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Within the last few decades, liquid chromatography-mass spectrometry (LC-MS) has become a preferred method for manifold issues in analytical biosciences, given its high selectivity and sensitivity. However, the analysis of fatty aldehydes, which are important components of cell metabolism, remains challenging. Usually, chemical derivatization prior to MS detection is required to enhance ionization efficiency. In this regard, the coupling of fatty aldehydes to hydrazines like 2,4-dinitrophenylhydrazine (DNPH) is a common approach. Additionally, hydrazones readily react with fatty aldehydes to form stable derivatives, which can be easily separated using high-performance liquid chromatography (HPLC) and subsequently detected by MS. Here, we exemplarily present the quantification of the long-chain fatty aldehyde (2E)-hexadecenal, a break-down product of the bioactive lipid sphingosine 1-phosphate (S1P), after derivatization with 2-diphenylacetyl-1,3-indandione-1-hydrazone (DAIH) via isotope-dilution HPLC-electrospray ionization-quadrupole/time-of-flight (ESI-QTOF) MS. Moreover, we show that the addition of N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC hydrochloride) as a coupling agent allows for simultaneous determination of fatty aldehydes and fatty acids as DAIH derivatives. Taking advantage of this, we describe in detail how to monitor the degradation of (2E)-hexadecenal and the concurrent formation of its oxidation product (2E)-hexadecenoic acid in lysates of human hepatoblastoma (HepG2) cells within this chapter.
Changes in body height throughout extended historic periods are very complex and dynamic processes. Thispilot study aimed to investigate the pattern of longitudinal height z-scores changes in children before and after entering kindergarten. In summer 2016, we measured height and weight of 32 children from 4 groups of two kindergartens aged 3–6 years. All ages were centered according to the age of entry into the kindergarten. For each child we determined mean z-scores for height before and after entering the kindergarten, and assessed the variances for each kindergarten group. Twenty-two children targeted in height z-scores towards average height of their respective kindergarten group, 10 children did not. Due to the small numbers, the convergence in height variance however, remained insignificant (chi-squared independence test, p = 0.127). Additional studies with larger sample sizes are needed to confirm this pilot study.
A balanced sphingolipid rheostat is indispensable for dendritic cell function and survival and thus initiation of an immune response. Sphingolipid levels are dynamically maintained by the action of sphingolipid enzymes of which sphingosine kinases, S1P phosphatases (SGPP-1/2) and S1P lyase (SGPL-1), are pivotal in the balance of S1P and sphingosine levels. In this study, we present that SGPP-1 and SGPL-1 are regulated in inflammatory dendritic cells and contribute to S1P fate. TLR-dependent activation caused SGPL-1 protein downregulation with subsequent decrease of enzymatic activity by two-thirds. In parallel, confocal fluorescence microscopy revealed that endogenous SGPP-1 was expressed in nuclei of naive dendritic cells and was translocated into the cytoplasmatic compartment upon inflammatory stimulation resulting in dephosphorylation of S1P. Mass spectrometric determination showed that a part of the resulting sphingosine was released from the cell, increasing extracellular levels. Another route of diminishing intracellular S1P was possibly taken by its export via ATP-binding cassette transporter C1 which was upregulated in array analysis, while the S1P transporter, spinster homolog 2, was not relevant in dendritic cells. These investigations newly describe the sequential expression and localization of the endogenous S1P regulators SGPP-1 and SGPL-1 and highlight their contribution to the sphingolipid rheostat in inflammation.
An auditory habituation design was used to investigate whether lexical-level phonological representations in the brain can be rapidly accessed after the onset of a spoken word. We studied the N1 component of the auditory event-related electrical potential, and measured the amplitude decrements of N1 associated with the repetition of a monosyllabic tone word and an acoustically similar pseudo-word in Mandarin Chinese. Effects related to the contrastive onset consonants were controlled for by introducing two control words. We show that repeated pseudo-words consistently elicit greater amplitude decrements in N1 than real words. Furthermore, this lexicality effect is free from sensory fatigue or rapid learning of the pseudo-word. These results suggest that a lexical-level phonological representation of a spoken word can be accessed as early as 110ms after the onset of the word-form.
N-terminal methacrylation of peptide MAXI, which is capable of conformational changes variation of the pH, results in a peptide, named VK20. Increasing the reactivity of this terminal group enables further coupling reactions or chemical modifications of the peptidc. However, this end group functionalization may influence the ability of confonnational changes of VK20; as well as its properties. In this paper; the influence of pH on the transition between random coil and beta-sheet conformation of VK20; including the transition kinetics, were investigated. At pH values of 9 and higher, the kinetics beta-sheet formation increased tor VK(2 0, compared to MAXI. The self-assembly into beta-sheets recognized by the formation of a physically crosslinked gel was furthermore indicated by a significant increase of G. An increase in pH (from 9 to 9.5) led to a faster gelation of the peptide VK20. Simultaneously, G was increased from 460 +/- 70 Pa (at pH 9) to 1520 +/- 180 Pa (at pH 9.5). At the nanoscale, the gel showed a highly interconnected fibrillar/network structure with uniform fibril widths of approximately 3.4 +/- 0.5 nm (N=30). The recovery of the peptide conformation back to random coil resulted in the dissolution of the gel; whereby the kinetics of the recovery depended on the pH. Conclusively, the ability of MAXI to undergo confommtional changes was not affected by N-terminal methacrylation whereas the kinetics of pH-sensitive beta-sheet formations has been increased.
Background: In Kenya, several species of the genus Maytenus are used in traditional medicine to treat many diseases including malaria. In this study, phytochemical constituents and extracts of Maytenus undata, M. putterlickioides, M. senegalensis and M. heterophylla were evaluated to determine compound/s responsible for antimalarial activity.
Objective: To isolate antiplasmodial compounds from these plant species which could be used as marker compounds in the standardization of their extracts as a phytomedicine for malaria.
Methods: Constituents were isolated through activity-guided fractionation of the MeOH/CHCl3 (1:1) extracts and in vitro inhibition of Plasmodium falciparum. Cytotoxicity was evaluated using Vero cells and the compounds were elucidated on the basis of NMR spectroscopy.
Results: Fractionation of the extracts resulted in the isolation of ten known compounds. Compound 1 showed promising antiplasmodial activity with IC50, 3.63 and 3.95 ng/ml against chloroquine sensitive (D6) and resistant (W2) P. falciparum, respectively and moderate cytotoxicity (CC50, 37.5 ng/ml) against Vero E6 cells. The other compounds showed weak antiplasmodial (IC50 > 1.93 mu g/ml) and cytotoxic (CC50 > 39.52 mu g/ml) activities against P. falciparum and Vero E6 cells, respectively.
Conclusion: (20 alpha)-3-hydroxy-2-oxo-24-nor-friedela-1(10),3,5,7-tetraen-carboxylic acid-(29)-methyl-ester (pristimerin) (1) was the most active marker and lead compound that warrants further investigation as a template for the development of new antimalarial drugs. Pristimerin is reported for the first time in M. putterlickioides. 3-Hydroxyolean-12-en-28-oic acid (oleanolic acid) (5), stigmast-5-en-3-ol (beta-sitosterol) (6), 3-oxo-28-friedelanoic acid (7), olean-12-en-3-ol (beta-amyrin) (8), lup-20(29)-en-3-ol (lupeol) (9) and lup-20(29)-en-3-one (lupenone) (10) are reported for the first time in M. undata.
Comparative research on aphasia and aphasia rehabilitation is challenged by the lack of comparable assessment tools across different languages. In English, a large array of tools is available, while in most other languages, the selection is more limited. Importantly, assessment tools are often simple translations and do not take into consideration specific linguistic and psycholinguistic parameters of the target languages. As a first step in meeting the needs for comparable assessment tools, the Comprehensive Aphasia Test is currently being adapted into a number of languages spoken in Europe. In this article, some key challenges encountered in the adaptation process and the solutions to ensure that the resulting assessment tools are linguistically and culturally equivalent, are proposed. Specifically, we focus on challenges and solutions related to the use of imageability, frequency, word length, spelling-to-sound regularity and sentence length and complexity as underlying properties in the selection of the testing material.
Substance-dependent individuals often lack the ability to adjust decisions flexibly in response to the changes in reward contingencies. Prediction errors (PEs) are thought to mediate flexible decision-making by updating the reward values associated with available actions. In this study, we explored whether the neurobiological correlates of PEs are altered in alcohol dependence. Behavioral, and functional magnetic resonance imaging (fMRI) data were simultaneously acquired from 34 abstinent alcohol-dependent patients (ADP) and 26 healthy controls (HC) during a probabilistic reward-guided decision-making task with dynamically changing reinforcement contingencies. A hierarchical Bayesian inference method was used to fit and compare learning models with different assumptions about the amount of task-related information subjects may have inferred during the experiment. Here, we observed that the best-fitting model was a modified Rescorla-Wagner type model, the “double-update” model, which assumes that subjects infer the knowledge that reward contingencies are anti-correlated, and integrate both actual and hypothetical outcomes into their decisions. Moreover, comparison of the best-fitting model's parameters showed that ADP were less sensitive to punishments compared to HC. Hence, decisions of ADP after punishments were loosely coupled with the expected reward values assigned to them. A correlation analysis between the model-generated PEs and the fMRI data revealed a reduced association between these PEs and the BOLD activity in the dorsolateral prefrontal cortex (DLPFC) of ADP. A hemispheric asymmetry was observed in the DLPFC when positive and negative PE signals were analyzed separately. The right DLPFC activity in ADP showed a reduced correlation with positive PEs. On the other hand, ADP, particularly the patients with high dependence severity, recruited the left DLPFC to a lesser extent than HC for processing negative PE signals. These results suggest that the DLPFC, which has been linked to adaptive control of action selection, may play an important role in cognitive inflexibility observed in alcohol dependence when reinforcement contingencies change. Particularly, the left DLPFC may contribute to this impaired behavioral adaptation, possibly by impeding the extinction of the actions that no longer lead to a reward.
Theoretischer Hintergrund: Einflüsse von therapeutenorientiertem Kompetenz-Feedback in der Psychotherapieausbildung wurden bislang wenig untersucht.
Fragestellung: Wie gehen Ausbildungstherapeuten mit Feedback um? Welchen Einfluss hat ein regelmäßiges Kompetenz-Feedback auf die Qualität psychotherapeutischer Behandlungen (insbesondere Therapiesitzungen, therapeutische Beziehung, Person des Therapeuten, Supervision)?
Methode: Elf Therapeuten wurden mithilfe eines halbstrukturierten Interviewleitfadens befragt. Die Auswertung erfolgte mittels qualitativer Inhaltsanalyse nach Mayring (2015).
Ergebnisse: Das auf Basis der Interviews erstellte Kategoriensystem umfasste die Kategorien „Erwartungen an das Feedback“, „Wahrnehmung des Feedbacks“, „Verarbeitung von und Umgang mit Feedback“, „Folgen, Auswirkungen und Veränderungen durch Feedback“ sowie „Verbesserungswünsche“.
Schlussfolgerungen: Therapeuten streben eine Umsetzung des Feedbacks an, welches sich auf die Behandlung, die Supervision, die eigene Person und die therapeutische Beziehung auswirkt.
In this study, a multiblock copolymer containing oligo(3-methyl-morpholine-2, 5-dione) (oMMD) and oligo(3-sec-butyl-morpholine-2, 5-dione) (oBMD) building blocks obtained by ring-opening polymerization (ROP) of the corresponding monomers, was synthesized in a polyaddition reaction using an aliphatic diisocyanate. The multiblock copolymer (pBMD-MMD) provided a molecular weight of 40, 000 g·mol−1, determined by gel permeation chromatography (GPC). Incorporation of both oligodepsipeptide segments in multiblock copolymers was confirmed by 1H NMR and Matrix Assisted Laser Desorption/Ionization Time Of Flight Mass Spectroscopy (MALDI-TOF MS) analysis. pBMD-MMD showed two separated glass transition temperatures (61 °C and 74 °C) indicating a microphase separation. Furthermore, a broad glass transition was observed by DMTA, which can be attributed to strong physical interaction i.e. by H-bonds formed between amide, ester, and urethane groups of the investigated copolymers. The obtained multiblock copolymer is supposed to own the capability to exhibit strong physical interactions.
Over the last decades, the percentage of the age group choosing to pursue university studies has increased significantly across the world. At the same time, there are university teachers who believe that the standards have fallen. There is little research on whether students nowadays demonstrate knowledge or abilities similar to that of the preceding cohorts. However, in times of educational expansion, empirical evidence on student test performance is extremely helpful in evaluating how well educational systems cope with the increasing numbers of students. In this study, we compared a sample of 2322 physics freshmen from 2013 with another sample of 2718 physics freshmen from 1978 at universities in Germany with regard to their physics knowledge based on their results in the same entrance test. Previous results on mathematics knowledge and abilities in the same sample of students indicated that there was no severe decline in their average achievement. This paper compares the physics knowledge of the same two samples of students. Contrary to their mathematics results, their physics results showed a substantial decrease in physics knowledge as measured by the test.
A strong sense of victimhood, a discourse of social suffering, and complementary bodily performances, which mobilize rancor, resentfulness, and revengefulness, are fundamental elements of Turkish-Islamist ideology. This article discusses the political dynamics and implications of such assertions of victimhood in the Turkish context. To underscore these dynamics, it analyses the role of the logic of pain in the subject formation of Turkish-Islamist identity and how this logic has been revitalized by constitutive and hegemonic social imagination, and circulated and intensified by a reactionary mood. Additionally, it aims to expose how this reactionary mood profoundly depends on contradictory subjectification processes, which simultaneously involve mobilization of feelings of impotency, non-responsibility, self-pitying, and sublimation of power. This subject formation opens the way for identification with authoritarian figures in the Turkish case.
Work-anxieties are costly and need early intervention. The perception of being able to cope with work is a basic requirement for work ability. This randomized controlled trial investigates whether a cognitive behavioural, work-anxiety-coping group (WAG) intervention leads to better work-coping perception than an unspecific recreational group (RG). Heterogeneous people in medical rehabilitation, who were due to return to work, were interviewed concerning their work-anxieties, and either randomly assigned to a WAG (n=85) or a RG (n=95). The participants (with an average of 50years old [range 23-64]; 51% women; 70% workers or employees, 25% academics, 5% unskilled) followed the group intervention for four or six sessions. The perceived work-coping was assessed by self-rating (Inventory for Job-Coping and Return Intention JoCoRi) after each group session. Although participants had a slight temporary decrease in work-coping after group session two (from M-1=2.47 to M-2=2.28, d(Cohen)=-.22), the WAG led to the improvement of perceived work-coping over the intervention course (from M-1=2.47 to M-6=2.65, d(Cohen)=.18). In contrast, participants from the RG reported lower work-coping after six group sessions (from M-1=2.26 to M-6=2.02, d(Cohen)=-.18). It is considered that people with work-anxieties need training in work-coping. By focusing on recreation only, this may lead to deterioration of work-coping. Indeed, intervention designers should be aware of temporary deterioration (side effects) when confronting participants with work-coping.
Coping, taming or solving
(2017)
One of the truisms of policy analysis is that policy problems are rarely solved. As an ever-increasing number of policy issues are identified as an inherently ill-structured and intractable type of wicked problem, the question of what policy analysis sets out to accomplish has emerged as more central than ever. If solving wicked problems is beyond reach, research on wicked problems needs to provide a clearer understanding of the alternatives. The article identifies and explicates three distinguishable strategies of problem governance: coping, taming and solving. It shows that their intellectual premises and practical implications clearly contrast in core respects. The article argues that none of the identified strategies of problem governance is invariably more suitable for dealing with wicked problems. Rather than advocate for some universally applicable approach to the governance of wicked problems, the article asks under what conditions different ways of governing wicked problems are analytically reasonable and normatively justified. It concludes that a more systematic assessment of alternative approaches of problem governance requires a reorientation of the debate away from the conception of wicked problems as a singular type toward the more focused analysis of different dimensions of problem wickedness.
Water management tools are necessary to guarantee the preservation of natural resources while ensuring optimum utilization. Linear regression models are a simple and quick solution for creating prognostic capabilities. Multivariate models show higher precision than univariate models. In the case of Waiwera, implementation of individual production rates is more accurate than applying just the total production rate. A maximum of approximately 1,075 m3/day can be pumped to ensure a water level of at least 0.5 m a.s.l. in the monitoring well. The model should be renewed annually to implement new data and current water level trends to keep the quality.
Predicting macroscopic elastic rock properties requires detailed information on microstructure
(2017)
Predicting variations in macroscopic mechanical rock behaviour due to microstructural changes, driven by mineral precipitation and dissolution is necessary to couple chemo-mechanical processes in geological subsurface simulations. We apply 3D numerical homogenization models to estimate Young’s moduli for five synthetic microstructures, and successfully validate our results for comparable geometries with the analytical Mori-Tanaka approach. Further, we demonstrate that considering specific rock microstructures is of paramount importance, since calculated elastic properties may deviate by up to 230 % for the same mineral composition. Moreover, agreement between simulated and experimentally determined Young’s moduli is significantly improved, when detailed spatial information are employed.
Integration and development of the energy supply in China and worldwide is a challenge for the years to come. The innovative idea presented here is based on an extension of the “power-to-gas-to-power” technology by establishing a closed carbon cycle. It is an implementation of a low-carbon energy system based on carbon dioxide capture and storage (CCS) to store and reuse wind and solar energy. The Chenjiacun storage project in China compares well with the German case study for the towns Potsdam and Brandenburg/Havel in the Federal State of Brandenburg based on the Ketzin pilot site for CCS.
Dissolved CO2 storage in geological formations with low pressure, low risk and large capacities
(2017)
Geological CO2 storage is a mitigation technology to reduce CO2 emissions from fossil fuel combustion. However, major concerns are the pressure increase and saltwater displacement in the mainly targeted deep groundwater aquifers due to injection of supercritical CO2. The suggested solution is storage of CO2 exclusively in the dissolved state. In our exemplary regional case study of the North East German Basin based on a highly resolved temperature and pressure distribution model and a newly developed reactive transport coupling, we have quantified that 4.7 Gt of CO2 can be stored in solution compared to 1.5 Gt in the supercritical state.
Using the recently built Global Naturalized Alien Flora (GloNAF) database, containing data on the distribution of naturalized alien plants in 483 mainland and 361 island regions of the world, we describe patterns in diversity and geographic distribution of naturalized and invasive plant species, taxonomic, phylogenetic and life-history structure of the global naturalized flora as well as levels of naturalization and their determinants. The mainland regions with the highest numbers of naturalized aliens are some Australian states (with New South Wales being the richest on this continent) and several North American regions (of which California with 1753 naturalized plant species represents the worlds richest region in terms of naturalized alien vascular plants). England, Japan, New Zealand and the Hawaiian archipelago harbour most naturalized plants among islands or island groups. These regions also form the main hotspots of the regional levels of naturalization, measured as the percentage of naturalized aliens in the total flora of the region. Such hotspots of relative naturalized species richness appear on both the western and eastern coasts of North America, in north-western Europe, South Africa, south-eastern Australia, New Zealand, and India. High levels of island invasions by naturalized plants are concentrated in the Pacific, but also occur on individual islands across all oceans. The numbers of naturalized species are closely correlated with those of native species, with a stronger correlation and steeper increase for islands than mainland regions, indicating a greater vulnerability of islands to invasion by species that become successfully naturalized. South Africa, India, California, Cuba, Florida, Queensland and Japan have the highest numbers of invasive species. Regions in temperate and tropical zonobiomes harbour in total 9036 and 6774 naturalized species, respectively, followed by 3280 species naturalized in the Mediterranean zonobiome, 3057 in the subtropical zonobiome and 321 in the Arctic. The New World is richer in naturalized alien plants, with 9905 species compared to 7923 recorded in the Old World. While isolation is the key factor driving the level of naturalization on islands, zonobiomes differing in climatic regimes, and socioeconomy represented by per capita GDP, are central for mainland regions. The 11 most widely distributed species each occur in regions covering about one third of the globe or more in terms of the number of regions where they are naturalized and at least 35% of the Earths land surface in terms of those regions areas, with the most widely distributed species Sonchus oleraceus occuring in 48% of the regions that cover 42% of the world area. Other widely distributed species are Ricinus communis, Oxalis corniculata, Portulaca oleracea, Eleusine indica, Chenopodium album, Capsella bursa-pastoris, Stellaria media, Bidens pilosa, Datura stramonium and Echinochloa crus-galli. Using the occurrence as invasive rather than only naturalized yields a different ranking, with Lantana camara (120 regions out of 349 for which data on invasive status are known), Calotropis procera (118), Eichhornia crassipes (113), Sonchus oleraceus (108) and Leucaena leucocephala (103) on top. As to the life-history spectra, islands harbour more naturalized woody species (34.4%) thanmainland regions (29.5%), and fewer annual herbs (18.7% compared to 22.3%). Ranking families by their absolute numbers of naturalized species reveals that Compositae (1343 species), Poaceae (1267) and Leguminosae (1189) contribute most to the global naturalized alien flora. Some families are disproportionally represented by naturalized aliens on islands (Arecaceae, Araceae, Acanthaceae, Amaryllidaceae, Asparagaceae, Convolvulaceae, Rubiaceae, Malvaceae), and much fewer so on mainland (e.g. Brassicaceae, Caryophyllaceae, Boraginaceae). Relating the numbers of naturalized species in a family to its total global richness shows that some of the large species-rich families are over-represented among naturalized aliens (e.g. Poaceae, Leguminosae, Rosaceae, Amaranthaceae, Pinaceae), some under-represented (e.g. Euphorbiaceae, Rubiaceae), whereas the one richest in naturalized species, Compositae, reaches a value expected from its global species richness. Significant phylogenetic signal indicates that families with an increased potential of their species to naturalize are not distributed randomly on the evolutionary tree. Solanum (112 species), Euphorbia (108) and Carex (106) are the genera richest in terms of naturalized species; over-represented on islands are Cotoneaster, Juncus, Eucalyptus, Salix, Hypericum, Geranium and Persicaria, while those relatively richer in naturalized species on the mainland are Atriplex, Opuntia, Oenothera, Artemisia, Vicia, Galium and Rosa. The data presented in this paper also point to where information is lacking and set priorities for future data collection. The GloNAF database has potential for designing concerted action to fill such data gaps, and provide a basis for allocating resources most efficiently towards better understanding and management of plant invasions worldwide.