Phase Equilibria,Crystal Chemistry and Physical Properties of Au-Ba-Ge Clathrates

In the Au-Ba-Ge system the clathrate type I solid solution, Ba₈Au _x Ge_46−x−y □ _y , extends at 800 °C from binary Ba₈Ge₄₃□₃ (□ is a vacancy) to Ba₈Au₆Ge₄₀. For the clathrate phase (1 ≤ x ≤ 6) cubic primitive symmetry (space group Pm[`3]n Pm{\bar{{3}}}n ) was confirmed by x-ray powder diffraction assisted by x-ray single crystal analyses of Ba₈Au_4.6Ge_40.3□_1.1. The lattice parameters of the solid solution show an almost linear increase with increasing gold content. Site preference from x-ray refinement shows that gold atoms preferably occupy the 6d site in random mixture with Ge and vacancies, which vanish at the solubility limit. Clathrate type ΙX (Ba₆Ge₂₅ type) has a maximum solubility of 2.7 at.% gold at 800 °C. Phase equlilibria at 800 °C are characterized by four ternary phases in the investigated region up to 33.3 at.% barium. The homogeneity range of Ba(Au_1−x Ge _x )₂ (AlB₂-type) and BaAu_1+x Ge_3−x has been established: Ba(Au_1−x Ge _x )₂ extends from BaAu_0.5Ge_1.5 to BaAu_0.9Ge_1.1 and BaAu_1+x Ge_3−x from BaAu_1.1Ge_2.9 (BaNiSn₃-type) to BaAu_2.7Ge_1.3 (Ce(Ni,Sb)₄-type). The crystal structures of two phases in the gold-rich part have been determined from single crystal x-ray data and were found to form new structure types: BaAu₃Ge with BaAu₃Ge-type (space group P4/nmm, a = 0.6459(2), c = 0.5487(2) nm) and BaAu_5+x Ge_2−x (x = 0, BaAu₅Si₂-type, space group Pnma, a = 0.8981(2), b = 0.7106(2) and c = 1.0363(2) nm), the latter revealing with increasing gold content a closely related derivative structure type (BaAu_5.3Ge_1.7, a = a_{\textBaAu5 \textSi2} ,  b = b_{\textBaAu5 \textSi2} ,  c = 2c_{\textBaAu5 \textSi2} a = a_{{{\text{BaAu}}_{5} {\text{Si}}_{2} }} ,\;b = b_{{{\text{BaAu}}_{5} {\text{Si}}_{2} }} ,\;c = 2c_{{{\text{BaAu}}_{5} {\text{Si}}{}_{2}}} ). Transport properties and particularly the thermoelectric behavior were studied for Ba₈Au₆Ge₄₀.     

Electron transfer capacities and reaction kinetics of peat dissolved organic matter

Information about electron-transfer reactions of dissolved organic matter (DOM) is lacking. We determined electron acceptor and donor capacities (EAC and EDC) of a peat humic acid and an untreated peat DOM by electrochemical reduction and reduction with metallic Zn and H2S (EAC), and by oxidation with complexed ferric iron (EDC) at pH 6.5. DOC concentrations (10-100 mg L(-1)) and pH values (4.5-8) were varied in selected experiments. EAC reached up to 6.2 mequiv x (g C)(-1) and EDC reached up to 1.52 mequiv-(g C)(-1). EDC decreased with pH and conversion of chelated to colloidal iron, and the electron-transfer capacity (ETC) was controlled by the redox potential Eh of the reactant (ETC = 1.016x Eh - 0.138; R(2) = 0.87; p = 0.05). The kinetics could be adequately described by pseudo first-order rate laws, one or two DOM pools, and time constants ranging from 2.1 x 10(-3) d-1 to 1.9 x 10(-2) d(-1) for the fast pool. Reactions were completed after 24-160 h depending on the redox couple applied. The results indicate that DOM may act as a redox buffer over electrochemical potentials ranging from -0.9 to +1.0 V.     

Separating the Role of Particles and the Suspending Fluid for the Flow of Soy Milks

The paper describes a model and a simple experimental method to determine suspension transport properties, separating the role of particles from the suspending fluid. Shear stresses are described as consisting of 2 components: 1st, a shear stress caused by the flow of the suspending fluid and 2nd, a shear stress caused by direct interaction between suspended particles. We show that the determination of these shear stresses of a complex (food) suspension is largely independent of the definition of its suspending fluid. The rheological behavior of soy milks at low and intermediate moisture contents was studied, and results are compared with those obtained previously. The method evidences that the high viscosity of soy milks is predominantly caused by direct particle interaction.     

Numerical simulation of two-phase flow in deformable porous media: Application to carbon dioxide storage in the subsurface

In this paper, conceptual modeling as well as numerical simulation of two-phase flow in deep, deformable geological formations induced by CO₂ injection are presented. The conceptual approach is based on balance equations for mass, momentum and energy completed by appropriate constitutive relations for the fluid phases as well as the solid matrix. Within the context of the primary effects under consideration, the fluid motion will be expressed by the extended Darcy's law for two phase flow. Additionally, constraint conditions for the partial saturations and the pressure fractions of carbon dioxide and brine are defined. To characterize the stress state in the solid matrix, the effective stress principle is applied. Furthermore, the interaction of fluid and solid phases is illustrated by constitutive models for capillary pressure, porosity and permeability as functions of saturation. Based on this conceptual model, a coupled system of nonlinear differential equations for two-phase flow in a deformable porous matrix (H²M model) is formulated. As the displacement vector acts as primary variable for the solid matrix, multiphase flow is simulated using both pressure/pressure or pressure/saturation formulations. An object-oriented finite element method is used to solve the multi-field problem numerically. The capabilities of the model and the numerical tools to treat complex processes during CO₂ sequestration are demonstrated on three benchmark examples: (1) a 1-D case to investigate the influence of variable fluid properties, (2) 2-D vertical axi-symmetric cross-section to study the interaction between hydraulic and deformation processes, and (3) 3-D to test the stability and computational costs of the H²M model for real applications.     

Structure–Property Relationships in Aligned Electrospun Barium Titanate Nanofibers

Barium titanate nanofibers were uniaxially aligned by electrospinning onto a rotating copper wire drum and alignment was maintained during calcination of the fibers. Two methods for maintaining alignment during calcination were tested, by either using carbon tape or a peeling off method to remove the aligned fibers from the mandrel followed by calcination. The carbon tape removal method led to the formation of shorter aligned nanowires while the peeling off method resulted in longer nanofibers. Additionally, the effects of calcination temperature and time on crystal structure were also examined. The degree of tetragonality in the barium titanate nanofibers increased at higher calcination temperatures and times. Piezoelectricity was confirmed in the nanofibers calcined using piezoeresponse force microscopy, yielding a d₃₃ value of 15.5 pm/V. Using the methods presented here, large quantities of aligned piezoelectric barium titanate and other ceramic fibers or wires can be produced to fulfill their demand in novel microelectronics.     

Gaucher Disease Diagnosis Using Lyso-Gb1 on Dry Blood Spot Samples: Time to Change the Paradigm?

For years, the gold standard for diagnosing Gaucher disease (GD) has been detecting reduced β-glucocerebrosidase (GCase) activity in peripheral blood cells combined with GBA1 mutation analysis. The use of dried blood spot (DBS) specimens offers many advantages, including easy collection, the need for a small amount of blood, and simpler transportation. However, DBS has limitations for measuring GCase activity. In this paper, we recount our cross-sectional study and publish seven years of experience using DBS samples and levels of the deacylated form of glucocerebroside, glucosylsphingosine (lyso-Gb1), for GD diagnosis. Of 444 screened subjects, 99 (22.3%) were diagnosed with GD at a median (range) age of 21 (1–78) years. Lyso-Gb levels for genetically confirmed GD patients vs. subjects negative to GD diagnosis were 252 (9–1340) ng/mL and 5.4 (1.5–16) ng/mL, respectively. Patients diagnosed with GD1 and mild GBA1 variants had lower median (range) lyso-Gb1, 194 (9–1050), compared to GD1 and severe GBA1 variants, 447 (38–1340) ng/mL, and neuronopathic GD, 325 (116–1270) ng/mL (p = 0.001). Subjects with heterozygous GBA1 variants (carrier) had higher lyso-Gb1 levels, 5.8 (2.5–15.3) ng/mL, compared to wild-type GBA1, 4.9 (1.5–16), ng/mL (p = 0.001). Lyso-Gb1 levels, median (range), were 5 (2.7–10.7) in heterozygous GBA1 carriers with Parkinson’s disease (PD), similar to lyso-Gb1 levels in subjects without PD. We call for a paradigm change for the diagnosis of GD based on lyso-Gb1 measurements and confirmatory GBA1 mutation analyses in DBS. Lyso-Gb1 levels could not be used to differentiate between heterozygous GBA1 carriers and wild type.     

Säulenchromatographische Abtrennung von Phospholipiden aus Gesamtlipidextrakten

Column Chromatographic Separation of Phospholipids from Total Lipid Extracts The separation of phospholipids out of total lipid extracts is described by using a column chromatographic method. Up to 800 mg total lipids in a mixture of chloroform and methanol (19 : 1, v/v) may be applied to dry-column-chromatography using 5 g silica gel as a matrix. Neutral lipids and free fatty acids are elutet by propanol-2. Following extraction of phospholipids is achieved by methanol, containing 0.5 ml/100 ml ammonia solution (25%). In the course of the preparation no lyso-phospholipids are formed and the composition of the phospholipidfraction is not altered. The recovery of applied phospholipids amounts 98-99.5%.     

Fire‐retardant hybrid thermosetting resins from unsaturated polyesters and polysilazanes

This introduces an organic–inorganic thermosetting hybrid resin system based on unsaturated polyester and polysilazanes. It shows the chemical modification of unsaturated polyester structures by end capping to enable the combination of both components. In general, halogen‐free unsaturated polyesters are not fire‐retardant and have to be equipped with additives. Fillers and intumescent additives are preponderantly used in today's fire‐retardant formulations. In contrast to these fire‐retardants, polysilazanes act as ceramizing agents. Polysilazanes are suitable fire‐retardants for resin transfer molding due to their low viscosity. Both burning behavior and glass transition temperature (T_g) are investigated as important application properties. In contrast to state‐of‐the‐art fire‐retardant formulations polysilazane‐based thermosetting hybrid resins burn with high intensity and fast extinction. Therefore, total heat and smoke emission is decreased. The formation of ceramic structures during burning results in high residual mechanical properties and a low mass loss. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40375.