A Sol-Gel/Solvothermal Synthetic Approach to Titania Nanoparticles for Raman Thermometry.

The accurate determination of the local temperature is one of the most important challenges in the field of nanotechnology and nanomedicine. For this purpose, different techniques and materials have been extensively studied in order to identify both the best-performing materials and the techniques with greatest sensitivity. In this study, the Raman technique was exploited for the determination of the local temperature as a non-contact technique and titania nanoparticles (NPs) were tested as nanothermometer Raman active material. Biocompatible titania NPs were synthesized following a combination of sol-gel and solvothermal green synthesis approaches, with the aim of obtaining pure anatase samples. In particular, the optimization of three different synthesis protocols allowed materials to be obtained with well-defined crystallite dimensions and good control over the final morphology and dispersibility. TiO2 powders were characterized by X-ray diffraction (XRD) analyses and room-temperature Raman measurements, to confirm that the synthesized samples were single-phase anatase titania, and using SEM measurements, which clearly showed the nanometric dimension of the NPs. Stokes and anti-Stokes Raman measurements were collected, with the excitation laser at 514.5 nm (CW Ar/Kr ion laser), in the temperature range of 293-323 K, a range of interest for biological applications. The power of the laser was carefully chosen in order to avoid possible heating due to the laser irradiation. The data support the possibility of evaluating the local temperature and show that TiO2 NPs possess high sensitivity and low uncertainty in the range of a few degrees as a Raman nanothermometer material.

Hybrid Sol-Gel Surface-Enhanced Raman Sensor for Xylene Detection in Solution.

This paper reports on the fabrication and characterization of a plasmonic/sol-gel sensor for the detection of aromatic molecules. The sol-gel film was engineered using polysilsesquioxanes groups to capture the analyte, through π-π interaction, and to concentrate it close to the plasmonic surface, where Raman amplification occurs. Xylene was chosen as an analyte to test the sensor. It belongs to the general class of volatile organic compounds and can be found in water or in the atmosphere as pollutants released from a variety of processes; its detection with SERS is typically challenging, due to its low affinity toward metallic surfaces. The identification of xylene was verified in comparison with that of other aromatic molecules, such as benzene and toluene. Investigations were carried out on solutions of xylene in cyclohexane, using concentrations in the range from 0 to 800 mM, to evaluate the limit of detection (LOD) of about 40 mM.

Evaluation of gold nanoparticles toxicity towards human endothelial cells under static and flow conditions.

A new in vitro model system, adding advection and shear stress associated with a flowing medium, is proposed for the investigation of nanoparticles uptake and toxicity towards endothelial cells, since these processes are normally present when nanoparticles formulations are intravenously administered. In this model system, mechanical forces normally present in vivo, such as advection and shear stress were applied and carefully controlled by growing human umbilical vein endothelial cells inside a microfluidic device and continuously infusing gold nanoparticle (Au NPs) solution in the device. The tests performed in the microfluidic device were also run in multiwells, where no flow is present, so as to compare the two model systems and evaluate if gold nanoparticles toxicity differs under static and flow culture conditions. Full characterization of Au NPs in water and in culture medium was accomplished by standard methods. Two-photon fluorescence correlation spectroscopy was also employed to map the flow speed of Au NPs in the microfluidic device and characterize Au NPs before and after interactions with the cells. Au NPs uptake in both in vitro systems was investigated through electron and fluorescence microscopy and ICP-AES, and NPs toxicity measured through standard bio-analytical tests. Comparison between experiments run in multiwells and in microfluidic device plays a pivotal role for the investigation of nanoparticle-cell interaction and toxicity assessment: our work showed that administration of equal concentrations of Au NPs under flow conditions resulted in a reduced sedimentation of nanoparticle aggregates onto the cells and lower cytotoxicity with respect to experiments run in ordinary static conditions (multiwells).

Micro-Raman for Local Strain Evaluation of GaN LEDs and Si Chips Assembled on Cu Substrates.

Integrated circuits are created by interfacing different materials, semiconductors, and metals, which are appropriately deposited or grown on substrates and layers soldered together. Therefore, the characteristics of starting materials and process temperatures are of great importance, as they can induce residual strains in the final assembly. Identifying and quantifying strain becomes strategically important in optimizing processes to enhance the performance, duration, and reliability of final devices. This work analyzes the thermomechanical local strain of semiconductor materials used to realize LED modules for lighting applications. Gallium Nitride active layers grown on sapphire substrates and Si chips are assembled by soldering with eutectic AuSn on copper substrates and investigated by Raman spectroscopy in a temperature range of -50 to 180 °C. From the Raman mapping of many different samples, it is concluded that one of the leading causes of strain in the GaN layer can be attributed to the differences in the thermal expansion coefficient among the various materials and, above all, among the chip, interconnection material, and substrate. These differences are responsible for forces that slightly bend the chip, causing strain in the GaN layer, which is most compressed in the central region of the chip and slightly stretched in the outer areas.

UV-curable SiO2-TiO2 films for the realization of diffractive optical elements.

Hybrid SiO2-TiO2 films are prepared starting from tetraisopropoxy titanate and 3-glycidoxipropyltrimethoxysilane, using the sol-gel process. During the sol synthesis titania clusters grow, conferring to the samples a photocatalytic activity. In this paper we exploit this property for the fabrication of surface-relief gratings. The realized structures are characterized by SEM, AFM and profilometric measurements, while the presence of titania clusters is confirmed by TEM analyses.

Contactless Temperature Sensing at the Microscale Based on Titanium Dioxide Raman Thermometry.

The determination of local temperature at the nanoscale is a key point to govern physical, chemical and biological processes, strongly influenced by temperature. Since a wide range of applications, from nanomedicine to nano- or micro-electronics, requires a precise determination of the local temperature, significant efforts have to be devoted to nanothermometry. The identification of efficient materials and the implementation of detection techniques are still a hot topic in nanothermometry. Many strategies have been already investigated and applied to real cases, but there is an urgent need to develop new protocols allowing for accurate and sensitive temperature determination. The focus of this work is the investigation of efficient optical thermometers, with potential applications in the biological field. Among the different optical techniques, Raman spectroscopy is currently emerging as a very interesting tool. Its main advantages rely on the possibility of carrying out non-destructive and non-contact measurements with high spatial resolution, reaching even the nanoscale. Temperature variations can be determined by following the changes in intensity, frequency position and width of one or more bands. Concerning the materials, Titanium dioxide has been chosen as Raman active material because of its intense cross-section and its biocompatibility, as already demonstrated in literature. Raman measurements have been performed on commercial anatase powder, with a crystallite dimension of hundreds of nm, using 488.0, 514.5, 568.2 and 647.1 nm excitation lines of the CW Ar+/Kr+ ion laser. The laser beam was focalized through a microscope on the sample, kept at defined temperature using a temperature controller, and the temperature was varied in the range of 283-323 K. The Stokes and anti-Stokes scattered light was analyzed through a triple monochromator and detected by a liquid nitrogen-cooled CCD camera. Raw data have been analyzed with Matlab, and Raman spectrum parameters-such as area, intensity, frequency position and width of the peak-have been calculated using a Lorentz fitting curve. Results obtained, calculating the anti-Stokes/Stokes area ratio, demonstrate that the Raman modes of anatase, in particular the Eg one at 143 cm-1, are excellent candidates for the local temperature detection in the visible range.

A fullerene-distyrylbenzene photosensitizer for two-photon promoted singlet oxygen production.

Novel compounds endowed with a high two-photon absorption (TPA) cross-section and a high singlet oxygen quantum yield, are sought after for their possible application in anti-cancer therapies. In this paper we present a prototype macromolecule bearing a distyrylbenzene dimer as TPA unit and a [60]fullerene moiety for singlet oxygen generation. Linear absorption and emission spectra are measured, to help understanding the interactions between the single molecular units. The TPA absorption properties of the distyrylbenzene alone as well as bound to the methanofullerene unit are recorded with the TPA-induced fluorescence technique. An appreciable enhancement of the TPA cross-section was observed in the molecular conjugate.Singlet oxygen generation has been detected exciting the sample both in the Vis and NIR through one- and two-photon absorption processes, respectively. Although functionalization decreases the overall singlet oxygen quantum yield of fullerene, the presence of the distyrylbenzene antenna allows two-photon generation of singlet oxygen through an energy transfer process.

Amplified spontaneous emission from opal photonic crystals engineered with structural defects.

In this work, we report on the optical properties and amplified spontaneous emissions (ASE) of polystyrene opals engineered with planar structural defects containing a conjugated polymer emitter. Defects in opals give rise to allowed states inside the photonic stop band, which are probed by transmittance and reflectance spectroscopy. The emission spectrum of the polymer embedded in the defect layer is strongly modified and fingerprints of defect states located inside the stop band are recognized. Amplified spontaneous emission for these engineered photonic crystals is clearly observed.

A Review on Surface-Enhanced Raman Scattering.

Surface-enhanced Raman scattering (SERS) has become a powerful tool in chemical, material and life sciences, owing to its intrinsic features (i.e., fingerprint recognition capabilities and high sensitivity) and to the technological advancements that have lowered the cost of the instruments and improved their sensitivity and user-friendliness. We provide an overview of the most significant aspects of SERS. First, the phenomena at the basis of the SERS amplification are described. Then, the measurement of the enhancement and the key factors that determine it (the materials, the hot spots, and the analyte-surface distance) are discussed. A section is dedicated to the analysis of the relevant factors for the choice of the excitation wavelength in a SERS experiment. Several types of substrates and fabrication methods are illustrated, along with some examples of the coupling of SERS with separation and capturing techniques. Finally, a representative selection of applications in the biomedical field, with direct and indirect protocols, is provided. We intentionally avoided using a highly technical language and, whenever possible, intuitive explanations of the involved phenomena are provided, in order to make this review suitable to scientists with different degrees of specialization in this field.

Effective two-photon absorption cross section of heteroaromatic quadrupolar dyes: dependence on measurement technique and laser pulse characteristics.

The linear and nonlinear optical properties of the heteroaromatic push-pull-push two-photon absorbing dye N-methyl-2,5-bis[1-(N-methylpyrid-4-yl)ethen-2-yl]-pyrrole ditriflate (PEPEP) are reported. The determination of the two-photon absorption (TPA) cross-section spectrum has been performed with different techniques: femtosecond TPA-white light continuum probe experiments, two-photon-induced fluorescence, and open aperture Z-scan measurements using both nanosecond and femtosecond laser pulses. The measured TPA cross sections and their wavelength dispersion show a marked dependence on the parameters of the laser pulses and on the measurement technique employed. These properties are discussed in terms of the different microscopic mechanisms that can contribute to the multiphoton absorption processes, with different weight depending on the measurement conditions and on the photophysical parameters of the dye.

Engineering of Semiconductor Nanocrystals for Light Emitting Applications.

Semiconductor nanocrystals are rapidly spreading into the display and lighting markets. Compared with liquid crystal and organic LED displays, nanocrystalline quantum dots (QDs) provide highly saturated colors, wide color gamut, resolution, rapid response time, optical efficiency, durability and low cost. This remarkable progress has been made possible by the rapid advances in the synthesis of colloidal QDs and by the progress in understanding the intriguing new physics exhibited by these nanoparticles. In this review, we provide support to the idea that suitably engineered core/graded-shell QDs exhibit exceptionally favorable optical properties, photoluminescence and optical gain, while keeping the synthesis facile and producing QDs well suited for light emitting applications. Solid-state laser emitters can greatly profit from QDs as efficient gain materials. Progress towards fabricating low threshold, solution processed DFB lasers that are optically pumped using one- and two-photon absorption is reviewed. In the field of display technologies, the exploitation of the exceptional photoluminescence properties of QDs for LCD backlighting has already advanced to commercial levels. The next big challenge is to develop the electroluminescence properties of QD to a similar state. We present an overview of QLED devices and of the great perspectives for next generation display and lighting technologies.

Novel heterocycle-based two-photon absorbing dyes.

[structure: see text]. The synthesis and nonlinear optical characterization of two novel heteroaromatic-based chromophores is described. The new dyes present an A-pi-D-pi-A general framework, where A is a pi-deficient heteroaromatic ring (pyridine, quinoline, benzothiazole) and D a pi-excessive pyrrolyl moiety. Both systems exhibit large two-photon absorption (TPA) values in the femtoseconds regime (TPA cross section as high as 150 x 10(-50) cm(4) s photon(-1) molecule(-1) with 150 fs laser pulses). Their TPA-based optical limiting activity is also shown.

Novel heteroaromatic-based multi-branched dyes with enhanced two-photon absorption activity.

The first examples of heterocycle-based multi-branched dyes with efficient two-photon absorption (TPA) activity are reported; the novel chromophores exhibit large TPA cross sections (as high as 1600 x 10(-50) cm4 s photon(-1) molecule(-1), measured with 150 fs laser pulses at 800 nm); a strong cooperative enhancement in the branched systems with respect to the one-dimensional sub-units is found.

Sensitive detection of Ochratoxin A in food and drinks using metal-enhanced fluorescence.

Easy, sensitive, rapid and low cost ochratoxin biosensors are strongly demanded in food analysis since Ochratoxin A (OTA) is a widely diffused food contaminant, highly detrimental for human health. In this work, a novel plasmonic based optical biosensor prototype for ochratoxin A is described. It exploits the metal-enhanced fluorescence phenomenon due to the silver film over nanosphere plasmonic substrate. Since ochratoxin A could be present in different food commodities, sensor performances have been tested on three different matrices (dried milk, juices, and wheat mix). Firstly, a common OTA extraction solvent and a labeling and detection protocol were defined for the analyzed matrices. Then, the efficiency of the Ag-FON surfaces in signal amplification for the detection of low ochratoxin A concentrations was defined. Using samples spiked with OTA-AF 647 or with unlabeled OTA we were able to detect the mycotoxin at concentrations lower than E.U. specifications of 0.5 µg/kg in wheat, milk and apple juice. The test performances are comparable to those of ELISA kits but the platform presented here, once optimized, present some perspective advantages, such as: low cost and time consuming, versatility of the protocol for the investigation of different matrices, employment also in non-qualified laboratories, small dimensions that allow its integration in a compact device for OTA on-site detection.

Investigation into the heterostructure interface of CdSe-based core-shell quantum dots using surface-enhanced Raman spectroscopy.

The structural nature of heterointerfaces in core-shell semiconductor quantum dots (QDs) plays a crucial role in tailoring their optical properties. In this work we have focused on using surface-enhanced Raman spectroscopy as a nondestructive tool to investigate the structural evolution of such interfaces in CdSe/CdS and CdSe/Cd0.5Zn0.5S colloidal QDs. A comparison between the two systems shows significant structural variation across the core-shell interfaces for the two different materials: a smooth interface for the former and an abrupt interface for the latter. This structural difference modifies the electronic structure within the QDs, which directly dictates the confinement behavior of the electrons and holes. The implications of this translate to a better understanding of why graded CdSe/CdS/Cd0.5Zn0.5S/ZnS QDs are so lucrative for linear and nonlinear fluorescence-based applications.

Facile production of up-converted quantum dot lasers.

We report a facile production of an up-converted surface-emitting DFB laser, performed by exploiting the versatility of sol-gel chemistry, the intriguing properties of well designed graded CdSe-CdS-Cd(0.5)Zn(0.5)S-ZnS colloidal quantum dots, and the scalability of nanoimprinting. Our laser prototype operates in the visible region following efficient optical pumping by either direct one-photon excitation or through the up-conversion of near infrared (NIR) light. By achieving cavity mode Q-factors in excess of 650 and retaining high lasing stabilities in air, this work highlights the feasibility of creating integrated lasing devices through solution based methods.

Two-photon absorption of Zn(II) octupolar molecules.

In this work we present an investigation of the non-linear optical (NLO) properties of two octupolar chromophores: [Zn(4,4'-bis(dibutylaminostyryl)-[2,2']-bipyridine)(3)](2+) and [Zn(4,4'-bis((E)-2-(N-(TEG)pyrrol-2-yl)vinyl)-[2,2']-bipyridine)(3)](2+) with Zn(ii) as the coordination center, using two-photon emission technique (TPE) in fs-pulse temporal regime. Compared to the free ligands, our results do not show a net increase in the two-photon absorption (TPA) cross-section for the octupolar complexes, once normalized to the ligand unit. This is in partial disagreement with a previous theoretical study investigating the first molecule where a significant increase of the TPA cross-section was predicted (X. J. Liu, et al., J. Chem. Phys., 2004, 120, 11 493).

One- and two-photon absorption and emission properties of a Zn(II) chemosensor.

This paper presents the synthesis and two photon-induced absorption (TPA) properties of a functionalized distyrylbenzene (DSB) 1 containing a tetra-azacyclododecane (cyclen) receptor for Zn(II). The influence of Zn(II) on one- and two-photon absorption characteristics of 1 has been investigated in dimethyl sulfoxide. The experiments show that the TPA action spectrum of uncomplexed 1, at 750 nm employing nanosecond-long excitation pulses, is 5 times more intense than that of the complexed form. This moderate contrast between the bound and unbound species confirms, however, the potential of this design scheme for the development of molecular structures with enhanced sensitivity and contrast to be used as Zn(II) sensors through TPA-induced fluorescence microscopy.

Organic functionalization and optical properties of carbon onions.

We report, for the first time, the organic functionalization of carbon onions. The functionalization was achieved via 1,3-dipolar cycloaddition of azomethine ylides to a mixture of amorphous carbon and concentric fullerenes. Once functionalized, the onions become soluble in organic solvents and it is possible to purify them from the rest of carbon. Their nonlinear optical properties have been studied in solution for application as broadband optical limiters. It was found that the functionalized onions are an example of soluble material that functions equally well in both the visible and the NIR regions.