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Amino-alkylphosphonic acid-grafted TiO2 materials are of increasing interest in a variety of applications such as metal sorption, heterogeneous catalysis, CO2 capture, and enzyme immobilization. To date, systematic insights into the synthesis-properties-performance correlation are missing for such materials, albeit giving important know-how towards their applicability and limitations. In this work, the impact of the chain length and modification conditions (concentration and temperature) of amino-alkylphosphonic acid-grafted TiO2 on the surface properties and adsorption performance of palladium is studied. Via grafting with aminomethyl-, 3-aminopropyl-, and 6-aminohexylphosphonic acid, combined with the spectroscopic techniques (DRIFT, 31P NMR, XPS) and zeta potential measurements, differences in surface properties between the C1, C3, and C6 chains are revealed. The modification degree decreases with increasing chain length under the same synthesis conditions, indicative of folded grafted groups that sterically shield an increasing area of binding sites with increasing chain length. Next, all techniques confirm the different surface interactions of a C1 chain compared to a C3 or C6 chain. This is in line with palladium adsorption experiments, where only for a C1 chain, the adsorption efficiency is affected by the precursor concentration used for modification. The absence of a straightforward correlation between the number of free NH2 groups and the adsorption capacity for the different chain lengths indicates that other chain-length-specific surface interactions are controlling the adsorption performance. The increasing pH stability in the order of C1 < C3 < C6 can possibly be associated to a higher fraction of inaccessible hydrophilic sites due to the presence of folded structures. Lastly, the comparison of adsorption performance and pH stability with 3-aminopropyl(triethoxysilane)-grafted TiO2 reveals the applicability of both grafting methods depending on the envisaged pH during sorption. ispartof: ACS OMEGA vol:7 issue:49 pages:45409-45421 ispartof: location:United States status: published

A comprehensive two-dimensional liquid chromatography-based biomimetic platform (LCxLC) has been developed and validated for drug diffusion studies. Human serum albumin (HSA) and immobilized artificial membrane (IAM) were thereby used in the first (1D) and second (2D) separation dimension, respectively. While the former was meant to emulate the blood, the latter was instead intended to mimic the intestinal mucosa epithelium. Therefore, the experimental conditions, i.e. pH, temperature and buffer composition, were modulated to reflect faithfully in vivo conditions. 30 compounds, whose effective intestinal permeability (Peff) assayed in situ on humans by a validated technique was known from the literature, were used as model drugs. A good and orthogonal separation was achieved for the whole dataset, although for a better distribution of the most polar compounds in the elution window a segmented gradient elution program had to be employed. Interestingly, the passively uptaken compounds having the most favourable Peff populated a specific area of the 2D plots, implying that the affinity for HSA and IAM has to lie in specific ranges in order for a compound to be satisfactorily absorbed from the intestinal lumen. Although these results should be regarded as preliminary, this work paves an entirely new and unprecedented way to profile pharmaceutically relevant compounds for their in vivo absorption and distribution potential.

Modification of metal oxides with organophosphonic acids (PAs) provides the ability to control and tailor the surface properties. The metal oxide phosphonic acid bond (M-O-P) is known to be stable under harsh conditions, making PAs a promising candidate for the recovery of metals from complex acidic leachates. The thiol functional group is an excellent regenerable scavenging group for these applications. However, the research on organophosphonic acid grafting with thiol groups is very limited. In this study, four different metal sorbent materials were designed with different thiol surface coverages. An aqueous-based grafting of 3-mercaptopropylphosphonic acid (3MPPA) on mesoporous TiO2 was employed. Surface grafted thiol groups could be obtained in the range from 0.9 to 1.9 groups per nm(2). The different obtained surface properties were studied and correlated to the Pd adsorption performance. High Pd/S adsorption efficiencies were achieved, indicating the presence of readily available sorption sites. A large difference in their selectivity towards Pd removal from a spend automotive catalyst leachate was observed due to the co-adsorption of Fe on the titania support. The highest surface coverage showed the highest selectivity (K-d: 530 mL g(-1)) and adsorption capacity (Q(max): 0.32 mmol g(-1)) towards Pd, while strongly reducing the co-adsorption of Fe on remaining TiO2 sites. This work is supported by the Research Foundation Flanders (FWO) and Hasselt University via the Hercules project AUHL/15/ 2 – GOH3816N. Part of the presented work was executed within the PLATIRUS project, which has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement No 730224. This work reects only the author's views and the agency is not responsible for any use that may be made of the information it contains. The authors are grateful to all project partners for discussions and input, and in particular to Monolithos Ltd (Athens. Greece) for providing the spend automotive catalyst material used in this work. V. Meynen acknowledges the Research FoundationFlanders (FWO) for project K801621N. All calculations were performed using the Hopper HPC infrastructure at the CalcUA core facility of the University of Antwerp, a division of the Flemish Supercomputer Center VSC, funded by the Hercules Foundation, the Flemish Government (department EWI) and the University of Antwerp. Furthermore, the authors would like to acknowledge S. Defoss´e and K. Leyssens for the N2 sorption measurements, J. Lievens and A. Deibe Varela for the Pd sorption experiments, K. Duyssens and W. Brusten for the ICP measurements and M. Mertens for the XRD measurements.

Comprehensive two-dimensional liquid chromatography (LC×LC) can provide enhanced resolving power and higher peak capacities for the separation of complex samples. The transfer of fractions of too high eluotropic strength from the first dimension, however, can lead to peak broadening. This process is related to the column dimensions, the flow rates, mobile phase compositions, and stationary phase compatibility. Temperature-responsive LC (TRLC) uses a smart polymer coupled to silica (poly(N-isopropylacrylamide), pNIPAAm), that exhibits a change in polarity upon modest variations in column temperature. Retention is thus modulated by temperature and not by organic solvents, allowing for the use of purely aqueous mobile phases. As these aqueous mobile phases depict a very low eluotropic strength on a reversed-phase column, it facilitates band refocusing at the second-dimension column head in TRLC×RPLC. One of the remaining obstacles of TRLC is the long analysis time. In this research, the potential of this column combination in terms of analyte refocusing will be exploited. First, it is shown that upwards flow gradients can be implemented in the first dimension of TRLC×RPLC. As the flow in the second dimension is maintained at a constant level, a first-dimension flow gradient does not lead to impaired sensitivity and has no negative effects on the resulting peak size. Then, the novel combination of a downwards temperature gradient with an upwards flow gradient will be introduced to speed up the analyses further. Analysis time was, depending on the method used, reduced by 36–54%, as demonstrated by the analysis of mixtures of food additives, phenolic compounds, and small molecule pharmaceuticals mimicking impurity analysis at a 0.05% level.

Dysphagia is a frequent symptom in Parkinson's disease (PD). Thickening liquids facilitates safe swallowing, however, low treatment compliance is a major issue, due to patients' dislike of thickened liquids. Some studies suggest a negative impact of gum-based thickeners, currently most used in clinical practice, on sensory properties compared to starch-based thickeners. This has not yet been investigated in PD. This study's aim was to compare taste, texture, and aroma of gum-based and starch-based thickened soups in participants with PD. Gum-based resource thicken up clear (RTUC) and starch-based kitchen products potato starch (PS) and quinoa flour (QF) were evaluated in broccoli soup. Texture, aroma, and taste were characterized by rheology, volatile, and sensory profiling. Thickened soups were evaluated in participants with PD and controls through a paired comparison test. Reduced release of 61.4%, 46.2%, and 38.5% of volatiles was observed after thickening with RTUC, PS, and QF, respectively. Overall taste intensity was reduced in RTUC- and PS-thickened soup, respectively. Taste and aroma of PS-thickened soup were considered more intense by 70.3% and 63.8% of all participants, respectively (n = 36 PD, n = 41 controls), 56.3% preferred the PS-thickened soup's texture . Taste and aroma of QF-thickened soup were considered more intense by 68.1% and 65.6% of all participants, respectively (n = 47 PD, n = 31 controls), 58.0% preferred the QF-thickened soup's texture. Starch-based thickeners demonstrated higher taste and aroma intensity. However, volatile and sensory profiling demonstrated reduced taste and aroma in all thickeners. Combining kitchen products with flavor enhancers may increase palatability of thickened beverages.

Tropical soils are mostly poor in phosphorus and sometimes in nitrogen and potassium. Arbuscular mycorrhizae increase the efficiency of chemical fertilizers applied to crops, and this work is part of this framework. NPK (nitrogen-phosphorus-potassium) was applied at 100 kg per ha and 200 kg per ha alone or in combination with inoculum from sorghum or leek in soil (pH 4.28). The trial was conducted on a 3 × 3 split-plot design with 3 replicates. Plant height, number of leaves and chlorophyll level in the leaves were evaluated. The frequency of root colonization by mycorrhizal fungi was also studied. The number of pods per plant, the number of seeds per pod and the yield were also evaluated. The results showed that vegetative parameters increased with the addition of fertilizers while production parameters varied little with fertilizers but significantly, when these fertilizers were associated with mycorrhizal inoculum. Treatments with 200 kg NPK combined with sorghum inoculum produced 512 kg of beans per ha, while 200 kg NPK alone produced 278 kg of beans per ha.

Industrial chicory (Cichorium intybus L.) is mainly grown for inulin production. To enhance production and uniformity, hybrid cultivars are preferred. Therefore, a controlled pollination system and homozygous parental lines are needed. The most desirable pollination control system is cytoplasmic male sterility (CMS). A new, naturally induced CMS has been reported by Van der Veken et al. (2018). To regenerate homozygous parental lines of modern industrial chicory cultivars, different haploid inducing techniques have been compared and evaluated. The only successful method was intergeneric hybridization with Cicerbita alpina (Dore et al., 1996), yielding haploid plants. Here we show that protoplast regeneration is an efficient tool for chromosome doubling of these haploids. The presented method can be used for chromosome doubling of slowly developing haploids.

Modification of metal oxides with organophosphonic acids (PAs) provides the ability to control and tailor the surface properties. The metal oxide phosphonic acid bond (M–O–P) is known to be stable under harsh conditions, making PAs a promising candidate for the recovery of metals from complex acidic leachates. The thiol functional group is an excellent regenerable scavenging group for these applications. However, the research on organophosphonic acid grafting with thiol groups is very limited. In this study, four different metal sorbent materials were designed with different thiol surface coverages. An aqueous-based grafting of 3-mercaptopropylphosphonic acid (3MPPA) on mesoporous TiO2 was employed. Surface grafted thiol groups could be obtained in the range from 0.9 to 1.9 groups per nm2. The different obtained surface properties were studied and correlated to the Pd adsorption performance. High Pd/S adsorption efficiencies were achieved, indicating the presence of readily available sorption sites. A large difference in their selectivity towards Pd removal from a spend automotive catalyst leachate was observed due to the co-adsorption of Fe on the titania support. The highest surface coverage showed the highest selectivity (Kd: 530 mL g−1) and adsorption capacity (Qmax: 0.32 mmol g−1) towards Pd, while strongly reducing the co-adsorption of Fe on remaining TiO2 sites.

Amino-alkylphosphonic acid grafted TiO2 materials are of increasing interest in a variety of applications such as metal sorption, heterogeneous catalysis, CO2 capture and enzyme immobilization. To date, systematic insights into the synthesis-properties-performance correlation are missing for such materials, albeit giving important know-how towards their applicability and limitations. In this work, the impact of the chain length and modification conditions (concentration and temperature) of amino-alkylphosphonic acid grafted TiO2 on the surface properties and adsorption performance of palladium is studied. Via grafting with aminomethyl-, 3-aminopropyl- and 6-aminohexylphosphonic acid, combined with the spectroscopic techniques (DRIFT, 31P NMR, XPS) and zeta potential measurements, differences in surface properties between the C1, C3 and C6 chain are revealed. The modification degree decreases with increasing chain length under the same synthesis conditions, indicative of folded grafted groups that sterically shield an increasing area of binding sites with increasing chain length. Next, all techniques confirm the different surface interactions of a C1 chain compared to a C3 or C6 chain. This is in line with palladium adsorption experiments, where only for a C1 chain, the adsorption efficiency is affected by the precursor concentration used for modification. The absence of a straightforward correlation between the number of free NH2 groups and the adsorption capacity for the different chain lengths, indicates that other chain-length specific surface interactions are controlling the adsorption performance. The increasing pH stability in the order of C1 < C3 < C6 can possibly be associated to a higher fraction of inaccessible hydrophilic sites due to the presence of folded structures. Lastly, the comparison of adsorption performance and pH stability with 3-aminopropyl(triethoxysilane) grafted TiO2 reveals the applicability of both grafting methods depending on the envisaged pH during sorption.

Shallow-depth sequencing of cell-free DNA, an inexpensive and standardized approach to obtain molecular information on tumors non-invasively, has been insufficiently explored for the diagnosis of lymphoma and disease follow-up. This study collected 318 samples, including longitudinal liquid and paired solid biopsies, from a prospectively- recruited cohort of 38 Hodgkin lymphoma (HL) and 85 aggressive B-cell non-HL patients, represented by 81 diffuse large B-cell lymphoma (DLBCL) cases. Following sequencing, copy number alterations and viral read fractions were derived and analyzed. At diagnosis, liquid biopsies showed detectable copy number alterations in 84.2% of HL patients (88.6% for classical HL) and 74.1% of DLBCL patients. Of the DLBCL patients, copy number profiles between liquid-solid pairs were highly concordant (r=0.815±0.043); and, compared to tissue, HL liquid biopsies had abnormalities with higher amplitudes (P=0.010). This implies that tumor DNA is more abundant in plasma. Additionally, 39.5% of HL and 13.6% of DLBCL cases had a significantly elevated number of plasma Epstein-Barr virus DNA fragments, achieving a sensitivity of 100% compared to the current standard. A longitudinal analysis determined that, when detectable, copy number patterns were similar across (re)staging moments in refractory or relapsed patients. Further, the overall profile anomaly correlated highly with the total metabolic tumor volume (P

Human activities benefit a range of animal species, the resulting presence of which in cities can have negative societal consequences. One example are food subsidies, which buffer natural variation in food availability and allow these species to maintain larger populations. These buffers will likely gain importance under future environmental change whereby natural food sources become decreasingly available. To inform on the current importance of different habitats for a bird reliant on human-made food subsidies (Lesser Black-backed Gull Larus fuscus), and its possible population response toward changes in climate and the availability of these subsidies, we characterized population-level short-term responses to variation in drivers of local food availability, both natural (weather related) and anthropogenic (fisheries activity). We expected foraging effort to vary in relation to local wind speed and soil moisture, as well as to the alternation of fisheries activity between weekdays and weekends. Individuals were predicted to adjust their foraging habitat use in response to these environmentally driven variations in effort. To this end, we analyzed GPS tracking data of 45 breeding individuals, between 2013 and 2018, nesting in the Port of Zeebrugge, Belgium. Effort was approximated as the energy expenditure rate per trip, the daily time spent away from the colony and the trip frequency, which were analyzed by means of linear mixed effects models. Habitat use per trip was compared between marine, agricultural fields and built-up areas (cities, industry and cattle farms), in a multinomial logistic model. Marine areas and agricultural fields were most frequently exploited, but all considered stressors (wind, dry conditions and inactivity of fisheries) resulted in a higher use of built-up areas. Stronger winds increased the energetic cost of foraging at sea, and thus diminished the use of marine areas, as also did the inactivity of fisheries in weekends. Dry conditions diminished the use of fields and decreased trip frequency. Built-up areas thus constitute a buffer for the variation in food availability at sea and in agricultural fields. The expected increase in frequency and severity of extreme weather events (storms and drought) under global change, combined with the disappearance of discards, may therefore result in a long-term increase in the use of urban habitats by opportunistic large Gull species.

We use GPS tracking data on 28 adult Lesser Black-backed Gulls to show how these long-lived birds benefit from experience during migration. We found that stopover fidelity across years strongly depended on food source reliability. Birds using more reliable food sources thereby showed more consistent migratory behavior across years and covered significantly less distance while foraging during stopovers. There is a growing awareness that experience may play a major role in migratory decisions, especially in long-lived species. However, empirical support remains to date scarce. Here, we use multiyear GPS-tracking data on 28 adult Lesser Black-backed Gulls (Larus fuscus), a long-lived species for which migratory strategies typically consist of a series of long stopovers, to assess how experience affects interannual variation in stopover selection. We expect that food source reliability should play a pivotal role, as it both reduces the uncertainty on food availability across years, and enables for more efficient foraging during stopovers by reducing searching efforts. We found that during stopovers gulls indeed developed high fidelity to particular foraging locations, which strongly reduced the daily distance travelled for foraging. When revisiting stopovers in consecutive years, birds used over 80% of foraging locations from the previous year. Although the average fidelity to stopovers across years was a high as 85%, stopovers where birds showed high foraging site fidelity were up to 60% more likely to be revisited compared to stopover with low foraging site fidelity. Accordingly, birds using more stopovers with reliable foraging opportunities showed significantly less interannual variation in their stopover use than birds using stopovers with less reliable foraging opportunities. Our results thus highlight the need to further deepen our understanding of the role of cognitive processes in individual variation in migratory behavior.

A promising strategy for the inhibition of the hydrogen evolution reaction along with the stabilization of the electrocatalyst in electrochemical CO2 reduction cells involves the application of a nanoscale amorphous carbon layer on top of the active catalyst layer in a gas diffusion electrode. Without modifying the chemical nature of the electrocatalyst itself, these amorphous carbon layers lead to the stabilization of the electrocatalyst, and a significant improvement with respect to the inhibition of the hydrogen evolution reaction was also obtained. The faradaic efficiencies of hydrogen could be reduced from 31.4 to 2.1% after 1 h of electrolysis with a 5 nm thick carbon layer. Furthermore, the impact of the carbon layer thickness (5–30 nm) on this inhibiting effect was investigated. We determined an optimal thickness of 15 nm where the hydrogen evolution reaction was inhibited and a decent stability was obtained. Next, a thickness of 15 nm was selected for durability measurements. Interestingly, these durability measurements revealed the beneficial impact of the carbon layer already after 6 h by suppressing the hydrogen evolution such that an increase of only 37.9% exists compared to 56.9% without the use of an additional carbon layer, which is an improvement of 150%. Since carbon is only applied afterward, it reveals its great potential in terms of electrocatalysis in general.

A simple, alternative, catalyst preparation method was proposed in order to combine the properties of photoactive and stable TiO2 with state-of-the art of IrO2 for the oxygen evolution reaction (OER). IrO2 nanoparticles were obtained in the process of photodeposition on the surface of TiO2 powder by UV illumination from appropriate Ir salt aqueous solution. Physicochemical characterization of the resulting IrO2/TiO2 composite, containing 25% w/w Ir, was carried out by transmission electron microscopy (TEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour of the prepared IrO2/TiO2 catalyst was compared with that of commercial unsupported IrO2. Cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry (CA) were performed to identify the surface electrochemistry and OER of the IrO2/TiO2 catalyst. Electrochemical impedance spectroscopy (EIS) was used to determine uncompensated and charge transfer resistance. CA experiments were carried out in order to evaluate the stability of the IrO2/TiO2 composite during OER in the dark and under UV light irradiation. The photodeposition method on a TiO2 support resulted in 1–2 nm Ir nanoparticles, very well dispersed on the surface and in their oxidized state (IrO2). Electrochemical results indicated that despite its lower conductivity, the IrO2/TiO2 composite exhibits comparable intrinsic electrocatalytic activity for OER with that of the commercial IrO2 catalyst. It was found that under UV light irradiation there has been improvement of the stability of the IrO2/TiO2 performance during oxygen evolution (presumably due to sustained activation of reactive species via photogenerated holes or OH radicals) as well as current enhancement (due to the interaction between the photogenerated holes in TiO2 support and IrO2 nanoparticles). These would be beneficial effects in prolonged water photo-electrolysis.

Temperature-responsive liquid chromatography (TRLC) allows for extensive retention and selectivity tuning through temperature in HPLC. This is achieved through the use of stationary phases comprising a temperature-responsive polymer which is able to undergo a reversible change of its surface from hydrophilic to hydrophobic upon an increase of the temperature. This interesting behaviour allows for retention behaviour to be controlled purely by a change in temperature,1,2 allowing for conventionally used mobile phase gradients to be replaced by temperature gradients. As a result, this technique allows for analyses to be performed under purely aqueous conditions.3,4 However, despite the promising nature of such form of retention control under isocratic mobile phase conditions, TRLC can suffer from excessive retention upon analysis of highly apolar solutes even at lower column temperatures where the surface of the polymer behaves hydrophilic. This is related both to a residual apolarity of the polymer chain, as well as due to the high inherent logP values and reduced water solubility of the more highly apolar compounds. Despite this apparent drawback, analyses in TRLC have already been performed under non-purely aqueous conditions and the use of co-solvents to the water have been proven to be possible.5–7 However, the exact impact for introduction of organic solvents was not yet investigated in a systematic way. Therefore, in this study the advantages and drawbacks for the use of organic co-solvents (methanol and acetonitrile) in TRLC was assessed on two types of temperature-responsive phases: poly-N-N-isopropylacrylamide (PNIPAAm) and poly-N-isopropylacrylamide (PNNPAAm). For this, the influence of organic co-solvents on the efficiency of the stationary phase as well as the cloud point temperature of the polymers is investigated with two representative test mixtures comprising of parabens and apolar steroids. [1] Lynen, F. et al. Evaluation of the temperature responsive stationary phase poly(N-isopropylacrylamide) in aqueous LC for the analysis of small molecules. Chromatographia 66, 143–150 (2007). [2] Ayano, E. et al. Study of temperature-responsibility on the surfaces of a thermo-responsive polymer modified stationary phase. J. Chromatogr. A 1119, 51–57 (2006). [3] Satti, A. J. et al. Tunable temperature responsive liquid chromatography through thiolactone-based immobilization of poly(N-isopropylacrylamide). J. Chromatogr. A 1426, 126–132 (2015). [4] Baert, M. et al. Exploration of the selectivity and retention behavior of alternative polyacrylamides in temperature responsive liquid chromatography. (2020). doi:10.1021/acs.analchem.0c01321 [5] Lamprou, A., Gavriilidou, A. F. M., Storti, G., Soos, M. & Morbidelli, M. Application of polymeric macroporous supports for temperature-responsive chromatography of pharmaceuticals. J. Chromatogr. A 1407, 90–99 (2015). [6] Song, Y. X., Wang, J. Q., Su, Z. X. & Chen, D. Y. High-performance liquid chromatography on silica modified with temperature-responsive polymers. Chromatographia 54, 208–212 (2001). [7] Go, H., Sudo, Y., Hosoya, K., Ikegami, T. & Tanaka, N. Effects of Mobile-Phase Composition and Temperature on the Selectivity of Poly(N-isopropylacrylamide)-Bonded Silica Gel in Reversed-Phase Liquid Chromatography. Anal. Chem. 70, 4086–4093 (1998).

Introduction/Background* The vascular endothelial growth factor (VEGF) plays an import role in emergence and spread of high-grade serous tubo-ovarian carcinoma (HGSTOC). Bevacizumab, a monoclonal antibody targeting VEGFA, has therefore been added to first-line treatment of advanced HGSTOC. We here map the dynamics of different stromal components of the tumour microenvironment under chemotherapy with or without bevacizumab. Methodology We performed single-cell RNA-sequencing on 62,461 cells sampled from 6 HGSTOC patients before and after neo-adjuvant platin-based chemotherapy with or without bevacizumab. We identified 44 stromal cell subclusters on which we applied Mixed-effects modelling of Associations of Single Cells to identify cell populations associated with bevacizumab exposure and pathological response using the chemotherapeutic response score. Result(s)* Our study revealed diverse stromal cell subsets associated with bevacizumab exposure. The addition of bevacizumab to frontline chemotherapy increased the odds of endothelial cell (ECs) prevalence by a 3-fold (OR 2.91, 95%CI:2.36-3.58; p Conclusion* We here provide initial evidence on the mechanisms underlying early response to bevacizumab and frontline chemotherapy in HGSTOC, including tip cell impairment, reduced hypoxia and a decrease in regulatory T cells. However, bevacizumab exposure increased the influx of PDGFC-expressing macrophages capable to bypass VEGFA-dependent angiogenesis.

Transient Receptor Potential (TRP) channels excel in cellular sensing as they allow rapid ion influx across the plasma membrane in response to a variety of extracellular cues. Recently, a distinct TRP expression signature was observed in stromal cells (ESC) and epithelial cells (EEC) of the endometrium, a tissue in which cell phenotypic plasticity is essential for normal functioning. However, it is unknown whether TRP channel expression is subject to the phenotypic switching that occurs during epithelial to mesenchymal transition (EMT) and mesenchymal to epithelial transition (MET), and whether TRP channel expression is associated with aggressive phenotypes in endometrial cancer (EC). Here, we induced EMT and MET in vitro using in primary EEC and ESC, respectively, and analyzed expression and functionality of TRP channels using RT-qPCR and intracellular Ca2+ imaging. The outcome of these experiments showed a strong association between TRPV2 and TRPC1 expression and the mesenchymal phenotype, whereas TRPM4 expression correlated with the epithelial phenotype. In line herewith, increased TRPV2 and TRPC1 expression levels were observed in both primary and metastatic EC biopsies and in primary EC cells with a high EMT status, indicating an association with an aggressive tumor phenotype. Remarkably, TRPV2 expression in primary EC biopsies was associated with tumor invasiveness and cancer stage. In contrast, increased TRPM4 expression was observed in EC biopsies with a low EMT status and less aggressive tumor phenotypes. Taken together, this dataset demonstrated for the first time that TRP channel expression is strongly linked to cellular phenotypes of the endometrium, and that phenotypic transitions caused by either experimental manipulation or malignancy could alter this expression in a predictable manner. These results implicate that TRP channels are viable biomarkers to identify high-risk EC, and potential targets for EC treatment.

Phenolic compounds are an interesting class of natural products because of their proposed contribution to health benefits of foods and beverages and as a bio-source of organic (aromatic) building blocks. Phenolic extracts from natural products are often highly complex and contain compounds covering a broad range in molecular properties. While many 1D-LC and mass spectrometric approaches have been proposed for the analysis of phenolics, this complexity inevitably leads to challenging identification and purification. New insights into the composition of phenolic extracts can be obtained through online comprehensive two-dimensional liquid chromatography (LC × LC) coupled to photodiode array and mass spectrometric detection. However, several practical hurdles must be overcome to achieve high peak capacities and to obtain robust methods with this technique. In many LC × LC configurations, refocusing of analytes at the head of the 2D column is hindered by the high eluotropic strength of the solvent transferred from the 1D to the 2D, leading to peak breakthrough or broadening. LC × LC combinations whereby a purely aqueous mobile phase is used in the 1D and RPLC is used in the 2D are unaffected by these phenomena, leading to more robust methods. In this contribution, the combination of temperature-responsive liquid chromatography (TRLC) with RPLC is used for the first time for the analysis of phenolic extracts of natural origin to illustrate the potential of this alternative combination for natural product analyses. The possibilities of the combination are investigated through analysis of wine extracts by TRLC × RPLC-DAD and TRLC × RPLC-ESI-MS.

Mycorrhization is known to have beneficial effects on growth vigour and protection against certain pathogens in several plant species including plantains, which has so far been little studied in the Kisangani forest region. This study aimed to determine the importance and biodiversity of mycorrhizae under plantains in the slash-and-burn and non-burn cropping systems. This research was carried out in two experimental sites located at Kisangani region in DR Congo, namely: Simi-Simi and Masako villages. Thus, 96 samples each consisting of the plantain roots and the rhizospheric soil, as well as 4 soil samples were analysed. The mycorrhization rate of the roots was calculated and sporal description to determine the mycorrhizal taxa was carried out. The overall mycorrhization rate was 40.75%. The mycorrhizal spore number was higher in non-burned fields than burned fields. There was no significant difference between the 2 practices at Masako, but the difference was significant at Simi-Simi. Moreover, vigorous plants revealed higher number of spores than non-vigorous plants. There was a significant difference between the two types of plantains. Genera of mycorrhizal spores identified were Glomus (54.96%), Gigaspora (27.84%), Acaulospora (10.50%) and Scutellospora (6.71%). The mycorrhizal sporal numbers significantly varied among plantain cultivars. The presence of tree species in the plantain plantations at high density positively influenced mycorrhization to a small extent. The above sporal genera showed a positive correlation with pH, nitrogen, clay, sand and phosphorus and negatively with organic carbon. These results showed the possibility of isolating high-performance biofertilizing mycorrhizal strains from vigorous plantain crops. Key words: Mycorrhizae, plantain, Kisangani, slash field, burned field, non-burned field.

Carbohydrate partitioning from leaves to sink tissues is essential for plant growth and development. The maize (Zea mays) recessive carbohydrate partitioning defective28 (cpd28) and cpd47 mutants exhibit leaf chlorosis and accumulation of starch and soluble sugars. Transport studies with 14C-sucrose (Suc) found drastically decreased export from mature leaves in cpd28 and cpd47 mutants relative to wild-type siblings. Consistent with decreased Suc export, cpd28 mutants exhibited decreased phloem pressure in mature leaves, and altered phloem cell wall ultrastructure in immature and mature leaves. We identified the causative mutations in the Brittle Stalk2-Like3 (BK2L3) gene, a member of the COBRA family, which is involved in cell wall development across angiosperms. None of the previously characterized COBRA genes are reported to affect carbohydrate export. Consistent with other characterized COBRA members, the BK2L3 protein localized to the plasma membrane, and the mutants condition a dwarf phenotype in dark-grown shoots and primary roots, as well as the loss of anisotropic cell elongation in the root elongation zone. Likewise, both mutants exhibit a significant cellulose deficiency in mature leaves. Therefore, BK2L3 functions in tissue growth and cell wall development, and this work elucidates a unique connection between cellulose deposition in the phloem and whole-plant carbohydrate partitioning.Funding InformationThe research was supported by US National Science Foundation Plant Genome Research Program grants (IOS-1025976 and IOS-1444448) to DMB.

Background: The end-tidal carbon dioxide (ETCO2) concentration during resuscitation (CPR) of an out-of-hospital cardiac arrest (OHCA) has an increasingly well-known prognostic value. Nevertheless, ...

For the corrosion protection of steel rebars in concrete, five different molybdate-phosphate conversion coatings were prepared, by changing the molybdate-phosphate ratio in the conversion baths. Their composition and morphology were studied with GD-OES, XPS, Raman spectroscopy and SEM-EDX and a schematic representation of their structure is suggested. Further, the corrosion resistance properties of the coatings were evaluated in a simulated concrete pore solution (CPS) containing chlorides, using anodic polarization measurements. Thanks to the elaborated surface analysis their corrosion behaviour could be correlated to their structure. The results show that by altering the molybdate-phosphate ratio the structure and, consequently, the corrosion protection properties change significantly. By optimizing this ratio a twofold protection mechanism could be attained, demonstrating both good barrier properties and consistent with active corrosion protection.

While competition is generally presumed to promote intraspecific niche diversification, populations of many apparent generalist species still exhibit considerable individual variation in foraging specialization. This suggests that different cost-benefit trade-offs may underlie individual variation in foraging specialization. Indeed, while specialization may improve foraging efficiency by a better knowledge of the spatio-temporal availability of resources, individuals may also become more vulnerable to fluctuations in these resources. In this study, we used multiyear GPS tracking data of 19 Herring Gulls (Larus argentatus) breeding along the Belgian coast to assess whether foraging effort and reproductive success varied among different levels of foraging specialization. First, we quantified spatial and habitat specialization during incubation and chick rearing for 31 individual breeding cycles during which birds raised young until the age of 21 days. Next, we tested whether spatial and habitat specialization were related to the daily distance covered (as a proxy for foraging effort), and to chick growth (as a proxy for reproductive success). We found that birds primarily varied in their extent of habitat specialization. Habitat specialization was associated with reduced daily distances covered and increased offspring growth rates, in particular the growth rate of the youngest chicks. Yet, positive effects of habitat specialization on chick growth decreased at high levels of spatial specialization. Our results thus demonstrate fitness benefits of foraging specialization during our 5-year study period, but also highlight the need for longer-term studies as environmental changes may cause benefits to vary throughout a lifetime. GPS tracking reveals that specialization reduces foraging effort and increases the breeding success of Belgian Herring Gulls.

Background: Escherichia coli W3110 and a group of six isogenic derivatives, each displaying distinct specific rates of glucose consumption were characterized to determine levels of GFP production and population heterogeneity. These strains have single or combinatory deletions in genes encoding phosphoenolpyruvate:sugar phosphotransferase system (PTS) permeases as PtsG and ManX, as well as common components EI, Hpr protein and EIIA, also the non-PTS Mgl galactose/glucose ABC transporter. They have been transformed for expressing GFP based on a lac-based expression vector, which is subject to bistability. Results: These strains displayed specific glucose consumption and growth rates ranging from 1.75 to 0.45 g/g h and 0.54 to 0.16 h-1, respectively. The rate of acetate production was strongly reduced in all mutant strains when compared with W3110/pV21. In bioreactor cultures, wild type W3110/pV21 produced 50.51 mg/L GFP, whereas strains WG/pV21 with inactive PTS IICBGlc and WGM/pV21 with the additional inactivation of PTS IIABMan showed the highest titers of GFP, corresponding to 342 and 438 mg/L, respectively. Moreover, we showed experimentally that bistable expression systems, as lac-based ones, induce strong phenotypic segregation among microbial populations. Conclusions: We have demonstrated that reduction on glucose consumption rate in E. coli leads to an improvement of GFP production. Furthermore, from the perspective of phenotypic heterogeneity, we observed in this case that heterogeneous systems are also the ones leading to the highest performance. This observation suggests reconsidering the generally accepted proposition stating that phenotypic heterogeneity is generally unwanted in bioprocess applications.[Figure not available: see fulltext.], SCOPUS: ar.j, info:eu-repo/semantics/published

Poly(2-alkyl/aryl-2-oxazoline)s (PAOx) are a class of cytocompatible polymers that have received growing interest over the past decade. This growing interest can mainly be attributed to their greater chemical versatility compared to other cytocompatible polymers, such as poly(ethylene glycol) (PEG), that originate from the diverse set of monomers compatible with the cationic ring-opening polymerization. Within this contribution we focus on the modification of methyl ester functional PAOx, on which we recently reported the quantitative conversion of methyl ester side chain bearing PAOx via direct amidation for a number of amines. While this approach is robust, it can be challenging to introduce certain amines, due to their high cost, poor solubility or additional functionalities. Here we evaluated three alternative amidation approaches of methyl ester side chain bearing PAOx with tyramine in terms of selectivity and quantitative conversion to the respective secondary amides. The amidation proceeded successfully via DMTMM coupling, PFP-activation and TBD catalysis, although only the latter 2 methods selectively yielded the desired product. In summary, we present valuable alternatives to our earlier reported method, contributing further to the biomedical application potential of PAOx.

The production of composite or double-layer (DL) bread was optimized to reduce the amount of the chemical preservative calcium propionate. It was validated using sourdough (SD) in the crust (0–80 g/100 g crust dough). Par-baked (PB) and fully baked (FB) breads were evaluated based on their shelf-life extending, bread technological and sensorial properties. The shelf-life of PB bread was increased with ≥60 g SD/100 g crust dough for air packaged and ≥20 g SD for modified atmosphere packaged (MAP) breads. Use of 60 g SD/100 g crust dough was sufficient to achieve the same level of preservation with or without MAP. Par-baked and fully baked bread were mould free for respectively 7 and 30 days using 60 g sourdough in 100 g crust dough. Specific volume decreased for PB bread containing 40–60 g SD/100 g crust dough and for FB bread with 80 g SD/100 g crust dough. Accordingly, crumb hardness was impaired under the latter conditions.

Natural gas as a fuel for heavy duty applications has advantages in terms of lower CO2 and PM compared to Diesel applications. This makes operating heavy duty applications on natural gas attractive. However, in terms of aftertreatment, the challenge becomes one of controlling methane emissions over a range of vehicle operating conditions. Methane light off occurs > 400 °C and requires highly loaded precious metal catalysts (Raj in Johnson Matthey Technol Rev 60:228–235, 2016). This temperature is manageable in stoichiometric applications. However, for lean operating applications, the exhaust temperature can be below this posing a significant challenge for CH4 control. When operating lean the NOx emissions also become a challenge hence the requirement for a dedicated NOx control system. As part of the EU funded HD GAS project, an aftertreatment system was developed to meet the challenges of both NOx and CH4 control for a lean operating natural gas heavy duty engine. Fundamental studies were performed by the academic partners focusing on CH4 and NOx control, with the implementation and calibration on the engine performed by the industrial partners. This paper will discuss the steps taken from fundamental catalyst characterisation and catalyst specification to full size catalyst implementation onto a newly developed natural gas engine in order to meet Euro VI emissions legislation.

Background Parental care benefits the offspring, but comes at a cost for each parent, which in biparental species gives rise to a conflict between partners regarding the within-pair distribution of care. Pair members could avoid exploitation by efficiently keeping track of each other’s efforts and coordinating their efforts. Parents may, therefore, space their presence at the nest, which could also allow for permanent protection of the offspring. Additionally, they may respond to their partner’s previous investment by co-adjusting their efforts on a trip-to-trip basis, resulting in overall similar parental activities within pairs. Methods We investigated the coordination of parental care measured as nest attendance and foraging effort in the Lesser black-backed gull (Larus fuscus), a species with long nest bouts that performs extended foraging trips out of sight of their partner. This was achieved by GPS-tracking both pair members simultaneously during the entire chick rearing period. Results We found that the timing of foraging trips (and hence nest attendance) was coordinated within gull pairs, as individuals left the colony only after their partner had returned. Parents did not match their partner’s investment by actively co-adjusting their foraging efforts on a trip-by-trip basis. Yet, pair members were similar in their temporal and energetic investments during chick rearing. Conclusion Balanced investment levels over a longer time frame suggest that a coordination of effort may not require permanent co-adjustment of the levels of care on a trip-to-trip basis, but may instead rather take place at an earlier stage in the reproductive attempt, or over integrated longer time intervals. Identifying the drivers and underlying processes of coordination will be one of the next necessary steps to fully understand parental cooperation in long-lived species.

Colloidal Cu-Ag nanocrystals measuring less than 10 nm across are promising candidates for integration in hybrid CO2 reduction reaction (CO2RR) interfaces, especially in the context of tandem catalysis and selective multicarbon (C2-C3) product formation. In this work, we vary the synthetic-ligand/copper molar ratio from 0.1 to 1.0 and the silver/copper atomic ratio from 0 to 0.7 and study the variations in the nanocrystals' size distribution, morphology and reactivity at rates of ≥100 mA cm-2 in a gas-fed recycle electrolyzer operating under neutral to mildly basic conditions (0.1-1.0 M KHCO3). High-resolution electron microscopy and spectroscopy are used in order to characterize the morphology of sub-10 nm Cu-Ag nanodimers and core-shells and to elucidate trends in Ag coverage and surface composition. It is shown that Cu-Ag nanocrystals can be densely dispersed onto a carbon black support without the need for immediate ligand removal or binder addition, which considerably facilitates their application. Although CO2RR product distribution remains an intricate function of time, (kinetic) overpotential and processing conditions, we nevertheless conclude that the ratio of oxygenates to hydrocarbons (which depends primarily on the initial dispersion of the nanocrystals and their composition) rises 3-fold at moderate Ag atom % relative to Cu NCs-based electrodes. Finally, the merits of this particular Cu-Ag/C system and the recycling reactor employed are utilized to obtain maximum C2-C3 partial current densities of 92-140 mA cm-2 at -1.15 VRHE and liquid product concentrations in excess of 0.05 wt % in 1 M KHCO3 after short electrolysis periods.

Information on soil properties is crucial for soil preservation, the improvement of food security, and the provision of ecosystem services. In particular, for the African continent, spatially explicit information on soils and their ability to sustain these services is still scarce. To address data gaps, infrared spectroscopy has achieved great success as a cost-effective solution to quantify soil properties in recent decades. Here, we present a mid-infrared soil spectral library (SSL) for central Africa (CSSL) that can predict key soil properties, allowing for future soil estimates with a minimal need for expensive and time-consuming wet chemistry. Currently, our CSSL contains over 1800 soil samples from 10 distinct geoclimatic regions throughout the Congo Basin and along the Albertine Rift. For the analysis, we selected six regions from the CSSL, for which we built predictive models for total carbon (TC) and total nitrogen (TN) using an existing continental SSL (African Soil Information Service, AfSIS SSL; n=1902) that does not include central African soils. Using memory-based learning (MBL), we explored three different strategies at decreasing degrees of geographic extrapolation, using models built with (1) the AfSIS SSL only, (2) AfSIS SSL combined with the five remaining central African regions, and (3) a combination of AfSIS SSL, the remaining five regions, and selected samples from the target region (spiking). For this last strategy we introduce a method for spiking MBL models. We found that when using the AfSIS SSL only to predict the six central African regions, the root mean square error of the predictions (RMSEpred) was between 3.85–8.74 and 0.40–1.66 g kg−1 for TC and TN, respectively. The ratio of performance to the interquartile distance (RPIQpred) ranged between 0.96–3.95 for TC and 0.59–2.86 for TN. While the effect of the second strategy compared to the first strategy was mixed, the third strategy, spiking with samples from the target regions, could clearly reduce the RMSEpred to 3.19–7.32 g kg−1 for TC and 0.24–0.89 g kg−1 for TN. RPIQpred values were increased to ranges of 1.43–5.48 and 1.62–4.45 for TC and TN, respectively. In general, predicted TC and TN for soils of each of the six regions were accurate; the effect of spiking and avoiding geographical extrapolation was noticeably large. We conclude that our CSSL adds valuable soil diversity that can improve predictions for the Congo Basin region compared to using the continental AfSIS SSL alone; thus, analyses of other soils in central Africa will be able to profit from a more diverse spectral feature space. Given these promising results, the library comprises an important tool to facilitate economical soil analyses and predict soil properties in an understudied yet critical region of Africa. Our SSL is openly available for application and for enlargement with more spectral and reference data to further improve soil diagnostic accuracy and cost-effectiveness.

Colloidal Cu–Ag nanocrystals measuring less than 10 nm across are promising candidates for integration in hybrid CO2 reduction reaction (CO2RR) interfaces, especially in the context of tandem catalysis and selective multicarbon (C2–C3) product formation. In this work, we vary the synthetic-ligand/copper molar ratio from 0.1 to 1.0 and the silver/copper atomic ratio from 0 to 0.7 and study the variations in the nanocrystals’ size distribution, morphology and reactivity at rates of ≥100 mA cm–2 in a gas-fed recycle electrolyzer operating under neutral to mildly basic conditions (0.1–1.0 M KHCO3). High-resolution electron microscopy and spectroscopy are used in order to characterize the morphology of sub-10 nm Cu–Ag nanodimers and core–shells and to elucidate trends in Ag coverage and surface composition. It is shown that Cu–Ag nanocrystals can be densely dispersed onto a carbon black support without the need for immediate ligand removal or binder addition, which considerably facilitates their application. Although CO2RR product distribution remains an intricate function of time, (kinetic) overpotential and processing conditions, we nevertheless conclude that the ratio of oxygenates to hydrocarbons (which depends primarily on the initial dispersion of the nanocrystals and their composition) rises 3-fold at moderate Ag atom % relative to Cu NCs-based electrodes. Finally, the merits of this particular Cu–Ag/C system and the recycling reactor employed are utilized to obtain maximum C2–C3 partial current densities of 92–140 mA cm–2 at −1.15 VRHE and liquid product concentrations in excess of 0.05 wt % in 1 M KHCO3 after short electrolysis periods.

Recently, interest has been directed towards the grafting of metal oxides with organophosphonic acids bearing terminal amine groups to extend the functionality and applicability of these materials. Previous reports mainly focus on the application perspective, while a detailed characterization of the surface properties at the molecular level and the correlation with the synthesis conditions are missing. In this work, mesoporous TiO2 powder is grafted with 3-aminopropylphosphonic acid (3APPA) under different concentrations (20, 75, 150 mM) and temperatures (50, 90 °C) and compared with propylphosphonic acid (3PPA) grafting to unambiguously reveal the impact of the amine group on the surface properties. A combination of complementary spectroscopic techniques and Density Functional Theory - Periodic Boundary Conditions (DFT/PBC) calculations are used. At 90 °C and high concentrations, lower modification degrees are obtained for 3APPA compared to 3PPA, due to amine-induced surface interactions. Both X-ray Photoelectron Spectroscopy (XPS) and Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy reveal that both NH2 and NH3+ groups are present, with also contributions of NH2 groups involved in hydrogen bonding interactions. A similar ratio of NH2/NH3+ (65:35) is obtained irrespective of the modification conditions, suggesting similar relative contributions of different surface conformations. Calculated adsorption energies from DFT calculations on 3APPA adsorption on anatase (101) in relation to the water coverage reveals a coexistence of various structures with the amine group involved in intra-adsorbate, inter-adsorbate and adsorbate-surface interactions. Further validation is obtained from the strong overlap of different 31P environments represented by the broad band (35-12 ppm) in experimental 31P Nuclear Magnetic Resonance (NMR) spectra and calculated 31P chemical shifts of all modelled monodentate and bidentate structures. Structures related to the tridentate binding mode are not formed due to geometric restrictions of the anatase (101) facet applied as model support in the calculations. Nevertheless, they could be present in the experimental samples as they are composed of anatase (representing multiple crystal facets) and an amorphous titania fraction.

The integration of high-aspect-ratio (AR) supervias (SV) into a 3 nm node test vehicle, bypassing an intermediate 21 nm pitch layer, is demonstrated. Place-and-route (PnR) simulations of the Power Delivery Network (PDN) proved IR-drop reduction with respect to the stacked-via configuration. SV first and SV last integration approaches were electrically tested using full barrierless ruthenium (Ru) on a dielectric low-k 3.0. A maximum AR = 3.8 was achieved with ~2.4 times lower resistance than the alternative stacked-via configuration. Thermal shock tests produced no SV failure after 1000 cycles between -50 °C and 125 °C, and 250 hours. Time-dependent-dielectric-breakdown (TDDB) tests between SV and M2 lines gave a TTF 63.2% (at 1 MV/cm) > 10 years, when 3 M2 tracks are blocked.

Animal models indicate that butyrate might reduce motor symptoms in Parkinson’s disease. Some dietary fibers are butyrogenic, but in Parkinson’s disease patients their butyrate stimulating capacity is unknown. Therefore, we investigated different fiber supplements’ effects on short-chain fatty acid production, along with potential underlying mechanisms, in Parkinson’s patients and age-matched healthy controls. Finally, it was investigated if this butyrate production could be confirmed by using fiber-rich vegetables. Different fibers (n = 40) were evaluated by in vitro fermentation experiments with fecal samples of Parkinson’s patients (n = 24) and age-matched healthy volunteers (n = 39). Short-chain fatty acid production was analyzed by headspace solid-phase micro-extraction gas chromatography-mass spectrometry. Clostridium coccoides and C. leptum were quantified through 16S-rRNA gene-targeted group-specific qPCR. Factors influencing short-chain fatty acid production were investigated using linear mixed models. After fiber fermentation, butyrate concentration varied between 25.6 ± 16.5 µmol/g and 203.8 ± 91.9 µmol/g for Parkinson’s patients and between 52.7 ± 13.0 µmol/g and 229.5 ± 42.8 µmol/g for controls. Inulin had the largest effect, while xanthan gum had the lowest production. Similar to fiber supplements, inulin-rich vegetables, but also fungal β-glucans, stimulated butyrate production most of all vegetable fibers. Parkinson’s disease diagnosis limited short-chain fatty acid production and was negatively associated with butyrate producers. Butyrate kinetics during 48 h fermentation demonstrated a time lag effect in Parkinson’s patients, especially in fructo-oligosaccharide fermentation. Butyrate production can be stimulated in Parkinson’s patients, however, remains reduced compared to healthy controls. This is a first step in investigating dietary fiber’s potential to increase short-chain fatty acids in Parkinson’s disease.

In this study, the possibilities of temperature responsive x reversed phase liquid chromatography (TRLC x RPLC) are assessed in terms of pharmaceutical impurity analysis. Due to the increased peak capacity per unit time they offer, two-dimensional LC approaches are gaining relevance for the analysis of complex drug formulations. Because the latter depicts a larger predisposition for the occurrence of an increased number of impurities, current 1D-HPLC approaches often prove insufficient. Since many LC x LC methods are limited by modulation, solvent compatibility, orthogonality, and sensitivity issues, the combination of TRLC x RPLC is explored in this work for pharmaceutical impurity analysis. As this combination of a purely aqueous separation with RPLC allows for systematic and optimization-free refocusing in the second dimension, it opens possibilities for generic LC x LC requiring minimal to no method development, in this way overcoming a major perceived contemporary hurdle of LC x LC. The approach is demonstrated with a representative mixture of 17 solutes comprising 11 corticosteroids and 6 progestogens. Orthogonality and peak capacities were assessed on three RP core-shell column selectivities (Poroshell EC-C18, phenyl-hexyl and PFP). Although the TRLC x EC-C18 combination offered somewhat better orthogonality, the combination with the PFP column proved the best for the separation at hand. Depending on the composition of the mixture, the use of full, shifted, or segmented gradients allowed facile optimization of the separation. The developed platform allowed detection of the impurities at the 0.05% level compared to a selected main compound, while also opening up possibilities for analysis of formulations comprising two active ingredients. (c) 2020 Elsevier B.V. All rights reserved.

Temperature responsive liquid chromatography (TRLC) allows for separation of organic solutes in purely aqueous mobile phases whereby retention is controlled through temperature. The vast majority of the work has thus far been performed on poly[N-isopropylacrylamide] (PNIPAAm)-based columns, while the performance of other temperature responsive polymers has rarely been compared under identical conditions. Therefore, in this work, two novel TRLC phases based on poly[N-n-propylacrylamide] (PNNPAAm) and poly[N,N-diethylacrylamide] (PDEAAm) are reported and compared to the state of the art PNIPAAm based column. Optimal comparison is thereby obtained by the use of controlled radical polymerizations, identical molecular weights, and by maximizing carbon loads on the silica supporting material. Analysis of identical test mixtures of homologue series and pharmaceutical samples revealed that PNNPAAm performs in a similar way as PNIPAAm while offering enhanced retention and a shift of the useable temperature range toward lower temperatures. PDEAAm offers a range of novel possibilities as it depicts a different selectivity, allowing for enhanced resolution in TRLC in, for example, coupled column systems. Reduced plate heights of 3 could be obtained on the homemade columns, offering the promise for reasonable column efficiencies in TRLC despite the use of bulky polymers as stationary phases in HPLC.

Demands for high strength aluminum alloys processed by Laser Powder Bed Fusion (LPBF) are high and keep rising. However, expensive new alloy compositions or crack formation in existing alloys hinder its wide applicability. It is known from recent work that addition of grain refiners leads to a fine grain structure enabling crack-free, high strength aluminum LPBF parts. In this research, 1 wt% of Zr was added to Al7050. Furthermore, an excess of Zn was provided in the powder material to compensate for Zn losses during LPBF and to maintain the Mg:Zn ratio required for formation of strong and coherent MgZn2 precipitates. After a solution and aging heat treatment, the newly developed alloy has an ultimate tensile strength of 500 MPa and Vickers micro-hardness of 200Hv-0.5kg. Although the elongation at break of the resulting parts is limited, this research shows promising results for future alloy design of affordable high strength aluminum alloys to be processed by LPBF. ispartof: Material Design & Processing Communications status: Published online

It has previously been demonstrated that peripheral blood lymphocytes of healthy women carrying BRCA1 or BRCA2 mutations exhibit increased chromosomal radiosensitivity, which is characterized by an enhanced formation of micronuclei. These results suggest that the deficient repair of DNA double‑strand breaks may also occur in breast epithelial cells of women exhibiting a reduced expression of wild‑type BRCA1/BRCA2 proteins due to the presence of germline mutations in BRCA1/2 genes. The aim of this study was to further investigate in vitro the effects of the reduced expression of BRCA1 and BRCA2 in MCF10A human non‑tumorigenic breast epithelial cells, tentatively mimicking the phenotype of heterozygous cells of carriers of BRCA1/2 mutations. By lentivirus‑mediated RNA interference, the stable reduction of BRCA1 and BRCA2 expression at the mRNA and protein level was achieved, thus generating the BRCA1i and BRCA2i cell lines. In these cells, homologous recombination was impaired, as significantly lower yields of RAD51 foci were obtained following exposure to 2 Gy ionizing radiation compared to the control MCF10A cells (BRCA1i cells, 58% reduction; BRCA2i cells, 64% reduction). Moreover, in the BRCA1i and BRCA2i cells, a dose‑dependent increase in micronuclei was observed compared to the cells which were not subjected to gene knockdown. Cell viability was also affected by partial BRCA1/2 knockdown. On the whole, the findings of this study indicated that in cells with a reduced BRCA1 or BRCA2 expression, the impairment of homologous recombination resulted in a >50% decrease in RAD51 foci following irradiation and increased chromosomal abnormalities (micronuclei). These findings suggest that the healthy breast tissue of BRCA1/2 mutation carriers may be prone to neoplastic transformation upon exposure to diagnostic or therapeutic radiation, and that the RAD51 foci assay may be useful for the assessment of the functionality of HR repair and radiosensitivity in these women.

PURPOSE OF REVIEW: This review provides an overview of the current clinical standard in low-grade serous ovarian cancer (LGSOC). The available evidence for surgery and standard treatments is elaborated. In addition, we discuss recent findings and novel treatments for LGSOC. RECENT FINDINGS: Two large multicenter trials studying MEK inhibitors in LGSOC have been presented in the last year. Binimetinib demonstrated an activity in LGSOC, especially in KRAS-mutated disease. Trametinib was associated with an improved progression-free survival in relapsed LGSOC. Based on the current results, MEK inhibitors could be an alternative treatment for LGSOC. Surgery is an important step in the treatment of LGSOC. Hormonal therapy and bevacizumab can be beneficial, next to chemotherapy. Targeted treatments, such as the MEK-inhibitor trametinib, seem to be efficient and should be introduced into clinical practice. ispartof: CURRENT ONCOLOGY REPORTS vol:22 issue:1 ispartof: location:United States status: published

International audience; Acebutolol is a β1-selective adrenergic receptor antagonist with moderate membrane-stabilizing activity and intrinsic sympathomimetic activity; accordingly, the drug is indicated in hypertension, angina pectoris, and arrhythmia. However, acebutolol's beta-blocking properties also extend the QRS and QTc intervals, and may predispose the patient to ventricular tachydysrhythmia. Here, we report autopsy and toxicological findings on a fatal case of acebutolol self-poisoning in a 70-year-old woman. Toxicological analyses of post-mortem samples (using a liquid chromatography high-resolution mass spectrometry (LC-HR-MS) method) highlighted high concentrations of acebutolol and its metabolite diacetolol in femoral blood (92.8 mg/L and 21.2 mg/L, respectively) and other matrices (cardiac blood, urine, bile, and gastric contents). A molecular networking approach provided useful information on acebutolol's metabolism and revealed the existence of an unknown phase II metabolite of acebutolol. Molecular networking also facilitated visualization of the complex LC-HR-MS/MS datasets and the sample-to-sample comparisons that confirmed massive acebutolol intoxication by ingestion.

IntroductionRecent studies demonstrated that the gut microbiome of Parkinson's Disease (PD) patients differs from that of age-matched healthy controls. Notably less butyrate-producing bacteria and low mucosal and fecal short chain fatty acid (SCFA) concentrations were found in PD patients. SCFA play a role in the interplay of health and disease: SCFA butyrate improves colon motility, protects the colonic epithelium and reduces inflammation. Administration of butyrate in animal models of PD improved motor impairment and dopamine deficiency and reduced early mortality. We hypothesize that certain orally supplemented dietary fibers can stimulate butyrate production in the colon of Parkinson's patients, and consequently can improve the motor impairment and their quality of life. This hypothesis still requires a step-wise approach. Our objective is to investigate the effect of different types of dietary fiber on the gut microbiota and SCFA production in PD patients and healthy elderly.Material and methodsPD patients and healthy controls (HC) were selected based on age (55–70 years old) and BMI (18.5 -25 kg/m2). For PD patients the Hoehn and Yahr score (I – III) was added to this selection. The effect of inulin varying in degree of polymerization (DP) (average DP ~10 vs. average DP ~23) on the SCFA production was evaluated by ex vivo fermentation experiments with fecal samples of PD patients and HC. Inulin (1% w/v) was incubated in small-scale batch fermentations for 24 h at 37°C in anaerobic conditions. SCFA production was analyzed by solid phase micro-extraction capillary gas chromatography-mass spectrometry detection (SPME-cGS-MS). The clostridia clusters IV and XIVa were quantified through 16s qPCR.Results and discussionShort chain (Sc) and long chain(Lc) inulin fermentation resulted in a mean total SCFA increase of respectively 490.3 ± 128.2μmol/ml and 384.3 ± 85.9μmol/ml in HC (n = 7) and 453.9 ± 99.2μmol/ml and 402.9μmol/ml ± 84.1μmol/ml in PD patients (n = 3). Sc inulin fermentation increased butyrate production with 200.0μg/ml ± 46.2μmol/ml in HC and 119.8 ± 94.4μg/ml in PD patients (p = 0.09). Lc inulin fermentation increased butyrate production with 174.9μmol/ml ± 82.2μmol/ml and 113.3μmol/ml ± 21.2μmol/ml in HC and PD patients, respectively (p = 0.25). Large variation between samples was observed in PD patients.ConclusionAlthough sample size is relatively small and data is still collected, we can conclude that both Sc and Lc inulin increase total SCFA and butyrate production in HC and PD patients. This ex vivo study shows that stimulation of the butyrate production is still possible in PD patients and could be beneficial.

Background Habitat loss can force animals to relocate to new areas, where they would need to adjust to an unfamiliar resource landscape and find new breeding sites. Relocation may be costly and could compromise reproduction. Methods Here, we explored how the Lesser black-backed gull (Larus fuscus), a colonial breeding seabird species with a wide ecological niche, responds to the loss of its breeding habitat. We investigated how individuals adjusted their foraging behaviour after relocating to another colony due to breeding site destruction, and whether there were any reproductive consequences in the first years after relocation. To this end, we compared offspring growth between resident individuals and individuals that recently relocated to the same colony due to breeding habitat loss. Using GPS-tracking, we further investigated the foraging behaviour of resident individuals in both colonies, as well as that of relocated individuals, as enhanced foraging effort could represent a potential driver of reproductive costs. Results We found negative consequences of relocation for offspring development, which were apparent when brood demand was experimentally increased. Recently relocated gulls travelled further distances for foraging than residents, as they often visited more distant foraging sites used by residents breeding in their natal colony as well as new areas outside the home range of the residents in the colony where they settled. Conclusions Our results imply that relocated individuals did not yet optimally adapt to the new food landscape, which was unexpected, given the social information on foraging locations that may have been available from resident neighbours in their new breeding colony. Even though the short-term reproductive costs were comparatively low, we show that generalist species, such as the Lesser black-backed gull, may be more vulnerable to habitat loss than expected. Long term studies are needed to investigate how long individuals are affected by their relocation in order to better assess potential population effects of (breeding) habitat loss.

Successful immunization often requires a primer, and after a certain lag time, a booster administration of the antigen. To improve the vaccinees' comfort and compliance, a single-injection vaccine formulation with a biphasic pulsatile release would be preferable. Previous work has shown that such a release profile can be obtained with compacts prepared from physical mixtures of various poly(DL-lactic(-co-glycolic) acid) types (Murakami et al., 2000). However, the mechanism behind this release profile is not fully understood. In the present study, the mechanism that leads to this biphasic pulsatile release was investigated by studying the effect of the glass transition temperature (Tg) of the polymer, the temperature of compaction, the compression force, the temperature of the release medium, and the molecular weight of the incorporated drug on the release behavior. Compaction resulted in a porous compact. Once immersed into release medium with a temperature above the Tg of the polymer, the drug was released by diffusion through the pores. Simultaneously, the polymer underwent a transition from the glassy state into the rubbery state. The pores were gradually closed by viscous flow of the polymer and further release was inhibited. After a certain period of time, the polymer matrix ruptured, possibly due to a build-up in osmotic pressure, resulting in a pulsatile release of the remaining amount of drug. The compression force and the molecular weight of the incorporated drug did not influence the release profile. Understanding this mechanism could contribute to further develop single-injection vaccines.

As a continuation of our previous work, which concerned the binding of aldehydes to bisulfite and cysteine, this article presents more results on the applicability of 4-vinylpyridine addition to beer prior to analysis aiming at release of aldehydes from these preformed bound states, thus making them quantifiable with the headspace solid-phase microextraction method combined with gas chromatography-mass spectrometry. This article also presents the first results on spiking beer samples with cysteine prior to forced-aging, pointing to the important role of cysteine in beer flavor stability. Both the levels in free and bound aldehydes show a relatively large degree of variation among different beers, but also between marker aldehydes. For some aldehydes (e.g., hexanal), the bound amount was shown to increase rather strongly upon forced beer aging, whereas for others (e.g., 2-methylpropanal), large amounts appeared to already be present in a bound state in the fresh samples. Spiking beer samples with cysteine prior to aging significantly lowered the aldehyde levels compared with nonspiked samples. Flavor stability of the cysteine-spiked beers was thereby greatly improved through aldehyde-cysteine adduct formation. It was further hypothesized that, in addition to efficient binding of aldehydes, cysteine also inhibits the formation of furfural during beer aging from Maillard reaction intermediates.

Atmospheric plasma technology is a promising next-generation alternative for replacing thermal chemical vapor deposition or wet chemical processes for the deposition of functional coatings. In this work, TiO2 films with various morphologies and thicknesses are synthesized in a controllable way by atmospheric Dielectric Barrier Discharges (DBD) under argon/oxygen ambient conditions. This method allows varying the density of the deposited coatings, from low density powders to dense compact anatase layers simple tuning of the parameters. The surface morphology and cross section of the as-synthesized films are observed by scanning electron microscopy (SEM). It is demonstrated that the total flow rate together with the absorbed power have a significant effect on the morphology of the film, which changes from granular to compact film by increasing the total flow rate or decreasing the power. In other words, changing the energy density (Ed) in the plasma allows to control the morphology of the TiO2 films. A deposition mechanism is proposed to explain the effect of the synthesis parameters on the formed films. The chemical and phase composition of these films before and after annealing for 2 h in air at 673 K are comparatively studied. The photocatalytic activities and the reusability of the TiO2 films is investigated by degrading a methylene blue (MB) solution under Ultra-Violet (UV) light. It is compared to the activity of a P25 film, deposited by drop-casting. The photocatalytic rate of the annealed TiO2 film synthesized at a total flow rate of 2.5 slm turns out to be about 2 and 15 times higher than the one of P25 and as-synthesized TiO2 films, respectively. The annealed TiO2 film were shown to be reusable for at least three cycles, without significant loss of photocatalytic activity.

Understanding how biodiversity (B) affects ecosystem functioning (EF) is essential for assessing the consequences of ongoing biodiversity changes. An increasing number of studies, however, show that environmental conditions affect the shape of BEF relationships. Here, we first use a game-theoretic community model to reveal that a unimodal response of the BEF slope can be expected along environmental stress gradients, but also how the ecological mechanisms underlying this response may vary depending on how stress affects species interactions. Next, we analysed a global dataset of 44 experiments that crossed biodiversity with environmental conditions. Confirming our main model prediction, the effect of biodiversity on ecosystem functioning tends to be greater at intermediate levels of environmental stress, but varies among studies corresponding to differences in stress-effects on species interactions. Together, these results suggest that increases in stress from ongoing global environmental changes may amplify the consequences of biodiversity changes.

Carbon-supported iron complexes were investigated as electrocatalysts for the reduction of nitric oxide (NO) in a H-2-NO fuel cell conceived for the production of hydroxylamine (NH2OH) with concomitant generation of electricity. Two types of iron complexes with tetradentate ligands, namely bis(salicylidene)ethylenediimine (Salen) and phthalocyanine (Pc), supported on activated carbon or graphite were prepared and evaluated as electrocatalysts, either without further treatment or after pyrolysis at 700 degrees C. The performance in the reduction of NO of gas diffusion cathodes based on these electrocatalysts was investigated in an electrochemical half cell (3-electrode configuration) using linear sweep voltammetry (LSV). The most promising electrocatalysts were studied further by chronoamperometric experiments in a H-2-NO fuel cell, which allowed comparison in terms of power output and hydroxylamine production. Depending on the concentration of the NO feed (6 or 18%), the best electrocatalytic performance was delivered either by FePc or FeSalen. The gas diffusion electrode based on FeSalen supported on activated carbon with 0.3 wt% Fe-loading provided the highest current density (86 A/m(2)) and the best current efficiency (43%) towards the desired NH2OH when operating at the higher NO concentration (18%). Moreover, FeSalen offers the advantage of being cheaper than FePc. The experimental work was complemented by density functional theory (DFT) calculations, which allowed to shed more light on the reaction mechanism for the reduction of nitric oxide at the atomistic level.