Toxic or beneficial? What is the role of food-relevant selenium species selenoneine?

Selenium (Se) is an essential trace element that is ubiquitously present in the environment in small concentrations. Essential functions of Se in the human body are manifested through the wide range of proteins, containing selenocysteine as their active center. Such proteins are called selenoproteins which are found in multiple physiological processes like antioxidative defense and the regulation of thyroid hormone functions. Therefore, Se deficiency is known to cause a broad spectrum of physiological impairments, especially in endemic regions with low Se content. Nevertheless, being an essential trace element, Se could exhibit toxic effects, if its intake exceeds tolerable levels. Accordingly, this range between deficiency and overexposure represents optimal Se supply. However, this range was found to be narrower than for any other essential trace element. Together with significantly varying Se concentrations in soil and the presence of specific bioaccumulation factors, this represents a noticeable difficulty in the assessment of Se epidemiological status. While Se is acting in the body through multiple selenoproteins, its intake occurs mainly in form of small organic or inorganic molecular mass species. Thus, Se exposure not only depends on daily intake but also on the respective chemical form, in which it is present. The essential functions of selenium have been known for a long time and its primary forms in different food sources have been described. Nevertheless, analytical capabilities for a comprehensive investigation of Se species and their derivatives have been introduced only in the last decades. A new Se compound was identified in 2010 in the blood and tissues of bluefin tuna. It was called selenoneine (SeN) since it is an isologue of naturally occurring antioxidant ergothioneine (ET), where Se replaces sulfur. In the following years, SeN was identified in a number of edible fish species and attracted attention as a new dietary Se source and potentially strong antioxidant. Studies in populations whose diet largely relies on fish revealed that SeN represents the main non-protein bound Se pool in their blood. First studies, conducted with enriched fish extracts, already demonstrated the high antioxidative potential of SeN and its possible function in the detoxification of methylmercury in fish. Cell culture studies demonstrated, that SeN can utilize the same transporter as ergothioneine, and SeN metabolite was found in human urine. Until recently, studies on SeN properties were severely limited due to the lack of ways to obtain the pure compound. As a predisposition to this work was firstly a successful approach to SeN synthesis in the University of Graz, utilizing genetically modified yeasts. In the current study, by use of HepG2 liver carcinoma cells, it was demonstrated, that SeN does not cause toxic effects up to 100 M concentration in hepatocytes. Uptake experiments showed that SeN is not bioavailable to the used liver cells. In the next part a blood-brain barrier (BBB) model, based on capillary endothelial cells from the porcine brain, was used to describe the possible transfer of SeN into the central nervous system (CNS). The assessment of toxicity markers in these endothelial cells and monitoring of barrier conditions during transfer experiments demonstrated the absence of toxic effects from SeN on the BBB endothelium up to 100 M concentration. Transfer data for SeN showed slow but substantial transfer. A statistically significant increase was observed after 48 hours following SeN incubation from the blood-facing side of the barrier. However, an increase in Se content was clearly visible already after 6 hours of incubation with 1 M of SeN. While the transfer rate of SeN after application of 0.1 M dose was very close to that for 1 M, incubation with 10 M of SeN resulted in a significantly decreased transfer rate. Double-sided application of SeN caused no side-specific transfer of SeN, thus suggesting a passive diffusion mechanism of SeN across the BBB. This data is in accordance with animal studies, where ET accumulation was observed in the rat brain, even though rat BBB does not have the primary ET transporter OCTN1. Investigation of capillary endothelial cell monolayers after incubation with SeN and reference selenium compounds showed no significant increase of intracellular selenium concentration. Speciesspecific Se measurements in medium samples from apical and basolateral compartments, as good as in cell lysates, showed no SeN metabolization. Therefore, it can be concluded that SeN may reach the brain without significant transformation. As the third part of this work, the assessment of SeN antioxidant properties was performed in Caco-2 human colorectal adenocarcinoma cells. Previous studies demonstrated that the intestinal epithelium is able to actively transport SeN from the intestinal lumen to the blood side and accumulate SeN. Further investigation within current work showed a much higher antioxidant potential of SeN compared to ET. The radical scavenging activity after incubation with SeN was close to the one observed for selenite and selenomethionine. However, the SeN effect on the viability of intestinal cells under oxidative conditions was close to the one caused by ET. To answer the question if SeN is able to be used as a dietary Se source and induce the activity of selenoproteins, the activity of glutathione peroxidase (GPx) and the secretion of selenoprotein P (SelenoP) were measured in Caco-2 cells, additionally. As expected, reference selenium compounds selenite and selenomethionine caused efficient induction of GPx activity. In contrast to those SeN had no effect on GPx activity. To examine the possibility of SeN being embedded into the selenoproteome, SelenoP was measured in a culture medium. Even though Caco-2 cells effectively take up SeN in quantities much higher than selenite or selenomethionine, no secretion of SelenoP was observed after SeN incubation. Summarizing, we can conclude that SeN can hardly serve as a Se source for selenoprotein synthesis. However, SeN exhibit strong antioxidative properties, which appear when sulfur in ET is exchanged by Se. Therefore, SeN is of particular interest for research not as part of Se metabolism, but important endemic dietary antioxidant.     

Can support by digital technologies stimulate intrapreneurial behaviour? The moderating role of management support for innovation and intrapreneurial self-efficacy

Drawing on theorising on digital technologies as external enablers of entrepreneurial activities and an interactionist perspective on corporate entrepreneurship, this article examines the relationship between digital technology support and employee intrapreneurial behaviour. We propose that management support for innovation as an organisational characteristic and intrapreneurial self-efficacy as an individual characteristic moderate this relationship. Findings from a metric conjoint experiment with 1360 decisions nested within 85 employees showed that support by social media, support by collaborative technologies, and support by intelligent decision support systems were significant predictors of employee intrapreneurial behaviour. However, the relative impact of support by these digital technologies varied with different levels of management support for innovation and intrapreneurial self-efficacy.     

Application issue of anthraquinonoid vat dyes on inherently flame-resistant fabrics

The vat dyeing process of specific fabrics with protective, inherently fire retardant properties that have a high content of aramid fibres in their composition, is presented. The research was performed on fabric samples that differ in raw material composition and aramid content. The samples were dyed in raw form (group 1) as well as after pretreatment with alkaline scouring (group 2). Measured limiting oxygen index (LOI) values showed that the selected fabrics meet the properties of inherently fire retardant fabrics. Dyeing was performed with Indanthren® Olive Green HB (manufactured by DyStar) vat dye, in exhaustion process, with a bath ratio of 1:30. The dye concentration was 3%, and sodium-hydrosulphite (Na₂S₂O₄) was used as a reducing agent. The colouristic analyses were performed based on spectrophotometric measurement and results interpretation according to CIELab system. The evaluation of primary tactile properties was performed which show an increase of smoothness and softness after scouring and dyeing. Also, wash fastness as well as light fastness tests have shown satisfactory fastness properties.     

Laser-Induced,Green and Biocompatible Paper-Based Devices for Circular Electronics

The growing usage and consumption of electronics-integrated items into the daily routine has raised concerns on the disposal and proper recycling of these components. Here, a fully sustainable and green technology for the fabrication of different electronics on fruit-waste derived paper substrate, is reported. The process relies on the carbonization of the topmost surface of different cellulose-based substrates, derived from apple-, kiwi-, and grape-based processes, by a CO₂ laser. By optimizing the lasing parameters, electronic devices, such as capacitors, biosensors, and electrodes for food monitoring as well as heart and respiration activity analysis, are realized. Biocompatibility tests on fruit-based cellulose reveal no shortcoming for on-skin applications. The employment of such natural and plastic-free substrate allows twofold strategies for electronics recycling. As a first approach, device dissolution is achieved at room temperature within 40 days, revealing transient behavior in natural solution and leaving no harmful residuals. Alternatively, the cellulose-based electronics is reintroduced in nature, as possible support for plant seeding and growth or even soil amendment. These results demonstrate the realization of green, low-cost and circular electronics, with possible applications in smart agriculture and the Internet-of-Thing, with no waste creation and zero or even positive impact on the ecosystem.     

Light‐induced cooperative electron–proton transfer in hydrogen‐bonded networks of N,N‐diaryl substituted 1,4‐bisimines and meso‐1,2‐diaryl‐1,2‐ethanediols

The 1:1 cocrystallization of 1,4‐diaryl‐1,4‐bisimines (Ar–CHN–CH₂‐)₂ 4 – 11 and substituted meso‐1,2‐diaryl‐1,2‐ethanediols 1 – 3 leads to supramolecular structures in which the diol is hydrogen bonded by one of its hydroxy groups to an imine nitrogen atom of a 1,4‐bisimine. The second functionality in each molecule leads to the generation of ladderlike polymeric structures where each molecule of the diol is linked to two molecules of the 1,4‐bisimine and vice versa. If the diol carries electron donor groups in the aromatic residue and the 1,4‐bisimine correspondingly acceptor groups, then charge transfer interactions are observed. The excited CT complex which corresponds to a radical ion pair is stabilized by migration of a proton of a hydroxy group to the nitrogen atom of an imino group. This is supported by the appearance of a N–H vibration in the IR spectra. The reorganization is also accompanied by changes in the UV/Vis spectra and by the generation of paramagnetism in the crystalline material. The results represent a type of photochromism which has its origin in a light‐induced cooperative electron–proton transfer. The photochromism is thermally reversible.     

Stereolithographic 3D Printing of Ceramics: Challenges and Opportunities for Structural Integrity

This article reviews the current activities at the Montanuniversität Leoben on the design, processing, and characterization of 3D printed advanced ceramics using the lithography-based manufacturing technology. An overview of the challenges and the opportunities offered to improve the mechanical properties of printing ceramics is given. Their brittle failure is analyzed within the framework of linear elastic fracture mechanics, considering specific aspects of additive manufacturing. Several issues associated with the printing process are addressed, such as surface quality, geometry control, influence of printing directions, as well as the need to establish testing protocols for 3D printed parts. Based on the layer-by-layer capabilities of the stereolithographic process, bio-inspired material design concepts are discussed aiming to enhance the mechanical resistance of 3D-printed ceramics. By tailoring the layer architecture and microstructure of the parts, high strength and fracture resistance may be achieved.     

Validation and Uncertainty Assessment of a Software-Integrated Workflow for pH Calculations

Accurate pH calculations are essential for scientists across different disciplines to design optimal reactor solutions, but they can be arduous to calculate for complex acid-base solutions. Visual Water is a powerful software tool that provides accurate pH calculations with automated mathematical uncertainty analysis. Its workflow is presented and validated using acids and bases, showing a deviation of < 0.2 pH units between measured and calculated pH values. This highlights the software's reliability, which can help to simplify the work of non-experts in water chemistry.