Abstract: The chromium-based metal organic framework MIL-101(Cr) served as a host for the in situ synthesis of Fe3O4 nano particles. This hybrid nanomaterial was tested as an adsorbent for arsenite and arsenate species in groundwater and surface water and showed excellent affinity towards As-III and As-V species. The adsorption capacities of 121.5 and 80.0 mg g(-1) for arsenite and arsenate species, respectively, are unprecedented. The presence of Ca2+, Mg2+, and phosphate ions and natural organic matter does not affect the removal efficiency or the selectivity. The structural integrity of the hybrid nanomaterial was maintained during the adsorption process and even after desorption through phosphate elution. Additionally, no significant leaching of Cr or Fe species was observed.

Abstract: The valley splitting of the conduction-band states in a thin silicon-on-insulator layer is investigated using the 30-band k . p theory. The system composed of a few nm thick Si layer embedded within thick SiO2 layers is analyzed. The valley split states are found to cross periodically with increasing quantum well width, and therefore the energy splitting is an oscillatory function of the quantum well width, with period determined by the wave vector K-0 of the conduction band minimum. Because the valley split states are classified by parity, the optical transition between the ground hole state and one of those valley split conduction band states is forbidden. The oscillations in the valley splitting energy decrease with electric field and with smoothing of the composition profile between the well and the barrier by diffusion of oxygen from the SiO2 layers to the Si quantum well. Such a smoothing also leads to a decrease of the interband transition matrix elements. The obtained results are well parametrized by the effective two-valley model, but are found to disagree from previous 30-band calculations. This discrepancy could be traced back to the fact that the basis for the numerical solution of the eigenproblem must be restricted to the first Brillouin zone in order to obtain quantitatively correct results for the valley splitting.

Abstract: A modelling study is performed of high-density low-pressure inductively coupled CF4/CHF3/H2/Cl2/O2/HBr plasmas under different gas mixing ratios. A reaction set describing the complete plasma chemistry is presented and discussed. The gas fraction of each component in this mixture is varied to investigate the sensitivity of the plasma properties, like electron density, plasma potential and species densities, towards the gas mixing ratios. This research is of great interest for microelectronics applications because these gases are often combined in two (or more)-component mixtures, and mixing gases or changing the fraction of a gas can sometimes yield unwanted reaction products or unexpected changes in the overall plasma properties due to the increased chemical complexity of the system. Increasing the CF4 fraction produces more F atoms for chemical etching as expected, but also more prominently lowers the density of Cl atoms, resulting in an actual drop in the etch rate under certain conditions. Furthermore, CF4 decreases the free electron density when mixed with Cl2. However, depending on the other gas components, CF4 gas can also sometimes enhance free electron density. This is the case when HBr is added to the mixture. The addition of H2 to the gas mixture will lower the sputtering process, not only due to the lower overall positive ion density at higher H2 fractions, but also because more H+, H2 + and H3 + are present and they have very low sputter yields. In contrast, a larger Cl2 fraction results in more chemical etching but also in less physical sputtering due to a smaller abundance of positive ions. Increasing the O2 fraction in the plasma will always lower the etch rate due to more oxidation of the wafer surface and due to a lower plasma density. However, it is also observed that the density of F atoms can actually increase with rising O2 gas fraction. This is relevant to note because the exact balance between fluorination and oxidation is important for fine-tuning the overall etch rate and for control of the sidewall profile. Finally, HBr is often used as a chemical etcher, but when mixed with F- or Cl-containing gases, HBr creates the same diluting effects as Ar or He, because a
higher fraction results in less chemical etching but more (physical) sputtering.

Abstract: We reveal the emergence of metallicKondo clouds in an atomistic carbon quantum dot, realized as a single-atom junction in a suitably patterned graphene nanoflake. Using density functional dynamical mean-field theory (DFDMFT) we show how correlation effects lead to striking features in the electronic structure of our device, and how those are enhanced by the electron-electron interactions when graphene is patterned at the atomistic scale. Our setup provides a well-controlled environment to understand the principles behind the orbital-selective Kondo physics and the interplay between orbital and spin degrees of freedom in carbon-based nanomaterials, which indicate new pathways for spintronics in atomically patterned graphene.

Abstract: Often real samples of graphene consist of islands of both monolayer and bilayer graphene. Bound states in such hybrid quantum dots are investigated for (i) a circular single-layer graphene quantum dot surrounded by an infinite bilayer graphene sheet and (ii) a circular bilayer graphene quantum dot surrounded by an infinite single-layer graphene. Using the continuum model and applying zigzag boundary conditions at the single-layer-bilayer graphene interface, we obtain analytical results for the energy levels and the corresponding wave spinors. Their dependence on perpendicular magnetic and electric fields are studied for both types of quantum dots. The energy levels exhibit characteristics of interface states, and we find anticrossings and closing of the energy gap in the presence of a bias potential.

Abstract: In this computational study, a gliding arc plasma reactor with a reverse-vortex flow stabilization is modelled for the first time by a fluid plasma description. The plasma reactor operates with argon gas at atmospheric pressure. The gas flow is simulated using the k-ε Reynolds-averaged Navier–Stokes turbulent model. A quasi-neutral fluid plasma model is used for computing the plasma properties. The plasma arc movement in the reactor is observed, and the results for the gas flow, electrical characteristics, plasma density, electron temperature, and gas temperature are analyzed.

Abstract: Pb2MnTeO6, a new double perovskite, was synthesized. Its crystal structure was determined by synchrotron X-ray and powder neutron diffraction. Pb2MnTeO6 is monoclinic (I2/m) at room temperature with a regular arrangement of all the cations in their polyhedra. However, when the temperature is lowered to similar to 120 K it undergoes a phase transition from I2/m to C2/c structure. This transition is accompanied by a displacement of the Pb atoms from the center of their polyhedra due to the 6s2 lone-pair electrons, together with a surprising off-centering of Mn2+ (d5) magnetic cations. This strong first-order phase transition is also evidenced by specific heat, dielectric, Raman, and infrared spectroscopy measurements. The magnetic characterizations indicate an anti-ferromagnetic (AFM) order below TN approximate to 20 K; analysis of powder neutron diffraction data confirms the magnetic structure with propagation vector k = (0 1 0) and collinear AFM spins. The observed jump in dielectric permittivity near similar to 150 K implies possible anti-ferroelectric behavior; however, the absence of switching suggests that Pb2MnTeO6 can only be antipolar. First-principle calculations confirmed that the crystal and magnetic structures determined are locally stable and that anti-ferroelectric switching is unlikely to be observed in Pb2MnTeO6.

Abstract: One of the most striking but unexplained phenomena in the natural degradation of glass is the transformation of an almost colorless, transparent and homogeneous glass into a colored, opaque and heterogeneous degradation layer. In many cases, the degradation layer consists of numerous lamellae with a thickness between 0.1 and 10 pm. However, both internal structure and formation proess of laminated degradation layers remain unclear. In this paper, a model is proposed where we assume that transformed (degraded) glass consists of a random packing of nano-sized silica particles while the lamellae are the result of different packing densities. The model is able to connect the texture of numerous lamellae observed by several types of microscopic techniques with the structure at molecular level determined by means of chemical analysis. In addition, the model is able to explain numerous properties such as the parameters responsible for the contrast between lamellae. This contrast can be caused by differences in color, density, elemental composition, or surface roughness. (C) 2016 Elsevier B.V. All rights reserved.

Abstract: We studied the solid-phase reaction between a thin Nifilm and a single crystal Ge(001) or Ge(111) substrate during a ramp anneal. The phase formation sequence was determined using in situX-ray diffraction and in situRutherford backscattering spectrometry (RBS), while the nature and the texture of the phases were studied using X-ray pole figures and transmission electron microscopy. The phase sequence is characterized by the formation of a single transient phase before NiGe forms as the final and stable phase. X-ray pole figures were used to unambiguously identify the transient phase as the ϵ-phase, a non-stoichiometric Ni-rich germanide with a hexagonal crystal structure that can exist for Ge concentrations between 34% and 48% and which forms with a different epitaxial texture on both substrate orientations. The complementary information gained from both RBS and X-ray pole figure measurements revealed a simultaneous growth of both the ϵ-phase and NiGe over a small temperature window on both substrate orientations.

Abstract: Pt/ZSM-5 catalysts with various crystal sizes were prepared via competitive ion-exchange, followed by a slow activation procedure. Even when using very large ZSM-5 crystals, highly dispersed Pt nano-clusters were contained within the zeolite crystal's voids, as ascertained by 2D pressure-jump IR spectroscopy of adsorbed CO and focussed ion-beam transmission electron microscopy. The shape-selective properties of the Pt/ZSM-5 catalysts were evaluated in the partial hydrogenation of soybean oil. Unique hydrogenation selectivities were observed, as the fatty acids located at the central position of the triacylglycerol (TAG) molecules were preferentially hydrogenated. The resulting oil has therefore high levels of intermediately melting TAGs, which are compatible with biolubricants due to their improved oxidative stability and still appropriate low-temperature fluidity. The TAG distribution in the partially hydrogenated soybean oil samples was independent from the zeolite crystal size, while the hydrogenation activity linearly increases with the crystal's external surface area. This trend was confirmed with a Pt loaded mesoporous ZSM-5 zeolite, obtained via a mild alkaline treatment. These observations imply and confirm a genuine pore mouth catalysis mechanism, in which only one fatty acid chain of the TAG is able to enter the micropores of ZSM-5, where the double bonds are hydrogenated by the crystal encapsulated Pt-clusters.

Abstract: Studying protein interactions is of vital importance both to fundamental biology research and to medical applications. Here, we report on the experimental proof of a universally applicable label-free homogeneous platform for rapid protein analysis. It is based on optically detecting changes in the rotational dynamics of magnetically agitated core-shell nanorods upon their specific interaction with proteins. By adjusting the excitation frequency, we are able to optimize the measurement signal for each analyte protein size. In addition, due to the locking of the optical signal to the magnetic excitation frequency, background signals are suppressed, thus allowing exclusive studies of processes at the nanoprobe surface only. We study target proteins (soluble domain of the human epidermal growth factor receptor 2 – sHER2) specifically binding to antibodies (trastuzumab) immobilized on the surface of our nanoprobes and demonstrate direct deduction of their respective sizes. Additionally, we examine the dependence of our measurement signal on the concentration of the analyte protein, and deduce a minimally detectable sHER2 concentration of 440 pM. For our homogeneous measurement platform, good dispersion stability of the applied nanoprobes under physiological conditions is of vital importance. To that end, we support our measurement data by theoretical modeling of the total particle-particle interaction energies. The successful implementation of our platform offers scope for applications in biomarker-based diagnostics as well as for answering basic biology questions.

Abstract: Nanocorrugation of 2D crystals is an important phenomenon since it affects their electronic and mechanical properties. The corrugation may have various sources; one of them is flexural phonons that, in particular, are responsible for the thermal conductivity of graphene. A study of corrugation of just the suspended graphene can reveal much of valuable information on the physics of this complicated phenomenon. At the same time, the suspended crystal nanorelief can hardly be measured directly because of high flexibility of the 2D crystal. Moreover, the relief portion related to rapid out-of-plane oscillations (flexural phonons) is also inaccessible by such measurements. Here we present a technique for measuring the Fourier components of the height-height correlation function H(q) of suspended graphene which includes the effect of flexural phonons. The technique is based on the analysis of electron diffraction patterns. The H(q) is measured in the range of wavevectors q approximately 0.4-4.5nm(-1). At the upper limit of this range H(q) does follow the T/kappaq(4) law. So, we measured the value of suspended graphene bending rigidity kappa=1.2+/-0.4eV at ambient temperature T approximately 300K. At intermediate wave vectors, H(q) follows a slightly weaker exponent than theoretically predicted q(-3.15) but is closer to the results of the molecular dynamics simulation. At low wave vectors, the dependence becomes even weaker, which may be a sign of influence of charge carriers on the dynamics of undulations longer than 10nm. The technique presented can be used for studying physics of flexural phonons in other 2D materials.

Abstract: Diamond is a promising material for a number of bio-applications, including the fabrication of platforms for attachment and investigation of neurons and of neuroprostheses, such as retinal implants. In the current work ultrananocrystalline diamond (UNCD) films were deposited by microwave plasma chemical vapor deposition, modified by UV/O-3 treatment or NH3 plasma, and comprehensively characterized with respect to their bulk and surface properties, such as crystallinity, topography, composition and chemical bonding nature. The interactions of insect circadian pacemaker neurons with UNCD surfaces with H-, O- and NH2-terminations were investigated with respect to cell density and viability. The fast and strong attachment achieved without application of adhesion proteins allowed for advantageous modification of dispersion protocols for the preparation of primary cell cultures. Centrifugation steps, which are employed for pelletizing dispersed cells to separate them from dispersing enzymes, easily damage neurons. Now centrifugation can be avoided since dispersed neurons quickly and strongly attach to the UNCD surfaces. Enzyme solutions can be easily washed off without losing many of the dispersed cells. No adverse effects on the cell viability and physiological responses were observed as revealed by calcium imaging. Furthermore, the enhanced attachment of the neurons, especially on the modified UNCD surfaces, was especially advantageous for the immunocytochemical procedures with the cell cultures. The cell losses during washing steps were significantly reduced by one order of magnitude in comparison to controls. In addition, the integration of a titanium grid structure under the UNCD films allowed for individual assignment of physiologically characterized neurons to immunocytochemically stained cells. Thus, employing UNCD surfaces free of foreign proteins improves cell culture protocols and immunocytochemistry with cultured cells. The fast and strong attachment of neurons was attributed to a favorable combination of topography, surface chemistry and wettability. (C) 2016 Elsevier B.V. All rights reserved.

Abstract: Trions and biexcitons in anisotropic two-dimensional materials are investigated within an effective mass theory. Explicit results are obtained for phosphorene and arsenene, materials that share features such as a direct quasiparticle gap and anisotropic conduction and valence bands. Trions are predicted to have remarkably high binding energies and an elongated electron-hole structure with a preference for alignment along the armchair direction, where the effective masses are lower. We find that biexciton binding energies are also notably large, especially for monolayer phosphorene, where they are found to be twice as large as those for typical monolayer transition metal dichalcogenides.

Abstract: Vegetables and fruits are an important part of a healthy food diet, however, the eco-sustainability of the production of these can still be significantly improved. European farmers and consumers spend an estimated Euro15.5 billion per year on inorganic fertilizers and the production of N-fertilizers results in a high carbon footprint. We investigated if fertilizer type and medium constituents determine microbial nitrogen conversions in organic growing media and can be used as a next step towards a more sustainable horticulture. We demonstrated that growing media constituents showed differences in urea hydrolysis, ammonia and nitrite oxidation and in carbon dioxide respiration rate. Interestingly, mixing of the growing media constituents resulted in a stimulation of the function of the microorganisms. The use of organic fertilizer resulted in an increase in amoA gene copy number by factor 100 compared to inorganic fertilizers. Our results support our hypothesis that the activity of the functional microbial community with respect to nitrogen turnover in an organic growing medium can be improved by selecting and mixing the appropriate growing media components with each other. These findings contribute to the understanding of the functional microbial community in growing media and its potential role towards a more responsible horticulture.