Abstract: Lipid oxidation is associated with several inflammatory and neurodegenerative diseases, but many questions to unravel its effects on biomembranes are still open due to the complexity of the topic. For instance, recent studies indicated that phase-separated domains can have a significant effect on membrane function. It is reported that domain interfaces are “hot spots” for pore formation, but the underlying mechanisms and the effect of oxidation-induced phase separation on membranes remain elusive. Thus, to evaluate the permeability of the membrane coexisting of liquid-ordered (Lo) and liquid-disordered (Ld) domains, we performed atomistic molecular dynamics simulations. Specifically, we studied the membrane permeability of nonoxidized or oxidized homogeneous membranes (single-phase) and at the Lo/Ld domain interfaces of heterogeneous membranes, where the Ld domain is composed of either oxidized or nonoxidized lipids. Our simulation results reveal that the addition of only 1.5% of lipid aldehyde molecules at the Lo/Ld domain interfaces of heterogeneous membranes increases the membrane permeability, whereas their addition at homogeneous membranes does not have any effect. This study is of interest for a better understanding of cancer treatment methods based on oxidative stress (causing among others lipid oxidation), such as plasma medicine and photodynamic therapy.

Abstract: The Sr3RFe4O10.5 (R=Y, Ho, Dy) anion-deficient perovskites were prepared using a solid-state reaction in evacuated sealed silica tubes. Transmission electron microscopy and 57Fe Mössbauer spectroscopy evidenced a complete A-cations and oxygen vacancies ordering. The structure model was further refined by ab initio structure relaxation, based on density functional theory calculations. The compounds crystallize in a tetragonal a≈2√2ap≈11.3 Å, с≈4сp≈16 Å unit cell (ap: parameter of the perovskite subcell) with the P42/mnm space group. Oxygen vacancies reside in the (FeO5/4□3/4) layers, comprising corner-sharing FeO4 tetrahedra and FeO5 tetragonal pyramids, which are sandwiched between the layers of the FeO6 octahedra. Smaller R atoms occupy the 9-fold coordinated position, whereas the 10-fold coordinated positions are occupied by larger Sr atoms. The Fe sublattice is ordered aniferromagnetically up to at least 500 K, while the rare-earth sublattice remains disordered down to 2 K.

Abstract: Measuring temperature in biological environments is an ambitious goal toward supporting medical treatment and diagnosis. Minimally invasive techniques based on optical probes require very specific properties that are difficult to combine within a single material. These include high chemical stability in aqueous environments, optical signal stability, low toxicity, high emission intensity, and, essential, working at wavelengths within the biological transparency windows so as to minimize invasiveness while maximizing penetration depth. We propose CaF2:Nd3+,Y3+ as a candidate for thermometry based on an intraband ratiometric approach, fully working within the biological windows (excitation at 808 nm; emission around 1050 nm). We optimized the thermal probes through the addition of Y3+ as a dopant to improve both emission intensity and thermal sensitivity. To define the conditions under which the proposed technique can be applied, gold nanorods were used to optically generate subtissue hot areas, while the resulting temperature variation was monitored with the new nanothermometers.

Abstract: The series Sr2MnO2Cu1.5(S1-xSex)(2) (0 <= x <= 1) contains mixed-valent Mn ions (Mn2+/Mn3+) in MnO2 sheets which are separated by copper-deficient antifluorite-type Cu(2-delta)Ch(2) layers with delta similar to 0.5. The compounds crystallize in the structure type first described for Sr2Mn3Sb2O2 and are described in the I4/mmm space group at ambient temperatures. Below about 250 K, ordering between Cu+ ions and tetrahedral vacancies occurs which is long-range and close to complete in the sulfide-containing end member of the series Sr2MnO2Cu1.5S2 but which occurs over shorter length scales as the selenide content increases. The superstructure is an orthorhombic 2 root 2a x root 2a x c expansion in Ibam of the room temperature cell. For x > 0.3 there are no superstructure reflections evident in the X-ray or neutron diffraction patterns, and the I4/mmm description is valid for the average structure at all temperatures. However, in the pure selenide end member, Sr2MnO2Cu1.5Se2, diffuse scattering in electron diffractograms and modulation in high resolution lattice image profiles may arise from short-range Cu/vacancy order. All members of the series exhibit long-range magnetic order. In the sulfide-rich end member and in compounds with x < 0.1 in the formula Sr2MnO2Cu1.5(S1-xSex)(2), which show well developed superstructures due to long-range Cu/vacancy order, the magnetic structure has a (1/4 1/4 0) propagation vector in which ferromagnetic zigzag chains of Mn moments in the MnO2 sheets are coupled antiferromagnetically in an arrangement described as the CE-type magnetic structure and found in many mixed-valent perovskite and Ruddlesden-Popper type oxide manganites. In these cases the magnetic cell is an a x 2b x c expansion of the low temperature Ibam structural cell. For x >= 0.2 in the formula Sr2MnO2Cu1.5(S1-xSex)(2) the magnetic structure has a (0 0 0) propagation vector and is similar to the A-type structure, also commonly adopted by some perovskite-related manganites, in which the Mn moments in the MnO2 sheets are coupled ferromagnetically and long-range antiferromagnetic order results from antiferromagnetic coupling between planes. In the region of the transition between the two different structural and magnetic long-range ordering schemes (0.1 < x < 0.2) the two magnetic structures coexist in the same sample. The evolution of the competition between magnetic ordering schemes and the length scale of the structural order with composition in Sr2MnO2Cu1.5(S1-xSex)(2) suggest that the changes in magnetic and structural order are related consequences of the introduction of chemical disorder.

Abstract: We explorethepotentialofmicrowave(MW)-plasma-based in situ
utilizationoftheMartianatmospherewithafocusonthenovelpos-
sibilityoffixingN2 forfertilizerproduction. Conversioninasimulant
plasma (i.e.,
96% CO2,
2% N2, and
2% Ar),performedunderen-
ergyconditionssimilartothoseoftheMarsOxygen In Situ Resource
UtilizationExperiment(MOXIE),currentlyonboardNASA’sPerse-
verancerover,demonstratesthatO/O2 formedthroughCO2 dissociation
facilitatesthefixationoftheN2 fractionviaoxidationtoNOx.
PromisingproductionratesforO2, CO,andNOx of 47.0,76.1,and
1.25g/h,respectively,arerecordedwithcorrespondingenergy
costs of0.021,0.013,and0.79kWh/g,respectively.Notably,O2
productionratesare
30 timeshigherthanthosedemonstrated
by MOXIE,whiletheNOx production raterepresentsan
7% fixa-
tionoftheN2 fraction presentintheMartian atmosphere.MW-
plasma-basedconversionthereforeshowsgreatpotentialasan in
situ resourceutilization(ISRU)technologyonMarsinthatitsimulta-
neouslyfixesN2 and producesO2.

Abstract: Molecular dynamics simulations were used to investigate the size-dependent melting mechanism of nickel nanoclusters of various sizes. The melting process was monitored by the caloric curve, the overall cluster Lindemann index, and the atomic Lindemann index. Size-dependent melting temperatures were determined, and the correct linear dependence on inverse diameter was recovered. We found that the melting mechanism gradually changes from dynamic coexistence melting to surface melting with increasing cluster size. These findings are of importance in better understanding carbon nanotube growth by catalytic chemical vapor deposition as the phase state of the catalyst nanoparticle codetermines the growth mechanism.

Abstract: A two-dimensional model is presented that describes the behavior of argon metastable atoms, copper atoms, and copper ions in an argon direct. current glow discharge, in the standard cell of the VG9000 glow discharge mass spectrometer for analyzing flat samples. The model is combined with a previously developed model for the electrons, argon ions, and atoms in the same cell to obtain an overall picture of the glow discharge, The results of the present model comprise the number densities of the described plasma species, the relative contributions of different production and loss processes for the argon metastable atoms, the thermalization profile of the sputtered copper atoms, the relative importance of the different ionization mechanisms for the copper atoms, the ionization degree of copper, the copper ion-to-argon ion density ratio, and the relative roles of copper ions, argon ions, and atoms in the sputtering process. All these quantities are calculated for a range of voltages and pressures, Moreover, since the sticking coefficient of copper atoms on solid surfaces is not well-known in the literature, the influence of this parameter on the results is briefly discussed.

Abstract: Perovskite-structured titanates with layered A-site ordering form remarkably complex superstructures. Using transmission electron microscopy, synchrotron X-ray and neutron powder diffraction, and ab initio structure relaxation, we present the structural solution of the incommensurately modulated Li3xNd2/3xTiO3 perovskites (x = 0.05, superspace group Pmmm(α1,1/2,0)000(1/2,β2 0)000, a = 3.831048(5) Å, b = 3.827977(4) Å, c = 7.724356(8) Å, q1 = 0.45131(8)a* + 1/2b*, q2 = 1/2a* + 0.41923(4)b*). In contrast to earlier conjectures on the nanoscale compositional phase separation in these materials, all peculiarities of the superstructure can be understood in terms of displacive modulations related to an intricate octahedral tilting pattern. It involves fragmenting the pattern of the out-of-phase tilted TiO6 octahedra around the a- and b-axes into antiphase domains, superimposed on the pattern of domains with either pronounced or suppressed in-phase tilt component around the c-axis. The octahedral tilting competes with the second order JahnTeller distortion of the TiO6 octahedra. This competition is considered as the primary driving force for the modulated structure. The A cations are suspected to play a role in this modulation affecting it mainly through the tolerance factor and the size variance. The reported crystal structure calls for a revision of the structure models proposed for the family of layered A-site ordered perovskites exhibiting a similar type of modulated structure.

Abstract: Porous metal oxides with nano-sized features attracted intensive interest in recent decades due to their high surface area which is essential for many applications, e.g. Li ion batteries, photocatalysts, fuel cells and dye-sensitized solar cells. Various approaches have so far been investigated to synthesize porous nanostructured metal oxides, including self-assembly and template-assisted synthesis. For the latter approach, forests of carbon nanotubes are considered as particularly promising templates, with respect to their one-dimensional nature and the resulting high surface area. In this work, we systematically investigate the formation of porous metal oxides (Al2O3, TiO2, V2O5 and ZnO) with different morphologies using atomic layer deposition on multi-walled carbon nanotubes followed by post-deposition calcination. X-ray diffraction, scanning electron microscopy accompanied by X-ray energy dispersive spectroscopy and transmission electron microscopy were used for the investigation of morphological and structural transitions at the micro- and nano-scale during the calcination process. The crystallization temperature and the surface coverage of the metal oxides and the oxidation temperature of the carbon nanotubes were found to produce significant influence on the final morphology.

Abstract: The local and average crystal structures and magnetic properties of the oxygen-deficient perovskite Sr2Fe1.5Cr0.5O5+y were studied using powder X-ray and neutron diffraction, neutron-pair distribution function analysis, and electron energy-loss spectroscopy. This material crystallizes in the cubic Pm3̅m space group, with a = 3.94491(14) Å. The oxygen vacancies are distributed randomly throughout the perovskite-type structure, and the average coordination number of the Fe(Cr) sites is 5. Refinement of the neutron diffraction data indicates y 0.05. This is in discordance with an earlier report on a material with the same nominal composition and cell constant. Electron energy-loss Cr L2,3-edge spectroscopy shows that Cr3+ is present, which is also contrary to previous speculation. Neutron-pair distribution function studies show that a brownmillerite-like model involving ordered vacancies and alternating octahedral and tetrahedral coordination at the metal sites, gives a better description of the local structure out to 5 Å. A remarkable phenomenon determined by neutron diffraction in Sr2Fe1.5Cr0.5O5 is the occurrence of a long-range G-type antiferromagnetic ordering with Tc ≈ 565 K because cubic oxygen-deficient perovskites with B-site disorder usually do not undergo transitions to magnetically ordered states. The observation of long-range antiferromagnetic order and the Tc value are in accordance with previous Mössbauer spectroscopic studies.

Abstract: On several paintings of James Ensor (1860−1949), a gradual fading of originally bright yellow areas, painted with the pigment cadmium yellow (CdS), is observed. Additionally, in some areas exposed to light, the formation of small white-colored globules on top of the original paint surface is observed. In this paper the chemical transformation leading to the color change and to the formation of the globules is elucidated. Microscopic X-ray absorption near-edge spectroscopy (ì-XANES) experiments show that sulfur, originally present in sulfidic form (S2−), is oxidized during the transformation to the sulfate form (S6+). Upon formation (at or immediately below the surface), the highly soluble cadmium sulfate is assumed to be transported to the surface in solution and reprecipitates there, forming the whitish globules. The presence of cadmium sulfate (CdSO4·2H2O) and ammonium cadmium sulfate [(NH4)2Cd(SO4)2] at the surface is confirmed by microscopic X-ray diffraction measurements, where the latter salt is suspected to result from a secondary reaction of cadmium sulfate with ammonia. Measurements performed on cross sections reveal that the oxidation front has penetrated into the yellow paint down to ca. 1−2 ìm. The morphology and elemental distribution of the paint and degradation product were examined by means of scanning electron microscopy equipped with an energy-dispersive spectrometer (SEM-EDS) and synchrotron radiation based micro-X-ray fluorescence spectrometry (SR ì-XRF). In addition, ultraviolet-induced visible fluorescence photography (UIVFP) revealed itself to be a straightforward technique for documenting the occurrence of this specific kind of degradation on a macroscale by painting conservators.

Abstract: Many western manuscripts were written using iron gall inks. These inks can damage the paper via two major mechanisms: (a) acid hydrolysis, enhanced by humidity, and (b) oxidative depolymerization provoked by the presence of oxygen and free iron(II) ions. The degradation of unsized Whatman paper impregnated with different combinations of iron sulfate, gallic acid, and gum arabic was studied at room temperature in order to assess the relative importance of each mechanism. The samples were stored in various environments including a dry and/or an oxygen-free atmosphere. The cellulose depolymerization was monitored by viscometry and related to changes in the oxidation state of iron, determined by X-ray absorption near-edge spectrometry. The results indicate that residual amounts of oxygen (less than 0.1%) promote cellulose depolymerization, whereas the level of relative humidity has no impact. The cellulose depolymerization also appears closely correlated to oxidative mechanisms. Regarding the oxidation of iron, it only occurs in the simultaneous presence of oxygen and moisture, suggesting the occurrence of rustlike oxidative mechanisms. Finally, the presence of gallic acid has a strong influence, which is only partially explained by its capacity to reduce iron(III) to iron(II).

Abstract: The crystal structure and the microstructure of epitaxial Sr4Fe6O13+/-delta thin films grown on a single-crystal SrTiO3 substrate by PLD have been investigated. A combination of electron diffraction and high-resolution microscopy allows us to refine the structure and to identify an incommensurate modulation in the Sr4Fe6O13+/-delta films. The incommensurate structure (q = alphaa(m)* approximate to 0.39alpha(m)*, superspace group Xmmm(alpha00)0s0) can be interpreted as an oxygen-deficient modification in the Fe2O2.5 double layers. Moreover, it is shown that the experimentally determined a component of the modulation can be used consistently to estimate the local oxygen content in the Sr4Fe6O13+/-delta films. The compound composition can therefore be described as Sr4Fe6O12+2alpha and the value alpha = 0.39 corresponds to a Sr4Fe6O12.78 composition. The misfit stress along the Sr4Fe6O13+/-delta/SrTiO3 interface is accommodated via both elastic deformation and inelastic mechanisms (misfit dislocations and 90degrees rotation twins). The present results also suggest the existence of SrFeO3 perovskite in the Sr4Fe6O13+/-delta films.