Showing papers by "Istituto Italiano di Tecnologia published in 2019"

Energy storage: The future enabled by nanomaterials

Abstract: Lithium-ion batteries, which power portable electronics, electric vehicles, and stationary storage, have been recognized with the 2019 Nobel Prize in chemistry. The development of nanomaterials and their related processing into electrodes and devices can improve the performance and/or development of the existing energy storage systems. We provide a perspective on recent progress in the application of nanomaterials in energy storage devices, such as supercapacitors and batteries. The versatility of nanomaterials can lead to power sources for portable, flexible, foldable, and distributable electronics; electric transportation; and grid-scale storage, as well as integration in living environments and biomedical systems. To overcome limitations of nanomaterials related to high reactivity and chemical instability caused by their high surface area, nanoparticles with different functionalities should be combined in smart architectures on nano- and microscales. The integration of nanomaterials into functional architectures and devices requires the development of advanced manufacturing approaches. We discuss successful strategies and outline a roadmap for the exploitation of nanomaterials for enabling future energy storage applications, such as powering distributed sensor networks and flexible and wearable electronics.

Rational molecular passivation for high-performance perovskite light-emitting diodes

Abstract: A major efficiency limit for solution-processed perovskite optoelectronic devices, for example light-emitting diodes, is trap-mediated non-radiative losses. Defect passivation using organic molecul ...

Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications, and Their Optical Properties.

Abstract: Metal halide perovskites represent a flourishing area of research, which is driven by both their potential application in photovoltaics and optoelectronics and by the fundamental science behind their unique optoelectronic properties. The emergence of new colloidal methods for the synthesis of halide perovskite nanocrystals, as well as the interesting characteristics of this new type of material, has attracted the attention of many researchers. This review aims to provide an up-to-date survey of this fast-moving field and will mainly focus on the different colloidal synthesis approaches that have been developed. We will examine the chemistry and the capability of different colloidal synthetic routes with regard to controlling the shape, size, and optical properties of the resulting nanocrystals. We will also provide an up-to-date overview of their postsynthesis transformations, and summarize the various solution processes that are aimed at fabricating halide perovskite-based nanocomposites. Furthermore, we...

Guidelines for the use of flow cytometry and cell sorting in immunological studies (second edition)

Abstract: These guidelines are a consensus work of a considerable number of members of the immunology and flow cytometry community. They provide the theory and key practical aspects of flow cytometry enabling immunologists to avoid the common errors that often undermine immunological data. Notably, there are comprehensive sections of all major immune cell types with helpful Tables detailing phenotypes in murine and human cells. The latest flow cytometry techniques and applications are also described, featuring examples of the data that can be generated and, importantly, how the data can be analysed. Furthermore, there are sections detailing tips, tricks and pitfalls to avoid, all written and peer-reviewed by leading experts in the field, making this an essential research companion.

Domain Generalization by Solving Jigsaw Puzzles

Abstract: Human adaptability relies crucially on the ability to learn and merge knowledge both from supervised and unsupervised learning: the parents point out few important concepts, but then the children fill in the gaps on their own. This is particularly effective, because supervised learning can never be exhaustive and thus learning autonomously allows to discover invariances and regularities that help to generalize. In this paper we propose to apply a similar approach to the task of object recognition across domains: our model learns the semantic labels in a supervised fashion, and broadens its understanding of the data by learning from self-supervised signals how to solve a jigsaw puzzle on the same images. This secondary task helps the network to learn the concepts of spatial correlation while acting as a regularizer for the classification task. Multiple experiments on the PACS, VLCS, Office-Home and digits datasets confirm our intuition and show that this simple method outperforms previous domain generalization and adaptation solutions. An ablation study further illustrates the inner workings of our approach.

Promoting transparency and reproducibility in enhanced molecular simulations

Abstract: The PLUMED consortium unifies developers and contributors to PLUMED, an open-source library for enhanced- sampling, free-energy calculations and the analysis of molecular dynamics simulations. Here, we outline our efforts to promote transparency and reproducibility by disseminating protocols for enhanced-sampling molecular simulations.

Stabilizing halide perovskite surfaces for solar cell operation with wide-bandgap lead oxysalts.

Abstract: We show that converting the surfaces of lead halide perovskite to water-insoluble lead (II) oxysalt through reaction with sulfate or phosphate ions can effectively stabilize the perovskite surface and bulk material. These capping lead oxysalt thin layers enhance the water resistance of the perovskite films by forming strong chemical bonds. The wide-bandgap lead oxysalt layers also reduce the defect density on the perovskite surfaces by passivating undercoordinated surface lead centers, which are defect-nucleating sites. Formation of the lead oxysalt layer increases the carrier recombination lifetime and boosts the efficiency of the solar cells to 21.1%. Encapsulated devices stabilized by the lead oxysalt layers maintain 96.8% of their initial efficiency after operation at maximum power point under simulated air mass (AM) 1.5 G irradiation for 1200 hours at 65°C.

Mechanistic Studies in Photocatalysis

Abstract: The fast-moving fields of photoredox and photocatalysis have recently provided fresh opportunities to expand the potential of synthetic organic chemistry. Advances in light-mediated processes have mainly been guided so far by empirical findings and the quest for reaction invention. The general perception, however, is that photocatalysis is entering a more mature phase where the combination of experimental and mechanistic studies will play a dominant role in sustaining further innovation. This Review outlines the key mechanistic studies to consider when developing a photochemical process, and the best techniques available for acquiring relevant information. The discussion will use selected case studies to highlight how mechanistic investigations can be instrumental in guiding the invention and development of synthetically useful photocatalytic transformations.

Innovative approaches for cancer treatment: current perspectives and new challenges.

Abstract: Every year, cancer is responsible for millions of deaths worldwide and, even though much progress has been achieved in medicine, there are still many issues that must be addressed in order to improve cancer therapy. For this reason, oncological research is putting a lot of effort towards finding new and efficient therapies which can alleviate critical side effects caused by conventional treatments. Different technologies are currently under evaluation in clinical trials or have been already introduced into clinical practice. While nanomedicine is contributing to the development of biocompatible materials both for diagnostic and therapeutic purposes, bioengineering of extracellular vesicles and cells derived from patients has allowed designing ad hoc systems and univocal targeting strategies. In this review, we will provide an in-depth analysis of the most innovative advances in basic and applied cancer research.

Thermoelectrics: From history, a window to the future

Abstract: Thermoelectricity offers a sustainable path to recover and convert waste heat into readily available electric energy, and has been studied for more than two centuries. From the controversy between Galvani and Volta on the Animal Electricity, dating back to the end of the XVIII century and anticipating Seebeck’s observations, the understanding of the physical mechanisms evolved along with the development of the technology. In the XIX century Orsted clarified some of the earliest observations of the thermoelectric phenomenon and proposed the first thermoelectric pile, while it was only after the studies on thermodynamics by Thomson, and Rayleigh’s suggestion to exploit the Seebeck effect for power generation, that a diverse set of thermoelectric generators was developed. From such pioneering endeavors, technology evolved from massive, and sometimes unreliable, thermopiles to very reliable devices for sophisticated niche applications in the XX century, when Radioisotope Thermoelectric Generators for space missions and nuclear batteries for cardiac pacemakers were introduced. While some of the materials adopted to realize the first thermoelectric generators are still investigated nowadays, novel concepts and improved understanding of materials growth, processing, and characterization developed during the last 30 years have provided new avenues for the enhancement of the thermoelectric conversion efficiency, for example through nanostructuration, and favored the development of new classes of thermoelectric materials. With increasing demand for sustainable energy conversion technologies, the latter aspect has become crucial for developing thermoelectrics based on abundant and non-toxic materials, which can be processed at economically viable scales, tailored for different ranges of temperature. This includes high temperature applications where a substantial amount of waste energy can be retrieved, as well as room temperature applications where small and local temperature differences offer the possibility of energy scavenging, as in micro harvesters meant for distributed electronics such as sensor networks. While large scale applications have yet to make it to the market, the richness of available and emerging thermoelectric technologies presents a scenario where thermoelectrics is poised to contribute to a future of sustainable future energy harvesting and management. This work reviews the broad field of thermoelectrics. Progress in thermoelectrics and milestones that led to the current state-of-the-art are presented by adopting an historical footprint. The review begins with an historical excursus on the major steps in the history of thermoelectrics, from the very early discovery to present technology. Then, the most promising thermoelectric material classes are discussed one by one in dedicated sections and subsections, carefully highlighting the technological solutions on materials growth that have represented a turning point in the research on thermoelectrics. Finally, perspectives and the future of the technology are discussed in the framework of sustainability and environmental compatibility. An appendix on the theory of thermoelectric transport in the solid state reviews the transport theory in complex crystal structures and nanostructured materials.

Sonophotocatalytic degradation mechanisms of Rhodamine B dye via radicals generation by micro- and nano-particles of ZnO

Abstract: In this work, it is proposed an environmental friendly sonophotocatalytic approach to efficiently treat polluted waters from industrial dyes exploiting ZnO micro- and nano-materials. For the first time, we deeply investigated the generation of reactive oxygen species (ROS) under ultrasound stimulation of different ZnO structures by Electron Paramagnetic Resonance Spectroscopy (EPR). Indeed, five zinc oxide (ZnO) micro- and nano-structures, i.e. Desert Roses (DRs), Multipods (MPs), Microwires (MWs), Nanoparticles (NPs) and Nanowires (NWs), were studied for the Rhodamine B (RhB) sonodegradation under ultrasonic irradiation. The DRs microparticles demonstrated the best sonocatalytic performance (100% degradation of RhB in 180 min) and the highest OH· radicals generation under ultrasonic irradiation. Strikingly, the coupling of ultrasound and sun-light irradiation in a sonophotodegradation approach led to 100% degradation efficiency, i.e. color reduction, of RhB in just 10 min, revealing a great positive synergy between the photocatalytic and sonocatalytic mechanisms. The RhB sonophotocatalytic degradation was also evaluated at different initial dye concentrations and with the presence of anions in solution. It was demonstrated a good stability over repeated cycles of dye treatment, which probe the applicability of this technique with industrial effluents. In conclusion, sonophotocatalytic degradation synergizing sunlight and ultrasound in the presence of DRs microparticles shows a great potential and a starting point to investigate further the efficient treatment of organic dyes in wastewater.

Measuring Hall Viscosity of Graphene’s Electron Fluid

Abstract: An electrical conductor subjected to a magnetic field exhibits the Hall effect in the presence of current flow. Here, we report a qualitative deviation from the standard behavior in electron systems with high viscosity. We found that the viscous electron fluid in graphene responds to nonquantizing magnetic fields by producing an electric field opposite to that generated by the ordinary Hall effect. The viscous contribution is substantial and identified by studying local voltages that arise in the vicinity of current-injecting contacts. We analyzed the anomaly over a wide range of temperatures and carrier densities and extracted the Hall viscosity, a dissipationless transport coefficient that was long identified theoretically but remained elusive in experiments.

3D Electron Diffraction: The Nanocrystallography Revolution.

Abstract: Crystallography of nanocrystalline materials has witnessed a true revolution in the past 10 years, thanks to the introduction of protocols for 3D acquisition and analysis of electron diffraction data. This method provides single-crystal data of structure solution and refinement quality, allowing the atomic structure determination of those materials that remained hitherto unknown because of their limited crystallinity. Several experimental protocols exist, which share the common idea of sampling a sequence of diffraction patterns while the crystal is tilted around a noncrystallographic axis, namely, the goniometer axis of the transmission electron microscope sample stage. This Outlook reviews most important 3D electron diffraction applications for different kinds of samples and problematics, related with both materials and life sciences. Structure refinement including dynamical scattering is also briefly discussed.

Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites

Abstract: Hybrid organic–inorganic semiconductors feature complex lattice dynamics due to the ionic character of the crystal and the softness arising from non-covalent bonds between molecular moieties and the inorganic network. Here we establish that such dynamic structural complexity in a prototypical two-dimensional lead iodide perovskite gives rise to the coexistence of diverse excitonic resonances, each with a distinct degree of polaronic character. By means of high-resolution resonant impulsive stimulated Raman spectroscopy, we identify vibrational wavepacket dynamics that evolve along different configurational coordinates for distinct excitons and photocarriers. Employing density functional theory calculations, we assign the observed coherent vibrational modes to various low-frequency (≲50 cm−1) optical phonons involving motion in the lead iodide layers. We thus conclude that different excitons induce specific lattice reorganizations, which are signatures of polaronic binding. This insight into the energetic/configurational landscape involving globally neutral primary photoexcitations may be relevant to a broader class of emerging hybrid semiconductor materials. High-resolution resonant impulsive stimulated Raman spectroscopy in two-dimensional hybrid metal halide perovskites provides evidence for polaronic effects on excitons, which couple to distinct low-frequency vibrational modes of the ionic lattice.

Controlling competing photochemical reactions stabilizes perovskite solar cells

Abstract: Metal halide perovskites have become a popular material system for fabricating photovoltaics and various optoelectronic devices. However, long-term reliability must be assured. Instabilities are manifested as light-induced ion migration and segregation, which can lead to material degradation. Discordant reports have shown a beneficial role of ion migration under illumination, leading to defect healing. By combining ab initio simulations with photoluminescence measurements under controlled conditions, we demonstrate that photo-instabilities are related to light-induced formation and annihilation of defects acting as carrier trap states. We show that these phenomena coexist and compete. In particular, long-living carrier traps related to halide defects trigger photoinduced material transformations, driving both processes. Defect formation can be controlled by blocking under-coordinated surface sites, which act as a defect reservoir. By use of a passivation strategy we are thus able to stabilize the perovskite layer, leading to improved optoelectronic material quality and enhanced photostability in solar cells. The photo-instability of perovskite solar cells is investigated and controlled by the use of a passivation strategy.

Super-resolution fight club: assessment of 2D and 3D single-molecule localization microscopy software.

Abstract: With the widespread uptake of two-dimensional (2D) and three-dimensional (3D) single-molecule localization microscopy (SMLM), a large set of different data analysis packages have been developed to generate super-resolution images. In a large community effort, we designed a competition to extensively characterize and rank the performance of 2D and 3D SMLM software packages. We generated realistic simulated datasets for popular imaging modalities-2D, astigmatic 3D, biplane 3D and double-helix 3D-and evaluated 36 participant packages against these data. This provides the first broad assessment of 3D SMLM software and provides a holistic view of how the latest 2D and 3D SMLM packages perform in realistic conditions. This resource allows researchers to identify optimal analytical software for their experiments, allows 3D SMLM software developers to benchmark new software against the current state of the art, and provides insight into the current limits of the field.

Nonvolatile Memories Based on Graphene and Related 2D Materials.

Abstract: The pervasiveness of information technologies is generating an impressive amount of data, which need to be accessed very quickly. Nonvolatile memories (NVMs) are making inroads into high-capacity storage to replace hard disk drives, fuelling the expansion of the global storage memory market. As silicon-based flash memories are approaching their fundamental limit, vertical stacking of multiple memory cell layers, innovative device concepts, and novel materials are being investigated. In this context, emerging 2D materials, such as graphene, transition metal dichalcogenides, and black phosphorous, offer a host of physical and chemical properties, which could both improve existing memory technologies and enable the next generation of low-cost, flexible, and wearable storage devices. Herein, an overview of graphene and related 2D materials (GRMs) in different types of NVM cells is provided, including resistive random-access, flash, magnetic and phase-change memories. The physical and chemical mechanisms underlying the switching of GRM-based memory devices studied in the last decade are discussed. Although at this stage most of the proof-of-concept devices investigated do not compete with state-of-the-art devices, a number of promising technological advancements have emerged. Here, the most relevant material properties and device structures are analyzed, emphasizing opportunities and challenges toward the realization of practical NVM devices.

Brillouin microscopy: an emerging tool for mechanobiology

Abstract: The role and importance of mechanical properties of cells and tissues in cellular function, development and disease has widely been acknowledged, however standard techniques currently used to assess them exhibit intrinsic limitations. Recently, Brillouin microscopy, a type of optical elastography, has emerged as a non-destructive, label- and contact-free method that can probe the viscoelastic properties of biological samples with diffraction-limited resolution in 3D. This led to increased attention amongst the biological and medical research communities, but it also sparked debates about the interpretation and relevance of the measured physical quantities. Here, we review this emerging technology by describing the underlying biophysical principles and discussing the interpretation of Brillouin spectra arising from heterogeneous biological matter. We further elaborate on the technique’s limitations, as well as its potential for gaining insights in biology, in order to guide interested researchers from various fields. This Review discusses the principles, advantages and limitations of Brillouin microscopy, a non-invasive tool for measuring mechanical properties of biological samples in three dimensions.

Selenium nanoparticles for targeted stroke therapy through modulation of inflammatory and metabolic signaling

Abstract: Ischemic cerebral stroke is a major cause of death and morbidity. Currently, no neuroprotective agents have been shown to impact the clinical outcomes in cerebral stroke cases. Here, we report therapeutic effects of Se nanoparticles on ischemic stroke in a murine model. Anti-transferrin receptor monoclonal antibody (OX26)-PEGylated Se nanoparticles (OX26-PEG-Se NPs) were designed and synthesized and their neuroprotective effects were measured using in vitro and in vivo approaches. We demonstrate that administration of the biodegradable nanoparticles leads to resolution of brain edema, protection of axons in hippocampus region, and myelination of hippocampal area after cerebral ischemic stroke. Our nanoparticle design ensures efficient targeting and minimal side effects. Hematological and biochemical analyses revealed no undesired NP-induced changes. To gain mechanistic insights into the therapeutic effects of these particles, we characterized the changes to the relevant inflammatory and metabolic signaling pathways. We assessed metabolic regulator mTOR and related signaling pathways such as hippo, Ubiquitin-proteasome system (ERK5), Tsc1/Tsc2 complex, FoxO1, wnt/β-catenine signaling pathway. Moreover, we examined the activity of jak2/stat3 signaling pathways and Adamts1, which are critically involved in inflammation. Together, our study provides a promising treatment strategy for cerebral stroke based on Se NP induced suppression of excessive inflammation and oxidative metabolism.

A Century of Robotic Hands

Abstract: This article reports on the state of the art of artificial hands, discussing some of the field's most important trends and suggesting directions for future research. We review and group the most im...

Formation of Surface Defects Dominates Ion Migration in Lead-Halide Perovskites

Abstract: We propose a new model of defect formation and ion migration at the surfaces/grain boundaries of lead-halide perovskites, based on ab initio calculations. Inspired by the spread of experimentally m...

Extractable Work, the Role of Correlations, and Asymptotic Freedom in Quantum Batteries.

Abstract: We investigate a quantum battery made of N two-level systems, which is charged by an optical mode via an energy-conserving interaction. We quantify the fraction of energy stored in the battery that can be extracted in order to perform thermodynamic work. We first demonstrate that this quantity is highly reduced by the presence of correlations between the charger and the battery or between the subsystems composing the battery. We then show that the correlation-induced suppression of extractable energy, however, can be mitigated by preparing the charger in a coherent optical state. We conclude by proving that the charger-battery system is asymptotically free of such locking correlations in the N→∞ limit.

Emissive Bi-doped double perovskite Cs2Ag1-xNaxInCl6 Nanocrystals

Abstract: We report the composition-dependent optical properties of Bi-doped Cs2Ag1–xNaxInCl6 nanocrystals (NCs) having a double perovskite crystal structure. Their photoluminescence (PL) was characterized b...

Defect Activity in Lead Halide Perovskites.

Abstract: The presence of various types of chemical interactions in metal-halide perovskite semiconductors gives them a characteristic "soft" fluctuating structure, prone to a wide set of defects. Understanding of the nature of defects and their photochemistry is summarized, which leverages the cooperative action of density functional theory investigations and accurate experimental design. This knowledge is used to describe how defect activity determines the macroscopic properties of the material and related devices. Finally, a discussion of the open questions provides a path towards achieving an educated prediction of device operation, necessary to engineer reliable devices.

Learning Discrete Structures for Graph Neural Networks

Abstract: Graph neural networks (GNNs) are a popular class of machine learning models whose major advantage is their ability to incorporate a sparse and discrete dependency structure between data points. Unfortunately, GNNs can only be used when such a graph-structure is available. In practice, however, real-world graphs are often noisy and incomplete or might not be available at all. With this work, we propose to jointly learn the graph structure and the parameters of graph convolutional networks (GCNs) by approximately solving a bilevel program that learns a discrete probability distribution on the edges of the graph. This allows one to apply GCNs not only in scenarios where the given graph is incomplete or corrupted but also in those where a graph is not available. We conduct a series of experiments that analyze the behavior of the proposed method and demonstrate that it outperforms related methods by a significant margin.

Scalable Production of Graphene Inks via Wet‐Jet Milling Exfoliation for Screen‐Printed Micro‐Supercapacitors

Abstract: The miniaturization of energy storage units is pivotal for the development of next-generation portable electronic devices. Micro-supercapacitors (MSCs) hold a great potential to work as on-chip micro-power sources and energy storage units complementing batteries and energy harvester systems. The scalable production of supercapacitor materials with cost-effective and high-throughput processing methods is crucial for the widespread application of MSCs. Here, we report wet-jet milling exfoliation of graphite to scale-up the production of graphene as supercapacitor material. The formulation of aqueous/alcohol-based graphene inks allows metal-free, flexible MSCs to be screen-printed. These MSCs exhibit areal capacitance (Careal) values up to 1.324 mF cm-2 (5.296 mF cm-2 for a single electrode), corresponding to an outstanding volumetric capacitance (Cvol) of 0.490 F cm-3 (1.961 F cm-3 for a single electrode). The screen-printed MSCs can operate up to power density above 20 mW cm-2 at energy density of 0.064 uWh cm-2. The devices exhibit excellent cycling stability over charge-discharge cycling (10000 cycles), bending cycling (100 cycles at bending radius of 1 cm) and folding (up to angles of 180°). Moreover, ethylene vinyl acetate-encapsulated MSCs retain their electrochemical properties after a home-laundry cycle, providing waterproof and washable properties for prospective application in wearable electronics.

The emerging role of epigenetics in human autoimmune disorders

Abstract: Epigenetic pathways play a pivotal role in the development and function of the immune system. Over the last decade, a growing body of studies has been published out seeking to explain a correlation between epigenetic modifications and the development of autoimmune disorders. Epigenetic changes, such as DNA methylation, histone modifications, and noncoding RNAs, are involved in the pathogenesis of autoimmune diseases mainly by regulating gene expression. This paper reviews the importance of epigenetic alterations during the development of the most prevalent human autoimmune diseases, such as systemic lupus erythematosus (SLE), rheumatoid arthritis (RA), systemic sclerosis (SSc), Sjogren’s syndrome (SS), autoimmune thyroid diseases (AITD), and type 1 diabetes (T1D), aiming to provide new insights in the pathogenesis of autoimmune diseases and the possibility to develop novel therapeutic approaches targeting the epigenome.