Evidence for the Band‐Edge Exciton of CuInS2 Nanocrystals Enables Record Efficient Large‐Area Luminescent Solar Concentrators

Ternary I‐III‐VI₂ nanocrystals (NCs), such as CuInS₂, are receiving attention as heavy‐metals‐free materials for solar cells, luminescent solar concentrators (LSCs), LEDs, and bio‐imaging. The origin of the optical properties of CuInS₂ NCs are however not fully understood. A recent theoretical model suggests that their characteristic Stokes‐shifted and long‐lived luminescence arises from the structure of the valence band (VB) and predicts distinctive optical behaviours in defect‐free NCs: the quadratic dependence of the radiative decay rate and the Stokes shift on the NC radius. If confirmed, this would have crucial implications for LSCs as the solar spectral coverage ensured by low‐bandgap NCs would be accompanied by increased re‐absorption losses. Here, by studying stoichiometric CuInS₂ NCs, it is revealed for the first time the spectroscopic signatures predicted for the free band‐edge exciton, thus supporting the VB‐structure model. At very low temperatures, the NCs also show dark‐state emission likely originating from enhanced electron‐hole spin interaction. The impact of the observed optical behaviours on LSCs is evaluated by Monte Carlo ray‐tracing simulations. Based on the emerging device design guidelines, optical‐grade large‐area (30×30 cm²) LSCs with optical power efficiency (OPE) as high as 6.8% are fabricated, corresponding to the highest value reported to date for large‐area devices.     

Solution‐Processed GaSe Nanoflake‐Based Films for Photoelectrochemical Water Splitting and Photoelectrochemical‐Type Photodetectors

Gallium selenide (GaSe) is a layered compound, which has been exploited in nonlinear optical applications and photodetectors due to its anisotropic structure and pseudodirect optical gap. Theoretical studies predict that its 2D form is a potential photocatalyst for water splitting reactions. Herein, the photoelectrochemical (PEC) characterization of GaSe nanoflakes (single‐/few‐layer flakes), produced via liquid phase exfoliation, for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in both acidic and alkaline media is reported. In 0.5 m H₂SO₄, the GaSe photoelectrodes display the best PEC performance, corresponding to a ratiometric power‐saved metric for HER (Φ_saved,HER) of 0.09% and a ratiometric power‐saved metric for OER (Φ_saved,OER) of 0.25%. When used as PEC‐type photodetectors, GaSe photoelectrodes show a responsivity of ≈0.16 A W^?1 upon 455 nm illumination at a light intensity of 63.5 µW cm^?2 and applied potential of ?0.3 V versus reversible hydrogen electrode (RHE). Stability tests of GaSe photodetectors demonstrated a durable operation over tens of cathodic linear sweep voltammetry scans in 0.5 m H₂SO₄ for HER. In contrast, degradation of photoelectrodes occurred in both alkaline and anodic operation due to the highly oxidizing environment and O₂‐induced (photo)oxidation effects. The results provide new insight into the PEC properties of GaSe nanoflakes for their exploitation in photoelectrocatalysis, PEC‐type photodetectors, and (bio)sensors.     

A decentralized kinematic control architecture for collaborative and cooperative multi-arm systems

In this paper a two-layer decentralized framework for kinematic control of cooperative and collaborative multi-robot systems is developed. The motion of the system is specified at the workpiece level, by adopting a task-oriented formulation for cooperative tasks. The first layer computes the motion of the single arms in the system. In detail, the control unit of each robot computes the end-effector motion references in a decentralized fashion on the basis of the knowledge of the assigned cooperative task and the motion references computed by its neighbors. Then, in the second layer, each control unit computes the reference joint motion of the corresponding manipulator from the end-effector reference motion. The approach is, then, tested in simulation on a work-cell composed by several manipulators, and experimentally on a dual-arm kinematically redundant work-cell composed by industrial manipulators.     

Boosting Perovskite Solar Cells Performance and Stability through Doping a Poly‐3(hexylthiophene) Hole Transporting Material with Organic Functionalized Carbon Nanostructures

Perovskite solar cells (PSCs) are demonstrating great potential to compete with second generation photovoltaics. Nevertheless, the key issue hindering PSCs full exploitation relies on their stability. Among the strategies devised to overcome this problem, the use of carbon nanostructures (CNSs) as hole transporting materials (HTMs) has given impressive results in terms of solar cells stability to moisture, air oxygen, and heat. Here, the use of a HTM based on a poly(3‐hexylthiophene) (P3HT) matrix doped with organic functionalized single walled carbon nanotubes (SWCNTs) and reduced graphene oxide in PSCs is proposed to achieve higher power conversion efficiencies (η = 11% and 7.3%, respectively) and prolonged shelf‐life stabilities (480 h) in comparison with a benchmark PSC fabricated with a bare P3HT HTM (η = 4.3% at 480 h). Further endurance test, i.e., up to 3240 h, has shown the failure of all the PSCs based on undoped P3HT, while, on the contrary, a η of ≈8.7% is still detected from devices containing 2 wt% SWCNT‐doped P3HT as HTM. The increase in photovoltaic performances and stabilities of the P3HT‐CNS‐based solar cell, with respect to the standard P3HT‐based one, is attributed to the improved interfacial contacts between the doped HTM and the adjacent layers.     

Isoenzymes of wheat o-diphenolase revealed by column isoelectric focusing

Summary Common wheat o-diphenolase at different purification steps has been submitted to column isoelectric focusing electrophoresis. The fraction purified with calcium phosphate gel shows multiple forms focused at pI 3.60, 4.95, 6.80, and 9.60. The enzyme activity and the purification degree of the four enzymatic components obtained have been calculated. The major fraction recovered after purification by chromatography on DEAE-cellulose does not display other multiple forms; however, it has some enzymatically inactive proteins well separated in the pH-gradient. The enzymatic protein, focused at pI 9.60, thus achieves a 1753-fold purification over the crude extract. The application of the technique allows a characterization of the wheat o-diphenolase and its recovery in highly purified form.

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Isoenzyme von o-Diphenoloxydase aus Weichweizen, identifiziert durch isoelektrisches Fokussieren über Säule

Zusammenfassung Weichweizen-o-Diphenoloxydasen verschiedener Reinigungsstufen wurden über eine Säule isoelektrisch focussiert. Das durch Calciumphosphatgel gereinigte Enzym (Fraktion C) zeigt 4 multiple Formen, focussiert bei pI 3,60; 4,65; 6,80 und 9,60. Die Aktivität und der Reinheitszustand von diesen vier Formen wurden berechnet. Die Fraktion C wurde durch Chromatographie über Cellulose weiter gereinigt. Die in größeren Mengen gewonnene Fraktion zeigte beim isoelektrischen Focussieren keine multiple Formen mehr, nur eine Trennung von enzymatisch inaktiven Proteinen beim pH-Gradienten. Das enzymatisch aktive Protein, focussiert bei pI 9,60, zeigte einen 1753 mal besseren Reinheitszustand als das Rohenzym. Die Anwendung dieser Technik erlaubt die Charakterisierung der Weichweizen-o-Diphenoloxydasen und ihre Gewinnung in einem hochgereinigten Zustand.

     

Peptides from water buffalo cheese whey induced senescence cell death via ceramide secretion in human colon adenocarcinoma cell line

Scope: Milk proteins are a source of bioactive peptides. Recent studies have indicated that protein‐derived peptides released in buffalo cheese acid whey exert a cytomodulatory effect in human epithelial colon cancer (CaCo2) cells. The aim of the present study was to explain the molecular mechanism involved in the response of CaCo2 cells to oxidative stress in the presence of peptide fractions of buffalo cheese whey, purified and characterized by mass spectrometry. Methods and results: We demonstrated that treatment of CaCo2 treated with H₂O₂ (H‐CaCo2) cells with a partially purified peptide sub‐fraction (f3) from buffalo cheese acid whey induced a reduction of mitochondrial superoxide anion with subsequent decrease in heat shock protein 70 and 90 expression. Moreover, we observed a 5‐fold decrease in cyclin A expression and cell cycle arrest in G1/G0 phases. These responses were associated with increased activity of alkaline phosphatase and beta‐galactosidase, markers of differentiation and senescence respectively. Conclusions: The structural characterization of the active peptide fraction and the elucidation of the effects induced by its treatment on H‐CaCo2 cells in vitro demonstrated an activity of this peptide sub‐fraction in the modulation of cell cycle, thus suggesting potential application for the development of nutraceuticals as well as health‐promoting functional foods.     

Formation and Degradation of Beta-casomorphins in Dairy Processing

Milk proteins including casein are sources of peptides with bioactivity. One of these peptides is beta-casomorphin (BCM) which belongs to a group of opioid peptides formed from β-casein variants. Beta-casomorphin 7 (BCM7) has been demonstrated to be enzymatically released from the A1 or B β-casein variant. Epidemiological evidence suggests the peptide BCM 7 is a risk factor for development of human diseases, including increased risk of type 1 diabetes and cardiovascular diseases but this has not been thoroughly substantiated by research studies. High performance liquid chromatography coupled to UV-Vis and mass spectrometry detection as well as enzyme–linked immunosorbent assay (ELISA) has been used to analyze BCMs in dairy products. BCMs have been detected in raw cow's milk and human milk and a variety of commercial cheeses, but their presence has yet to be confirmed in commercial yoghurts. The finding that BCMs are present in cheese suggests they could also form in yoghurt, but be degraded during yoghurt processing. Whether BCMs do form in yoghurt and the amount of BCM forming or degrading at different processing steps needs further investigation and possibly will depend on the heat treatment and fermentation process used, but it remains an intriguing unknown.