Use of a liquid chromatograph-ion trap mass spectrometer for end-group characterization of various polyethoxylate materials

The separation and detection properties of various ethoxylated polymers were investigated with atmospheric pressure ionization liquid chromatography/mass spectrometry (LC/MS). Interesting chromatographic elution behavior based on functionality was noted. LC/MS using in-source CID (collision-induced dissociation) and tandem mass spectrometry (MS/MS) detection was compared for end-group identification. Excellent end-group identification was achieved when the end-group molecular weight (MW) was greater than 100 Da and the average MW of the polymer was less than 400 Da by both MS/MS and in-source CID. In cases where the end-group MW was less than 100 Da, because of the low mass cut-off in a quadrapole ion trap analyzer, in-source CID produced the only characteristic end-group ions. The use of a dual scan function allowed investigation of the oligomeric distribution followed by a narrow low-mass scan using in-source CID to generate end-group information. This approach is applicable on instruments without MS/MS capability.     

PBAT/organoclay composite films: preparation and properties

Environmental problems caused by the increased waste associated with short-term use of plastic materials, particularly by the food packaging industry, prompted the search for biodegradable alternatives. This contribution studied one of these alternatives, poly(butylene adipate-co-terephthalate)—PBAT, a polymer that is fully biodegradable in common landfills, compounded with a small amount of Cloisite 20A organoclay. Materials were mixed in a laboratory internal mixer and films prepared in a chill roll extruder. Results show that the presence of organoclay does not increase degradation of the polymer matrix during processing, nor affects its crystallization characteristics. However, organoclay addition significantly diminished oxygen and carbon dioxide permeability of the films, making them a very interesting alternative for the food packaging industry.     

Tuning Sulfur Oxidation States on Thioether‐Bridged Peptide Macrocycles for Modulation of Protein Interactions

Thioethers, sulfoxides, and sulfonium ions, despite diverse physicochemical properties, all engage in noncovalent interactions with proteins. Thioether‐containing macrocycles are also attracting attention as protein–protein interaction (PPI) inhibitors. Here, we used a model PPI between α‐helical mixed lineage leukemia (MLL) protein and kinase‐inducible domain interacting (KIX) domain to evaluate oxidation effects on sulfurcontaining macrocycle structure, stability, and protein affinity. Desolvation effects from various polarity states were evaluated computationally and experimentally at the side chain, amino acid, and peptide level. Sulfur‐containing side chains spanned polarity ranges between all‐hydrocarbon and lactam bridges for modulating solubility, cellular uptake, and affinity. Helical propensity studies showed that, although oxidized sulfur‐containing side chains could be tolerated, conformational effects were sequence‐dependent. In some cases, proteolytic stability, binding capacity with KIX, and increased helicity were obtained as first steps toward developing PPI inhibitors.     

Integrating monitoring networks to obtain estimates of ground-level ozone concentrations --a proof of concept in Tuscany (central Italy)

Prior to 2000 a network of conventional ozone (O3) analysers existed in the Province of Firenze (Tuscany, central Italy). Between 2000 and 2004 the network was extended to incorporate a newly designed bioindicator network of tobacco plants (Nicotiana tabacum Bel W3). The objective was to set-up an integrated monitoring system to obtain estimates of ground-level O3 concentrations over the whole study area (3513 km2) in order to fill data gaps and cover reporting requirements. The existing conventional monitors were purposefully located mainly in urban areas. A total of 45 biomonitoring sites were selected using a systematic design to cover the target area. Two to five additional biomonitoring sites were co-located with conventional O3 analysers for calibration purposes, and five more sites for independent validation of modelled O3 concentrations. Visible Leaf Injury Index (LII) on the tobacco plants was significantly correlated (P: 0.018/0.0014) with a series of O3 exposure variables (mean of weekly 1-hour maxima, M1; mean of 7-hour means, M7; 24-hour mean, M24; and weekly AOT40). LII was found to be a significant predictor of weekly means of the O3 exposure variables with a standard error of estimates between 13.6 and 24.3 microg m(-3) (absolute values). LII was mapped with an ad-hoc spatial model over the study area at a 22 km grid resolution, and mapped values were used to predict O3 concentrations by means of a first order linear model. Results showed that high estimates of O3 (up to 188 microg m(-3) as mean of weekly maxima, M1) occurred more frequently in hilly and mountainous areas, with a spatial pattern changing on an annual basis. Predicted O3 concentrations were not significantly different from the measured concentrations (P: 0.34), although marked differences were observed for individual sites and years. The study provided evidence that integration of monitoring networks using different methods can be a viable option to obtain estimates of O3 concentrations over large areas.     

Polyamine Metabolism under Different Light Regimes in Wheat

Although the relationship between polyamines and photosynthesis has been investigated at several levels, the main aim of this experiment was to test light-intensity-dependent influence of polyamine metabolism with or without exogenous polyamines. First, the effect of the duration of the daily illumination, then the effects of different light intensities (50, 250, and 500 μmol m^–2 s^–1) on the polyamine metabolism at metabolite and gene expression levels were investigated. In the second experiment, polyamine treatments, namely putrescine, spermidine and spermine, were also applied. The different light quantities induced different changes in the polyamine metabolism. In the leaves, light distinctly induced the putrescine level and reduced the 1,3-diaminopropane content. Leaves and roots responded differently to the polyamine treatments. Polyamines improved photosynthesis under lower light conditions. Exogenous polyamine treatments influenced the polyamine metabolism differently under individual light regimes. The fine-tuning of the synthesis, back-conversion and terminal catabolism could be responsible for the observed different polyamine metabolism-modulating strategies, leading to successful adaptation to different light conditions.     

Direct and Indirect Effect of TGFβ on Treg Transendothelial Recruitment in HCC Tissue Microenvironment

The balance between anti-tumor and tumor-promoting immune cells, such as CD4+ Th1 and regulatory T cells (Tregs), respectively, is assumed to dictate the progression of hepatocellular carcinoma (HCC). The transforming growth factor beta (TGFβ) markedly shapes the HCC microenvironment, regulating the activation state of multiple leukocyte subsets and driving the differentiation of cancer associated fibroblasts (CAFs). The fibrotic (desmoplastic) reaction in HCC tissue strongly depends on CAFs activity. In this study, we attempted to assess the role of TGFβ on transendothelial migration of Th1-oriented and Treg-oriented CD4+ T cells via a direct or indirect, CAF-mediated mechanisms, respectively. We found that the blockage of TGFβ receptor I-dependent signaling in Tregs resulted in impaired transendothelial migration (TEM) of these cells. Interestingly, the secretome of TGFβ-treated CAFs inhibited the TEM of Tregs but not Th1 cells, in comparison to the secretome of untreated CAFs. In addition, we found a significant inverse correlation between alpha-SMA and FoxP3 (marker of Tregs) mRNA expression in a microarray analysis involving 78 HCCs, thus suggesting that TGFβ-activated stromal cells may counteract the trafficking of Tregs into the tumor. The apparent dual behavior of TGFβ as both pro- and anti-tumorigenic cytokines may add a further level of complexity to the mechanisms that regulate the interactions among cancerous, stromal, and immune cells within HCC, as well as other solid tumors, and contribute to better manipulation of the TGFβ signaling as a therapeutic target in HCC patients.     

Oxidative Stress and Respiratory Diseases in Preterm Newborns

Premature infants are exposed to increased generation of reactive oxygen species, and on the other hand, they have a deficient antioxidant defense system. Oxidative insult is a salient part of lung injury that begins as acute inflammatory injury in respiratory distress disease and then evolves into chronic and structural scarring leading to bronchopulmonary dysplasia. Oxidative stress is also involved in the pathogenesis of pulmonary hypertension in newborns through the modulation of the vascular tone and the response to pulmonary vasodilators, with consequent decrease in the density of the pulmonary vessels and thickening of the pulmonary arteriolar walls. Oxidative stress has been recognized as both a trigger and an endpoint for several events, including inflammation, hypoxia, hyperoxia, drugs, transfusions, and mechanical ventilation, with impairment of pulmonary function and prolonged lung damage. Redoxomics is the most fascinating new measure to address lung damage due to oxidative stress. The new challenge is to use omics data to discover a set of biomarkers useful in diagnosis, prognosis, and formulating optimal and individualized neonatal care. The aim of this review was to examine the most recent evidence on the relationship between oxidative stress and lung diseases in preterm newborns. What is currently known regarding oxidative stress-related lung injury pathogenesis and the available preventive and therapeutic strategies are also discussed.     

Gemeinsame österreichisch-ungarische Sedimentforschung im Rahmen des EFRE-Projektes SEDDON

The multiple uses of the Danube River for navigation, hydropower production and as a drinking water supply influence its ecological quality. Flow restrictions due to regulation as well as impacts on the sediment regime such as retention in the catchment area and interruption of the sediment continuum result in changes of the hydromorphological structures and can produce major problems in the context of sediment management. In light of these facts, cross-border investigations of sediment transport at the Danube River are called for. As there are no uniform research approaches shared by Austria and Hungary, the EU-funded project SEDDON (Sediment Research and Management at the Danube River) aims to compare different monitoring and modeling techniques used to determine sediment transport, and to develop mutual solutions. Further, the laboratory equipment currently used for hydraulic model experiments is evaluated and a research channel with a free flowing discharge of up to 10 m³/s without pumping will be constructed, allowing large-scale joint laboratory tests concerning sediment to be performed.