Electrochemical rewiring through quantum conductance effects in single metallic memristive nanowires.

Memristive devices have been demonstrated to exhibit quantum conductance effects at room temperature. In these devices, a detailed understanding of the relationship between electrochemical processes and ionic dynamic underlying the formation of atomic-sized conductive filaments and corresponding electronic transport properties in the quantum regime still represents a challenge. In this work, we report on quantum conductance effects in single memristive Ag nanowires (NWs) through a combined experimental and simulation approach that combines advanced classical molecular dynamics (MD) algorithms and quantum transport simulations (DFT). This approach provides new insights on quantum conductance effects in memristive devices by unravelling the intrinsic relationship between electronic transport and atomic dynamic reconfiguration of the nanofilment, by shedding light on deviations from integer multiples of the fundamental quantum of conductance depending on peculiar dynamic trajectories of nanofilament reconfiguration and on conductance fluctuations relying on atomic rearrangement due to thermal fluctuations.

Electrical and Thermal Conductivities of Single CuxO Nanowires.

Copper oxide nanowires (NWs) are promising elements for the realization of a wide range of devices for low-power electronics, gas sensors, and energy storage applications, due to their high aspect ratio, low environmental impact, and cost-effective manufacturing. Here, we report on the electrical and thermal properties of copper oxide NWs synthetized through thermal growth directly on copper foil. Structural characterization revealed that the growth process resulted in the formation of vertically aligned NWs on the Cu growth substrate, while the investigation of chemical composition revealed that the NWs were composed of CuO rather than Cu2O. The electrical characterization of single-NW-based devices, in which single NWs were contacted by Cu electrodes, revealed that the NWs were characterized by a conductivity of 7.6 × 10-2 S∙cm-1. The effect of the metal-insulator interface at the NW-electrode contact was analyzed by comparing characterizations in two-terminal and four-terminal configurations. The effective thermal conductivity of single CuO NWs placed on a substrate was measured using Scanning Thermal Microscopy (SThM), providing a value of 2.6 W∙m-1∙K-1, and using a simple Finite Difference model, an estimate for the thermal conductivity of the nanowire itself was obtained as 3.1 W∙m-1∙K-1. By shedding new light on the electrical and thermal properties of single CuO NWs, these results can be exploited for the rational design of a wide range of optoelectronic devices based on NWs.

Ultrasonic Spray Coating to Optimize Performance of Bio-Electrochemical Systems.

This work investigates the optimization of carbon-based electrodes employed in bio-electrochemical systems (BES) through the deposition of nanostructured layers of poly(3,4-ethylene-dioxy-thiophene) poly(styrene-sulfonate) (PEDOT:PSS) on commercial carbon paper electrodes via ultrasonic spray coating (USC). This innovative application of USC demonstrated that uniform and controlled depositions of PEDOT:PSS can be successfully performed on carbon-based electrodes. To this end, the morphology and spatial uniformity of depositions were verified via scanning electron microscopy and Raman spectroscopy. Electrochemical characterizations of fabricated electrodes demonstrated a more than two-fold increase in the electrochemical active surface area with respect to bare carbon paper. A lab-scale experiment on BES was performed, selecting microbial fuel cells (MFCs) as the reference devices. Devices featuring USC-deposited PEDOT:PSS electrodes showed a three-fold-higher energy recovery with respect to control cells, reaching a maximum value of (13 ± 2) J·m-3. Furthermore, the amount of PEDOT:PSS required to optimize MFCs' performance is in line with values reported in the literature for other deposition methods. In conclusion, this work demonstrates that USC is a promising technique for application in BES.

A Nanofiber-Based Gas Diffusion Layer for Improved Performance in Air Cathode Microbial Fuel Cells.

This work investigates a new nanostructured gas diffusion layer (nano-GDL) to improve the performance of air cathode single-chamber microbial fuel cells (a-SCMFCs). The new nano-GDLs improve the direct oxygen reduction reaction by exploiting the best qualities of nanofibers from electrospinning in terms of high surface-area-to-volume ratio, high porosity, and laser-based processing to promote adhesion. By electrospinning, nano-GDLs were fabricated directly by collecting two nanofiber mats on the same carbon-based electrode, acting as the substrate. Each layer was designed with a specific function: water-resistant, oxygen-permeable polyvinylidene-difluoride (PVDF) nanofibers served as a barrier to prevent water-based electrolyte leakage, while an inner layer of cellulose nanofibers was added to promote oxygen diffusion towards the catalytic sites. The maximum current density obtained for a-SCMFCs with the new nano-GDLs is 132.2 ± 10.8 mA m-2, and it doubles the current density obtained with standard PTFE-based GDL (58.5 ± 2.4 mA m-2) used as reference material. The energy recovery (EF) factor, i.e., the ratio of the power output to the inner volume of the device, was then used to evaluate the overall performance of a-SCMFCs. a-SCMFCs with nano-GDL provided an EF value of 60.83 mJ m-3, one order of magnitude higher than the value of 3.92 mJ m-3 obtained with standard GDL.

Effect of electrode materials on resistive switching behaviour of NbOx-based memristive devices.

Memristive devices that rely on redox-based resistive switching mechanism have attracted great attention for the development of next-generation memory and computing architectures. However, a detailed understanding of the relationship between involved materials, interfaces, and device functionalities still represents a challenge. In this work, we analyse the effect of electrode metals on resistive switching functionalities of NbOx-based memristive cells. For this purpose, the effect of Au, Pt, Ir, TiN, and Nb top electrodes was investigated in devices based on amorphous NbOx grown by anodic oxidation on a Nb substrate exploited also as counter electrode. It is shown that the choice of the metal electrode regulates electronic transport properties of metal-insulator interfaces, strongly influences the electroforming process, and the following resistive switching characteristics. Results show that the electronic blocking character of Schottky interfaces provided by Au and Pt metal electrodes results in better resistive switching performances. It is shown that Pt represents the best choice for the realization of memristive cells when the NbOx thickness is reduced, making possible the realization of memristive cells characterised by low variability in operating voltages, resistance states and with low device-to-device variability. These results can provide new insights towards a rational design of redox-based memristive cells.

Resistive switching and role of interfaces in memristive devices based on amorphous NbOx grown by anodic oxidation.

Memristive devices based on the resistive switching mechanism are continuously attracting attention in the framework of neuromorphic computing and next-generation memory devices. Here, we report on a comprehensive analysis of the resistive switching properties of amorphous NbOx grown by anodic oxidation. Besides a detailed chemical, structural and morphological analysis of the involved materials and interfaces, the mechanism of switching in Nb/NbOx/Au resistive switching cells is discussed by investigating the role of metal-metal oxide interfaces in regulating electronic and ionic transport mechanisms. The resistive switching was found to be related to the formation/rupture of conductive nanofilaments in the NbOx layer under the action of an applied electric field, facilitated by the presence of an oxygen scavenger layer at the Nb/NbOx interface. Electrical characterization including device-to-device variability revealed an endurance >103 full-sweep cycles, retention >104 s, and multilevel capabilities. Furthermore, the observation of quantized conductance supports the physical mechanism of switching based on the formation of atomic-scale conductive filaments. Besides providing new insights into the switching properties of NbOx, this work also highlights the perspective of anodic oxidation as a promising method for the realization of resistive switching cells.

Clinical-Molecular Prospective Cohort Study in Non-Small Cell Lung Cancer (PROMOLE study): A Comprehensive Approach to Identify New Predictive Markers of Pharmacological Response.

Lung cancers account for over 90% of thoracic malignancies and the rapid development of specific cytotoxic drugs and molecular therapies requires a detailed identification of the different histologies, gene drivers or immune microenvironment biomarkers. Nevertheless, the heterogeneous clonal evolution, the emergency of drug-induced resistance and the limited occurrence of genetic alterations claim the need of a deep integration of the tumor's and the patient's biological features. The aim of the present study is to generate a tecnological platform for precision medicine in order to set predictive personalized algorithms for patient diagnosis and therapy. All resectable patients having histologically confirmed stage IB-IIIA non-small cell lung cancer will be enrolled for tissue sampling. A large biobank of lung cancer samples and the corresponding healthy tissues and biological components (ie, blood, stools, etc.) with complete clinical, pathological and molecular information will be collected. The platform will include: a) digital patient data collection; b) whole NGS molecular analyses (exome, transcriptome, methylome) for tumor characterization; c) exploitation and collection of organoids from tissue patients; d) Surface Amplified Raman Spectroscopy; e) microfluidic-based technological drug screening; f) preclinical in vivo models based on patient-derived xenografts; g) generation of specific predictive algorithms taking into account all collected multiparameters. The project will lay the basis of a knowledge hub and qualified technology aimed not only at answering the medical and scientific community's questions, but also meant to be useful to individual patients by predicting the response to adjuvant and second-line drugs in case of relapse of the disease.

DLP 3D Printing Meets Lignocellulosic Biopolymers: Carboxymethyl Cellulose Inks for 3D Biocompatible Hydrogels.

The development of new bio-based inks is a stringent request for the expansion of additive manufacturing towards the development of 3D-printed biocompatible hydrogels. Herein, methacrylated carboxymethyl cellulose (M-CMC) is investigated as a bio-based photocurable ink for digital light processing (DLP) 3D printing. CMC is chemically modified using methacrylic anhydride. Successful methacrylation is confirmed by 1H NMR and FTIR spectroscopy. Aqueous formulations based on M-CMC/lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP) photoinitiator and M-CMC/Dulbecco's Modified Eagle Medium (DMEM)/LAP show high photoreactivity upon UV irradiation as confirmed by photorheology and FTIR. The same formulations can be easily 3D-printed through a DLP apparatus to produce 3D shaped hydrogels with excellent swelling ability and mechanical properties. Envisaging the application of the hydrogels in the biomedical field, cytotoxicity is also evaluated. The light-induced printing of cellulose-based hydrogels represents a significant step forward in the production of new DLP inks suitable for biomedical applications.

Real-time and reversible light-actuated microfluidic channel squeezing in dye-doped PDMS.

The azobenzene chromophore is used as a functional dye for the development of smart microfluidic devices. A single layer microfluidic channel is produced, exploiting the potential of a dye doped PDMS formulation. The key advantage of this approach is the possibility to control the fluid flow by means of a simple light stimulus. Furthermore, the deformation can be controlled in time, space and intensity, giving rise to several degrees of freedom in the actuation of the channel squeezing. A future perspective will be the implementation of the microfluidic platform with structured light, to have the possibility to control the flow in a parallel and reversible manner at several points, modifying the pattern in real time.

In Situ Thermal Generation of Silver Nanoparticles in 3D Printed Polymeric Structures.

Polymer nanocomposites have always attracted the interest of researchers and industry because of their potential combination of properties from both the nanofillers and the hosting matrix. Gathering nanomaterials and 3D printing could offer clear advantages and numerous new opportunities in several application fields. Embedding nanofillers in a polymeric matrix could improve the final material properties but usually the printing process gets more difficult. Considering this drawback, in this paper we propose a method to obtain polymer nanocomposites by in situ generation of nanoparticles after the printing process. 3D structures were fabricated through a Digital Light Processing (DLP) system by disolving metal salts in the starting liquid formulation. The 3D fabrication is followed by a thermal treatment in order to induce in situ generation of metal nanoparticles (NPs) in the polymer matrix. Comprehensive studies were systematically performed on the thermo-mechanical characteristics, morphology and electrical properties of the 3D printed nanocomposites.