3D structure reconstruction of nanoengineered polymeric capsules using Coherent X-Ray diffraction imaging.

Nanoengineered polymeric capsules (NPCs) are smart objects that can be filled in with some desired chemical substance. They are considered among the most versatile tools in biology, pharmacy, medicine etc. Most often they have been used as containers for drug delivery. Main tools for studying their structure are electron (SEM, TEM) and fluorescence microscopies. In the case of electron microscopies, the main peculiarity was connected to the necessity of dried samples usage. In the case of fluorescence microscopy, the possible resolution is restricted by diffraction limits. The natural environment of the NPCs is liquid medium. In this paper we have developed a method of NPCs' structure investigation in liquid medium using coherent X-ray diffraction imaging (CXDI). The main points of this article are summarized as:•The procedure of NPCs' synthesis using layer-by-layer technique including gold nanoparticles;•Coherent X-ray diffraction imaging of the samples in liquid medium;•Imaging of objects without freezing of the sample.

Functionalization of TiO2 sol-gel derived films for cell confinement.

The neuroscience field has increased enormously over the last decades, achieving the possible real application of neuronal cultures not only for reproducing neural architectures resembling in vivo tissues, but also for the development of functional devices. In this context, surface patterning for cell confinement is crucial, and new active materials together with new protocols for preparing substrates suitable for confining cells, guiding their processes in the desired configuration are extremely appreciated. Here, TiO2 sol-gel derived films were selected as proof-of-concept materials to grow neurons in suitable confined configurations, taking advantage of the biocompatible properties of modified TiO2 substrates. TiO2 sol-gel derived films were made compatible with the growth of neurons thanks to a stable and controlled poly-lysine coating, obtained by silanization chemistry and streptavidin-biotin interactions. Moreover, a spotting protocol, here described and optimized, allowed the simple preparation of arrays of neurons, where cell adhesion was guided in specific areas and the neurites development driven in the desired arrangement. The resulting arrays were successfully tested for the growth and differentiation of neurons, demonstrating the possible adhesion of cells in specific areas of the film, therefore paving the way to applications such as the direct growth of excitable cells nearby electrodes of devices, with an evident enhancement of cell-electrodes communication.

Prototyping a memristive-based device to analyze neuronal excitability.

Many efforts have been spent in the last decade for the development of nanoscale synaptic devices integrated into neuromorphic circuits, trying to emulate the behavior of natural synapses. The study of brain properties with the standard approaches based on biocompatible electrodes coupled to conventional electronics, however, presents strong limitations, which in turn could be overcame by the in-situ growth of neuronal networks coupled to memristive devices. To meet this challenging task, here two different chips were designed and fabricated for culturing neuronal cells and sensing their electrophysiological activity. The first chip was designed to be connected to an external memristor, while the second chip was coated with TiO2 films owning memristive properties. The biocompatibility of chips was preliminary analyzed by culturing the hybrid motor-neuron cell line NSC-34 and by measuring the electrical activity of cells interfacing the chip with a standard patch-clamp setup. Next, neurons were seeded on chips and their activity measured with the same setup. For both cell types total current and voltage responses were evoked and recorded with optimal results with no breakdowns. In addition, an external stimulation was applied to cells through chip electrodes, being effective and causing no damage or pitfalls to the cells. Finally, the whole bio-hybrid system, i.e. the chip interconnected with a commercial memristor, was tested with promising results. Spontaneous electrical activity of neurons grown on the chip was indeed present and this signal was collected and sent to the memristor, changing its state. Taken together, we demonstrated the ability of memristor to work with a synaptic/plastic response together with natural systems, opening the way for the further implementation of basic computing elements able to perform both storage and processing of data, as in natural neurons.

Charge-separation enhancement in inverted polymer solar cells by molecular-level triple heterojunction: NiO-np:P3HT:PCBM.

Hole collection and transport are crucial physical processes in bulk-heterojunction (BHJ) solar cells, which represent major bottlenecks due to their limitations in power conversion efficiency (PCE). Hence, a more efficient alternative is needed to accept and transport holes to the collection electrode in BHJ solar cells. Here, we bring both electron and hole collection centres close to the point of exciton generation by infiltrating P3HT poly(3-hexylthiophene):PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) blend into a highly porous interconnected p-type NiO-nanoparticle (NiO-np) network, through solvent-assisted grafting. In this study, a hybrid polymer solar cell is demonstrated with a P3HT:PCBM:NiO-np triple-heterojunction active layer which showed greatly improved rectification behaviour, long electron lifetime and generated higher PCE of 4% under AM 1.5 solar illumination with a 75% increase in PCE with respect to the P3HT:PCBM device. The optimum NiO-np amount and active-layer thickness were found to be 2% and 250 nm, respectively.

Raman micro-spectroscopy study of living SH-SY5Y cells adhering on different substrates.

In this paper we test the ability of Raman micro-spectroscopy and Raman mapping to investigate the status of cells grown in adhesion on different substrates. The spectra of immortalized SH-SY5Y cells, grown on silicon and on metallic substrates are compared with those obtained for the same type of cells adhering on organic polyaniline (PANI), a memristive substrate chosen to achieve a living bio-hybrid system. Raman spectra give information on the status of the single cell, its local biochemical composition, and on the modifications induced by the substrate interaction. The good agreement between Raman spectra collected from cells adhering on different substrates confirms that the PANI, besides allowing the cell growth, doesn't strongly affect the general biochemical properties of the cell. The investigation of the cellular state in a label free condition is challenging and the obtained results confirm the Raman ability to achieve this information.

Porphyrin conjugated SiC/SiOx nanowires for X-ray-excited photodynamic therapy.

The development of innovative nanosystems opens new perspectives for multidisciplinary applications at the frontier between materials science and nanomedicine. Here we present a novel hybrid nanosystem based on cytocompatible inorganic SiC/SiOx core/shell nanowires conjugated via click-chemistry procedures with an organic photosensitizer, a tetracarboxyphenyl porphyrin derivative. We show that this nanosystem is an efficient source of singlet oxygen for cell oxidative stress when irradiated with 6 MV X-Rays at low doses (0.4-2 Gy). The in-vitro clonogenic survival assay on lung adenocarcinoma cells shows that 12 days after irradiation at a dose of 2 Gy, the cell population is reduced by about 75% with respect to control cells. These results demonstrate that our approach is very efficient to enhance radiation therapy effects for cancer treatments.

A hybrid living/organic electrochemical transistor based on the Physarum polycephalum cell endowed with both sensing and memristive properties.

A hybrid bio-organic electrochemical transistor was developed by interfacing an organic semiconductor, poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate), with the Physarum polycephalum cell. The system shows unprecedented performances since it could be operated both as a transistor, in a three-terminal configuration, and as a memristive device in a two terminal configuration mode. This is quite a remarkable achievement since, in the transistor mode, it can be used as a very sensitive bio-sensor directly monitoring biochemical processes occurring in the cell, while, as a memristive device, it represents one of the very first examples of a bio-hybrid system demonstrating such a property. Our system combines memory and sensing in the same system, possibly interfacing unconventional computing. The system was studied by a full electrical characterization using a series of different gate electrodes, namely made of Ag, Au and Pt, which typically show different operation modes in organic electrochemical transistors. Our experiment demonstrates that a remarkable sensing capability could potentially be implemented. We envisage that this system could be classified as a Bio-Organic Sensing/Memristive Device (BOSMD), where the dual functionality allows merging of the sensing and memory properties, paving the way to new and unexplored opportunities in bioelectronics.

ZnO nanowires-C microfiber hybrid nanosensor for liquefied petroleum gas detection.

Zinc oxide nanowires are integrated onto carbon microfibers using a two-step approach which includes electrochemical deposition of zinc and its thermal oxidation. Such nano-on-micro hybrid architecture is then used as resistive gas sensor. Some properties like mechanical flexibility, low cost and large-area fabrication make this design appealing for different applications. The huge surface-to-volume ratio of such structure comes from being structured at both microscale and nanoscale (ZnO nanowires and C microfiber) and leads to a strong and rapid response/recovery times when it is used as a gas sensor. The fabrication process of the ZnO-microC device is very simple and doesn't involve any expensive lithographic step. The sensors show excellent liquefied petroleum gas sensing properties, with very fast response on gas exposure (about 3 s) and very good reversibility (less than 2%). In addition, the carbon microfiber substrate allows the use of the ZnO-microC sensor also in applications where flexibility is required (for example integrated in fabric).

Biocompatibility and wettability of crystalline SiC and Si surfaces.

Crystalline silicon carbide (SiC) and silicon (Si) biocompatibility was evaluated by directly culturing three mammalian cell lines on these semiconducting substrates. Cell proliferation and adhesion quality were studied using MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assays and fluorescent microscopy. The reported results show that SiC is indeed a more biocompatible substrate than Si. The surface wettability of SiC and Si samples was evaluated through static contact angle measurements, which provided interesting information regarding the influence of different cleaning procedures on the SiC surfaces. The cell proliferation data are discussed in light of the contact angle measurements results. This joint analysis leads to interesting conclusions that may help to uncover the main factors that define a semiconductor's biocompatibility.

Hyperthermal molecular beam deposition of highly ordered organic thin films.

We use a seeded supersonic molecular beam to control the kinetic energy of pentacene (C22H14) during deposition and growth on Ag(111). Highly ordered thin films are grown at low substrate temperatures (approximately 200 K) at kinetic energies of a few electron volts, as shown by low energy He diffraction and x-ray reflectivity spectra. In contrast, deposition of thermal molecules yields only amorphous films. Growth at room or higher temperature substrates yields films of poorer quality irrespective of the depositing beam energy. We find that after the first wetting layer is completed, a new ordered phase is formed, whose in-plane lattice spacings match one of the bulk crystal planes. The high quality of the films can be interpreted as the result of local annealing induced by the impact of the impinging high-energy molecules.

SF6 scattering from graphite surfaces: comparison of effects induced by thermal and laser controlled vibrational excitation.

We report scattering experiments of multiphoton vibrationally excited SF6 molecules from graphite surfaces demonstrating ro-vibrational excitation in the collision. The beam scattering experiments were carried out at different initial kinematic conditions and as a function of the surface temperature. The energy transfer depends both on the initial state of the molecule and on the momentum transferred as well as on the temperature of the surface. The role of surface atomic corrugation is evidenced.