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A small 4-channels time-delayed complex perceptron is used as a silicon photonics neural network (NN) device to compensate for chromatic dispersion in optical fiber links. The NN device is experimentally tested with non-return-to-zero optical signals at 10 Gbps after propagation through up to 125 km optical fiber link. During the learning phase, a separation-loss function is optimized in order to maximally separate the transmitted levels of 0s from the 1s, which implies an optimization of the bit-error-rate. Testing of the NN device shows that the excess losses introduced by the NN device are compensated by the gain in transmitted signal equalization for a link longer than 100 km. The measured data are reproduced by a model which accounts for the optical link and the neural network device. This allows simulating the network performances for higher data rates, where the device shows improvement with respect to the benchmark both in terms of performance as well as ease of use., Comment: 14 pages, 6 figures

Amino-terminated surfaces can be effectively obtained by means of silanizing agents, realizing surfaces suitable for the purification of biomarkers of several pathologies. Since the level of biomarkers, such as microRNAs and cell-free DNA, into circulation may be extremely low, new and ameliorated capturing molecules and protocols are highly required. In this work, a new silane, acetone-imine propyl trimethoxysilane (AIPTMS), is synthesized with a simple and elegant reaction, via the nucleophilic addition of the primary amino group to the carbonyl group of acetone. AIPTMS and APTMS were used to silanize silicon oxide surfaces, which were characterized chemically (XPS) and morphologically (AFM). The two types of surfaces were chemically similar, but behaved very differently both for surface morphology and functional properties. The AIPTMS-modified surface was indeed very smooth and homogeneous with respect to the APTMS-modified surface. Moreover, the AIPTMS surface captured larger amounts of nucleic acids almost immediately after preparation, while APTMS-based functional surfaces needed longer time to reach comparable efficiency. AIPTMS shows several advantages over standard aminosilanes, as it realizes a more homogeneous surface coverage that, in turn, produces an improved response towards the capture of nucleic acids. AIPTMS is a very promising reagent for the reliable and reproducible preparation of active biofunctional surfaces for the purification and analysis of circulating biomarkers.

With the purpose of designing active patches for photodynamic therapy of melanoma, transparent and soft hydrogel membranes (HMs) have been fabricated by cation-induced gelation of rod-like cellulose nanocrystals (CNCs) bearing negatively charged carboxylic groups. Na+ , Ca2+ , Mg2+ have been used as cross-linkers of cellulose nanocrystal (CNC). The biosafety of this material and of its precursors has been evaluated in vitro in cell cultures. Morphological changes, cell organelles integrity, and cell survival with the tetrazolium salt reduction (MTT) assay were utilized as tests of cytotoxicity. Preliminary investigation was performed by addition of the hydrogel components to the cell culture medium and by incubations of the CNC-HM in direct and indirect contact with a confluent monolayer of A375 melanoma cells. Direct contact assays suffered from interference of physical stress. Careful evaluation of cytotoxicity was obtained considering the overall picture provided by microscopy and biochemical tests performed with the CNC-HM in indirect contact with two melanoma cell lines (A375, M14) and human fibroblasts. CNCs have been demonstrated to be a safe precursor material and CNC-HMs have a good biocompatibility provided that the excess of cations, in particular of Ca2+ is removed. These results indicate that CNC and can be safely used to fabricate biomedical devices such as transparent hydrogel patches, although attention must be paid to the fabrication procedure.

The widely tunable physical and chemical characteristics of hydrogels make them advantageous in biomedical and pharmaceutical applications, yet their hydrophilic nature might discourage their use as drug delivery systems for poorly water soluble molecules. In this work we demonstrate the sustained release of a large amount of a lipophilic drug (clofazimine) from nanocellulose hydrogels. Hydrogels are formed via ionotropic gelation and loaded with up to 37 % w/w) of the hydrophobic molecule. The kinetic profile avoids the initial burst release and we demonstrate that the surfactant co-loading is a successful strategy to increase by about 50 times the drug solubility in water, without the need of complex fabrication steps.

During the last years, organometallic lead halide perovskites (LHP) have been widely studied as outstanding materials for photovoltaics and photonics applications [1] . These emerging semiconductors are fabricated by cheap and straightforward solution process techniques on polycrystalline film of the compound CH 3 NH 3 PbX 3 (X=Cl, Br, I). Their outstanding properties of these films include large absorption coefficients above the bandgap, high electronic mobilities, high quantum yield of emission at room temperature or tunable band-gap with the composition [1] . In this work, we exploit the excellent light emitting and photodetection properties of CH 3 NH 3 PbI 3 thin films to integrate a waveguide amplifier and a photodetector within the same LHP thin film deposited in both rigid (SiO 2 /Si) and flexible (nanocellulose) substrates. As illustrated in Figure 1a , the device is based on the refractive index contrast between the LHP, a poly(methyl methacrylate) capping layer the substrate to engineer the number of propagating modes and their propagation constant [1] . In particular, the geometrical parameters of the structure were carefully designed to propagate an excitation beam injected at the input edge of the structure together with the photoluminescence (PL) emitted by the LHP through a mode that is extremely confined in the semiconductor film (see Fig. 1a ). As a result, this bilayer structure demonstrates amplified the spontaneous emission (ASE) with extraordinary low thresholds (2 nJ) [2] . Moreover, the incorporation of electrodes on the top of the LHP allows us to study a photocurrent dependent on the excitation light ( Fig. 1b ), and with it to monitor electrically the generation of PL and ASE ( Fig. 1c ). Experimental results (symbols in Fig. 3c) are properly reproduced with the simulations carried out with a rate equation model (solid lines in Fig. 3c). Here, we carefully compare the generation of optical gain and photocurrent in rigid and flexible substrates and demonstrate that the choice flexible substrate does not significantly alter the performances of the device [3] . Therefore, this approach illustrates a new amplifier-photodetector device that can pave the road towards a flexible and wearable technology LHP based technology.

The influence of the physical, rheological, and process parameters on the cellulose nanocrystal (CNC) drops before and after external gelation in a CaCl2 solution was investigated. The dominant role of the CNC’s colloidal suspension properties, such as the viscous force, inertial, and surface tension forces in the fluid dynamics was quantitatively evaluated in the formation of drops and jellified beads. The similarity and difference between the behavior of carbohydrate polymers and rod-like crystallites such as CNC were enlightened. Pump-driven and centrifugally-driven external gelation approaches were followed to obtain CNC hydrogel beads with tunable size and regular shape. A superior morphological control—that is, a more regular shape and smaller dimension of the beads—were obtained by centrifugal force-driven gelation. These results suggest that even by using a simple set-up and a low-speed centrifuge device, the extrusion of a colloidal solution through a small nozzle under a centrifugal field is an efficient approach for the production of CNC hydrogel beads with good reproducibility, control over the bead morphology and size monodispersion.

A ceramic composite was produced by mixing cubic zirconia with graphene nano-platelets. The samples were consolidated by flash sintering in argon atmosphere to avoid the oxidation of graphene at high temperature. The applied electrical field ranged between 50 V cm and 500 V cm, while the current density limit was set between 35 mA mm and 175 mA mm. The presence of the conductor filler reduced the onset flash temperature, and a good densification of the composite was obtained. Remarkably, the same level of densification was not possible on pure cubic zirconia samples (possessing the same geometry) as they got physically damaged at the flash ignition (likely due to internal temperature gradients). After sintering, part of the conductive filler was still partially present within the ceramic matrix although some zirconium carbide was also formed., V.M. Sglavo and M. Biesuz kindly acknowledge the support from the Italian Ministry of University and Research (MIUR) within the programs PRIN2017 - 2017FCFYHK“DIRECTBIOPOWER” and Departments of Excellence 2018–2022 (DII-UNITN). M. Biesuz kindly acknowledge thesupport from MIUR within the programs PRIN2017 - 2017PMR932 “Nanostructured Porous Ceramics for Environmental and EnergyApplications”

Porous silicon micro-particles (micro-pSi) with size in the range of 1–10 μm are obtained by etching of silicon wafers followed by sonication. The derivatization of the micro-pSi surface by wet chemistry (silylation and coupling with a diamine) yields an interface, which exposes negative (carboxylic) or positive (amine) groups at pH 7.4. The surface modification, beyond the introduction of groups for the drug loading by covalent or electrostatic interactions, stabilizes the intense orange luminescence characteristic of the silicon nano-crystallites. Derivatization by amines introduces also a second emission in the blue region, which follows a different excitation pathway and can be attributed to the interface defects. The micro-pSi are efficiently internalized by human dendritic cells and do not show any toxic effect even at a concentration of 1 mg mL−1. The intrinsic luminescence of the differently functionalized micro-pSi is preserved inside the cells and permits the selective and efficient tracking of the microparticles without using molecular tags and thus leaving the organic coating available for the interaction with the drug. The results obtained suggest that the functionalized micro-pSi are an efficient platform for simultaneous imaging and delivery of therapeutic agents to the disease site.

We demonstrate that the release of a poorly soluble molecule from nanoporous carriers is a complex process that undergoes heterogeneous surface nucleation events even under significantly diluted release conditions, and that those events heavily affect the dynamics of release. Using beta-carotene and porous silicon as loaded molecule and carrier model, respectively, we show that the cargo easily nucleates at the pore surface during the release, forming micro- to macroscopic solid particles at the pores surface. These particles dissolve at a much slower pace, compared to the rate of dissolution of pure beta-carotene in the same solvent, and they negatively affect the reproducibility of the release experiments, possibly because their solubility depends on their size distribution. We propose to exploit this aspect to use release kinetics as a better alternative to the induction time method, and to thereby detect heterogenous nucleation during release experiments. In fact, release dynamics provide much higher sensitivity and reproducibility as they average over the entire sample surface instead of depending on statistical analysis over a small area to find clusters.

The European food sector generates about 250 million tons/yr of by-products and waste, of which around 10% from fruit and vegetable processing, with a heavy environmental burden. The agri-food residues (AFR) contain a significant fraction of cellulose and bioactive compounds (mainly antioxidants), which, if recovered, are high added-value material components. The reduction of cellulose down to nano-sized crystalline structures (nanocellulose, NC) provides versatile building blocks, which self-assemble into new materials with superior performances. Despite wood-derived NC is generally considered a green material, its production process is environmentally unfriendly and its large scale utilization would contribute to deforestation. Therefore, more sustainable sources, such as AFR, are desired. The PANACEA project, within the frame of PRIN 2017 call supported by the Italian Ministry of University and Research, proposes an approach based on the recovery of cellulose and bioactive compounds from AFR, with high yield, at various degrees of hierarchical organization, by cascading different physical and chemical processes of increasing complexity. More specifically, physical processes and microbial digestion are exploited to obtain micro-sized cellulose structures while preserving their bioactivity. Chemical and enzymatic processes are used to isolate, purify and functionalize NC at different levels of hierarchical organization, and to design advanced functional materials such as food ingredients, edible coatings, functional colloids, biocides and flame retardants. The sustainable integrated valorization of AFR is addressed through (i) ad hoc pre-treatment of different AFR (Tomato peels, Wheat straw, Coffee residues, Rice bran, Grape marcs, Orange peels), available all year round and with different composition, (ii) application of proprietary high-pressure homogenization (HPH) techniques to micronize the residues in water and completely disintegrate the vegetable cells, with integrated physical fractionation to recover insoluble fibers, (iii) combination with chemical fractionation or high P/T autohydrolysis, or enzymatic treatments. The fabrication of NC structures with tunable size, crystallinity, and surface properties is important to bridge the gap between the production of cellulose and cellulose hybrids and the final applications and is pursued through (i) the size-reduction of NC, or enzymatic lysis, (ii) functionalization via amination or phosphorylation, or (iii) via physical immobilization or covalent bonding with limonene. The characterization of NC in terms of (i) yields, purity, physicochemical, structural, and functional properties, using a multi-technique approach, is associated to the evaluation of (ii) bio-accessibility (through the simulated digestive process) of bioactive compounds and fibers, (iii) film-forming capacity, (iv) gas-barrier properties, (v) rheological behavior, as well as (vi) energy, water, and reagents consumptions. Finally, the PANACEA project also addresses the exploitation of NC-based colloids for novel materials and applications, such as (i) edible coatings, antimicrobial varnishes, and oil structuring materials, (ii) packaging films with gas-barrier properties, and (iii) fabrics and foams with flame-retardant properties (iv) advanced nanocomposite films, (v) Pickering emulsions, and (vi) antimicrobial films and coatings. The main contribution of the PANACEA project to the advancement of the knowledge is expected in (i) the deployment of greener and sustainable, cascading processes exploiting raw AFR functionalities, (ii) the tailored valorization of different AFR by developing physical, chemical, and biological procedures for sculpting the nanostructures, and (iii) the development of sustainable, high performing advanced materials such as edible coatings and gas barrier packages for the food industry, foams, and textiles with flame retardant properties, biocides for organic pest control in agriculture.

Here were report a study of picene nano-cristalline thin films doped with pentacene molecules. The thin films were grown by supersonic molecular beam deposition with a doping concentration that ranges between less than one molecules of pentacene every 104 picene molecules up to about one molecule of pentacene every 102 of picene. Morphology and opto-electronic properties of the films were studied as a function of the concentration of dopants. The optical response of the picene films, characterized by absorption, steady-state and time-resolved photoluminescence measurements, changes dramatically after the doping with pentacene. An efficient energy transfer from the picene host matrix to the pentacene guest molecules was observed giving rise to an intense photoluminescence coming out from pentacene. This efficient mechanism opens the possibility to exploit applications where the excitonic states of the guest component, pentacene, are of major interest such as MASER. The observed mechanism could also serve as prototypical system for the study of the photophysics of host guest systems based on different phenacenes and acenes., Comment: 15 pages, 6 figures

Bilayer membranes for food packaging applications were prepared by depositing on polylactic acid (PLA) substrates pure cellulose nanofibers' (CNF) coatings and nanocomposite coatings made of CNF with dispersed TiO2 nanoparticles. The gas barrier properties of the bilayer membranes were studied by gas phase permeation technique using CO2, N2, D2, He and ambient air as test gases. Few micrometer thick pure and nanocomposite CNF coatings act as effective gas permeation barriers impeding the CO2, N2 and O2 transport and reducing the He and D2 transport rates by 3 orders of magnitude when compared with the PLA substrate. Gas transport through the coatings obeys the solution-diffusion mechanism: D2 permeation process shows activation energy values of 44 ± 6 kJ/mol and 40 ± 6 kJ/mol in the pure and nanocomposite CNF coating, respectively. The addition of the TiO2 nanoparticles reduces the penetrant diffusivity by increasing the tortuosity of the penetrant migration path but does not affect the gas barrier performances. UV–Vis spectroscopy analyses show that the optical transparency of the PLA support is slightly decreased by the CNF coating: at 600 nm the optical transmittance decreases, in fact, from 95% to 91%. TiO2 nanoparticles strongly absorb UV radiation and slightly reduce the PLA transparency in the optical range due to light scattering effects.

Graphene laminated (GL) coatings formed by stacked few layer graphene (FLG) nanocrystals were deposited on low-density polyethylene (PE) films by the mechanical rubbing technique. Molecular transport through the bilayer membrane was studied by the gas phase permeation technique by monitoring the CO2, N-2 and H-2(2) transport fluxes in transient conditions. The results evidenced that the transport exhibited anomalous character. The experimental data could be reproduced assuming that the penetrant concentration in the GL coating, c(int)(t), reached a saturation value c(s) following compressed exponential kinetics c(int)(t) = c(s)[1 - e(-(lambda relt)beta)]. The relaxation time tau(rel) = 1/lambda(rel) showed thermally activated behavior, and its value increased with the kinetic diameter of the penetrant molecules. The critical exponent beta = 1.5 +/- 0.1 for CO2 and N-2 and beta = 2.0 +/- 0.1 for H-2(2) did not change with temperature. Positron annihilation lifetime spectroscopy (PALS) analysis indicated that the average cross-section (h(g)) of the cavities in the GL coating exhibited comparable size to the kinetic diameter (sigma(k)) of the penetrant molecules. The results could be explained by assuming that the molecular infiltration in the GL structure occurred in nano-channels having distributed path lengths where the penetrant transport obeyed a configurational diffusion mechanism.

The interest towards aptamer-based surfaces in the field of bioaffinity assays is constantly growing. A crucial aspect is related to the ability of maintaining the high specificity of these molecules once immobilized on the surface. In this article we compare the immobilization of aptamers on a silanized silicon nitride surface as well as on a soft polymeric layer. An innovative immobilization approach, based on a copolymer, N-dimethylacrylamide-N-acryloyloxysuccinimide-3-(trimethoxysilyl)propylmethacrylate (DMA-NAS-MAPS) coating, able to crosslink itself to the substrate and to bind amino-modified biomolecules is proposed. Comparing this coating with a more classical functionalization process based on silane chemistry, we propose that the better results obtained on the polymeric layer are due to an increased binding efficiency of the aptamers bound to a soft material. The high specificity of immobilized DNA-aptamers is demonstrated using two sequences specific for thrombin detection and a non-sense sequence as negative control. The coating provides higher sensitivity compared to classical self-assembled silane coatings, probably due to a better mobility of bound aptamers. The aptamer immobilization on both surfaces was characterized and optimized using atomic force microscopy, X-ray photoelectron spectroscopy, contact angle and fluorescence microscopy. The comparison between the two different functionalizations highlights the better performances of the copolymer coating in terms of protein recognition, demonstrating thrombin detection down to 0.011 nM in buffer solution and 4.9 nM in complete human serum. Moreover, the localized immobilization of the aptameric sequences, utilized in this work, suggests the possibility of employing this platform also for multianalyte detection.

We have studied the kinetics of gas transport through films made of self-assembled cellulose nanofibrils (CNF) by a time-resolved mass spectroscopy technique. Few micrometers thick films deposited on polylactic acid (PLA) substrates act as impermeable barriers for CO2, O2, and N2 and reduce the 2H2 (deuterium) and He permeation flux by a factor of ∼103 with respect to the uncoated substrate. Penetrant transport is controlled by the solution-diffusion mechanism and the coating acts as a diffusive barrier. 2H2 and He diffusivity values are in the 10–10 and 10–9 cm2 s–1 range, respectively, and their migration occurs by thermally activated process with 39 ± 1 and 33 ± 2 kJ mol–1 activation energy. Positron annihilation lifetime spectroscopy analysis indicates that the diffusive path between the packed nanofibrils consists of elongated cavities with cross-sectional size ∼ 0.31 nm. Results evidence that the selective transport of the small size penetrants is due to sieving effects and that small penetrant tran...

Selective functionalization of the external/internal pore surface of porous silicon is of interest for the numerous potential applications of this material, in particular in pharmacology. With the aim of obtaining porous silicon platforms compatible with the aqueous environment and providing hydrophobic pores to load poorly water soluble molecules, we set-up a three step functionalization procedure consisting in two hydrosilylation reactions separated by the selective etching of the external surface. This procedure was applied both, to porous layers and porous microparticles. The characterization of the functionalized material by conventional techniques such as contact angle and FTIR showed a change of the properties of porous structures in line with the expected surface modifications. However, these techniques do not permit to clearly distinguish between internally and externally grafted functional groups. For this reason, an innovative procedure based on angle-resolved XPS was set-up and applied to differently functionalized pSi layers. By this technique, we obtained indications of prevalent grafting of hydrophilic moieties on the external surface and hydrophobic ones inside the pores.

A functionalization strategy, consisting of a silylation reaction by acrylic acid followed by diamine coupling, preserves and stabilizes the photoluminescence (PL) of porous silicon (pSi) microparticles suspended in ethanol. We found that under the condition of efficient amine coupling, besides the orange emission typical of the native pSi, an emission band in the blue region appears. The investigation of the interaction between pSi and diamine shows that diamine quenches and shifts the orange band meanwhile it induces an increase of the intensity of the blue one. PL lifetimes of the orange and blue bands are in the micro and nano second range, respectively. These values and their wavelength dependence clearly prove that the two bands have different origin: quantum confinement and nitrogen impurities introduced at silicon/silicon oxide interface, respectively. Thus, they can be used to discriminate between the pSi microparticles obtained by silylation, which expose carboxylic groups and the pSi microparticles after the diamine coupling, which bear amine functionalities at the surface. The increase in the stability of the PL emission of pSi in aqueous solution after functionalization, with quantum yields of the order of 1–2%, supports the use in biological systems of these brightly emitting, largely porous microparticles, bearing positive or negative surface charge.

In this study we investigated the fabrication of small hydrogel objects by the coordination-driven assembly of supramolecular rod-like crystallites of nanocellulose, using ionotropic gelation as a methodological approach and Ca2+ as a gelling agent. We proved that the gelation process is diffusion-mediated and fitting the equations modelling this process to the profile of the Ca2+ front, a Ca2+ diffusion coefficient in the incipient hydrogel of (4.5 ± 1.1) × 10−6 cm2 s−1 was calculated. At the steady-state a spatially homogeneous distribution of Ca2+-crosslinked sites in the hydrogel network was observed. External ionotropic gelation produced beads, wires or disks, while core–shell capsules were obtained by inverse ionotropic gelation. We demonstrated that equilibrium and dynamics of the distribution of Ca2+ offer the opportunity to design precisely the size and shape of these small hydrogel objects. In particular, the core size and the shell thickness of the capsules can be tailored under kinetic controlled conditions. The proposed approach, with supramolecular structures of the natural source as assembling components and the water-in-water fabrication process, is fast, simple, and requires only sustainable chemistry and is easily implementable in automatic microfluidic platforms.

International audience; We report the first synthesis of silicon nanocrystals embedded in a silicon nitride matrix through a direct pyrolysis of a preceramic polymer (perhydropolysilazane). Structural analysis carried out by XRD, XPS, Raman and TEM reveals the formation of silicon quantum dots and correlates the microstructures with the annealing temperature. The photoluminescence of the nanocomposites was investigated by both linear and nonlinear measurements. Furthermore we demonstrate an enhanced chemical resistance of the nitride matrix, compared to the typical oxide one, in both strongly acidic and basic environments. The proposed synthesis via polymer pyrolysis is a striking innovation potentially allowing a mass-scale production nitride embedded Si nanocrystals.

Biosensing analytical platforms rely on the intimate structure–function relationship of immobilized probes. In this context, hydrogels are appealing semi-wet systems to locally confine biomolecules while preserving their structural integrity and function. Yet, limitations imposed by biomolecule diffusion rates or fabrication difficulties still hamper their broad application. Here, using a self-assembling peptide, a printable and self-adhesive hydrogel was obtained and applied to fabricate arrays of localized bio-functional 3D microenvironments on analytical interfaces. This soft matrix represents a robust and versatile material, allowing fast and selective tuning of analyte diffusion, which is exploited here to run in-gel immunoassays under solution-like conditions in an unprecedented (

A quantum random number generator (QRNG) based on a silicon nanocrystals (Si-NCs) light emitting device (LED) coupled with a silicon single photon avalanche photodiode (Si-SPAD) is presented. A simple setup is used for the generation of random bits. The modeled approach assures a negligible bias on datasets of ∼100 Mbits length. The raw data pass all the statistical tests in the National Institute of Standards and Technology (NIST) suite without any post-processing operations. The bit-rate of 0.6 Mbps is achieved. The information-theoretically provable randomness extractor of Toeplitz-hashing function is applied to longer datasets (∼1 Gbits) to extract the randomness, to minimize the bias, and consequently pass all the NIST tests. Stabilizing the temperature, resetting the applied current to the LED, or a feedback system can also be used as parameter control solutions to generate good quality, long datasets of random numbers suitable for cryptographic applications.

Silicon is the most common semiconductor in technology. Its main limit is the lacking of efficient light emission properties. Here quantum effects are exploited to fabricate optically active silicon photonics elements. The manuscript reports recent results obtained in different research fields spanning from bio- to integrated-photonics and nonlinear optics.

Topology affects physical and biological properties of DNA and impacts fundamental cellular processes, such as gene expression, genome replication, chromosome structure and segregation. In all organisms DNA topology is carefully modulated and the supercoiling degree of defined genome regions may change according to physiological and environmental conditions. Elucidation of structural properties of DNA molecules with different topology may thus help to better understand genome functions. Whereas a number of structural studies have been published on highly negatively supercoiled DNA molecules, only preliminary observations of highly positively supercoiled are available, and a description of DNA structural properties over the full range of supercoiling degree is lacking. Atomic Force Microscopy (AFM) is a powerful tool to study DNA structure at single molecule level. We here report a comprehensive analysis by AFM of DNA plasmid molecules with defined supercoiling degree, covering the full spectrum of biologically relevant topologies, under different observation conditions. Our data, supported by statistical and biochemical analyses, revealed striking differences in the behavior of positive and negative plasmid molecules.

Silicon nanocrystals (Si-nc) are reviewed here for their interesting optical applications. On the one hand, they do exhibit quantum confinement effects. This allows turning silicon into a light-emitting material where luminescence can be excited by electrical injection. On the other hand, small sizes, large surfaces, and dielectric mismatch between the core and the surrounding matrix increase dramatically the nonlinear optical coefficients. This allows using Si-nc as a nonlinear material in different waveguide configurations. In this paper, we discuss specifically two different applications of Si-nc: (i) as a nonlinear material in various devices, e.g., in bistable optical cavities, in waveguide optical mode monitors that are based on two-photon excited luminescence detection, and in wavelength shifters by using four-wave mixing (FWM); (ii) as an entropy source for quantum random number generation, the key device for cryptography. (a) Top view optical image of a Si-nc-based whispering-gallery mode (WGM) microdisk resonator, vertically coupled with a bus waveguide. (b) Detail of the coupling zone. (c) Normalized waveguide transmission spectrum over a wide spectral range. The inset shows a blow up of a resonance with the radial and azimuthal mode orders and the Q factor value indicated.

Matrix Assisted Laser Desorption Ionization (MALDI) is a soft ionization method with widespread analytical applications. One of its limits is the spurious signal in the low mass region, due to the required use of matrices to desorb and ionize the analytes. The possibility to avoid their use will ease both sample preparation and mass spectrum interpretation because the low mass region will not be crowded by peaks of the matrix. In recent years, nanostructured materials have been proposed as matrix-free substrates, but their use is limited to specific combination of nanostructures and analytes, while no general matrix-free approach has yet been demonstrated. Here we propose a radically new type of transducer and we demonstrate that fluorosilanized bulk surfaces achieve similar detection limit of nanostructured substrates. The results of our work suggest that desorption/ionization (D/I) is a purely interfacial effect, with negligible contribution from the chemical nature of the underlying substrate, provided that the substrate contains fluorine species, is an electrical conductor and a good UV absorber.

Sol-gel transition of carboxylated cellulose nanocrystals has been investigated using rheology, SAXS, NMR and optical spectroscopies to unveil the distinctive roles of ultrasound treatments and addition of various cations. Besides cellulose fiber fragmentation, sonication treatment induces fast gelling of the solution. The gelation is independent of the addition of cations, while the final rheological properties are highly influenced by the type, concentration and sequence of the operations since the cations must be added prior to sonication to produce stiff gels. The gel elastic modulus was found to increase proportionally to the ionic charge rather than the cationic size. In cases where ions were added after sonication, SAXS analysis of the Na+ hydrogel and Ca2+ hydrogel indicated the presence of structurally ordered domains in which water is confined, and 1H-NMR investigation showed the dynamics of water exchange within the hydrogels. Conversely, separated phases containing essentially free water were characteristic of the hydrogels obtained by sonication after Ca2+ addition, confirming that this ion induces irreversible fiber aggregation. The rheological properties of the hydrogels depend on the duration of the ultrasound treatments, enabling the design of programmed materials with tailored energy dissipation response.

Nowadays sensors are everywhere around us. We are monitoring nearly all aspects of our daily life: from health to security, from domotic to environmental aspects. The availability of smaller, more efficient and intelligent systems is highly valued to increase the quality and the accuracy of such analysis and of our well-being.

In this review materials and technologies of the hybrid approach to integrated photonics (IP) are addressed. IP is nowadays a mature technology and is the most promising candidate to overcome the main limitations that electronics is facing due to the extreme level of integration it has achieved. IP will be based on silicon photonics in order to exploit the CMOS compatibility and the large infrastructures already available for the fabrication of devices. But silicon has severe limits especially concerning the development of active photonics: its low efficiency in photons emission and the limited capability to be used as modulator require finding suitable materials able to fulfill these fundamental tasks. Furthermore there is the need to define standardized processes to render these materials compatible with the CMOS process and to fully exploit their capabilities. This review describes the most promising materials and technological approaches that are either currently implemented or may be used in the coming future to develop next generations of hybrid IP devices.