Boosting Contact Electrification by Amorphous Polyvinyl Alcohol Endowing Improved Contact Adhesion and Electrochemical Capacitance.

Ion conductive hydrogels are relevant components in wearable, biocompatible, and biodegradable electronics. Polyvinyl-alcohol (PVA) homopolymer is often the favored choice for integration into supercapacitors and energy harvesters as in sustainable triboelectric nanogenerators (TENGs). However, to further improve hydrogel-based TENGs, a deeper understanding of the impact of their composition and structure on devices performance is necessary. Here, it is shown how ionic hydrogels based on an amorphous-PVA (a-PVA) allow to fabricate TENGs that outperform the one based on the homopolymer. When used as tribomaterial, the Li-doped a-PVA allows to achieve a twofold higher pressure sensitivity compared to PVA, and to develop a conformable e-skin. When used as an ionic conductor encased in an elastomeric tribomaterial, 100 mW cm-2 average power is obtained, providing 25% power increase compared to PVA. At the origin of such enhancement is the increased softness, stronger adhesive contact, higher ionic mobility (> 3,5-fold increase), and long-term stability achieved with Li-doped a-PVA. These improvements are attributed to the high density of hydroxyl groups and amorphous structure present in the a-PVA, enabling a strong binding to water molecules. This work discloses novel insights on those parameters allowing to develop easy-processable, stable, and highly conductive hydrogels for integration in conformable, soft, and biocompatible TENGs.

Evaluating Toxicity of Chemicals using a Zebrafish Vibration Startle Response Screening System.

We developed a simple screening system for the evaluation of neuromuscular and general toxicity in zebrafish embryos. The modular system consists of electrodynamic transducers above which tissue culture dishes with embryos can be placed. Multiple such loudspeaker-tissue culture dish pairs can be combined. Vibrational stimuli generated by the electrodynamic transducers induce a characteristic startle and escape response in the embryos. A belt-driven linear drive sequentially positions a camera above each loudspeaker to record the movement of the embryos. In this way, alterations to the startle response due to lethality or neuromuscular toxicity of chemical compounds can be visualized and quantified. We present an example of the workflow for chemical compound screening using this system, including the preparation of embryos and treatment solutions, operation of the recording system, and data analysis to calculate benchmark concentration values of compounds active in the assay. The modular assembly based on commercially available simple components makes this system both economical and flexibly adaptable to the needs of particular laboratory setups and screening purposes.

2D Materials-Based Electrochemical Triboelectric Nanogenerators.

The integration of 2D materials in triboelectric nanogenerators (TENGs) is known to increase the mechanical-to-electrical power conversion efficiency. 2D materials are used in TENGs with multiple roles as triboelectric material, charge-trapping fillers, or as electrodes. Here, novel TENGs based on few-layers graphene (FLG) electrodes and stable gel electrolytes composed of liquid phase exfoliated 2D-transition metal dichalcogenides and polyvinyl alcohol are developed. TENGs embedding FLG and gel composites show competitive open-circuit voltage (≈ 300 V), instant peak power (530 mW m-2 ), and stability (> 11 months). These values correspond to a seven-fold higher electrical output compared to TENGs embedding bare FLG electrodes. It is demonstrated that such a significant improvement depends on the high electrical double-layer capacitance (EDLC) of FLG electrodes functionalized with the gel composites. The wet encapsulation of the TENGs is shown to be an effective strategy to increase their power output further highlighting the EDLC role. It is also shown that the EDLC is dependent upon the transition metal (W vs Mo) rather than the relative abundance of 1T or 2H phases. Overall, this work lays down the roots for novel sustainable electrochemical-(e)-TENGs developed exploiting strategies typically used in electrochemical capacitors.

Intrinsically distinct hole and electron transport in conjugated polymers controlled by intra and intermolecular interactions.

It is still a matter of controversy whether the relative difference in hole and electron transport in solution-processed organic semiconductors is either due to intrinsic properties linked to chemical and solid-state structure or to extrinsic factors, as device architecture. We here isolate the intrinsic factors affecting either electron or hole transport within the same film microstructure of a model copolymer semiconductor. Relatively, holes predominantly bleach inter-chain interactions with H-type electronic coupling character, while electrons' relaxation more strongly involves intra-chain interactions with J-type character. Holes and electrons mobility correlates with the presence of a charge transfer state, while their ratio is a function of the relative content of intra- and inter-molecular interactions. Such fundamental observation, revealing the specific role of the ground-state intra- and inter-molecular coupling in selectively assisting charge transport, allows predicting a more favorable hole or electron transport already from screening the polymer film ground state optical properties.

Uniaxial Alignment of Conjugated Polymer Films for High-Performance Organic Field-Effect Transistors.

Polymer semiconductors have been experiencing a remarkable improvement in electronic and optoelectronic properties, which are largely related to the recent development of a vast library of high-performance, donor-acceptor copolymers showing alternation of chemical moieties with different electronic affinities along their backbones. Such steady improvement is making conjugated polymers even more appealing for large-area and flexible electronic applications, from distributed and portable electronics to healthcare devices, where cost-effective manufacturing, light weight, and ease of integration represent key benefits. Recently, a strong boost to charge carrier mobility in polymer-based field-effect transistors, consistently achieving the range from 1.0 to 10 cm2 V-1 s-1 for both holes and electrons, has been given by uniaxial backbone alignment of polymers in thin films, inducing strong transport anisotropy and favoring enhanced transport properties along the alignment direction. Herein, an overview on this topic is provided with a focus on the processing-structure-property relationships that enable the controlled and uniform alignment of polymer films over large areas with scalable processes. The key aspects are specific molecular structures, such as planarized backbones with a reduced degree of conformational disorder, solution formulation with controlled aggregation, and deposition techniques inducing suitable directional flow.

Transparent and Highly Responsive Phototransistors Based on a Solution-Processed, Nanometers-Thick Active Layer, Embedding a High-Mobility Electron-Transporting Polymer and a Hole-Trapping Molecule.

Organic materials are suitable for light sensing devices showing unique features such as low cost, large area, and flexibility. Moreover, transparent photodetectors are interesting for smart interfaces, windows, and display-integrated electronics. The ease of depositing ultrathin organic films with simple techniques enables low light absorbing active layers, resulting in the realization of transparent devices. Here, we demonstrate a strategy to obtain high efficiency organic photodetectors and phototransistors based on transparent active layers with a visible transmittance higher than 90%. The photoactive layer is composed of two phases, each a few nanometers thick. First, an acceptor polymer, which is a good electron-transporting material, on top of which a small molecule donor material is deposited, forming noncontinuous domains. The small molecule phase acts as a trap for holes, thus inducing a high photoconductive gain, resulting in a high photoresponsivity. The organic transparent detectors proposed here can reach very high external quantum efficiency and responsivity values, which in the case of the phototransistors can be as high as ∼74000% and 340 A W-1 at 570 nm respectively, despite an absorber total thickness below 10 nm. Moreover, frequency dependent 2D photocurrent mapping allows discrimination between the contribution of a fast but inefficient and highly spatially localized photoinduced injection mechanism at the electrodes, and the onset of a slower and spatially extended photoconductive process, leading to high responsivity.

Live cell imaging shows hepatocyte growth factor-induced Met dimerization.

The canonical model of receptor tyrosine kinase (RTK) activation assumes that ligand-induced dimerization of inactive receptor monomers is a prerequisite for autophosphorylation. For several RTK families, recent results of fluorescence microscopy provided evidence for preformed receptor dimers that may or may not require ligand binding for kinase activity. Here we report, for the first time, the application of advanced quantitative fluorescence microscopy techniques to study changes in the oligomerization state of the RTK Met in response to stimulation by its endogenous ligand hepatocyte growth factor (HGF). We used inducible C-terminal fusions between Met and enhanced green fluorescent protein (EGFP) or red fluorescent protein (RFP) in combination with fluorescence resonance energy transfer (FRET)-based fluorescence-lifetime imaging microscopy (FLIM) and fluorescence correlation spectroscopy (FCS). A small fraction of HGF-independent Met dimers appeared to be present in cells even at low receptor density. At high receptor density, both the fraction of Met dimers and the level of Met autophosphorylation increased in the absence of HGF. Stimulation with HGF at low receptor density significantly increased the fraction of Met dimers on live cells. We found no indications of Met oligomers larger than dimers. Our findings thus confirm a model of Met activation through HGF-induced dimerization and at the same time they support previous reports of Met dimers in unstimulated cells. The tools established in this work will be useful to further characterize the mechanism of Met activation and to define the contribution of co-receptors.

Macroscopic and high-throughput printing of aligned nanostructured polymer semiconductors for MHz large-area electronics.

High-mobility semiconducting polymers offer the opportunity to develop flexible and large-area electronics for several applications, including wearable, portable and distributed sensors, monitoring and actuating devices. An enabler of this technology is a scalable printing process achieving uniform electrical performances over large area. As opposed to the deposition of highly crystalline films, orientational alignment of polymer chains, albeit commonly achieved by non-scalable/slow bulk alignment schemes, is a more robust approach towards large-area electronics. By combining pre-aggregating solvents for formulating the semiconductor and by adopting a room temperature wired bar-coating technique, here we demonstrate the fast deposition of submonolayers and nanostructured films of a model electron-transporting polymer. Our approach enables directional self-assembling of polymer chains exhibiting large transport anisotropy and a mobility up to 6.4 cm(2) V(-1) s(-1), allowing very simple device architectures to operate at 3.3 MHz. Thus, the proposed deposition strategy is exceptionally promising for mass manufacturing of high-performance polymer circuits.

Electronic transport regimes through an alkoxythiolated diphenyl-2,2'-bithiophene-based molecular junction diodes: critical assessment of the thermal dependence.

The detailed understanding of electronic transport through a single molecule or an ensemble of self-assembled molecules embedded between two metallic leads is still a matter of controversy. Multiple factors influence the charge transport in the molecular junction, with particular attention to be given to the band states of the electrodes, molecular orbital energies, bias potential and importantly molecule-electrode electronic coupling. Moreover it is not trivial to disentangle molecular contributions from other possible conduction pathways directly coupling the opposite electrodes. We here investigate the electronic transport properties of an ensemble molecular junction embedding an alkylthiol derivative of a diphenol substituted bithiophene (DPBT) by means of current vs. voltage and temperature dependent measurements. We explored different junction configurations using: micropores (Au//DPBT//Au and Au//DPBT-polymer conductor//Au) and conductive-atomic force microscopy (c-AFM). In all cases, we found a transition voltage V(T) of ∼0.35 V. The consistent presence of a similar V(T) in all the tested configurations is a strong, but not conclusive, indication of a molecular signature in the charge transport, which we assessed and confirmed by temperature dependent measurements. We found a transition from an incoherent resonant tunneling at low biases and close to room temperature, where transport is thermally activated with an activation energy of ∼85 meV, to a coherent tunneling at voltages higher than V(T). Unlike many other molecular junctions reported in the literature, resonant conditions commonly attributed to a hopping transport regime can be found already at room temperature and very low biases for a molecule only ∼1.5 nm long. This paper is the first report to clearly show temperature activated transport through a short and not fully conjugated molecule. Moreover, we could clearly identify a regime at low temperatures and low bias where the transport mechanism is controlled by the thermal conductivity of the metal electrodes rather than the molecule.

Photoactive molecular junctions based on self-assembled monolayers of indoline dyes.

We demonstrate the feasibility of a photodetector based on an ensemble molecular junction, where a self-assembled monolayer of an organic donor-acceptor dye is directly sandwiched between two electrodes. In such a device, upon photoexcitation and generation of a charge-transfer state on the molecule, charges are dissociated and directly collected at the electrodes without the need of transport through a bulk phase, as in usual photodetectors. We show that the device can work in photovoltaic regime and the spectral response can be tuned by varying the light absorbing dye. Therefore, the electro-optical properties of the downscaled device can be unambiguously related to the physical-chemical properties of the molecules, a commonly difficult point to demonstrate in a molecular junction device, because of the uncertainties of the interplay between molecules and electrodes. The proposed device, which relies on a simple self-assembly process, has a strong potentiality for fast responding, downscaled detectors, ultimately limited by charge dissociation dynamics, and can be considered also as a useful tool to investigate fundamental electro-optical processes in molecular monolayers.

All-organic and fully-printed semitransparent photodetectors based on narrow bandgap conjugated molecules.

All-organic, fully-printed and semitransparent photodetectors with a broad wavelength band response, based on a ternary blend comprising narrow band-gap small molecules, are demonstrated. The ternary blend with a semiconducting polymer allows for the optimal printing of small molecules, suppressing strong phase segregation, and uncontrolled crystallization. The insertion of a suitable interlayer enables the adoption of polymer, transparent, top and bottom printed electrodes, thus making light detection possible from both device sides.

Internalization of Met requires the co-receptor CD44v6 and its link to ERM proteins.

Receptor Tyrosine Kinases (RTKs) are involved in many cellular processes and play a major role in the control of cell fate. For these reasons, RTK activation is maintained under tight control. Met is an essential RTK that induces proliferation, differentiation, migration, survival and branching morphogenesis. Deregulation of Met by overexpression, amplification or lack of effective degradation leads to cancer and metastasis. We have shown that Met relies on CD44v6 for its activation and for signaling in several cancer cell lines and also in primary cells. In this paper, we show that internalization of Met is dependent on CD44v6 and the binding of Ezrin to the CD44v6 cytoplasmic domain. Both CD44v6 and Met are co-internalized upon Hepatocyte Growth Factor induction suggesting that Met-induced signaling from the endosomes relies on its collaboration with CD44v6 and the link to the cytoskeleton provided by ERM proteins.

Recombination dynamics of charge pairs in a push-pull polyfluorene-derivative.

We investigate the properties of long-lived species in F8BT films through time-resolved photoluminescence (PL) measurements at room temperature and 10 K. The kinetics consist of an initial exponential decay (τ = 2.26 ns) followed by a weak power-law decay (I(t) [proportionality] t(-1)) up to at least 1 ms, both of which depend weakly on temperature. From fluence-dependent PL and ultrafast transient absorption (TA) measurements, we confirm that this emission arises from the recombination of geminate charge-pairs generated through singlet-singlet annihilation. This behavior is a consequence of the donor-acceptor nature of this polymer, which enhances singlet-singlet annihilation and facilitates the formation of long-lived geminate-pairs from energetic singlet states.

c-Met recruits ICAM-1 as a coreceptor to compensate for the loss of CD44 in Cd44 null mice.

CD44 isoforms act as coreceptors for the receptor tyrosine kinases c-Met and VEGFR-2. However, Cd44 knockout mice do not show overt phenotypes, in contrast to Met and Vegfr-2 knockout mice. We hypothesized that CD44 is being compensated for by another factor in Cd44 null mice. Using RNAi technology and blocking experiments with antibodies, peptides, and purified ectodomains, as well as overexpression studies, we identified intercellular adhesion molecule-1 (ICAM-1) as a new coreceptor for c-Met in CD44-negative tumor cells and in primary hepatocytes obtained from Cd44 null mice. Most strikingly, after partial hepatectomy, CD44v6-specific antibodies inhibited liver cell proliferation and c-Met activation in wild-type mice, whereas ICAM-1-specific antibodies interfered with liver cell proliferation and c-Met activation in Cd44 knockout mice. These data show that ICAM-1 compensates for CD44v6 as a coreceptor for c-Met in Cd44 null mice. Compensation of proteins by members of the same family has been widely proposed to explain the lack of phenotype of several knockout mice. Our experiments demonstrate the functional substitution of a protein by a heterologous one in a knockout mouse.

Conjugated zwitterionic polyelectrolyte as the charge injection layer for high-performance polymer light-emitting diodes.

A new zwitterionic conjugated polyelectrolyte without free counterions has been used as an electron injection material in polymer light-emitting diodes. Both the efficiency and maximum brightness were considerably improved in comparison with standard Ca cathode devices. The devices showed very fast response times, indicating that the improved performance is, in addition to hole blocking, due to dipoles at the cathode interface, which facilitate electron injection.

Self-assembly of alkoxy-substituted bis(hydrazone)-based organic ligands and of a metallosupramolecular grid on graphite.

Self-assembly of a bis(hydrazone) chelating ligand functionalized with octadecyloxy substituents is described, as well as the reproducible thermally activated self-assembly of its metallosupramolecular cationic Co(II) [2x2] grid-type complex, on a highly oriented pyrolitic graphite (HOPG) substrate. Scanning tunnelling microscopy measurements at the solid/liquid interface reveal that the grid units of the annealed films are oriented edge-on to the basal plane of the HOPG, which indicates that the influence of the octadecyl chains is not sufficient to tie the grids into a face-on orientation. To gain a detailed understanding of the self-assembly behaviour of the grid on HOPG, the results for the grid itself have been compared to those of its constituent ligands.

Azobenzenes as light-controlled molecular electronic switches in nanoscale metal-molecule-metal junctions.

Conductance switching associated with the photoisomerization of azobenzene-based (Azo) molecules was observed in nanoscopic metal-molecule-metal junctions. The junctions were formed by using a conducting atomic force microscope (C-AFM) approach, where a metallic AFM tip was used to electrically contact a gold-supported Azo self-assembled monolayer. The measured 30-fold increase in conductance is consistent with the expected decrease in tunneling barrier length resulting from the conformational change of the Azo molecule.