Water Structure in the First Layers on TiO2: A Key Factor for Boosting Solar-Driven Water-Splitting Performances.

The water hydrogen-bonded network is strongly perturbed in the first layers in contact with the semiconductor surface. Even though this aspect influences the outer-sphere electron transfer, it was not recognized that it is a crucial factor impacting the solar-driven water-splitting performances. To fill this gap, we have selected two TiO2 anatase samples (with and without B-doping), and by extensive experimental and computational investigations, we have demonstrated that the remarkable 5-fold increase in water-splitting photoactivity of the B-doped sample cannot be ascribed to effects typically associated to enhanced photocatalytic properties, such as band gap, heterojunctions, crystal facets, and other aspects. Studying these samples by combining FTIR measurements under controlled humidity with first-principles simulations sheds light on the role and nature of the first-layer water structure in contact with the photocatalyst surfaces. It turns out that the doping hampers the percolation of tetrahedrally coordinated water molecules while enhancing the population of topological H-bond defects forming approximately linear H-bonded chains. This work unveils how doping the semiconductor surface affects the local electric field, determining the water splitting rate by influencing the H-bond topologies in the first water layers. This evidence opens new prospects for designing efficient photocatalysts for water splitting.

Absorption and Fluorescence Emission Investigations on Supramolecular Assemblies of Tetrakis-(4-sulfonatophenyl)porphyrin and Graphene Quantum Dots.

The one-pot synthesis of N-doped graphene quantum dots (GQDs), capped with a positively charged polyamine (trien), has been realized through a microwave-assisted pyrolysis on solid L-glutamic acid and trien in equimolar amounts. The resulting positively charged nanoparticles are strongly emissive in aqueous solutions and are stable for months. The interaction with the anionic tetrakis(4-sulphonatophenyl)porphyrin (TPPS4) has been investigated at neutral and mild acidic pH using a combination of UV/vis absorption spectroscopy together with static and time-resolved fluorescence emission. At pH = 7, the experimental evidence points to the formation of a supramolecular adduct mainly stabilized by electrostatic interactions. The fluorescence emission of the porphyrin is substantially quenched while GQDs remain still emissive. On decreasing the pH, protonation of TPPS4 leads to formation of porphyrin J-aggregates through the intermediacy of the charged quantum dots.

Intra-protein interacting collective modes in the terahertz frequency region.

Understanding how proteins work requires a thorough understanding of their internal dynamics. Proteins support a wide range of motions, from the femtoseconds to seconds time scale, relevant to crucial biological functions. In this context, the term "protein collective dynamics" refers to the complex patterns of coordinated motions of numerous atoms throughout the protein in the sub-picosecond time scale (terahertz frequency region). It is hypothesized that these dynamics have a substantial impact on the regulation of functional dynamical mechanisms, including ligand binding and allosteric signalling, charge transport direction, and the regulation of thermodynamic and thermal transport properties. Using the theoretical framework of hydrodynamics, the collective dynamics of proteins had previously been described in a manner akin to that of simple liquids, i.e. in terms of a single acoustic-like excitation, related to intra-protein vibrational motions. Here, we employ an interacting-mode model to analyse the results from molecular dynamics simulations and we unveil that the vibrational landscape of proteins is populated by multiple acoustic-like and low-frequency optic-like modes, with mixed symmetry and interfering with each other. We propose an interpretation at the molecular level of the observed scenario that we relate to the side-chains and the hydrogen-bonded networks dynamics. The present insights provide a perspective for understanding the molecular mechanisms underlying the energy redistribution processes in the interior of proteins.

Influence of the device used for obstructive sleep apnea diagnosis on body position: a comparison between polysomnography and portable monitor.

PURPOSE: Different devices have been used for the diagnosis of obstructive sleep apnea (OSA), which differ in the number of sensors used. The numerous sensors used in more complex sleep studies such as in-lab polysomnography may influence body position during sleep. We hypothesized that patients submitted to in-lab polysomnography (PSG) would spend more time in the supine position than patients submitted to an ambulatory Portable Monitor (PM) sleep study. METHODS: Body position during PSG and PM studies was compared among two distinct groups of patients matched for age, body-mass index (BMI), apnea-hypopnea index (AHI), and gender. Predictors of time spent in the supine position were determined using a multiple linear regression model. RESULTS: Of 478 participants who underwent either PSG or PM studies, mean age: 61[43-66] years; males: 43.9%; BMI: 28.4[26.1-31.1]kg/m2; AHI 14[7-27] events/hour). Participants who underwent PSG studies spent more time in the supine position (41[16-68]% than participants who underwent PM studies (34[16-51]%), P = 0.014. Participants with OSA spent more time in the supine position than participants without OSA, both among the PSG and PM groups P < 0.05). Gender, BMI, OSA severity, and sleep study type were independent predictors of time spent in the supine position. CONCLUSION: In-lab PSG may increase time spent in the supine position and overestimate OSA severity compared to a PM sleep study. OSA diagnosis is also associated with increased time spent in the supine position. The potential influence on the sleeping position should be taken into account when choosing among the different sleep study types for OSA diagnosis.

Extending the Colloidal Transition Metal Dichalcogenide Library to ReS2 Nanosheets for Application in Gas Sensing and Electrocatalysis.

Among the large family of transition metal dichalcogenides, recently ReS2 has stood out due to its nearly layer-independent optoelectronic and physicochemical properties related to its 1T distorted octahedral structure. This structure leads to strong in-plane anisotropy, and the presence of active sites at its surface makes ReS2 interesting for gas sensing and catalysts applications. However, current fabrication methods use chemical or physical vapor deposition (CVD or PVD) processes that are costly, time-consuming and complex, therefore limiting its large-scale production and exploitation. To address this issue, a colloidal synthesis approach is developed, which allows the production of ReS2 at temperatures below 360 °C and with reaction times shorter than 2h. By combining the solution-based synthesis with surface functionalization strategies, the feasibility of colloidal ReS2 nanosheet films for sensing different gases is demonstrated with highly competitive performance in comparison with devices built with CVD-grown ReS2 and MoS2 . In addition, the integration of the ReS2 nanosheet films in assemblies together with carbon nanotubes allows to fabricate electrodes for electrocatalysis for H2 production in both acid and alkaline conditions. Results from proof-of-principle devices show an electrocatalytic overpotential competitive with devices based on ReS2 produced by CVD, and even with MoS2 , WS2 , and MoSe2 electrocatalysts.

Knockout driven fragmentation of porphyrins.

We have studied collisions between tetraphenylporphyrin cations and He or Ne at center-of-mass energies in the range 50-110 eV. The experimental results were interpreted in view of density functional theory calculations of dissociation energies and classical molecular dynamics simulations of how the molecules respond to the He/Ne impact. We demonstrate that prompt atom knockout strongly contributes to the total destruction cross sections. Such impulse driven processes typically yield highly reactive fragments and are expected to be important for collisions with any molecular system in this collision energy range, but have earlier been very difficult to isolate for biomolecules.

Ion-induced molecular growth in clusters of small hydrocarbon chains.

We report on studies of collisions between 3 keV Ar+ projectile ions and neutral targets of isolated 1,3-butadiene (C4H6) molecules and cold, loosely bound clusters of these molecules. We identify molecular growth processes within the molecular clusters that appears to be driven by knockout processes and that could result in the formation of (aromatic) ring structures. These types of reactions are not unique to specific projectile ions and target molecules, but will occur whenever atoms or ions with suitable masses and kinetic energies collide with aggregates of matter, such as carbonaceous grains in the interstellar medium or aerosol nanoparticles in the atmosphere.

Influence of packing on low energy vibrations of densified glasses.

A comparative study of Raman scattering and low temperature specific heat capacity has been performed on samples of B2O3, which have been high-pressure quenched to go through different glassy phases having growing density to the crystalline state. It has revealed that the excess volume characterizing the glassy networks favors the formation of specific glassy structural units, the boroxol rings, which produce the boson peak, a broad band of low energy vibrational states. The decrease of boroxol rings with increasing pressure of synthesis is associated with the progressive depression of the excess low energy vibrations until their full disappearance in the crystalline phase, where the rings are missing. These observations prove that the additional soft vibrations in glasses arise from specific units whose formation is made possible by the poor atomic packing of the network.

Polypyrrole Solid-State Supercapacitors Drawn on Paper.

Solid-state supercapacitors with areal capacitance in the order of 100 mF⋅cm-2 are developed on paper substrates, using eco-friendly, low-cost materials and a simple technology. The electrochemically active material used as the electrode is prepared from a stable water-based ink, obtained by doping commercial polypyrrole (PPY) powder with dodecylbenzene sulfonic acid (DBSA), and characterized by optical and electrical measurements, Raman investigation and Atomic Force Microscopy. The PPY:DBSA ink can be directly applied on paper by means of rechargeable water pens, obtaining, after drying, electrically conducting solid state tracks. The PPY:DBSA layers are then interfaced to one another through a polymer gel based on potassium hydroxide and chitosan, acting both as the ion-conducting medium and as the separator. The areal capacitance of the devices developed by following such a simple rule can be improved when the PPY:DBSA ink is applied in combination with other nanostructured carbon material.

Monitoring of anthropogenic microplastic pollution in antarctic fish (emerald rockcod) from the Terranova Bay after a quarter of century.

Monitoring the occurrence of microplastic contamination in the Antarctic area is the key to implement policy measures for waste regulations in the research stations. Antarctic fish Trematomus bernachii is a suitable species for establishing microplastic contamination and for investigating changes over time in the concentration and type of microplastics in the Antarctic region. In this paper a total of 78 fish, caught during the 37th Italian Antarctic expedition (2021-2022) in the Ross Sea (Antarctica) were analysed. Different microfibers and dyes were identified by Raman spectroscopy and the results were compared with those obtained for fish sampled in 1998. Differences in polymer type emerged with a predominance of synthetic fibers with respect to natural ones. These changes appear to be related to the increased human activities in the Antarctica over the last twenty years and highlights the need to improve the environmental sustainability of the numerous research stations operating throughout that area.

Muscle and visceral fat infiltration: A potential mechanism to explain the worsening of obstructive sleep apnea with age.

STUDY OBJECTIVES: Aging is a major risk factor for obstructive sleep apnoea (OSA) and is associated with increased upper airway collapsibility, but the mechanisms are largely unknown. We hypothesized that the increase in OSA severity and upper airway collapsibility with age are partially mediated by upper airway, visceral and muscle fat infiltration. METHODS: Male subjects underwent full polysomnography, upper airway collapsibility determination (Pcrit) after sleep induction with midazolam, upper airway and abdominal computed tomography. Tongue and abdominal muscle fat infiltration were assessed by the determination of muscle attenuation with computed tomography. RESULTS: Eighty-four males with a wide range of age (47 ± 13 years, range 22-69 years) and apnea-hypopnea index (AHI) (30 [14-60] events/h, range 1-90 events/h), were studied. Younger and older males were grouped according to the mean age. Despite similar body mass-index (BMI), older subjects had higher AHI, higher Pcrit, larger neck and waist circumference, higher visceral and upper airway fat volumes (P < 0.01) as compared to younger subjects. Age was associated with OSA severity, Pcrit, neck and waist circumference, upper airway fat volume and visceral fat (P < 0.05), but not with BMI. Older subjects had lower tongue and abdominal muscle attenuation as compared to younger subjects (P < 0.001). Age was inversely associated with tongue and abdominal muscle attenuation, indicating muscle fat infiltration. CONCLUSIONS: The associations between age, upper airway fat volume, visceral and muscle fat infiltration may help to explain the worsening of OSA and increased upper airway collapsibility with aging.

Advances in Perovskites for Photovoltaic Applications in Space.

Perovskites have emerged as promising light harvesters in photovoltaics. The resulting solar cells (i) are thin and lightweight, (ii) can be produced through solution processes, (iii) mainly use low-cost raw materials, and (iv) can be flexible. These features make perovskite solar cells intriguing as space technologies; however, the extra-terrestrial environment can easily cause the premature failure of devices. In particular, the presence of high-energy radiation is the most dangerous factor that can damage space technologies. This Review discusses the status and perspectives of perovskite photovoltaics in space applications. The main factors used to describe the space environment are introduced, and the results concerning the radiation hardness of perovskites toward protons, electrons, neutrons, and γ-rays are presented. Emphasis is given to the physicochemical processes underlying radiation damage in such materials. Finally, the potential use of perovskite solar cells in extra-terrestrial conditions is discussed by considering the effects of the space environment on the choice of the architecture and components of the devices.

TiO2 Nanoparticles Dispersion in Block-Copolymer Aqueous Solutions: Nanoarchitectonics for Self-Assembly and Aggregation.

Achieving homogenous dispersion of nanoparticles inside a polymeric matrix is a great challenge for numerous applications. In the present study, we aim at understanding the role of different factors on the dispersion properties of TiO2 in pluronic F-127 mixtures. The mixtures were prepared with different pH and guest/host ratios and investigated by UV-Vis spectroscopy, dynamic light scattering, infrared spectroscopy and electrical conductivity. Depending on the preparation conditions, different amounts of TiO2 were loaded within the copolymer as quantitatively determined by UV-Vis spectroscopy. The different content of nanoparticles has direct implications on the gelation and micellization of pluronic analyzed by dynamic light scattering. The information derived on the self-assembly behavior was interpreted in relation to the infrared and conductivity measurements results. Together, these results shed light on the most favorable conditions for improving the nanoparticle dispersion inside the copolymer matrix and suggest a possible strategy to design functional nanoparticle-polymer systems.

Anthropogenic microparticles in the emerald rockcod Trematomus bernacchii (Nototheniidae) from the Antarctic.

Anthropogenic microparticles (AMs) were found for the first time in specimens of Trematomus bernacchii collected in 1998 in the Ross Sea (Antarctica) and stored in the Antarctic Environmental Specimen Bank. Most of the identified AMs were fibers of natural and synthetic origin. The natural AMs were cellulosic, the synthetic ones were polyester, polypropylene, polypropylene/polyester, and cellulose acetate. The presence of dyes in the natural AMs indicates their anthropogenic origin. Five industrial dyes were identified by Raman spectroscopy with Indigo occurring in most of them (55%). Our research not only adds further data to the ongoing knowledge of pollution levels in the Antarctic ecosystem, it provides an interesting snapshot of the past, highlighting that microplastics and anthropogenic fiber pollution had already entered the Antarctic marine food web at the end of the '90 s. These findings therefore establish the foundations for understand the changes in marine litter pollution over time.

Interface Engineering for Perovskite Solar Cells Based on 2D-Materials: A Physics Point of View.

The last decade has witnessed the advance of metal halide perovskites as a promising low-cost and efficient class of light harvesters used in solar cells (SCs). Remarkably, the efficiency of lab-scale perovskite solar cells (PSCs) reached a power conversion efficiency of 25.5% in just ~10 years of research, rivalling the current record of 26.1% for Si-based PVs. To further boost the performances of PSCs, the use of 2D materials (such as graphene, transition metal dichalcogenides and transition metal carbides, nitrides and carbonitrides) has been proposed, thanks to their remarkable optoelectronic properties (that can be tuned with proper chemical composition engineering) and chemical stability. In particular, 2D materials have been demonstrated as promising candidates for (i) accelerating hot carrier transfer across the interfaces between the perovskite and the charge extraction layers; (ii) improving the crystallization of the perovskite layers (when used as additives in the precursor solution); (iii) favoring electronic bands alignment through tuning of the work function. In this mini-review, we discuss the physical mechanisms underlying the increased efficiency of 2D material-based PSCs, focusing on the three aforementioned effects.

Polypyrrole and Graphene Nanoplatelets Inks as Electrodes for Flexible Solid-State Supercapacitor.

Flexible energy storage devices and supercapacitors in particular have become very attractive due to the growing demand for wearable consumer devices. To obtain supercapacitors with improved performance, it is useful to resort to hybrid electrodes, usually nanocomposites, that combine the excellent charge transport properties and high surface area of nanostructured carbon with the electrochemical activity of suitable metal oxides or conjugated polymers. In this work, electrochemically active conducting inks are developed starting from commercially available polypyrrole and graphene nanoplatelets blended with dodecylbenzenesulfonic acid. Films prepared by applying the developed inks are characterized by means of Raman measurements, Fourier Transform Infrared (FTIR) analysis, and Atomic Force Microscopy (AFM) investigations. Planar supercapacitor prototypes with an active area below ten mm2 are then prepared by applying the inks onto transparency sheets, separated by an ion-permeable nafion layer impregnated with lithium hexafluorophospate, and characterized by means of electrical measurements. According to the experimental results, the devices show both pseudocapacitive and electric double layer behavior, resulting in areal capacitance that, when obtained from about 100 mF⋅cm-2 in the sample with polypyrrole-based electrodes, increases by a factor of about 3 when using electrodes deposited from inks containing polypyrrole and graphene nanoplateles.

Two-Step Thermal Annealing: An Effective Route for 15 % Efficient Quasi-2D Perovskite Solar Cells.

Invited for this month's cover are collaborators from University of Pavia, École Polytechnique Fédérale de Lausanne, University of Messina and Istituto Italiano di Tecnologia. The cover picture shows the crystal structure of a Ruddlesden-Popper quasi-2D perovskite with chemical formula (PEA)2 MA39 Pb40 I121 (with PEA: phenylethylammonium and MA: methylammonium). The subscript 40 indicates the number of PbI6 octahedra separated by a double layer of PEA cations. Such quasi-2D perovskites exhibit efficient photovoltaic performances and higher stability with respect to the pure 3D counterpart (MAPbI3 ). This article is part of the Special Collection on "Perovskite Materials and Devices". Read the full text of the article at 10.1002/cplu.202000777.

Two-Step Thermal Annealing: An Effective Route for 15 % Efficient Quasi-2D Perovskite Solar Cells.

Low-dimensional perovskites (LDP) are nowadays recognized as promising materials for the realization of highly performing photovoltaic cells. However, issues related to film morphology, composition, crystal quality and material homogeneity limit the device performances and reproducibility. In this work, we implement a robust method for the deposition of a LDP mixing methylammonium (MA) and phenylethylammonium (PEA) cations to create the mixed system (PEA)2 MA39 Pb40 I121 by using a two-step thermal annealing treatment (at 60 and 100 °C). Our approach results in LDP films with high crystal quality and enhanced carrier lifetime, which double the power conversion efficiency of reference devices, reaching up to 15 %.