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The authors of this book present a study of the first Arab novels that dealt with the Arab Spring in the period 2011-2013. They show the rapid reaction of Arab novelists to what happened in their countries at that time. Dozens of narrative works have been published that heralded the advent of change and the victory of popular movements, glorifying the rebellious uprisings against tyrannical regimes. Few predicted the outbreak of the revolution before the occurrence of these major events. They also presented a comprehensive picture of what was going on in Arab societies during that difficult period. The revolutions left many victims, and for this reason pessimism and despair permeate some texts, but others paint a bright picture of the future of the Arab Spring, which may lead to the realization of the dream of freedom and democracy. The young generation, which by means of the internet and social media contributed to the outbreak of the revolution, is ready to fight for its own ideals and freedom. Its representatives are fascinated by the power of revolution and the rapid course of events. They boldly face death in the hope that the sacrifice of their lives will bring about a better future for their children. It was young people, not politicians and party leaders, who planned the revolution demanding freedom, dignity, equality and justice.

Introduction In European traditional medicine, common ash leaf infusion is recommended by European Medicines Agency to treat minor articular pain and to increase the amount of urine for flushing minor urinary complaints. However, a comprehensive ultra-high-performance liquid chromatography diode array detector electrospray ionisation tandem mass spectrometry (UHPLC-DAD-ESI-MS/MS) analysis of this pharmacopeial plant material has never been performed. Moreover, the number of biological and pharmacological investigations proving the usefulness of this plant material in recommended traditional uses is surprisingly small. Objective Phytochemical profiling of ash leaf samples from different commercial and natural sources and the determination of the in vitro effects on inflammatory mediators in a model of human neutrophils. Methods Ash leaf samples were characterised by total hydroxycinnamic acid content and by high-performance thin layer chromatography (HPTLC), UHPLC-DAD-ESI-MS/MS methods. The effects of leaf infusions on reactive oxygen species (ROS), tumor necrosis factor (TNF-α), interleukin 8 (IL-8), interleukin 1β (IL-1β), and monocyte chemoattractant protein 1 (MCP-1) production by neutrophils were measured using luminol-dependent chemiluminescence and enzyme-linked immunosorbent assay (ELISA). Results In ash leaf samples 64 compounds were identified or partly identified together with four unknown compounds. The major compounds detected belong to different structural groups, including phenolic acid derivatives, phenylethanoids, flavonoids, iridoids, secoiridoids and lignans. The major compounds detected in ash samples were chlorogenic acid, quercetin-3-O-rutinoside, verbascoside, oleuropein and ligstroside. However, one sample contained coumarin derivatives. This finding suggested adulteration with other Fraxinus species and/or plant parts. All infusions were able to inhibit ROS, cytokine and chemokine production. Conclusions The performed phytochemical and biological analyses contribute to the knowledge about this pharmacopeial plant material and supports its traditional use to treat minor inflammatory complaints.

In traditional European medicine, common lilac (Syringa vulgaris L., Oleaceae) bark has been used in the form of an infusion, decoction or alcoholic extract as an antipyretic and a cold and cough treatment. Our primary study showed that alcoholic extract of the bark was able to decrease the release of interleukin- 8 in an in vitro model The aim of the study was to investigate the phytochemical composition of common lilac bark extract by the HPLC-DAD-MS/MS method, isolate the dominant compounds and investigate their effects on the proinflammatory functions of human neutrophils and monocytes/macrophages. Syringin (sinapyl alcohol-O-glucoside), olivil-4′-O-glucoside, sinapyl aldehyde-O-glucoside and forsythoside B were isolated using RP-18, Sephadex LH-20 column chromatography and preparative chromatography. The structures were confirmed by the UV, MS and 1H and 13C NMR spectra. The effects on cytokine (TNF-α, IL-1β, IL-6) and chemokine (IL-8 and MCP-1) production by neutrophils and monocytes/macrophages were measured using an enzyme-linked immunosorbent assay (ELISA). Moderate anti-inflammatory activity was observed in the neutrophil model for all compounds compared with oleuropein, a common compound in the Oleaceae family with well-documented anti-inflammatory effects. However, syringin at concentration of 50 μM significantly inhibited TNF-α production and stimulated TGF-β release in LPS-treated monocytes/macrophages. Our results demonstrated that common lilac bark is a valuable source of active compounds, especially syringin.

Acmella oleracea (jambu) is a South American plant whose pharmacological properties include antimalarial, anesthetic, and anti-inflammatory activities. However, the compounds contributing to the anti-inflammatory effect have received little attention. In this study, the active compound spilanthol was isolated using a Green Chemistry approach and presented significant anti-inflammatory activity in a lipopolysaccharide-activated human neutrophil model. First, the aerial parts of jambu were extracted and fractionated using supercritical carbon dioxide. The spilanthol-enriched fractions obtained were then subjected to further purification by flash chromatography, yielding spilanthol with 97% purity. Use of enzyme-linked immunosorbent assay (ELISA) revealed a reduction in the release of Interleukin-8 and Tumor Necrosis Factor - alpha by leukocytes exposed to spilanthol. In conclusion, this new approach enabled spilanthol to be obtained at high purity, in a fairly rapid procedure, while the results of the in vitro anti-inflammatory activity study indicated that the compound could be a promising new therapeutic agent.

During chronic inflammation, neutrophils acting locally as effector cells not only activate antibacterial defense but also promote the inflammatory response. Interleukin 8 (IL-8), the main cytokine produced by activated neutrophils, positively correlates with the severity of respiratory tract diseases. By screening European plants traditionally used for treating respiratory tract diseases, we found that extracts of aerial parts of Eupatorium cannabinum inhibit IL-8 release from neutrophils. Using bioassay-guided fractionation, we identified five sesquiterpene lactones, eupatoriopicrin (1), 5′-deoxyeupatoriopicrin (2), hiyodorilactone A (3), 3-hydroxy-5′-O-acetyleupatoriopicrin = hiyodorilactone D (4), and hiyodorilactone B (5), that efficiently (IC50 < 1 μM) inhibited IL-8 and TNF-α release in lipopolysaccharide (LPS)-stimulated human neutrophils. Moreover, all these sesquiterpene lactones suppressed the adhesion of human neutrophils to an endothelial monolayer by downregulating the expression of the β2 i...

Continuous destruction of the solid electrolyte interphase (SEI) on the graphite-based negative electrode during cycling operation is a significant degradation mechanism that raises safety concerns and limits the cycle life of LiNi0.5Mn1.5O4 (LNMO)/graphite full-cells. Herein, we report on gassing phenomena which are typically concomitant with SEI destruction processes. Abrupt H2 evolution is observed by differential electrochemical mass spectrometry and pressure measurements at the end of discharge. Using a lithium reference electrode reveals that the gassing, which intensifies with cycling, is caused by an increase in the anode potential. Lithium is irreversibly consumed upon SEI formation, but this loss is not compensated for by the intrinsic degradation of LNMO in the first cycle. When the potential of the anode on discharge increases above approximately 0.9 V, the SEI is instantly damaged, causing gas generation, and eventually capacity fade. We show that this (“mediator-free”) cross-talk phenomenon ...

Aim of the study: Taking into account that overactivated leukocytes are an important factor in the development of many chronic diseases, we investigated the activity of phytochemically characterized (HPLC-DAD-MSn) extracts from forsythia leaves and flowers on the pro- and anti-inflammatory functions of leukocytes (effects on IL-1β, IL-8, TNF-α, and TGFβ release) and their adherence to endothelial cells. Using bio-guided fractionation, we isolated the active compounds and determined their biological activity, and we included the positive control quercetin. Methods: The effect on IL-1β, TNF-α, IL-8, and TGF-α production by leukocytes was measured by enzyme-linked immunosorbent assay (ELISA). The surface expression of adhesion molecules was analyzed with flow cytometry, and the neutrophil attachment to the endothelial cells was assessed fluorimetrically. The effects on p38MAPK, ERK1/2 and JNK phosphorylation were determined using western blots. Results: Leaf extracts had the effect of decreasing TNF-α production in neutrophils and monocyte/macrophage cells. The bio-guided fractionation led to the isolation of the following lignan aglycones: (+)-pinoresinol, (+)-epipinoresinol, (−)-matairesinol, (+)-phillygenin, and (−)-arctigenin. Only phillygenin was able to stimulate the anti-inflammatory function of macrophages by inducing TGF-β release and IL-10 receptor surface expression. Arctigenin, phillygenin, and a metabolite produced by the gut microbiota, enterolactone, decreased TNF-α and IL-1β production and neutrophil adhesion to endothelial cells, probably by attenuating the p38 and ERK kinase pathways. Conclusion: Forsythia x intermedia is a valuable source of active lignans, which may be potential candidates for treating inflammatory diseases that are associated with the excessive production of cytokines such as TNF-α and IL-1β.

In an initial screening, the dichloromethane extract from the leaves of Melodorum fruticosum showed distinct inhibitory effects on the release of interleukin‐8 (IL‐8) in human neutrophils. Therefore, the aim of the present study was the phytochemical and pharmacological investigation of this extract, to better understand which compounds might be responsible for the anti‐inflammatory effect. Phytochemical analysis led to the isolation of 12 known compounds and two new natural products, 5‐hydroxy‐6‐(2‐hydroxybenzyl)‐4′,7‐dimethoxyflavanone (13) and 2′,4′‐dihydroxy‐3′‐(2‐hydroxybenzyl)‐4,6′‐dimethoxychalcone (14). The influence of the isolated compounds on the production and release of the pro‐inflammatory factors IL‐8, tumor necrosis factor alpha (TNF‐α), reactive oxygen species (ROS), and adhesion molecules (CD62L and CD11b) in human neutrophils was evaluated. Three constituents, melodamide A, 2′,4′‐dihydroxy‐4,6′‐dimethoxychalcone, and 2′,6′‐dihydroxy‐4′‐methoxychalcone, showed significant inhibition of IL‐8 release (IC50=6.6, 8.6, and 11.6 μm, respectively) and TNF‐α production (IC50=4.5, 13.3, and 6.2 μm, respectively).

This chapter examines the development of the novel in Bahrain. It first provides an overview of the beginnings of the literary movement in Bahrain, noting the role played by the press in the development of modern Bahraini literature, particularly prose genres. It then looks at the first generation of Bahraini authors, including Muḥammad ‘Abd al-Malik, who began publishing short stories in 1966, and ‘Abd Allah Khalīfa, whose early fiction contains realistic representations of life centered on the sea. The chapter also discusses a number of Bahraini novels written by the second generation of Bahraini authors, including Walīd Hāshim, Fatḥiyya Nā ṣir, and Aḥmad al-Mu’adhdhin.

This chapter traces the origins of the novelistic tradition in Oman. It first considers the history of prose writing in Oman, focusing on the undisputed pioneer of Omani fiction, ‘Abd Allah al-Ṭ ā’ī (1927–1973). It then discusses the works of major contemporary novelists such as Sayf bin Sa‘īd al-Sa‘dī and Su‘ūd bin Sa‘d al-Muẓaffar. The chapter explores some of the themes used in the Omani novel, including social changes, the perceived loss of moral values, and the relationship between city and countryside. It also discusses the beginning of Omani women’s literature and the contributions of women authors such as Emily Ruete, Badriyya al-Shiḥ ḥ ī’s, Jūkha al-Ḥ ārthī, and Ghāliya F. T. Āl Sa‘īd.

Thirteen new compounds including caffeoyl-glucaric and p-coumaroyl-altraric acid derivatives, one monoterpenoid glucoside, four secoiridoid glycosides, and three hydroxycinnamoyl phenylpropanoid glycosides esterified with an oleoside 11-methyl ester along with fifteen known compounds were isolated from flowers of Syringa vulgaris L. (Oleaceae). Their structures were elucidated by high-resolution spectroscopic methods. The tested compounds were able to decrease the production of reactive oxygen species. Moreover, oleoechinacoside (13), demethylhydroxyoleonuezhenide (14), demethyloleonuezhenide (15), syringaoleoacteoside (25) and oleoacteoside (26) at the concentration of 50μM, moderately suppressed the LPS-stimulated release of pro-inflammatory chemokine IL-8 and TNF-α from human neutrophils. Moreover, oleonuezhenide (12), oleoside 11-methyl ester (16) and oleoacteoside (26) at the concentration of 50μM were able to induce the surface expression of interleukin 10 receptor, which is suppressed by the incubation of monocyte/macrophage cells with LPS.

Carpesium divaricatum Sieb. & Zucc. has a long history of use as both a medicinal and a food plant. However, except for terpenoids, its chemical constituents have remained poorly investigated. The composition of hydroalcoholic extract from aerial parts of C. divaricatum was analyzed by HPLC-DAD-MSn, revealing the presence of numerous caffeic acid derivatives that were formerly unknown constituents of the plant. In all, 17 compounds, including commonly found chlorogenic acids and rarely occurring butyryl and methylbutyryl tricaffeoylhexaric acids, were tentatively identified. Fractionation of lipophilic extract from cultivated shoots led to the isolation of 12-oxo-phytodienoic acid (12-OPDA), which is a newly identified constituent of the plant. The compound, at concentrations of 0.5, 1.0, and 2.5 μM, significantly reduced IL-8, IL-1β, TNFα, and CCL2 excretion by lipopolysaccharide (LPS)-stimulated human neutrophils. Reactive oxygen species (ROS) production induced by f-MLP was also significantly diminished in the neutrophils pretreated by 12-OPDA. The newly identified constituents of the plant seem to be partly responsible for its pharmacological activity and elevate the value of C. divaricatum as a potential functional food.

The cycling performance and in operando gas analysis of LiNi0.5Mn1.5O4 (LNMO)/graphite cells with reasonably high loading, containing a "standard" carbonate-based electrolyte is reported. The gas evolution over the first couple of cycles was thoroughly investigated via differential electrochemical mass spectrometry (DEMS), neutron imaging and pressure measurements. The main oxidation and reduction products were identified as CO2, H2 and C2H4. In different sets of experiments graphite was substituted with delithiated LiFePO4 (LFP) and LNMO with LFP to distinguish between processes occurring at either anode or cathode and gain mechanistic insights. Both C2H4 and H2 were found to be mainly formed at the anode side, while CO2 is generated at the cathode. The results from DEMS analysis further suggest that the Ni redox couples play a profound role in the evolution of CO2 at the LNMO/electrolyte interface. Lastly, it is shown that the cycling stability and capacity retention of LNMO/graphite cells can be considerably improved by a simple cell formation procedure.

The synthesis and fundamental spectroscopic properties of eight hemicyanine (HC) dyes are presented. The dyes were prepared by the condensation of N-methyl-5,6,7,8-tetrahydroisoquinolinium iodide with p-(N,N-dialkylamino)benzaldehydes. The compounds were characterised by nuclear magnetic resonance spectroscopy and their purity was checked with the use of thin-layer chromatography. The spectroscopic properties of the dyes were determined in three organic solvents. The electronic absorption spectra of the dyes demonstrate moderate sensitivity to the nature of the substituent present in the aromatic ring and low solvent polarity dependence. In contrast to this, the positions of fluorescence bands are affected by the structure of an electron donor and solvent polarity. The 4-[N-(5,6,7,8-tetrahydroisoquinolinium-5-ylidene)methyl]-N,N-dialkylaniline iodides were applied as fluorescent probes for the monitoring of the progress of free radical polymerisation. The study on the changes in the fluorescence intensity and spectroscopic shifts of the dyes was carried out during thermally initiated polymeriszation of methyl methacrylate. The purpose of these studies was to find a relationship between the changes in the shape and intensity of probe fluorescence and the degree of monomer conversion into polymer.

Adenosine receptor (AR) antagonists belong to two major groups of compounds: xanthines and non-xanthines. Recently several annelated xanthine derivatives have been described as selective A 1 , A 2A , A 2B and A 3 ARs antagonists. Contrary to dipropyl derivatives, in the group of dimethyl (un)substituted arylalkyl pyrimido[2,1- f ]purindiones selective mainly adenosine A 2A receptor antagonists were identified. Their activity depended on aryl substitution and its distance from pyrimido[2,1- f ]purindione.

Cold-pressed rapeseed oil is among the most popular virgin oils. Different processing methods yield oils varying in chemical composition and oxidative stability. The experiment aimed at identifying the differences (mostly in volatiles) between rapeseed oil obtained from peeled seeds (RO) and oils obtained by three pre-treatment methods: pressing whole seeds (WSO), flakes (FO) and roasted flakes (RFO). Volatiles were analysed using GCxGC-ToFMS and data were processed using statistical multivariate analysis. Fatty acid composition was determined using GC-FID. The oils’ oxidative stabilities were measured using peroxide value, free fatty acids’ value, absorbance at 236 and 238nm and chlorophyll content. Also, a sensory panel evaluation was performed. PCA was found to be effective tool for differentiating the oils on the basis of their volatile compounds. RO was most similar to WSO from the second pressing. Fatty acid composition analysis yielded differences between the experimental oils and RO. RO had the highest PV, p-AV and Totox values. WSO from the first pressing (WSO1) had the highest oxidative stability. Sensory analysis found that WSO1 was most similar to RO. Both oils had an intense cabbage-like and fruity odour. The study showed that the results of volatile compounds’ analysis differs from those of sensory analysis. Practical applications: The results demonstrate that the rapeseed oil obtained from whole seeds may have a volatile compounds composition that is similar to that of rapeseed oil obtained from peeled seeds. PCA makes it possible to differentiate between samples varying in pre-treatment method as well as between samples subjected to the same pre-treatment method, but obtained from a second pressing. Sensory panel performed by trained panellists may demonstrate which oils are most desirable when rated for selected attributes. The results of sensory panel may differ from those of volatile compoundanalysis performed with GCxGC-ToFMS.

Pain disorders of the spine are the most common causes of appointments with physiotherapists. It has been estimated that nine out of ten adults at least once in their lifetime experience spine pains and five out of ten working people have this kind of ailments a minimum once a year.The evaluation of the occurrence of spine pains in people who are professionally active with regards to obeying the rules of work ergonomics.The research group has been composed of 100 people professionally active from south-eastern Poland. Their ages have been from 20 to 50 years (average age has been 35 years). In the research the authors' own survey and VAS scale have been used on which the surveyed person has marked the intensity of pain experience in the area of the spine.Greater pain in the spine has been experienced by people who have never obeyed the rules of, among others, manual lifting and/or carrying the maximum load, lifting and carrying heavy objects, in their work. The lowest degree of pain has been experienced by those who obeyed the above-mentioned rules.Assuming the incorrect body posture during the everyday activities and disobeying the rules of ergonomics resulting from lack of knowledge are crucial factors in the occurrence of spine pains. People who disobey rules of ergonomics experienced spine pain to a higher degree.

The aim of this article is to briefly present progress in the development of the potent adenosine receptor (AR) antagonists with high selectivity for either A1, A2A, or A2B ARs. The structural requirements for each AR subtype were discussed as well as their potential therapeutic use. In the search for new AR antagonists, series of imidazo-, pyrimido-, and diazepino-purindione derivatives as well as oxazolo-, oxazino-, and oxazepino-purindiones were designed, synthesized, and preliminarily evaluated in pharmacological studies. Oxygencontaining tricyclic derivatives were shown to be moderately potent AR antagonists exhibiting selectivity either for A1 or A2A ARs. Tricyclic purindiones with nitrogen in the third ring were generally more A2A AR selective. The compounds tested in vivo according to the Antiepileptic Drug Development Program of the National Institutes of Health (USA) were generally active as anticonvulsants in chemically induced seizures. The endogenous nucleoside adenosine is an autacoid produced in many organs and tissues, exhibiting diverse potent physiological actions in the cardiovascular, nervous, pulmonary, renal, and immune systems. Extracellular adenosine either released from cells or ATP hydrolysis regulates several physiological functions by activation on specific cell membrane receptors. The combination of pharmacological studies and molecular cloning revealed the existence of four distinct adenosine receptor (AR) subtypes, which are identified and classified as A1, A2A, A2B, and A3, all belonging to the G protein-coupled, 7-transmembrane-segment receptors superfamily. Whereas the adenosine A1 and A3 receptor subtypes are coupled to the Gi protein, inhibiting adenylate cyclase, A2A and A2B subtypes stimulate this enzyme via Gs. A1 and A3 ARs may also be coupled to other second messenger systems, such as activation of phospholipase C (PLC), and A1 ARs can also lead to a stimulation of K + channels or an inhibition of Ca2+ channels [1]. Moreover, ARs are involved in interactions with receptors for other neurotransmitters and/or neuromodulators, namely receptors for neuropeptides (CGRP and VIP), ionotropic (NMDA) and *Plenary lecture presented at the Hungarian–German–Italian–Polish Joint Meeting on Medicinal Chemistry, Budapest, Hungary, 2–6 September 2001. Other presentations are published in this issue, pp. 1387–1509. †Corresponding author metabotropic (mGlu I and III) glutamate receptors, GABA and nicotinic autofacilitatory, muscarinic, and dopamine receptors [2–4]. ARs have been cloned from several mammalian species [1], including humans (human recombinant ARs were expressed in mammalian cell lines—CHO, HEK [5–7]). It was found that, for example, the human A1 AR differs by 18 amino acids from the dog A1 sequence and 16 amino acids from the rat A1 sequence, the human A2A AR differs by 28 amino acids from the dog A2A sequence [7]. ARs have become important targets for drug development. Selective interaction with AR subtypes offers very broad therapeutic potentials, including the regulation of the electrophysiological properties of the heart, kidney functions, immune system (including inflammatory activity), some central nervous system functions, and cell growth [8–12]. The main interest of this work concerns current developments of selective A1 and A2 AR antagonists. The A1 AR is found in high density in the brain (cortex, hippocampus) and in lower density in peripheral organs and tissues such as heart, kidney, lung, and fat cells. Adenosine A1 antagonists have the main therapeutic potentials as kidney-protective diuretics and agents for the treatment of dementias, including Alzheimer’s disease, depression, cardiac failure, and asthma [9,13]. During the past 20 years, a large number of A1 AR antagonists have been developed including bior tricyclic heterocyclic derivatives [13–15]. Important classes of A1-selective antagonists comprise xanthine derivatives with bulky 8-substituents, adenine derivatives with bulky N6-substituents, 7-deaza and 7-deaza-8-aza analogs of adenine, pyrazolo[1,5-a]pyridines, and other heterocyclic compounds (Fig. 1). K. KIEC-KONONOWICZ et al. © 2001 IUPAC, Pure and Applied Chemistry 73, 1411–142

Gas evolution has a profound effect on the functioning of state of the art lithium-ion batteries. On the one hand, it is the natural concomitant of SEI formation; on the other hand, because of the demand for high terminal voltages, it is the consequence of electrolyte or electrode material oxidation. This happens on the expense of the efficiency. Furthermore, the presence of gases in the cell raises safety problems. In general it is important to understand gas formation processes. First, to be able to develop novel electrolyte mixtures or tailor electrolyte additives that form a stable SEI. Second, to optimize the surface and/or structure of cathode materials to influence both their bulk oxidative properties upon delithiation and electrocatalytic activities. Differential electrochemical mass spectrometry (DEMS) is one of the most appropriate tools to qualitatively elucidate gas evolution reactions in electrochemical systems. Herein, we report on the in situ gas analysis by means of differential electrochemical mass spectrometry and infrared spectroscopy (DEMS-DEIRS) of various battery systems. We analyze the SEI formation on different anode materials and the influence of various electrolyte additives. The impact of temperature and constant voltage/OCV periods on the first charge cycle (so-called formation process) is investigated. Their effect on both the gassing and electrolyte salt decomposition is described. The stability problem of the most common electrolytes at high voltages is discussed through the example of either NMC (LiNixMnyCozO2) type materials or with high voltage spinels (LiNi0.5Mn1.5O4). The electrocatalytic activity of the individual active material particles seems to play a decisive role in the oxidative decomposition processes. Through the application of modified cathode surfaces a relation between surface activity and the amount of produced gases is revealed. Beyond the decomposition of the electrolyte, oxygen evolution is the crucial factor at high cathode potentials. This effect is particularly apparent for overlithiated and high Ni content materials. Monitoring gassing over 20 cycles uncovers interesting changes being only recognizable in “long term” tests. We demonstrate the importance of potentiodynamic cycling in addition to the traditional galvanostatic test with DEMS-DEIRS in the exploration of reaction mechanisms. Pressure measurements complete the analysis in terms of validation of gas amounts.

Aging in Li-ion batteries is accompanied by structural and compositional changes of the active and passive material of the electrodes. Visualization of spatial correlation between morphological properties and chemical phase can help to find origins of aging and failure mechanisms and to understand the ongoing processes. Micro X-ray fluorescence (XRF) analysis allows for chemical imaging of elemental distributions of multiple 3d elements simultaneously, or distribution of the state of charge even at low concentrations or under operando conditions. Utilizing focused synchrotron radiation, representative volumes of the electrodes can be studied with sub-micrometer resolution on acceptable time scales. Cutting edge instrumentation in this field is the Maia fluorescence detector. It allows for ultra-fast mapping of areas of multiple mm² with high spatial resolution within minutes. This allows e.g. examination of large electrode areas. The backscattering geometry of the detector enables easy mounting of flat samples such as electrodes or pouch-cells. By variation of the energy in the vicinity of an absorption edge, conclusions on local variations of the state of charge can be drawn, probing the oxidation state of the redox-active element. Furthermore, confocal XRF enables spatially resolved measurements of the deposition of transition metals on the graphitic anode without destruction. This will help to understand the impact on capacity fade and degradation. For the present study, samples of LiNi0.5Mn1.5O4 electrodes cycled vs. Li or graphite were investigated at beamline P06 at DESY, Hamburg Germany.1 The experiment revealed significant inhomogeneities in the local Ni/Mn ratio upon cycling which is correlated to thinning of the electrode. Higher cycling rates showed an increased impact and higher material losses. Inhomogeneities in the phase transformation were also found during the charge and discharge process. The graphitic anodes showed significant amounts of deposited transition metals, few wt%, both Ni and Mn, deeply penetrating into the pores of the electrode. On the other hand, a study on commercial LiFePO4 cathodes with outstanding rate capabilities showed an extremely high degree of homogeneity throughout the investigated areas. These methods are by no means limited to the investigated materials, but are easily transferred to other transition metal containing electrode materials. 1. U. Boesenberg et al., Chem.Mater., 27, 2525–2531 (2015)

Lithium ion batteries are generally considered to be the technology of choice for hybrid electric and full electric vehicles. However, further enhancement in the energy and power densities of lithium ion batteries is necessary to fulfill the requirements imposed by automotive applications [1, 2]. High voltage LiNi0.5Mn1.5O4 spinel (LNMO) appears to be a very promising cathode-active material in combination with state-of-the-art graphite anodes. This is due, in part, to its low cost, high theoretical specific capacity (147 mAh g–1) and high nominal operating voltage (4.7 V vs. Li/Li+). However, there are severe performance limitations that need to be overcome before commercialization can be contemplated. LNMO/Li half-cells typically show high cycling stability, even at elevated temperatures [3]. Full-cells made of LNMO cathode and graphite anode suffer from capacity fading upon cycling. In recent years, several degradation mechanisms have been identified and correlated with the overall performance. Major issues arise from electrolyte decomposition [4, 5] accompanied by formation of gaseous species [6] and manganese dissolution [7]. In this study, we focus on the in situ gas analysis of LNMO based full-cells during charge and discharge. Two different cell systems, LNMO/graphite and LNMO/LiFePO4, are investigated. In the LNMO/graphite system both electrodes contribute to the gassing processes. By using delithiated LiFePO4 as anode, gas evolution on LNMO can be studied separately, because no gaseous byproducts are formed on LiFePO4. The evolving gases were studied using an analysis setup allowing for in situ investigation by means of mass spectrometry (DEMS: differential electrochemical mass spectrometry). A visualization of forming gas bubbles and a quantitative estimation of the formed gas volume in the cell was achieved by in operando neutron imaging. Mechanistic insights into the decomposition processes were gained by correlating the cell potential to the pattern of the evolving gases. The influence of other electrochemical parameters, like constant voltage steps, charge/discharge current rate and formation processes (i.e., pre-aging of the electrodes at different temperatures), on the gassing behavior and gas composition was also investigated. These effects and their impact on the cycling stability are discussed. References: [1] J. Vetter, P. Novak, M. R. Wagner, C. Veit, K. C. Moller, J. O. Besenhard, M. Winter, M. Wohlfahrt-Mehrens, C. Vogler, A. Hammouche, Journal of Power Sources 2005, 147, 269-281. [2] M. Winter, R. J. Brodd, Chem. Rev. 2004, 104, 4245-4269. [3] B. Markovsky, Y. Talyossef, G. Salitra, D. Aurbach, H. J. Kim, S. Choi, Electrochemistry Communications 2004, 6, 821-826. [4] D. Aurbach, B. Markovsky, G. Salitra, E. Markevich, Y. Talyossef, M. Koltypin, L. Nazar, B. Ellis, D. Kovacheva, Journal of Power Sources 2007, 165, 491-499. [5] L. Yang, B. Ravdel, B. L. Lucht, Electrochemical and Solid State Letters 2010, 13, A95-A97. [6] M. Onuki, S. Kinoshita, Y. Sakata, M. Yanagidate, Y. Otake, M. Ue, M. Deguchi, Journal of the Electrochemical Society 2008, 155, A794-A797. [7] N. P. W. Pieczonka, Z. Liu, P. Lu, K. L. Olson, J. Moote, B. R. Powell, J.-H. Kim, The Journal of Physical Chemistry C 2013, 117, 15947-15957.