanotopography, with a surprising sensitivity to variations of few nanometers. We showed that focal adhesion complexes, which allow cellular sensing, are strongly affected by nanostructured surfaces, leading to a marked decrease in cell adhesion. Moreover, cells adherent on nanorough surfaces exhibit loss of neuron polarity, Golgi apparatus fragmentation, nuclear condensation, and actin cytoskeleton that is not functionally organized. Apoptosis/necrosis assays established that nanoscale features induce cell death by necrosis, with a trend directly related to roughness values. Finally, by seeding SH-SY5Y cells onto micropatterned flat and nanorough gold surfaces, we demonstrated the possibility to realize substrates with cytophilic or cytophobic behavior, simply by fine-tuning their surface topography at nanometer scale. Specific and functional adhesion of cells occurred only onto flat gold stripes, with a clear self-alignment of neurons, delivering a simple and elegant approach for the design and development of biomaterials with precise nanostructure-triggered biological responses.

Control and ultrafast dynamics of a two-fluid polariton switch.

We investigate the cross interactions in a two-component polariton quantum fluid coherently driven by two independent pumping lasers tuned at different energies and momenta. We show that both the hysteresis cycles and the on-off threshold of one polariton signal can be entirely controlled by a second polariton fluid. Furthermore, we study the ultrafast switching dynamics of a driven polariton state, demonstrating the ability to control the polariton population with an external laser pulse, in less than a few picoseconds.

Improvements of optical tactile sensors for robotic system by gold nanocomposite material.

In this work we propose the evolution of a new class of optical pressure sensors suitable for robot tactile sensing. The sensors are based on a tapered optical fiber, where optical signals travel embedded into a PDMS-gold nanocomposite material. By applying different pressure forces on the PDMS-based nanocomposite we measure in real time the change of the optical transmitted intensity due to the coupling between the gold nanocomposite material and the tapered fiber region. The intensity reduction of the transmitted light intensity is correlated with the pressure force magnitude.

Wettability control by laser texturing process generating localized gold nanoparticles on polymeric thin films.

In this work a new approach is introduced for surface properties control by laser texturing process. By UV laser irradiation, we are able to control the surface wettability of a chitosan polymeric film in which is introduced a chloroauric acid salt by immersion. Specifically the UV irradiation is responsible for the creation of gold nanoparticles at the irradiated surface of the polymeric film. This photolytic process allows us to localize and design accurately surface patterns and moreover to tune metallic particle size in the range of nanoscale. After the characterization of our gold textured surfaces by atomic force and scanning electron microscopies, we demonstrate the link between wettability surface properties and gold nanoparticles size. The experimental results indicate the influence of the laser intensity, the irradiation time and the polymer film thickness (by increasing the gold concentration) on the gold nanoparticle density and size.

Modular plastic chip for one-shot human papillomavirus diagnostic analysis.

In this article, we report the design and development of a plastic modular chip suitable for one-shot human papillomavirus (HPV) diagnostics, namely detection of the viral presence and relative genotyping, by two sequential steps performed directly on the same device. The device is composed of two modular and disposable plastic units that can be assembled or used separately. The first module is represented by a polydimethylsiloxane (PDMS) microreactor that is exploited for real-time polymerase chain reaction (PCR) and, thus, is suitable for detecting the presence of virus. The second unit is a PDMS microwell array that allows virus genotyping by a colorimetric assay, based on DNA hybridization technology developed on plastic, requiring simple inspection by the naked eye. The two modules can be easily coupled to reusable hardware, enabling the heating/cooling processes and the real-time detection of HPV. By coupling real-time assay and colorimetric genotyping on the same chip, the assembled device may provide a low-cost tool for HPV diagnostics, thereby favoring the prediction of cancer risk in patients.

Nanowalled polymer microtubes fabricated by using strained semiconductor templates.

Herein we describe the realization of nanowalled polymeric microtubes through a novel and versatile approach combining the layer-by-layer (LbL) deposition technique, the self-rolling of hybrid polymer/semiconductor microtubes and the subsequent removal of the semiconductor template. The realized channels were characterized in detail using scanning electron and atomic force microscopes. Additionally, we report on the incorporation of a dye molecule within the nanowalls of such microtubes, demonstrating a distribution of the fluorescence signal throughout the whole channel volume. This approach offers the possibility to tailor the properties of micro/nanotubes in terms of size, wall thickness and composition, thus enabling their employment for several applications.

Exploring local flexibility/rigidity in psychrophilic and mesophilic carbonic anhydrases.

Molecular flexibility and rigidity are required to determine the function and specificity of protein molecules. Some psychrophilic enzymes demonstrate a higher catalytic efficiency at low temperatures, compared to the efficiency demonstrated by their meso/thermophilic homologous. The emerging picture suggests that such enzymes have an improved flexibility of the structural catalytic components, whereas other protein regions far from functional sites may be even more rigid than those of their mesophilic counterparts. To gain a deeper insight in the analysis of the activity-flexibility/rigidity relationship in protein structure, psychrophilic carbonic anhydrase of the Antarctic teleost Chionodraco hamatus has been compared with carbonic anhydrase II of Bos taurus through fluorescence studies, three-dimensional modeling, and activity analyses. Data demonstrated that the cold-adapted enzyme exhibits an increased catalytic efficiency at low and moderate temperatures and, more interestingly, a local flexibility in the region that controls the correct folding of the catalytic architecture, as well as a rigidity in the hydrophobic core. The opposite result was observed in the mesophilic counterpart. These results suggest a clear relationship between the activity and the presence of flexible and rigid protein substructures that may be useful in rational molecular and drug design of a class of enzymes playing a key role in pathologic processes.

Disposable plastic microreactors for genomic analyses.

We show the design, development and assessment of disposable, biocompatible, fully plastic microreactors, which are demonstrated to be highly efficient for genomic analyses, such as amplification of DNA, quantitative analyses in real time, multiplex PCR (both in terms of efficiency and selectivity), as compared to conventional laboratory equipment for PCR. The plastic microreactors can easily be coupled to reusable hardware, enabling heating/cooling processes and, in the case of qPCR applications, the real-time detection of the signal from a suitable fluorescent reporter present in the reaction mixture during the analysis. The low cost production of these polymeric microreactors, along with their applicability to a wide range of biochemical targets, may open new perspectives towards practical applications of biochips for point of care diagnostics.

Single-molecule mechanical unfolding of amyloidogenic beta2-microglobulin: the force-spectroscopy approach.

The recombinant production of a novel chimeric polyprotein is described. The new protein contains either wild-type beta(2)-microglobulin (beta(2)m) or its truncated variant (DeltaN6 beta(2)m) (see picture). Structural characterization is achieved by means of single-molecule force spectroscopy studies of specific beta(2)m regions which could be involved in amyloidogenesis.

Patterned structures of in situ size controlled CdS nanocrystals in a polymer matrix under UV irradiation.

A method of in situ formation of patterns of size controlled CdS nanocrystals in a polymer matrix by pulsed UV irradiation is presented. The films consist of Cd thiolate precursors with different carbon chain lengths embedded in TOPAS polymer matrices. Under UV irradiation the precursors are photolyzed, driving to the formation of CdS nanocrystals in the quantum size regime, with size and concentration defined by the number of incident UV pulses, while the host polymer remains macroscopically/microscopically unaffected. The emission of the formed nanocomposite materials strongly depends on the dimensions of the CdS nanocrystals, thus, their growth at the different phases of the irradiation is monitored using spatially resolved photoluminescence by means of a confocal microscope. X-ray diffraction measurements verified the existence of the CdS nanocrystals, and defined their crystal structure for all the studied cases. The results are reinforced by transmission electron microscopy. It is proved that the selection of the precursor determines the efficiency of the procedure, and the quality of the formed nanocrystals. Moreover it is demonstrated that there is the possibility of laser induced formation of well-defined patterns of CdS nanocrystals, opening up new perspectives in the development of nanodevices.

Scalar time domain modeling and coupling of second harmonic generation process in GaAs discontinuous optical waveguide.

We present in this work the scalar potential formulation of second harmonic generation process in chi((2)) nonlinear analysis. This approach is intrinsically well suited to the applications of the concept of circuit analysis and synthesis to nonlinear optical problems, and represents a novel alternative method in the analysis of nonlinear optical waveguide, by providing a good convergent numerical solution. The time domain modeling is applied to nonlinear GaAs asymmetrical waveguide with dielectric discontinuities in the hypothesis of quasi phase matching condition in order to evaluate the efficiency conversion of the second harmonic signal. The accuracy of the modeling is validated by the good agreement with the published experimental results. The effective dielectric constant method allows to extend the analysis also to 3D optical waveguides.

Design and modeling of tapered waveguide for photonic crystal slab coupling by using time-domain Hertzian potentials formulation.

This work introduces a new simulation approach to the evaluation of the time-domain electromagnetic (EM) field useful in the modeling of tapered waveguide for the Photonic Crystal Slab (PCS) coupling. Only solutions of two scalar Helmholtz-equations are used in the evaluation of electric and magnetic Hertzian-potentials that yields the EM field and the frequency response of the tapered waveguide. By considering simultaneously an analytical and a numerical approximation it is possible to reduce the computational burden. In order to compare the computational time we analyze the 2D structure by also using the Finite Difference Time Domain (FDTD) method and by the 3D Finite Element Method (FEM). The method is applied by starting from design criteria of the tapered structures in order to set the correct geometrical and physical parameters, and considers the field-perturbation effect in proximity of the dielectric discontinuities by generators modeling.

Study of the surface morphology of a cholesteryl tethering system for lipidic bilayers.

The immobilization of functional molecules embedded in lipidic membranes onto inorganic substrates is of great interest for numerous applications in the fields of biosensors and biomaterials. We report on the preparation and the morphological characterization of a tethering system for lipidic bilayers, which is based on cholesteryl derivatives deposited on hydrophilic surfaces by self-assembling and microcontact printing techniques. The investigation of the structural properties of the realized films by atomic, lateral, and surface potential microscopy allowed us to assess the high quality of the realized cholesteryl layers.

Optical properties of N-succinimidyl bithiophene and the effects of the binding to biomolecules: comparison between coupled-cluster and time-dependent density functional theory calculations and experiments.

We report a joint theoretical-experimental study on the optical properties of 5-N-succinimidyl-2,2'-bithiophene (NS-2T), a prototype system for a new class of biomarkers. Time-dependent density functional theory (TD-DFT) and approximate coupled-cluster single and doubles (CC2) calculations are performed in the ground and excited states. Theoretical results are compared with absorption, photoluminescence (PL), time-resolved PL, and PL quantum efficiency measurements. The excited state of NS-2T has a larger dipole moment as compared to that of the ground state, explaining the experimental shift of the PL peak in solvents of different polarity, and a smaller intersystem crossing (ISC) rate as compared to that of isolated bithiophene (2T), explaining the increased PL quantum efficiency. We also studied two model systems to describe the effects of the covalent binding of NS-2T to biomolecules and proteins with the epsilon-NH(2) lysine groups. These model systems show optical properties closer to 2T, as the PL quantum efficiency is reduced due to the increased ISC rate. Theoretical calculations and experimental results show that covalent binding of NS-2T to a biomolecule will blue-shift the absorption but not the photoluminescence. CC2 and TD-DFT can very well describe the absorption and photoluminescence energies of all three systems, but the presence of several charge-transfer transitions in the TD-DFT spectrum of NS-2T required the use of a correlated method to validate the TD-DFT results.

Making silicon hydrophobic: wettability control by two-lengthscale simultaneous patterning with femtosecond laser irradiation.

We report on the wettability properties of silicon surfaces, simultaneously structured on the micrometre-scale and the nanometre-scale by femtosecond (fs) laser irradiation to render silicon hydrophobic. By varying the laser fluence, it was possible to control the wetting properties of a silicon surface through a systematic and reproducible variation of the surface roughness. In particular, the silicon-water contact angle could be increased from 66° to more than 130°. Such behaviour is described by incomplete liquid penetration within the silicon features, still leaving partially trapped air inside. We also show how controllable design and tailoring of the surface microstructures by wettability gradients can drive the motion of the drop's centre of mass towards a desired direction (even upwards).

Formation and characterization of glutamate dehydrogenase monolayers on silicon supports.

In this paper we have tested two different procedures (the "three-step" and the "four-step" procedures) for the covalent immobilization of glutamate dehydrogenase (GDH) onto silicon supports. Atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FT-IR), fluorescence spectroscopy and an enzymatic assay were used to probe the structure and activity of the immobilized enzyme. Our results demonstrate that coupling through the "three-step" procedure does not significantly affect either the fold pattern or the activity of the enzyme, suggesting that this method could be ideally suited to the development of high quality monolayers for use in enzyme-based planar biosensors.

Nonradiative relaxation in thiophene-S,S-dioxide derivatives: the role of the environment.

The intramolecular radiative and nonradiative relaxation processes of three thiophene-S,S-dioxide derivatives with different molecular rigidity are investigated in different solutions and in inert matrix. We show that the fluorescence quantum efficiency and the relaxation dynamics are strongly dependent on the environment viscosity, whereas they are almost independent of the environment polarity. We demonstrate that this strong dependence is due to an environment dependent nonradiative decay rate, whereas no relevant variations of the radiative decay rate are observed. We demonstrate that the dipole coupling with the solvent does not provide an efficient nonradiative decay channel and that the S(n) - S(1) vibrational relaxation is very efficient in all of the molecules and for all of the investigated environments. Moreover first-principles time-dependent density-functional theory calculations in the correct, i.e., excited-state, molecular conformation, suggest that significant contributions of intersystem crossing to the triplet manifold can be excluded. We then conclude that the main nonradiative process determining the fluorescence quantum efficiency of this class of molecules is S(1) - S(0) internal conversion (IC). An explanation for the IC rate dependence in terms of the environment viscosity, molecular rigidity, S(1) - S(0) energy-gap, and molecular volume is presented.

Photoluminescence Efficiency of Substituted Quaterthiophene Crystals.

The photoluminescence (PL) efficiency of substituted alpha-conjugated quaterthiophene crystals shows marked differences depending on crystal packing and molecular geometry. This effect is studied by evaluating the role of the intermolecular interactions and the effects of the single molecule conformation on the intersystem crossing (ISC) rate. The comparison of these calculations with absolute quantum efficiency measurements and with the experimental temperature dependence of the PL decay time, indicates that the differences in PL efficiency are not inherent to crystal packing effects but they are determined by the ISC rate.

A modeling and convolution method to measure compositional variations in strained alloy quantum dots.

We have developed a method to quantitatively measure the absolute composition of nanometer sized capped quantum dots in semiconductor alloys. The method uses spatially resolved electron energy-loss spectroscopy in a scanning transmission electron microscope to measure compositional profiles across the center of the quantum dot and the adjacent nanometer wide wetting layer. The measurements from the wetting layer are used to derive a spatial broadening function which includes the effects of probe size, instabilities and beam spreading in the sample. This broadening function is employed to simulate compositional profiles from the quantum dots. Information on the dimensions of dots is extracted from annular dark-field images. The method is applied to In(y)Ga(1-y)As (y = 0.5) quantum dots grown on a GaAs substrate. In this system, a simple truncated cone model is found to give an adequate description of the compositional variations across the dot. We find a substantial enrichment in In at the center of the dots, in agreement with theoretical predictions.