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Fabrication of three-dimensional (3D) structures and functional tissues directly in live animals would enable minimally invasive surgical techniques for organ repair or reconstruction. Here, we show that 3D cell-laden photosensitive polymer hydrogels can be bioprinted across and within tissues of live mice, using bio-orthogonal two-photon cycloaddition and crosslinking of the polymers at wavelengths longer than 850 nm. Such intravital 3D bioprinting—which does not create by-products and takes advantage of commonly available multiphoton microscopes for the accurate positioning and orientation of the bioprinted structures into specific anatomical sites—enables the fabrication of complex structures inside tissues of live mice, including the dermis, skeletal muscle and brain. We also show that intravital 3D bioprinting of donor-muscle-derived stem cells under the epimysium of hindlimb muscle in mice leads to the de novo formation of myofibres in the mice. Intravital 3D bioprinting could serve as an in vivo alternative to conventional bioprinting. Three-dimensional cell-laden photosensitive polymer hydrogels can be bioprinted in tissues of live animals, by bio-orthogonal two-photon cycloaddition and crosslinking of the polymers.

Solution processed TiO2 anatase film was used as sensitive layer for H2 detection for two plasmonic sensor configurations: A grating-coupled surface plasmon resonance sensor and a localized surface plasmon resonance sensor with gold nanoparticles. The main purpose of this paper is to elucidate the different H2 response observed for the two types of sensors which can be explained considering the hydrogen dissociation taking place on TiO2 at high temperature and the photocatalytic activity of the gold nanoparticles.

Hydrogels are widely used as matrices for cell growth due to the their tuneable chemical and physical properties, which mimic the extracellular matrix of natural tissue. The microfabrication of hydrogels into arbitrarily complex 3D structures is becoming essential for numerous biological applications, and in particular for investigating the correlation between cell shape and cell function in a 3D environment. Micrometric and sub-micrometric resolution hydrogel scaffolds are required to deeply investigate molecular mechanisms behind cell-matrix interaction and downstream cellular processes. We report the design and development of high resolution 3D gelatin hydrogel woodpile structures by two-photon crosslinking. Hydrated structures of lateral linewidth down to 0.5 µm, lateral and axial resolution down to a few µm are demonstrated. According to the processing parameters, different degrees of polymerization are obtained, resulting in hydrated scaffolds of variable swelling and deformation. The 3D hydrogels are biocompatible and promote cell adhesion and migration. Interestingly, according to the polymerization degree, 3D hydrogel woodpile structures show variable extent of cell adhesion and invasion. Human BJ cell lines show capability of deforming 3D micrometric resolved hydrogel structures. Statement of Significance The design and development of high resolution 3D gelatin hydrogel woodpile structures by two-photon crosslinking is reported. Significantly, topological and mechanical conditions of polymerized gelatin structures were suitable for cell accommodation in the volume of the woodpiles, leading to a cell density per unit area comparable to the bare substrate. The fabricated structures, presenting micrometric features of high resolution, are actively deformed by cells, both in terms of cell invasion within rods and of cell attachment in-between contiguous woodpiles. Possible biological targets for this 3D approach are customized 3D tissue models, or studies of cell adhesion, deformation and migration.

Structurally and mechanically similar to the extracellular matrix (ECM), biomimetic hydrogels offer a number of opportunities in medical applications. However, the generation of synthetic microenvironments that simulate the effects of natural tissue niches on cell growth and differentiation requires new methods to control hydrogel feature resolution, biofunctionalization and mechanical properties. Here we show how these goals can be achieved by using a pullulan-based hydrogel, engineered in composition and server as cell-adhesive hydrogel, 3D photo-printable in dimension, ranging from the macro- to the micro-scale dimensions, and of tunable mechanical properties. For this, we used absorbers that limit light penetration, achieving 3D patterning through stereolithography with feature vertical resolution of 200 μm and with overall dimension up to several millimeters. Furthermore, we report the fabrication of 3D pullulan-modified hydrogels by two-photon lithography, with sub-millimetric dimensions and minimum feature sizes down to some microns. These materials open the possibility to produce multiscale printed scaffolds that here we demonstrate to be inert for cell adhesion, but biologically compatible and easily functionalizable with cell adhesive proteins. Under these conditions, successful cell cultures were established in 2D and 3D. Keywords: Hydrogel, Biomaterials, Polysaccharide, Pullulan, 3D printing, Two photon laser lithography, Mesenchymal stromal cells

Solution processed TiO2 anatase film was used as sensitive layer for H2 detection for two plasmonic sensor configurations: A grating-coupled surface plasmon resonance sensor and a localized surface plasmon resonance sensor with gold nanoparticles. The main purpose of this paper is to elucidate the different H2 response observed for the two types of sensors which can be explained considering the hydrogen dissociation taking place on TiO2 at high temperature and the photocatalytic activity of the gold nanoparticles.

Shaping ceramic materials at the nanoscale in 3D is a phenomenal engineering challenge, that can offer new opportunities in a number of industrial applications, including metamaterials, nano‐electromechanical systems, photonic crystals, and damage‐tolerant lightweight materials. 3D fabrication of sub‐micrometer ceramic structures can be performed by two‐photon laser writing of a preceramic polymer. However, polymer conversion to a fully ceramic material has proven so far unfeasible, due to lack of suitable precursors, printing complexity, and high shrinkage during ceramic conversion. Here, it is shown that this goal can be achieved through an appropriate engineering of both the material and the printing process, enabling the fabrication of preceramic 3D shapes and their transformation into dense and crack‐free SiOC ceramic components with highly complex, 3D sub‐micrometer architectures. This method allows for the manufacturing of components with any 3D specific geometry with fine details down to 450 nm, rapidly printing structures up to 100 µm in height that can be converted into ceramic objects possessing sub‐micrometer features, offering unprecedented opportunities in different application fields.

Due to its chemical specificity, the near edge X-ray absorption fine structure spectroscopy is an interesting technique to study the changes in hybrid organic-inorganic photoresists. In this work, we analyzed the chemical changes occurring in photoresists synthesized from organically modified precursors and transition metal alkoxides by sol-gel route. These systems are nonchemically amplified resists for ultraviolet, extreme ultraviolet, and electron beam lithography. They are based on Si, Zr, and Ti oxides or a combination of these. The experiments were conducted at the PolLux beamline of the Swiss Light Source, by a scanning transmission X-ray microscopy, which combines the spatially-resolved microscopy and fine structure spectroscopy at once. The absorption spectra were collected in the energy range of the carbon edge (≈ 290 eV) before and after in situ exposure of the photoresists to 500 eV photons. The variations in peak intensity after exposure reveal the changes in the chemical environment of carbon and the chemical configuration of the organic ligands, regardless of the inorganic part. It was found that the photon exposure induced sizable photodegradation or photopolymerization of organic groups (phenyl or methyl methacrylate, respectively). These mechanisms contribute to the foundation for the exposure reaction in negative-tone hybrid photoresists. Interestingly, it was also found that the detachment of the phenyl ligand occurs in a variety of possible pathways to condensation. We believe that our results and approach can provide a better understanding of photochemistry of resists, in particular for extreme ultraviolet lithography.

A novel approach to fabricate ceramic structures at multiple scales in a single component, based on the hybridization of additive manufacturing technologies, was developed by combining 3D macro-stereolithography (Digital Light Processing, DLP) with two-photon lithography (2PL), to produce cm-sized sample geometries with sub-μm surface features. The preceramic structures in the sub-μm scale were realized by 2PL directly on easily manageable DLP macro-sized samples of the same ceramic composition. In this way, preceramic structures presenting both features typical of DLP printers (with a minimum size of around 50 μm) and features well below their resolution limit were realized. We report here, for the first time, the realization of polymer-derived ceramic SiOC ceramic components structured in 3D across several length scales (with micron and mesoscale 3D features), produced by pyrolysis at 1000 °C of preceramic parts, without shape distortion during the pyrolysis step.

A halogen-anion fluorescent solid-state sensor based on natively porous films doped with a quinolinium derivative is reported. The sensitive films are prepared with a low temperature sol–gel synthesis starting from bridged silsesquioxane precursors, and 6-methoxyquinolinium moieties are covalently linked to the organic–inorganic hybrid network. This sensor system is reversible and allows selective detection and measurement of halogen anion concentrations in the physiological range by a dynamic quenching effect of the sensitive fluorophore. The quenching constants are unaffected by dye inclusion in the bridged polysilsesquioxane matrix.

International audience; A sol-gel process was exploited to produce porous inorganic thin films from phenyl-bridged silsesquioxanes. The evolution of both structural and optical properties of the starting hybrid so-gel films were monitored, during synthesis and successive thermal curing steps, by Fourier transform infrared (FT-IR) spectroscopy, differential thermal analysis (DTA), thermogravimetric analysis (TGA) and spectroscopic ellipsometry (SE). Involved chemical species, structural and chemical modifications were identified when thermal treatments at increasing temperatures in the range of 60-800 degrees C were applied to the hybrid films. The progressive formation of a crosslinked silica network, template elimination and film densification were observed, resulting in completely inorganic porous thin films of low refractive index. The distinctiveness of this system directly comes from the extremely controlled and uniform dispersion of the porogen at a molecular level, which is intrinsic to the bridged silsesquioxane precursor choice. A quantitative porosity analysis was performed by environmental ellipsometric porosimetry (EEP), studying inorganic film optical and mechanical properties under different relative humidity conditions. A transmission electron microscopy (TEM) in-situ characterization of porosity size and distribution confirms the presence of a spatially structured organization of pores of a few nanometers in diameter.

Electroless metal deposition is a simple and convenient technique to fabricate metallic films and to provide isotropic metal functionalization of 3D structures with complex geometries. In this work, we describe the synthesis of silver coatings by means of a modified Tollens reaction and their use as optical coating. The chemical composition of the metallization bath is here addressed to optimize the metal coating deposition. The synthesis parameters have been tailored in order to deposit very smooth films which were characterized by scanning electron microscopy, atomic force microscopy, and optical spectroscopy. 2D diffraction gratings and sinusoidal plasmonic gratings were produced with the proposed method. Optical characterization confirmed the plasmonic activities of the resultant structures, proving the efficiency of the described method for optical applications. Thermal annealing was found to improve the surface roughness of the coating and therefore the optical properties of the plasmonic gratings.

Natively porous hybrid organic-inorganic sol-gel systems have been engineered to be used as functional positive photoresists, aimed to the realization of microsensors in a single-step process. Interesting results have been obtained combing three main sol-gel system features: the direct pattern-ability through X-ray lithography, being processable without the addition of a photocatalyst; the functionalizability, properly designing the organic component of the hybrid network or incorporating active species; the open micro or mesoporosity, tailored by the synthesis process and precursor choice. The photoprocessable porous films have been synthesized starting from a Bridged Polysilsesquioxane (BPS) precursor, 1,4-bis(triethoxysilyl)benzene. The correlation between chemical properties of the solgel material and its patternability is described in detail. X-ray exposure leads to a progressive alkyl and aromatic compound elimination and promotes inorganic condensation in the system, allowing the selective dissolution of irradiated cross-linked films in suitable etchants. Patterns of final resolution lower than 100 nm have been realized on BPS-based films synthesized in acid conditions, a procedure that allows to take advantage of a straightforward embedding protocol for active species in the sol-gel matrix. The BPS-based system has been doped with a covalently linked quinolinium dye, obtaining thin sensing films patternable by X-ray lithography. A feasibility test for the fabrication of optical microdevices, where fluorescence properties are obtained directly on the patterned coatings, has been provided. (C) 2010 Elsevier B.V. All rights reserved.

Nanoporous TiO2 anatase film has been investigated as sensitive layer in Surface Plasmon Resonance sensors for the detection of hydrogen and Volatile Organic Compounds, specifically methanol and isopropanol. The sensors consist of a TiO2 nanoporous matrix deposited above a metallic plasmonic grating, which can support propagating Surface Plasmon Polaritons. The spectral position of the plasmonic resonance dip in the reflectance spectra was monitored and correlated to the interaction with the target gases. Reversible blue-shifts of the resonance frequency, up to more than 2 THz, were recorded in response to the exposure to 10000 ppm of H2 in N2 at 300°C. This shift cannot be explained by the mere refractive index variation due to the target gas filling the pores, that is negligible. Reversible red-shifts were instead recorded in response to the exposure to 3000 ppm of methanol or isopropanol at room temperature, of magnitudes up to 14 THz and 9 THz, respectively. In contrast, if the only sensing mechanism was the mere pores filling, the shifts should have been larger during the isopropanol detection. We therefore suggest that other mechanisms intervene in the analyte/matrix interaction, capable to produce an injection of electrons into the sensitive matrix, which in turn induces a decrease of the refractive index.

Mesoporous silica particles prepared through a simplified Stober method and low temperature solvent promoted surfactant removal are evaluated as dissolution enhancers for poorly soluble compounds, using a powerful anticancer agent belonging to pyrroloquinolinones as a model for anticancer oral therapy, and anti-inflammatory ibuprofen as a reference compound. Mesoporous powders composed of either pure silica or silica modified with aminopropyl residues are produced. The influence of material composition and drug chemical properties on drug loading capability and dissolution enhancement are studied. The two types of particles display similar size, surface area, porosity, erodibility, drug loading capability and stability. An up to 50% w/w drug loading is reached, showing correlation between drug concentration in adsorption medium and content in the final powder. Upon immersion in simulating body fluids, immediate drug dissolution occurred, allowing acceptor solutions to reach concentrations equal to or greater than drug saturation limits. The matrix composition influenced drug solution maximal concentration, complementing the dissolution enhancement generated by a mesoporous structure. This effect was found to depend on both matrix and drug chemical properties allowing us to hypothesise general prediction behaviour rules.

In this work, three TiO 2 thin films with thicknesses of 22.7, 48.5 and 102.9 nm were grown on Si (100) substrates by the technique of electron beam evaporation. The films were deposited at a substrate temperature of 150°C with a deposition rate of 0.3-0.5 A/sec. The films thicknesses were characterized by spectroscopic ellipsometry and profilometry. The surface roughness was measured by AFM obtaining RMS of less than 0.7nm. Investigations performed by XPS method have shown that stoichiometric TiO 2 was obtained on all the samples with no suboxide presences. Reflectance measurements of the samples were performed in EUV and SX spectral regions from 25.5 to 454.2eV using synchrotron radiation. Analyzing the refractive index N=n+ik of TiO 2 thin films, optical constants (n,k) in this energy range were both determined by fitting the Fresnel equations with least-square fitting methods.

The development of innovative materials for sensitive and selective gas sensing is a very relevant field for the current nanotechnology research. A strong effort is dedicated to the fabrication of low-cost and efficient nanoscale devices capable of a fast detection. Resistive electrical devices are the most adopted solutions for in-situ and real-time detection, but their main drawbacks are the low selectivity, response drift, electromagnetic noise dependence and need of contact measurements. Optical gas sensors allow to overcome such limits, and could moreover exhibit thermal and mechanical stability, operate at room temperature, and be integrated on-chip. Within this framework, plasmon-based optical devices are knowing an increasing development and diffusion. Herein plasmonic sensors for aromatic hydrocarbon detection are presented. These systems are based on aryl-bridged polysilsesquioxanes (aryl-PSQs), obtained either \(\textcircled{1}\) coupling such hybrid films with Au nanoparticles (NPs), aiming to the excitation of localized surface plasmon resonances (LSPRs), or \(\textcircled{2}\) depositing them onto metallic waveguiding layers, to form gratings supporting the propagation of surface plasmon polaritons (SPPs). Aryl-PSQs are sol-gel materials characterized by a native controlled porosity and other functionalities (Loy and Shea, Chem Rev 95:1431–1442, 1995; Dabrowski et al., Appl Surf Sci 253:5747–5751, 2007; Brigo et al., Nanotechnology 23:325302, 2012). Temperature programmed desorption investigations of xylene on phenyl-bridged (ph-PSQ) and diphenyl-bridged (diph-PSQ) PSQ films indicate a specific π −π interaction between the organic component of the films and xylene molecules: the interaction energy is quantified in 38 ± 14 kJ/mol and 115 ± 13 kJ/mol, respectively (Brigo et al., J Mater Chem C 1:4252, 2013). For type \(\textcircled{1}\) sensors, a thin film of aryl-PSQ was deposited on a submonolayer of Au NPs coating a fused silica substrate. These sensors were tested monitoring the variation of the LSPRs under cycles of exposure to N2 and to 30 ppm xylene in N2.

Engineered organic-inorganic hybrid materials, HyMat, offer new opportunities for the easy, fast and cheap development of miniaturized functional devices. The integration of inorganic oxide networks, organic functional groups and optically active molecules or nanoparticles allows to obtain combinations of properties and structures otherwise impossible with traditional materials. In particular, a simple and highly versatile synthesis platform enabling preparation of HyMat is presented, which is built up by a bottom-up sol-gel approach at low processing temperatures. A few types of key building blocks pave the way for accessing HyMat and make up their formulation, providing a means to synthesize innovative materials enabling to get: - optically active micro and nanostructures; - miniaturized sensors for analytes in gaseous or liquid media; - direct patternability with a range of lithographic techniques; - variable inorganic and organic compositions, and controlled porosity. Examples of micro and nanostructures based on these spin-on materials with ceramic (i.e. SiO 2 , GeO 2 , Al 2 O 3 , ZrO 2 , TiO 2 ,) and hybrid compositions will be presented for different applications including plasmonic or fluorescent sensors, dry-etching masks with outstanding resistance, optically active micro and nanostructured platforms and high resolution patterns.

We report the achievement of sensitive gas detection using periodic silver nanoprisms fabricated by a simple and low-cost lithographic technique. The presence of sharp tips combined with the periodic arrangement of the nanoprisms allowed the excitement of isolated and interacting localized surface plasmon resonances. Specific sensing capabilities with respect to aromatic hydrocarbons were achieved when the metal nanoprism arrays were coupled in the near field with functional hybrid films, providing a real-time, label-free, and reversible methodology. Ultra-high-vacuum temperature-programmed desorption measurements demonstrated an interaction energy between the sensitive film and analytes in the range of 55-71 kJ/mol. The far-field optical properties and the detection sensitivity of the sensors, modeled using a finite element method, were correlated to experimental data from gas sensing tests. An absorbance variation of 1.2% could be observed and associated with a theoretical increase in the functional film refractive index of ∼0.001, as a consequence to the interaction with 30 ppm xylene. The possibility of detecting such a small variation in the refractive index suggests the highly promising sensing capabilities of the presented technique.

Transparent conductive oxides are emerging materials in several fields, such as photovoltaics, photoelectrochemistry, and optical biosensing. Their high chemical inertia, which ensured long-term stability on one side, makes challenging the surface modification of transparent conductive oxides; long-term robust modification, high yields, and selective surface modifications are essential prerequisite for any further developments. In this work, we aim at inducing chemical functionality on fluorine-doped tin oxide surfaces (one of the most inexpensive transparent conductive oxide) by means of electrochemical grafting of aryl diazonium cations. The grafted layers are fully characterized by photoemission spectroscopy, cyclic voltammetry, and atomic force microscopy showing linear correlation between surface coverage and degree of modification. The electrochemical barrier effect of modified surfaces was studied at different pH to characterize the chemical nature of the coating. We showed immuno recognition of biotin complex built onto grafted fluorine-doped tin oxides, which opens the perspective of integrating FTO samples with biological-based devices.

We fabricated stable gold nanostars (AuNSs) with tunable extinction properties from the visible spectral region up to 1800 nm, depending on the average values of core size and branch length. The results of their UV–Vis and transmission electron microscopy characterization are compared with computational data from finite elements method, which makes use of an approximated model of the branched structures. The theoretical computations put in evidence the existence of hot spots located on the tips of the nanostars even up to 1800 nm wavelength, which opens the way to the improvement of diagnostics in the IR region. Preliminary Fourier transform Raman experiments performed after functionalization with a fluorescent dye bearing end thiol groups seem to confirm the field enhancing capability of the nanostructures at 1064 nm.

A nanocomposite system based on titania-bound indium tin oxide (ITO) nanoparticles has been developed as directly patternable material for the realization of two dimensional (2D) plasmonic gratings through nanoimprint lithography. An optical and electrical characterization of the ITO-based films has been performed. The imprinting process has been optimized in order to obtain a faithful negative replication of an array of nanopyramids on a hard master, in terms of period and depth of the structures. The morphology of the fabricated 2D gratings has been characterized with Atomic Force and Scanning Electron Microscopy. Experimental measurements and theoretical simulations of the far-field properties of the ''naked'' photonic grating, before coupling with an emitter or depositing a thin metal film on top, have been carried out for incident light in the 300-1500nm wavelength range. A good qualitative agreement for transmittance data has been obtained. Simulated data for reflectance properly reproduce the experimental result only at long wavelengths, in the near-infrared region. Suggestions for further model implementations are proposed. The plasmonic architecture will be eventually designed and realized by applying the suitable metal coating.

We present and characterize an organic?inorganic hybrid sol?gel material, phenyl-bridged polysilsesquioxane (ph-PSQ), for use as a new high resolution resist for electron beam lithography (EBL). The resist has a unique characteristic as the only positive tone silica-based resist available for EBL. Exploring the processing parameters has revealed that it is possible to switch the behaviour from negative to positive tone by application of a post-exposure bake (PEB). Based on the results from micro-FTIR spectroscopy, a description of the tone switching mechanisms is proposed. The negative tone behaviour is explained by the etch rate difference between silanol groups and cross-linked silica, present in unexposed and in exposed areas of the films, respectively. In the case of positive tone, after a PEB, the etch rate difference between a thermally densified cross-linked silica network and cage-like silica structures allows us to reveal the pattern. Contrast and sensitivity are estimated under different processing conditions, and the significant parameters for line edge roughness minimization are pointed out. Dense patterns down to 25?nm half-pitch and isolated structures down to 30?nm are demonstrated, exploiting the positive tone, and dense patterns down to 60?nm half-pitch are demonstrated in the negative tone. Etching selectivities in fluorinated gases for ph-PSQ nanostructures on silicon substrates are 1?9 for the positive tone and 1?12 for the negative tone.

A positive tone resist for UV and X-ray lithography synthesized starting from an organically modified silicon alkoxide, bis(triethoxysilyl)benzene, through the sol–gel method, either in basic or in acid catalysis, is presented. Being directly photo-processable, the sol–gel system combines the opportunity to avoid the use of a sacrificial layer in the fabrication process, with the possibility to fit electro-optical and structural properties of the final device material to specific requirements. In addition, the positive tone behaviour allows to preserve the organic functionality of the system after irradiation. A study of the optical and structural modifications induced on the resist by irradiation has been carried out by FT-IR spectroscopy, UV–vis spectroscopy and spectroscopic ellipsometry. An interpretation of the mechanisms leading to exposed cross-linked film development is given. Experiments have demonstrated the possibility of obtaining structures on films with lateral dimensions spanning from the micron scale up to less than a hundred nm, opening the way to a possible exploitation of such positive tone functional system in the field of miniaturized sensors.

The direct nanopatterning of a novel hybrid organic-inorganic sol-gel film based on bridged polysilsesquioxanes (BPS) using X-ray synchrotron radiation is reported. The main advantages of a direct fabrication technique with respect to conventional photolithography are represented by the possibility to bypass some typical post-exposure lithographic steps and to avoid the use of a sacrificial layer. The distinctive features rendering hybrid BPS-based material innovative for photolithographic applications are: the patternability as resist, the positive tone behaviour exhibited under X-ray irradiation, the porous structure demonstrated at low temperature, and the possibility to widely tailor material electro-optical and structural properties to experimental needs. A systematic investigation of the interactions between sol-gel BPS films based on the bis(triethoxysilyl)benzene precursor and soft X-rays is conducted. Under X-ray exposure, BPS-based films suffer structural changes attributed to the organic bridge breaking, and become soluble in suitable acidic aqueous solutions, producing final lithographies of sub-micron resolution, high contrast and good edge definition.

We report on the absorption properties of hybrid sol-gel materials based on the 3-glycidoxypropyltrymethoxysilane (GPTMS) precursor in the spectral region 0.5–7 THz. THz transmission properties of such materials are quite good and, even if not comparable with the most transparent polymers, still their chemico-physical, structural, and electro-optical properties make them attractive alternative systems for applications in the THz field. An attempt to explain the relationship between compositional and structural characteristics of the investigated materials with their transmission behaviour is presented.

Covalent functionalization with a reactive azo-dye of tentagel resin beads bearing hydroxyl linkers led to a micro-sized optical sensor for pH detection. A PDMS/glass microfluidic cell has been constructed using replica molding combined with a fast prototyping procedure based on commercially available thiolene-based photocurable adhesives and used for studying the acid-base and time-response properties of the bead sensor under flow conditions. (C) 2007 Elsevier B.V All rights reserved.

A versatile micro- particle imaging velocimetry ( mu- PIV) recording system is described, which allows us to make fluid velocity measurements in a wide range of flow conditions both inside microchannels and at liquid - solid interfaces by using epifluorescence and total internal reflection fluorescence excitation. This set- up has been applied to study the slippage of water over flat surfaces characterized by different degrees of hydrophobicity and the effects that a grooved surface has on the fluid flow inside a microchannel. Preliminary measurements of the slip length of water past various flat surfaces show no significant dependence on the contact angle.

Nanostructured plasmonic sensors are fabricated as sinusoidal surface plasmon metallic gratings (SPGs) embedded in a functional and porous hybrid sol-gel material, phenyl-bridged polysilsesquioxane (ph-PSQ). The metal layer is in contact with the environment through the sol-gel film, which works as sensitive element, changing its dielectric properties upon interaction with aromatic hydrocarbons. The combination of sensitivity, transparency and patternability offered by ph-PSQs gives the exceptional possibility to fabricate innovative optical sensors with straightforward processes. An embedded SPG is a thin metal slab waveguide, in which the surface plasmon polaritons (SPPs) at the two metal-dielectric interfaces superpose, resulting in two physical coupled modes: the long range SPPs (LRSPPs) and the short range SPPs (SRSPPs). An extended experimental and theoretical characterization of the optical properties of the plasmonic device was performed. The sensor performance was tested against the detection of 30 ppm xylene, monitoring the influence of the target gas on the SPPs modes. A reversible red-shift of the reflectance dips of both LRSPP and SRSPP resonances in the 1.9-2.9 nm range was observed and correlated to the interaction with the analyte. An enhancement in sensitivity associated with the rotation of the grating grooves with respect to the scattering plane (azimuthal rotation) was verified within the experimental errors. Collected data are compatible with theoretical predictions assuming a variation of the film refractive index of 0.011 +/- 0.005.

Surface plasmon resonance gas sensors based on organic–inorganic hybrid thin films coupled to gold nanoparticles were fabricated and tested against the detection of xylene at the concentration of 30 ppm. Such nanocomposites are prepared either by dispersing Au nanoparticles inside an aryl-bridged polysilsesquioxane system, synthesized via a sol–gel process, or by depositing an aryl-bridged polysilsesquioxane film on Au nanoparticle sub-monolayers. Ultra-high-vacuum temperature programmed desorption of xylene on both the aryl-bridged polysilsesquioxane films and the nanocomposite Au/hybrid system was investigated, resulting in an interaction energy between the sensitive film and the gas molecules in the 38–139 kJ mol−1 range. The functional activity of the nanostructured composites as xylene gas optical sensors was tested monitoring gold localized surface plasmon resonance, and was shown to be reversible. The detection sensitivity was calculated in 0.1 ppb through a calibration procedure in the 16–30 ppm range, and a threshold limit of detection of 265 ppb xylene was estimated as three standard deviations of the baseline noise. Typical response and regeneration times are of one min and about one ten of minutes, respectively.