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Increasing efforts have been focused on development of novel therapeutic approaches based on a carrier mixed with polymeric microparticles (MPs) for promoting bioactive factors delivery. Polymers a...

Quantum dot solar cells are based on the concept of harvesting different parts of the solar light spectrum with a single, cheap semiconductor by simply changing the size of the nanoparticles. Of the many compositions explored, germanium is one of the most interesting as it has the major advantage of a large Bohr radius, which allows for the fabrication of larger particles. Moreover, germaniums possess very high optical absorption, and a small band gap give it free parameters to optimize the quantum dot solar cell. In a previous work, the germanium quantum dots were used in a Gratzel type solar cell containing an electrolyte, which is not desirable for applications. In this work instead, the n-doped germanium quantum dots were combined with a p-doped a-Si layer, making it the first all solid-state solar cell made from nanoparticles from a gas aggregation nanoparticle source. Remarkably, the effect of quantum confinement in both the germanium quantum dot assembled layer and a-Si was observed by peaks in the spectral response experiments. This work forms an important step toward realizing a germanium quantum dot based solar cell and studying quantum dot based solids.

The exploitation of self-assembled systems to improve the solubility of drugs is getting more and more attention. Among the different types of self-assembled biomaterials, peptides and in particular peptides containing non-coded amino acids (NCAPs) are promising because their use opens the door to more stable materials inducing increased stability to proteolysis. New classes of NCAP, Ac-Ala-X-Ala-Aib- AlaCONH2 (X ¼ alpha-aminoisobutyric acid (Aib) or X ¼ cyclopentane amino acid (Ac5c)) have been prepared and the correlation between the different secondary peptide structure and solvent (i.e. CD3CN, CD3OH, H2O/D2O) verified by NMR. Furthermore, the formation of a nanocolloidal system in water was deeply studied by DLS and the morphology of the obtained spherical aggregates with nanometric dimensions was assessed by TEM. Aib containing pentapeptide was selected for greater ease of synthesis. Its ability to encapsulate curcumin, as a model insoluble drug molecule, was investigated using fluorescence emission and confocal microscopy analyses. Two different approaches were used to study the interaction between curcumin and peptide aggregates. In the first approach peptide aggregates were formed in the presence of curcumin, while in the second approach curcumin was added to the already formed peptide aggregates. We succeeded in our challenge by using the second approach and 53.8% of added curcumin had been encapsulated.

Compared to two-dimensional cell cultures, three-dimensional ones potentially allow recreating natural tissue environments with higher accuracy. The three-dimensional approach is being investigated in the field of tissue engineering targeting the reconstruction of various tissues, among which skeletal muscle. Skeletal muscle is an electroactive tissue which strongly relies upon interactions with the extracellular matrix for internal organization and mechanical function. Studying the optimization of myogenesis in vitro implies focusing on appropriate biomimetic stimuli, as biochemical and electrical ones. Here we present a three-dimensional polyurethane-based soft porous scaffold (porosity ~ 86%) with a Young's modulus in wet conditions close to the one of natural skeletal muscle tissue (~ 9 kPa). To study the effect of external stimuli on muscle cells, we functionalized the scaffold with extracellular matrix components (laminin and fibronectin) and observed an increase in myoblast proliferation over three days. Furthermore, the combination between laminin coating and electrical stimulation resulted in more spread and thicker myotubes compared to non-stimulated samples and samples receiving the single (non-combined) inputs. These results pave the way to the development of mature muscle tissue within three-dimensional soft scaffolds, through the combination of biochemical and electrical stimuli.

Subnanometer copper tetramer–zirconia catalysts turn out to be highly efficient for CO2 hydrogenation and its conversion to methane. The cluster size and substrate morphology are controlled to optimize the catalytic performance. The two types of zirconia supports investigated are prepared by atomic layer deposition (∼3 nm thick film) and supersonic cluster beam deposition (nanostructured film, ∼100 nm thick). The substrate plays a crucial role in determining the activity of the catalyst as well as its cyclability over repeated thermal ramps. A temperature-programmed reaction combined with in situ X-ray characterization reveals the correlation between the evolution in the oxidation state and catalytic activity. Ex situ photoelectron spectroscopy indicates Cu clusters with stronger interactions with the nanostructured film, which can be the cause for the higher activity of this catalyst. Density functional theory calculations based on the Cu4O2 cluster supported on a ZrOx subunit reveal low activation barriers and provide mechanism for CO2 hydrogenation and its conversion to methane. Altogether, the results show a new way to tune the catalytic activity of CO2 hydrogenation catalysts through controlling the morphology of the support at the nanoscale.

Germanium quantum dots are very interesting for applications such as solar cells, photodetectors, and light emitters because their small bandgap can be tuned over a wide energy range by changing the particle size. One obstacle to applications is the presence of defects, both in the interior and at the surface of the nanoparticles. The defects function as nonradiative recombination centers or trap charge carriers, which will hinder further optical performance. Introducing hydrogen, as employed in a-Si:H solar cells, has proven to be a good method to counter such detrimental defect effects. In this work, germanium quantum dots were fabricated by an ultraclean, vacuum-based nanoparticle reactor in which hydrogen was supplied during growth. Optical spectroscopy of the a-Ge:H quantum dots, together with Raman and X-ray photoelectron spectroscopy, revealed a direct bandgap and that the presence of hydrogen resulted in amorphous Ge:H quantum dots. These a-Ge:H quantum dots are a step forward toward reducing charge carrier recombination in quantum dot solar cells.

Ionic liquids are employed in energy storage/harvesting devices, in catalysis and biomedical technologies, due to their tunable bulk and interfacial properties. In particular, the wettability and the structuring of the ionic liquids at the interface are of paramount importance for all those applications exploiting ionic liquids tribological properties, their double layer organization at electrified interfaces, and interfacial chemical reactions. Here we report an experimental investigation of the wettability and organization at the interface of an imidazolium-based ionic liquid ([Bmim][NTf2]) and gold surfaces, that are widely used as electrodes in energy devices, electronics, fluidics. In particular, we investigated the role of the nanostructure on the resulting interfacial interactions between [Bmim][NTf2] and atom-assembled or cluster-assembled gold thin films. Our results highlight the presence of the solid-like structured ionic liquid domains extending several tens of nanometres far from the gold interfaces, and characterized by different lateral extension, according to the wettability of the gold nanostructures by the IL liquid-phase.

Mechanosensing, the ability of cells to perceive and interpret the microenvironmental biophysical cues (such as the nanotopography), impacts strongly on cellular behaviour through mechanotransductive processes and signalling. These events are predominantly mediated by integrins, the principal cellular adhesion receptors located at the cell/extracellular matrix (ECM) interface.Because of the typical piconewton force range and nanometre length scale of mechanotransductive interactions, achieving a detailed understanding of the spatiotemporal dynamics occurring at the cell/microenvironment interface is challenging; sophisticated interdisciplinary methodologies are required. Moreover, an accurate control over the nanotopographical features of the microenvironment is essential, in order to systematically investigate and precisely assess the influence of the different nanotopographical motifs on the mechanotransductive process.In this framework, we were able to study and quantify the impact of microenvironmental nanotopography on early cellular adhesion events by means of adhesion force spectroscopy based on innovative colloidal probes mimicking the nanotopography of natural ECMs.These probes provided the opportunity to detect nanotopography-specific modulations of the molecular force loading dynamics and integrin clustering at the level of single binding events, in the critical time window of nascent adhesion formation. Following this approach, we found that the nanotopographical features are responsible for an excessive force loading in single adhesion sites after 20 – 60 s of interaction, causing a drop in the number of adhesion sites. However, by manganese treatment we demonstrated that the availability of activated integrins is a critical regulatory factor for these nanotopography-dependent dynamics.

Water splitting will be one of the most strategic techniques in the upcoming hydrogen-based economy. In this context, the development of efficient and low-cost Pt-free electrocatalysts is crucial t...

We present the synthesis and the characterization of a novel cellulose-based electroactive hydrogel obtained through a simple water-based process. Its swelling and electroactive properties are here studied especially in low salinity water solutions. By combining smart materials and three-dimensional printing technique, we assessed that hydrogels can be shaped as natural algae and their motion can be controlled with electric signals to mimic natural seaweed movements under the effect of water flow. This could constitute a first step toward the development of hybrid habitats where artificial smart algae could cohabit with real living organisms or microorganisms.

We report on the proof of principle of a scalable method for writing the magnetic state by electron-stimulated molecular dissociative adsorption on ultrathin Co on Re(0001). Intense microfocused low-energy electron beams are used to promote the formation of surface carbides and graphitic carbon through the fragmentation of carbon monoxide. Upon annealing at the CO desorption temperature, carbon persists in the irradiated areas, whereas the clean surface is recovered elsewhere, giving origin to chemical patterns with nanometer-sharp edges. The accumulation of carbon is found to induce an in-plane to out-of-plane spin reorientation transition in Co, manifested by the appearance of striped magnetic domains. Irradiation at doses in excess of 1000 L of CO followed by ultrahigh vacuum annealing at 380 °C determines the formation of a graphitic overlayer in the irradiated areas, under which Co exhibits out-of-plane magnetic anisotropy. Domains with opposite magnetization are separated here by chiral Neél walls. Our fabrication protocol adds lateral control to spin reorientation transitions, permitting to tune the magnetic anisotropy within arbitrary regions of mesoscopic size. We envisage applications in the nano-engineering of graphene-spaced stacks exhibiting the desired magnetic state and properties.

Tendon tears are a relevant concern for today’s national health systems because of their social impact and high recurrence rate. The current gold standard for fixing tendon tears is surgical repair; however, this strategy is not able to fully re-establish tendon integrity and functionality. Tissue engineering approaches aim at promoting tissue regeneration by delivering the opportune signals to the injured site combining biomaterials, cells and biochemical cues. Electrospinning is currently one of the most versatile polymer processing techniques that allows manufacturing of nano- and micro-fibres substrates. Such fibrous morphology is deemed to be an ideal substrate to convey topographical cues to cells. Here we evaluated the potential of polycaprolactone processed by means of electrospinning technology for tendon tissue engineering. Fibrous free-of-defects substrate with random and aligned fibres were successfully fabricated. Rat tenocytes were used to assess the cytocompatibility of the substrates for application as tendon tissue engineered devices. Tenocytes were able to proliferate and adapt to the substrates topography acquiring an elongated morphology, which is the precondition for oriented collagen deposition, when seeded on aligned fibres. Real time Polymerase Chain Reaction (Rt-PCR) also revealed the overall maintenance of tenocyte phenotype over 7 days culture. To verify suitability for in vivo implantation, the level of inflammatory cytokine genes expressed by THP-1 cells cultured in presence of electrospun polycaprolactone substrates was evaluated. Inflammatory response was limited. The novel preliminary in vitro work presented herein showing tenocytes compatibility and limited inflammatory cytokines synthesis suggests that electrospun polycaprolactone may be taken into consideration as substrate for tendon healing applications.

Studies on the optical absorbance spectra of Fricke xylenol orange gel dosimeters were performed, in the wavelength range from 300 nm to 800 nm, in order to highlight some particular characteristics that can affect the achievable precision. The spectra are different mainly due to the different types of xylenol orange that was used and to a lower extent due to the different gelling agents (agarose or gelatine). The characteristic of variation of absorbance spectra versus dose, however, are similar in the various cases and can explain some peculiarities, as apparent effects of dose threshold. Changes of spectral shapes appear over the time after irradiation. Magnetic resonance measurements performed at various times after irradiation only reveal the slow changes due to the auto-oxidation effect, proving therefore that the modality of chelation of ferric ions by xylenol orange can affect the observed changes in the optical absorbance spectra.

This study presents an innovative method for the synthesis of polymeric nanoparticles (NPs) for central nervous system (CNS) targeting. The method is based on Ultraviolet light (UV)-induced crosslinking of diacrylamide-terminated oligomers of poly(amidoamine)s (PAAs), a widely used class of synthetic polymers in biomedical field research, especially in drug delivery thanks to their excellent biocompatibility and controlled biodegradability. Previous attempts aiming at preparing PAA-based NPs by self-assembly were challenged by lack of structural stability and consequently their early degradation and premature drug release. Here, the UV-induced crosslinked PAA NPs demonstrated to overcome main disadvantages of the self-assembled ones, as they showed improved stability and controlled release properties. Besides the remarkable efficiency to produce monodisperse and stable PAA NPs, the UV-induced crosslinking method is featured by great versatility and low environmental impact, since it does not require use of organic solvents and multiple purification steps. The capability of PAA NPs to encapsulate a fluorescently labelled model protein was experimentally demonstrated in this study. Cell culture experiments showed that PAA NPs were biocompatible and highly permeable across an in vitro blood-brain barrier model, thus highlighting their great potential as drug delivery vectors for CNS delivery.

The Fricke gels (FG) composition has been modified over the years in order to improve their dosimetric characteristic for spatial dose evaluation in radiotherapy. Some problems, in particular those related to the diffusion of ferric ions in the gel matrix, have limited the clinical use of FG and still represent significant challenges for the scientific community working in the field of gel dosimetry. In this work, FG based on poly-vinyl alcohol (PVA) as the gelling agent, glutaraldehyde (GTA) as a cross-linker and FG based on gelatine loaded with silicate nano-clay (laponite) were developed with the aim to overcome the diffusion drawbacks affecting the traditional FG. Neither the sensitivity to the radiation dose nor the diffusion coefficient were significantly altered by the addition of laponite into the Fricke xylenol orange gel formulation employed. By contrast, lower diffusion rates were obtained with PVA-GTA gels, suggesting that this matrix could have a promising use in the field of 3D dosimetry.The Fricke gels (FG) composition has been modified over the years in order to improve their dosimetric characteristic for spatial dose evaluation in radiotherapy. Some problems, in particular those related to the diffusion of ferric ions in the gel matrix, have limited the clinical use of FG and still represent significant challenges for the scientific community working in the field of gel dosimetry. In this work, FG based on poly-vinyl alcohol (PVA) as the gelling agent, glutaraldehyde (GTA) as a cross-linker and FG based on gelatine loaded with silicate nano-clay (laponite) were developed with the aim to overcome the diffusion drawbacks affecting the traditional FG. Neither the sensitivity to the radiation dose nor the diffusion coefficient were significantly altered by the addition of laponite into the Fricke xylenol orange gel formulation employed. By contrast, lower diffusion rates were obtained with PVA-GTA gels, suggesting that this matrix could have a promising use in the field of 3D dosimetry.

Purpose of this study is to test if possible effects of gelation temperature and pH on the cross-linking process between poly(vinyl alcohol) (PVA) and glutaraldehyde (GTA), have consequences on the dosimetric properties of PVA-GTA Xylenol Orange Fricke gel dosimeters. Therefore, dose-response curves and Fe3+ diffusion rate of PVA-GTA Fricke gel dosimeters prepared using different sulfuric acid concentrations and different gelation temperature were investigated by optical absorbance measurements. The results demonstrated that the sulfuric acid concentration determines both the dose sensitivity of the PVA-GTA Xylenol Orange Fricke gel dosimeters and the interval of linearity of the dose-response curve. Although the effects of gelation temperature and sulfuric acid concentration on the PVA-GTA cross-linking process may occur, no significant consequences on diffusion properties of PVA polymer network were observed. Indeed, Fe3+ diffusion rates in all investigated samples were very similar, and less than half of those achievable in Fricke gel dosimeters prepared with natural gel matrices like gelatin and agarose.

In an attempt to mitigate the effects of climate changes, modern societies are facing a revolution in energy supply. Future economy will be increasingly dominated by carbon-free and renewable energy sources. In this context, hydrogen will play a fundamental role in the energy transition from fossil to green sources. It offers the possibility to smooth the intermittency typical of many renewable energy sources and it constitutes an ideal complement for batteries in the transport sector. Hydrogen can be easily produced employing water electrolysis, stored in large amounts and subsequently re-electrified in fuel cells. Efficient water electrolysis, however, makes use of noble metal electrocatalysts to lower the overpotential required for the Hydrogen Evolution Reaction (HER) to take place. Due to the limited availability and consequent high cost of noble metals, research is currently focusing on the development of low-cost alternative catalytic materials. One of the most studied electrocatalytic compounds are transition metal phosphides [1]. These materials present remarkable advantages over commonly used Pt based catalysts: comparable performances, lower cost, high abundancy and ease of manufacturing. In the present work, transition metal phosphides were fabricated through a simple and costless codeposition-annealing process. Amorphous Ni-P and Co-P alloys were codeposited with red phosphorus particles and subsequently annealed [2]. The annealing step was applied to promote the formation of intermetallics through interdiffusion between pure phosphorus particles and the metallic matrix. As a result, different phase pure metal phosphides were obtained. The most important advantage of this methodology is the possibility to overcome the compositional limit typical of electrodeposited phosphorus-based alloys. Elemental phosphorus codeposition allows to reach P concentrations higher than 50 % at., whereas simple Ni-P solid solution electrodeposition is compositionally limited to 25 % at. Enhancing P content is fundamental to obtain phosphorus rich compounds like Ni2P and Co2P, which are characterized by high catalytic activities for HER [3]. Furthermore, the technique allows to confine elemental P inside the coating during the annealing step. This peculiarity strongly optimizes material usage and it limits the presence of gaseous phosphorus, which is typical of many phosphorization processes used in literature to obtain metal phosphides [4] and it can result into the formation of the unstable white P allotrope. Obtained nickel and cobalt phosphides were characterized with different techniques (SEM, XRD, EDS) to assess their morphology, phase structure and chemical composition. A special emphasis was placed on XPS characterization. Thanks to its ability to analyze the first superficial layers of the coatings, XPS was employed to determine the chemical state of the elements present on the surface of the electrocatalysts. Being electrocatalysis an interfacial phenomenon, this allowed to link material surface properties with observed electrocatalytic performances. The electrocatalytic HER activity and stability of the different transition metal phosphides were tested in 0.5 M H2SO4. In all cases, remarkable results were obtained, with the lowest overpotential obtained in the case of Co-P/P codeposition and subsequent annealing at 290 °C: 62 mV vs. RHE at a current density of 10 mA/cm2 in 0.5 M H2SO4 solution. This result is in line with the literature available on cobalt phosphides as electrocatalysts [5]. [1] P. Xiao et al., Adv. Energy Mater. 5, 1500985 (2015) [2] R. Bernasconi et al., ACS Appl. Energy Mater. 3(7), 6525–6535 (2020) [3] A. R. J. Kucernak et al., J. Mater. Chem. A 2, 17435 (2014) [4] X. Wang et al., Angew. Chem. 54(28), 8188 (2015) [5] Saadi et al., J. Phys. Chem. C 118(50), 29294–29300 (2014)

Fricke gel dosimeters were prepared using a matrix based on poly(vinyl-alcohol) chemical cross-linked with glutaraldehyde and loaded with Xylenol Orange. The samples were irradiated with gamma rays to doses in the range of 5–30 Gy and the consequent color changes were investigated by using spectrophotometric and colorimetric techniques. Starting from the measurement of the transmittance spectra, an analysis of the color of the dosimeters was carried out considering the CIELAB color space. It allowed to highlight correlations between the color coordinates and the dose. Furthermore, the auto-oxidation processes occurring in the samples were studied by colorimetric measurements on both un-irradiated and irradiated samples at different times, up to two-week post-irradiation. The results showed no significant differences in the oxidation effect on the dosimeters, at least in the investigated dose interval. The study suggested that colorimetric analysis, combined with the spectrophotometric one, can be a useful tool for characterizing the samples in view of a standardization of Fricke gel dosimetry.

Light-driven water splitting is one of the most promising approaches for using solar energy in light of more sustainable development. In this paper, a highly efficient p-type copper(II) oxide photocathode is studied. The material, prepared by thermal treatment of CuI nanoparticles, is initially partially reduced upon working conditions and soon reaches a stable form. Upon visible-light illumination, the material yields a photocurrent of 1.3 mA cm(-2) at a potential of 0.2 V vs a reversible hydrogen electrode at mild pH under illumination by AM 1.5 G and retains 30% of its photoactivity after 6 h. This represents an unprecedented result for a nonprotected Cu oxide photocathode at neutral pH. The photocurrent efficiency as a function of the applied potential was determined using scanning electrochemical microscopy. The material was characterized in terms of photoelectrochemical features; X-ray photoelectron spectroscopy, X-ray absorption near-edge structure, fixed-energy X-ray absorption voltammetry, and extended X-ray absorption fine structure analyses were carried out on pristine and used samples, which were used to explain the photoelectrochemical behavior. The optical features of the oxide are evidenced by direct reflectance spectroscopy and fluorescence spectroscopy, and Mott-Schottky analysis at different pH values explains the exceptional activity at neutral pH.

The Barium (BSCF) and Lanthanum (LSCF) strontium cobalt–ferrite, are among the most studied mixed ionic electronic conducting materials having interesting properties as Oxygen Transport Membranes. In this paper the two materials are analysed after long term aging at high temperatures and permeation tests. Several characterisation techniques are used to understand degradation mechanisms. Surface layers were analysed by X-ray photoelectron spectroscopy: LSCF is stable, while on BSCF a thin layer of carbonates forms. Quantitative synchrotron radiation diffraction measurements of hexagonal phase content in aged BSCF allows determining Avrami coefficients at 780, 800 and 820 °C. This process is associated to the enrichment of Fe in the regions of grains near the lamellar hexagonal phase, as WDS maps show. Bulk measurements of X-ray Absorption Near Edge Structure (XANES) and the analysis of the Co2p doublet in XPS spectra confirm a reduction of Co ions oxidation number after long time at intermediate temperatures.

We present the synthesis, fabrication and electro-mechanical characterization of a novel electro-responsive hydrogel based on Na-4-vinylbenzenesulfonate (Na-4-VBS) that can operate as a fast response bending actuator in a low voltage regime (0.2–5 V), in NaCl aqueous solutions. The bending speed can reach values up to 22°/s at 3 V and of 2.7°/s at 1 V. The responsive behavior of the benders was observed in physiological environments as well, such as phosphate buffer solution (PBS) and Dulbecco’s Modified Eagle’s Medium (DMEM) and exhibited similar performance. The material is a co-polymer comprising also hydroxyethyl methacrylate (HEMA) and acrylonitrile (AN), to confer high hydrophilicity to the structure and to enhance its elastic properties. According to the swelling and electro-mechanical testing results, the electrically driven deformation of the hydrogels was interpreted as a dynamic osmotic equilibrium effect taking place at the interface between the polymer and the surrounding medium, induced by the free ionic species migration throughout the polymer. This material constitutes a promising solution for the design and production of highly performing soft underwater actuators and biomimetic smart systems that can be controllably operated at the macro and mesoscale in fluids of biological interest, with minimal power consumption and below the standard potential of water electrolysis.

A highly crosslinked composite dextran-based scaffold (named DexFoam) was tailored to overcome specific deficiencies of polymeric and ceramic bone scaffolds and to guarantee a bone-mimicking microenvironment for the proliferation of human mesenchymal stem cells in vitro. The creep resistance for up to 90% compressive stain, the capability to regain the original shape after deformation, and the good thermal stability in both physiological and “body limit” conditions make DexFoam a valid alternative to the currently available bone scaffolds. Histopathological evaluation for host reaction and tissue colonization of DexFoam scaffold, implanted subcutaneously in mice, demonstrated its in vivo biocompatibility and biodegradability.

In the perspective of sustainable development, future economy will be increasingly dominated by carbon-free and renewable energy sources. In this context, hydrogen will play a fundamental role in the energy transition from fossil to green sources. Hydrogen can be easily produced employing water electrolysis, stored in large amounts and subsequently re-electrified in fuel cells. It offers the possibility to smooth the intermittency typical of many renewable energy sources and it constitutes an ideal complement for batteries in the transport sector. Efficient water electrolysis, however, makes use of noble metal electrocatalysts to lower the overpotential required for the Hydrogen Evolution Reaction (HER) to take place. Due to the limited availability and consequent high cost of noble metals, research is currently focusing on the development of low-cost alternative catalytic materials. One of the most studied electrocatalytic compounds are transition metal phosphides [1]. These materials present remarkable advantages over commonly used Pt based catalysts: lower cost, high abundancy and ease of manufacturing. In many cases, phosphides offer performances comparable to the noble metal electrocatalysts. In the present work, transition metal phosphides were fabricated through a simple and costless codeposition-annealing process. Amorphous Ni-P and Co-P alloys were codeposited with red phosphorus particles and subsequently annealed. The annealing step was applied to promote the formation of intermetallics and the interdiffusion between pure phosphorus particles and the metallic matrix. As a result, different phase pure metal phosphides were obtained. The most important advantage of this methodology is the possibility to overcome the compositional limit typical of electrodeposited phosphorus-based alloys [2]. Elemental phosphorus codeposition allows to reach P concentrations higher than 50 % at., whereas simple Ni-P solid solution electrodeposition is compositionally limited to 25 % at. Enhancing P content is fundamental to obtain phosphorus rich compounds like Ni2P and Co2P, which are characterized by high catalytic activities for HER [3]. Another interesting benefit of the technique presented is the confinement of elemental P inside the coating during the annealing step. This peculiarity strongly optimizes material usage and it limits the presence of gaseous phosphorus, which is typical of many phosphorization processes used in literature to obtain metal phosphides [4] and it can result into the formation of the unstable white P allotrope. Specifically, Ni-P and Co-P were codeposited with red P particles and process conditions were optimized to maximize elemental P particles concentration. Annealing temperature and duration were varied to investigate their influence on final electrocatalytic perfrormances. Characterization techniques like XRD, SEM, EDS, cross-sectional analysis and XPS were used to determine phase composition of the materials obtained and to characterize their morphology. The electrocatalytic HER activity and stability of the different transition metal phosphides were tested in 0.5 M H2SO4. In all the cases, remarkable results were obtained, which matched up well with present existing literature where similar electrocatalysts have been fabricated through different methods [5]. The lowest overpotential was obtained in the case of Co-P/P codeposition and subsequent annealing at 290 °C: 62 mV vs. RHE at a current density of 10 mA/cm2 in 0.5 M H2SO4 solution. [1] P. Xiao et al., Adv. Energy Mater. 5, 1500985 (2015) [2] R. L. Zeller and U. Landau, J. Electrochem. Soc. 139(12), 3464 (1992) [3] A. R. J. Kucernak et al., J. Mater. Chem. A 2, 17435 (2014) [4] X. Wang et al., Angew. Chem. 54(28), 8188 (2015) [5] Z. Pu et al., Chem.Mater. 26(15), 4326 (2014)

The use of synthetic gel matrices prepared with poly(vinyl-alcohol) (PVA) cross-linked by glutaraldehyde (GTA) contributed to enhance the interest toward radiochromic Fricke gel (FG) dosimeters. As it occurs in several chemical dosimeters, the response of PVA-GTA Fricke gels could be affected by temperature. Aim of this work is to study the dependence of the dosimetric properties of PVA-GTA Fricke gel dosimeters both on the irradiation temperature and on temperature changes possibly occurring between the irradiation and readout phases. Such effects were investigated by means of magnetic resonance imaging (MRI) and optical absorbance (OA) measurements. The results did not reveal any significant dependence of the sensitivity of the dosimeters on the irradiation temperature in the investigated interval 20°C-35°C. By contrast, auto-oxidation phenomena confirmed to be a critical aspect for FG dosimeters, also in case of use of PVA matrix. The extent such phenomena, that might impair the accuracy of dose estimations, proved to critically depend on the temperature at which FG dosimeters are subjected before and after irradiation, as well as on the duration of possible thermal-stress.

Soft robotics is an emerging field targeting at the development of robotic bodies and architectures characterized by flexibility, adaptability, and motility typical of that of biological systems. The use of electroactive ionic polymer–metal nanocomposites able to reversibly deform in response to low-intensity electric fields constitutes a promising solution for the implementation of actuators into soft robots. Currently, the use of this class of nanocomposites is hampered by several drawbacks, mainly related to the mismatch between the mechanical properties of the polymer and the metallic electrodes compromising their stability and resilience upon cyclic deformation. Here, we report and discuss on the use of supersonic cluster beam implantation (SCBI) as an effective strategy for the fabrication of soft electroactive ionic polymeric nanocomposite actuators. SCBI relies on the use of supersonically accelerated beams of neutral metal nanoparticles that can be aerodynamically collimated and directed onto a polymeric target to generate thin nanostructured metal layers physically interpenetrating with the polymer. Soft electroactive actuators based on engineered ionogel and ionogel-based hybrid nanocomposites provided with monolithically integrated cluster-assembled gold electrodes will be discussed. These systems can undergo long-term bending deformation in a low-voltage regime, due to the nanostructured electrode resilience. The use of cluster-assembled nanostructured electrodes opens new opportunities for the high-throughput manufacturing of soft ionic actuators with excellent mechanical resiliency, high-performance actuation, and high durability.

There is lack of investigation capturing the complex mechanical interaction of tissue-engineered intervertebral disk (IVD) constructs in physiologically relevant environmental conditions. In this study, mechanical characterization of anisotropic electrospinning (ES) substrates made of polycaprolactone (PCL) was carried out in wet and dry conditions and viability of human bone marrow derived mesenchymal stem cells (hMSCs) seeded within double layers of ES PCL were also studied. Cyclic compression of IVD-like constructs composed of an agarose core confined by ES PCL double layers was implemented using a bioreactor and the cellular response to the mechanical stimulation was evaluated. Tensile tests showed decrease of elastic modulus of ES PCL as the angle of stretching increased, and at 60 deg stretching angle in wet, the maximum ultimate tensile strength (UTS) was observed. Based on the configuration of IVD-like constructs, the calculated circumferential stress experienced by the ES PCL double layers was 40 times of the vertical compressive stress. Confined compression of IVD-like constructs at 5% and 10% displacement dramatically reduced cell viability, particularly at 10%, although cell presence in small and isolated area can still be observed after mechanical conditioning. Hence, material mechanical properties of tissue-engineered scaffolds, composed of fibril structure of polymer with low melting point, are affected by the testing condition. Circumferential stress induced by axial compressive stimulation, conveyed to the ES PCL double layer wrapped around an agarose core, can affect the viability of cells seeded at the interface, depending on the mechanical configuration and magnitude of the load.

Fat grafting is emerging as a promising alternative to silicon implants in breast reconstruction surgery. Unfortunately, this approach does not provide a proper mechanical support and is affected by drawbacks such as tissue resorption and donor site morbidity. Synthetic scaffolds can offer a valuable alternative to address these challenges, but poorly recapitulate the biochemical stimuli needed for tissue regeneration. Here, we aim at combining the positive features of a structural, synthetic polymer to an engineered, devitalized extracellular matrix (ECM) to generate a hybrid construct that can provide a mix of structural and biological stimuli needed for adipose tissue regeneration. A RGD-mimetic synthetic scaffold OPAAF, designed for soft tissue engineering, was decorated with ECM deposited by human adipose stromal cells (hASCs). The adipoinductive potential of the hybrid ECM-OPAAF construct was validated in vitro, by culture with hASC in a perfusion bioreactor system, and in vivo, by subcutaneous implantation in nude mouse. Our findings demonstrate that the hybrid ECM-OPAAF provides proper mechanical support and adipoinductive stimuli, with potential applicability as off-the-shelf material for adipose tissue reconstruction. Statement of Significance In this study we combined the functionalities of a synthetic polymer with those of an engineered and subsequently devitalized extracellular matrix (ECM) to generate a hybrid material for adipose tissue regeneration. The developed hybrid ECM-OPAAF was demonstrated to regulate human adipose stromal cells adipogenic commitment in vitro and adipose tissue infiltration in vivo. Our findings demonstrate that the hybrid ECM-OPAAF provide proper mechanical support and adipoinductive stimuli and represents a promising off-the-shelf material for adipose tissue reconstruction. We believe that our approach could offer an alternative strategy for adipose tissue reconstruction in case of mastectomy or congenital abnormalities, overcoming the current limitations of autologous fat based strategies such as volume resorption and donor site morbidity.

Neuronal cells are competent in precisely sensing nanotopographical features of their microenvironment. The perceived microenvironmental information will be “interpreted” by mechanotransductive processes and impacts on neuronal functioning and differentiation. Attempts to influence neuronal differentiation by engineering substrates that mimic appropriate extracellular matrix (ECM) topographies are hampered by the fact that profound details of mechanosensing/-transduction complexity remain elusive. Introducing omics methods into these biomaterial approaches has the potential to provide a deeper insight into the molecular processes and signalling cascades underlying mechanosensing/-transduction but their exigence in cellular material is often opposed by technical limitations of major substrate top-down fabrication methods. Supersonic cluster beam deposition (SCBD) allows instead the bottom-up fabrication of nanostructured substrates over large areas characterised by a quantitatively controllable ECM-like nanoroughness that has been recently shown to foster neuron differentiation and maturation. Exploiting this capacity of SCBD, we challenged mechanosensing/-transduction and differentiative behaviour of neuron-like PC12 cells with diverse nanotopographies and/or changes of their biomechanical status, and analysed their phosphoproteomic profiles in these settings. Versatile proteins that can be associated to significant processes along the mechanotransductive signal sequence, i.e. cell/cell interaction, glycocalyx and ECM, membrane/f-actin linkage and integrin activation, cell/substrate interaction, integrin adhesion complex, actomyosin organisation/cellular mechanics, nuclear organisation and transcriptional regulation, were affected. The phosphoproteomic data suggested furthermore an involvement of ILK, mTOR, Wnt and calcium signalling in these nanotopography- and/or cell mechanics-related processes. Altogether, potential nanotopography-sensitive mechanotransductive signalling hubs participating in neuronal differentiation were dissected.

Natural network-structured hydrogels ( e.g. bacterial cellulose (BC)) can be synthesised with specific artificial hydrogels ( e.g. poly(2-hydroxyethyl methacrylate) (PHEMA)) to form a tougher and stronger nanofibre-reinforced composite hydrogel, which possesses micro- and nano-porous structure. These synthetic hydrogels exhibit a number of advantages for biomedical applications, such as good biocompatibility and better permeability for molecules to pass through. In this paper, the mechanical properties of this nanofibre-reinforced hydrogel containing BC and PHEMA have been characterised in terms of their tangent modulus and fracture stress/strain by uniaxial compressive testing. Numerical simulations based on Mooney-Rivlin hyperelastic theory are also conducted to understand the internal stress distribution and possible failure of the nanofibre-reinforced hydrogel under compression. By comparing the mechanical characteristics of BC, PHEMA, and PHEMA-based nanofibre reinforced hydrogel (BC-PHEMA) under the compression, it is possible to develop a suitable scaffold for tissue engineering on the basis of fundamental understanding of mechanical and fracture behaviours of nanofibre-reinforced hydrogels.

We present a room-temperature bonding technique which enables the sealing of micromolded water-swollen poly-2-hydroxy ethyl methacrylate (PHEMA)-based hydrogel modules to thermoplastic and elastomeric platforms. The core mechanism of the proposed method is to favor the formation of hydrogen bonds at the interface between the surface-reactive hydrated hydrogel components and the functionalized hydrophobic materials, by contacting the polymeric layers via a mild compression. Plasma oxygen and silanization processes using 3-amino-propyl trimethoxy silane have been optimized to generate surface hydroxyl functionalities on poly-methyl methacrylate (PMMA) and poly-dimethyl siloxane (PDMS) platforms which can react with the OH groups’ enriched surface of the microstructured PHEMA. The resulting microsystems can operate in a continuous perfusion mode while being soaked in water to keep the hydrogel hydrated. The method could also be applied to bond PHEMA thin layers (300 μm thick) to PMMA and PDMS microfluidic components. The sealing properties of the produced devices were demonstrated by liquid leakage tests and further validated by hydration–dehydration cycles of the systems and by monitoring methylene blue diffusion through the hydrogel matrix at the modules interface. The presented technique is suitable for cells-based hybrid materials microfluidic devices rapid prototyping.

Periodontitis treatments usually require local administration of antimicrobial drugs with the aim to reduce the bacterial load inside the periodontal pocket. Effective pharmaceutical treatments may require sustained local drug release for several days in the site of interest. Currently available solutions are still not able to fulfill the clinical need for high-quality treatments, mainly in terms of release profiles and patients' comfort. This work aims to fill this gap through the development of an in situ gelling system, capable to achieve controlled and sustained release of antimicrobial agents for medium-to-long-term treatments. The system is composed of micrometer-sized β-cyclodextrin-based hydrogel (bCD-Jef-MPs), featured by a strong hydrophilic character, suspended in a synthetic block-co-polymer solution (Poloxamer 407), which is capable to undergo rapid thermally induced sol-gel phase transition at body temperature. The chemical structure of bCD-Jef-MPs was confirmed by cross-correlating data from Fourier transform infrared (FTIR) spectroscopy, swelling test, and degradation kinetics. The thermally induced sol-gel phase transition is demonstrated by rheometric tests. The effectiveness of the described system to achieve sustained release of antimicrobial agents is demonstrated in vitro, using chlorhexidine digluconate as a drug model. The results achieved in this work disclose the potential of the mentioned system in effectively treating periodontitis lesions.

We report the synthesis, fabrication and characterization of a hybrid hydrogel/cellulose nanocomposite, which exhibits high-performance electro–mechanical underwater actuation and high sensitivity in response to electrical stimuli below the standard potential of water electrolysis. The macromolecular structure of the material is constituted by an electroactive hydrogel, obtained through a photo-polymerization reaction with the use of three vinylic co-monomers: Na-4-vinylbenzenesulfonate, 2-hydroxyethylmethacrylate, and acrylonitrile. Different amounts (from 0.1% to 1.4% w/w) of biodegradable cellulose nanocrystals (CNCs) with sulfonate surface groups, obtained through the acidic hydrolysis of sulphite pulp lapsheets, are physically incorporated into the gel matrix during the synthesis step. Freestanding thin films of the nanocomposites are molded, and their swelling, mechanical and responsive properties are fully characterized. We observed that the embedding of the CNCs enhanced both the material Young's modulus and its sensitivity to the applied electric field in the sub-volt regime (down to 5 mV cm−1). A demonstrator integrating multiple actuators that cooperatively bend together, mimicking the motion of an electro-valve, is also prototyped and tested. The presented nanocomposite is suitable for the development of soft smart components for bio-robotic applications and cells-based and bio-hybrid fluidic devices fabrication.

Loss of skeletal muscle tissue caused by traumatic injury or damage due to myopathies produces a deficit of muscle function for which there is still no clinical treatment. Transplantation of myogenic cells, themselves or combined with materials, has been proposed to increase the regenerative capacity of skeletal muscle but it is hampered by many limitations, such as low cell survival and engraftment or immunological reaction and low biocompatibility of the exogenous materials. Recently, myoblast sheet engineering, obtained with thermoresponsive culture dishes, has attracted attention as a new technique for muscle damage treatment. For this purpose, a series of thermoresponsive hydrogels, constituted by poly(N-isopropylacrylamide-co-2-hydroxyethylmethacrylate) [p(NIPAAM-co-HEMA)] were synthesized by a simple and inexpensive free-radical polymerization of the two co-monomers with a redox initiator. Different ratios of N-isopropylacrylamide (NIPAAm) and 2-hydroxyethylmethacrylate (HEMA) have been examined to evaluate the effects on physicochemical, mechanical and optical hydrogel properties. The murine muscle cell line C2 C12 has been exploited to test the cytotoxicity of the thermoresponsive hydrogels, depending on different synthesis conditions. In this study, we have identified a thermoresponsive hydrogel that allows cell adhesion and viability, together with the detachment of viable sheet of muscle cells, giving the chance to develop further applications for muscle damage and disease. Copyright © 2014 John Wiley & Sons, Ltd.

Poly(d,l-lactic-co-glycolic acid) (PLGA) nanoparticles (NPs) are among the most studied systems for drug and gene targeting. So far, the synthesis of stable and uniform PLGA NPs has involved the use of a large excess of polyvinyl surfactants such as poly(vinyl alcohol) (PVA) and polyvinylpyrrolidone (PVP), whose removal requires multistep purification procedures of high ecological and economic impact. Hence the development of environment-friendly and cost-effective synthetic procedures for the synthesis of PLGA NPs would effectively boost their use in clinics. This work aims to address this issue by investigating more efficacious alternatives to the so far employed polyvinyl surfactants. More specifically, we developed an innovative synthetic process to achieve stable and uniformly distributed PLGA NPs that involves the use of calcium stearate (CSt), gaining benefits of its high biocompatibility and efficacy at low concentrations and avoiding consequently expensive purification steps. With the help of minimum quantities of polysorbate 60 and sorbitane monostearate, CSt-stabilized PLGA NPs with different sizes and structures were synthesized. The influence of CSt on the encapsulation efficiency of bioactive molecules has been also investigated. The effective encapsulation of both hydrophobic (curcumin) and hydrophilic (fibrinogen labeled with Alexa647) biomolecules into NPs was demonstrated by confocal microscopy, and their release quantified by spectrofluorimetric analyses. Finally, degradation and cytotoxicity studies showed that CSt stabilized NPs were stable under physiological conditions and with good biocompatibility, thus looking promising for further investigation as controlled release devices.

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Purpose Quality assurance procedures required in the modern radiotherapy would greatly benefit by the development of tissue equivalent dosimeters able of rendering 3D dose profiles with high spatial resolution. In this scenario, Fricke gel (FG), consisting in gel matrices infused with Fricke ferrous sulphate solution combined with xylenol orange, could be good candidates, but some limits have prevented their introduction in clinical practice. Recently, new FG formulations based on gel matrices of poly-vinyl alcohol (PVA) cross-linked with glutaraldehyde (GTA) have shown important decrease of the limitations affecting FGs obtained with gelatin or agarose. Purpose of this study is the characterization of the optical absorbance (OA) and dosimetric properties of PVA-GTA FG dosimeters. Methods PVA-GTA FG dosimeters were prepared using 9.1 w/w of Mowiol®-PVA and 26.4 mM of GTA. The dosimeters, placed in spectrophotometry cuvettes (10 mm optical path), were uniformly irradiated using 6 and 15 MV X-rays generated by a Varian Clinac-2100. OA spectra were measured by means of an Agilent Cary-100 spectrophotometer. Dosimetric properties of PVA-GTA-FG dosimeters, such as reproducibility, dose–response, sensitivity, dose-rate dependence and energy dependence, were studied. Furthermore, FG in form of layers (3 mm optical path) were irradiated producing steep dose gradients and used to investigate ferric ions diffusion phenomena by means of sequential light transmittance images. Results The analysis of the OA spectra of the PVA-GTA-FG dosimeters in the wavelength interval of interest for dosimetry purposes (around 550–600 nm) revealed an intra-batch reproducibility of the order of 1.5%. The OA proved to increase linearly with increasing dose, in the investigated interval 0–15 Gy, if the wavelength used for the analysis is properly chosen. The optical response of the PVA-GT-FG dosimeters was independent of both energy and dose-rate. Furthermore, PVA-GTA matrix enables to achieve ferric ions diffusion rates approximatively 3 times lower than those observed in natural gel matrices. Conclusions This study confirmed the interesting properties of PVA-GTA FG dosimeters and indicated the best parameters for their optical analysis. Currently, studies are in progress in order to optimize Magnetic Resonance Imaging procedures for the assessment of 3D dose distributions in PVA-GTA FG phantoms.

Electroactive ionic gel/metal nanocomposites are produced by implanting supersonically accelerated neutral gold nanoparticles into a novel chemically crosslinked ion conductive soft polymer. The ionic gel consists of chemically crosslinked poly(acrylic acid) and polyacrylonitrile networks, blended with halloysite nanoclays and imidazolium-based ionic liquid. The material exhibits mechanical properties similar to that of elastomers (Young's modulus ≈ 0.35 MPa) together with high ionic conductivity. The fabrication of thin (≈100 nm thick) nanostructured compliant electrodes by means of supersonic cluster beam implantation (SCBI) does not significantly alter the mechanical properties of the soft polymer and provides controlled electrical properties and large surface area for ions storage. SCBI is cost effective and suitable for the scaleup manufacturing of electroactive soft actuators. This study reports the high-strain electromechanical actuation performance of the novel ionic gel/metal nanocomposites in a low-voltage regime (from 0.1 to 5 V), with long-term stability up to 76 000 cycles with no electrode delamination or deterioration. The observed behavior is due to both the intrinsic features of the ionic gel (elasticity and ionic transport capability) and the electrical and morphological features of the electrodes, providing low specific resistance (

Nucleus pulposus (NP) tissue damage can induce detrimental mechanical strain on the biomechanical performance of intervertebral discs (IVDs), causing subsequent disc degeneration. A novel, photocurable, injectable, synthetic polymer hydrogel (pHEMA-co-APMA grafted with PAA) has already demonstrated success in encapsulating and differentiating human mesenchymal stem cells (hMSCs) toward an NP phenotype during hypoxic conditions. After demonstration of promising results in our previous work, in this study we have further investigated the inclusion of mechanical stimulation and its impact on hMSC differentiation toward an NP phenotype through the characterization of matrix markers such as SOX-9, aggrecan, and collagen II. Furthermore, investigations were undertaken in order to approximate delivery parameters for an injection delivery device, which could be used to transport hMSCs suspended in hydrogel into the IVD. hMSC-laden hydrogel solutions were injected through various needle gauge sizes in order to determine its impact on postinjection cell viability and IVD tissue penetration. Interpretation of these data informed the design of a potential minimally invasive injection device, which could successfully inject hMSCs encapsulated in a UV-curable polymer into NP, prior to photo-cross-linking in situ.

Background Thanks to mechanotransductive components cells are competent to perceive nanoscale topographical features of their environment and to convert the immanent information into corresponding physiological responses. Due to its complex configuration, unraveling the role of the extracellular matrix is particularly challenging. Cell substrates with simplified topographical cues, fabricated by top-down micro- and nanofabrication approaches, have been useful in order to identify basic principles. However, the underlying molecular mechanisms of this conversion remain only partially understood. Results Here we present the results of a broad, systematic and quantitative approach aimed at understanding how the surface nanoscale information is converted into cell response providing a profound causal link between mechanotransductive events, proceeding from the cell/nanostructure interface to the nucleus. We produced nanostructured ZrO2 substrates with disordered yet controlled topographic features by the bottom-up technique supersonic cluster beam deposition, i.e. the assembling of zirconia nanoparticles from the gas phase on a flat substrate through a supersonic expansion. We used PC12 cells, a well-established model in the context of neuronal differentiation. We found that the cell/nanotopography interaction enforces a nanoscopic architecture of the adhesion regions that affects the focal adhesion dynamics and the cytoskeletal organization, which thereby modulates the general biomechanical properties by decreasing the rigidity of the cell. The mechanotransduction impacts furthermore on transcription factors relevant for neuronal differentiation (e.g. CREB), and eventually the protein expression profile. Detailed proteomic data validated the observed differentiation. In particular, the abundance of proteins that are involved in adhesome and/or cytoskeletal organization is striking, and their up- or downregulation is in line with their demonstrated functions in neuronal differentiation processes. Conclusion Our work provides a deep insight into the molecular mechanotransductive mechanisms that realize the conversion of the nanoscale topographical information of SCBD-fabricated surfaces into cellular responses, in this case neuronal differentiation. The results lay a profound cell biological foundation indicating the strong potential of these surfaces in promoting neuronal differentiation events which could be exploited for the development of prospective research and/or biomedical applications. These applications could be e.g. tools to study mechanotransductive processes, improved neural interfaces and circuits, or cell culture devices supporting neurogenic processes. Electronic supplementary material The online version of this article (doi:10.1186/s12951-016-0171-3) contains supplementary material, which is available to authorized users.

In this study, we present a microdevice coated with titanium dioxide for cells and particles separation and handling. The microsystem consists of a pair of planar interdigitated gold micro-electrode arrays on a quartz substrate able to generate a traveling electric completed with a microfabricated three-dimensional glass structure for cell confinement. Dielectrophoretic forces were exploited for both vertical and lateral cell motions. In order to provide a biocompatible passivation layer to the electrodes a highly biocompatible nanostructured titanium dioxide film was deposited by supersonic cluster beam deposition (SCBD) on the electrode array. The dielectrophoretic effects of the chip were initially tested using polystyrene beads. To test the biocompatibility and capability of dielectrophoretic cell movement of the device, four cell lines (NIH3T3, SH-SY5Y, MDCK, and PC12) were used. Separation of beads from SH-SY5Y cells was also obtained.

Intermittent contact mode atomic force microscopy (AFM) was used to visualize the native plasma membrane of Xenopus laevis oocytes. Oocyte membranes were purified via ultracentrifugation on a sucrose gradient and adsorbed on mica leaves. AFM topographs and the corresponding phase images allowed for visualization and identification of both oocyte plasma membrane patches and pure lipid bilayer regions with a height of about 5 nm within membrane patches. The quantitative analysis showed a normal distribution for the lateral dimension and height of the protein complexes centered on 16.7 +/- 0.2 nm (mean +/- SE, n = 263) and 5.4 +/- 0.1 nm (n = 262), respectively. The phase signal, providing material-dependent information, allowed for the recognition of structural features observed in AFM topographs.

"Synchrotron radiation-based experimental techniques are largely employed for the characterization of the reactivity of finite size systems; in particular, x-ray absorption spectroscopy (XAS) is a suitable tool to shed light on the local electronic structure and chemical status of atoms in nano-objects, as it is very sensitive to the local bonding environment of the probed site. In supported clusters intrinsic properties and reactivity are largely distorted and obscured by the changes imposed by the growth procedure and by the influence of the substrate, so the attainability of experiments on free clusters reacting with species in the gas phase is a primary goal in the development of cluster science. In this paper we report a proof of principle of the applicability of gas phase XAS technique to titanium and titanium oxide, hydride and hydrate systems. Experiments are performed by coupling a pulsed microplasma cluster source (PMCS) with a third generation synchrotron light source, and measuring the intensity of the electron yield coming from the interaction of VUV photons with the clusters seeded in a supersonic beam."