X-ray photoelectron spectroscopy and Raman microscopy of a ferroan platinum crystal from the Kondyor Massif,Russian Far East

X-ray Photoelectron Spectroscopy was used to study a ferroan platinum crystal from the Kondyor Massif, Russian Far East. Prior to the X-ray Photoelectron Spectroscopic analyses, the nature of the crystal was confirmed by X-ray diffraction. The survey scan showed mainly the presence of Pt and Fe, with smaller amounts of O and Si. The high resolutions spectra of the Pt 4f and Fe 2p showed 18.3 atom% Fe in the crystal, which puts the composition on the lower boundary for ferroan platinum and confirms earlier analyses using other methods such as Scanning Electron Microscopy-Energy Dispersive X-ray analysis/microprobe. The binding energy of the Pt 4f5/2 was 74.0?eV and Pt 4f7/2 70.5?eV, while the Fe 2p3/2 for metallic Fe was observed at 707.2?eV. The Fe 2p3/2 for metallic Fe was significantly sharper than that of Fe 2p3/2 at 710.7?eV associated with surface material. The Raman spectrum was dominated by the Pt–Pt stretching mode at 253?cm^?1. Changed orientation resulted in the observation of two bands at 127 and 139?cm^?1, interpreted as being due to stretching modes of two Pt–Pt bonds with the third bond to Fe and Pt fixed. The presence of Ca-Fe-Al-Mg-Si-O on the surface was probably associated with the presence of a clinopyroxene. These minerals can be expected since the crystal came originally from a clinopyroxenite-dunite matrix. The spectra showed a variety of interferences, e.g. Al 2p with Pt 4f, Mg 2p with Fe 3p, and Ca 2p1/2 with Mg Auger, making exact determinations of the ratios of these elements difficult.     

Synthetic studies towards the penicisulfuranols: Synthesis of an advanced spirocyclic diketopiperazine intermediate

The 2,5-diketopiperazine (DKP) moiety is a core feature of many natural products and medicinally relevant scaffolds. As part of our efforts directed towards a total synthesis of penicisulfuranol B, we have developed and report herein: (1) the preparation of an N-hydroxy diketopiperazine intermediate accessible via a molybdenum-mediated oxidation of a parent diketopiperazine, and (2) further synthetic studies leading to a novel spirocyclic dihydrobenzofuran-containing diketopiperazine.     

Crystal structures of a family of layered coordination polymers containing divalent metal ions (Mn<Superscript>2+</Superscript>, Co<Superscript>2+</Superscript>, Ni<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript>) and the 3-amino 4-methyl benzoate ion

The syntheses and crystal structures of the layered coordination polymers M(C₈H₈NO₂)₂ [M = Mn (1), Co (2), Ni (3) and Zn (4)] are described. These isostructural compounds contain centrosymmetric trans-MN₂O₄ octahedra as parts of infinite sheets; the ligand bonds to three adjacent metal ions in μ³-N,O,O′ mode from both its carboxylate O atoms and its amine N atom. In each case, weak intra-sheet N–H?O and C–H?O hydrogen bonds may help to consolidate the structure. Crystal data: 1, C₁₆H₁₆MnN₂O₄, M _r = 355.25, monoclinic, P2₁/c (No. 14), a = 10.6534(2) Å, b = 4.3990(1) Å, c = 15.5733(5) Å, β = 95.1827(10)°, V = 726.85(3) ų, Z = 2, R(F) = 0.026, wR(F ²) = 0.067. 2, C₁₆H₁₆CoN₂O₄, M _r = 359.24, monoclinic, P2₁/c (No. 14), a = 10.6131(10) Å, b = 4.3374(4) Å, c = 15.3556(17) Å, β = 95.473(4)°, V = 703.65(12) ų, Z = 2, R(F) = 0.041, wR(F ²) = 0.091. 3, C₁₆H₁₆N₂NiO₄, M _r = 359.02, monoclinic, P2₁/c (No. 14), a = 10.6374(4) Å, b = 4.2964(2) Å, c = 15.2827(8) Å, β = 95.9744(14)°, V = 694.66(6) ų, Z = 2, R(F) = 0.028, wR(F ²) = 0.070. 4, C₁₆H₁₆N₂O₄Zn, M _r = 365.68, monoclinic, P2₁/c (No. 14), a = 10.6385(5) Å, b = 4.2967(3) Å, c = 15.2844(8) Å, β = 95.941(3)°, V = 694.89(7) ų, Z = 2, R(F) = 0.038, wR(F ²) = 0.107.     

Guest‐Induced Transformation of a Porphyrin‐Edged FeII4L6 Capsule into a CuIFeII2L4 Fullerene Receptor

The combination of a bent diamino(nickel(II) porphyrin) with 2‐formylpyridine and Fe^II yielded an Fe^II₄L₆ cage. Upon treatment with the fullerenes C₆₀ or C₇₀, this cage was found to transform into a new host–guest complex incorporating three Fe^II centers and four porphyrin ligands, in an arrangement that is hypothesized to maximize π interactions between the porphyrin units of the host and the fullerene guest bound within its central cavity. The new complex shows coordinative unsaturation at one of the Fe^II centers as the result of the incommensurate metal‐to‐ligand ratio, which enabled the preparation of a heterometallic cone‐shaped Cu^IFe^II₂L₄ adduct of C₆₀ or C₇₀.     

The turbulent wake of a circular cylinder rotating about the streamwise axis

This paper presents measurements in the turbulent wake of a circular cylinder rotating with its axis normal to the free-stream velocity; in other words, the axis of rotation was parallel to the streamwise direction. All three mean velocities and six Reynolds stresses were obtained at three positions downstream of the cylinder, with and without rotation of the free-stream. Most emphasis is given to the latter results because of the better flow quality. The ratio of the circumferential velocity of the cylinder to the free-stream velocity — the swirl number — had a maximum value of 0.6. Measurements for two combinations of the free-stream and angular velocities showed the velocity deficit in the wake to be a multi-valued function of the swirl number, implying that the rotation affected the separation of the cylinder's boundary layer in a complex manner. In the turbulent wake, the rotation did not significantly alter the magnitudes of the normal stresses, but caused large changes to the shape of the profiles of the axial and cross-stream normal stresses. Eventually, the primary (cross-stream) shear stress became almost entirely positive, but there was no corresponding change to the (cross-stream) gradient of the streamwise mean velocity. Despite these alterations to the turbulence, the rotationally-activated generation terms in the Reynolds transport equations never dominated the terms that are common to the wakes of rotating and non-rotating cylinders.This work was supported by the Australian Research Council. Most of the data acquisition software was written by Mr J. J. Smith.     

Circumference and Pathwidth of Highly Connected Graphs

Birmele [J Graph Theory 2003] proved that every graph with circumference t has treewidth at most . Under the additional assumption of 2‐connectivity, such graphs have bounded pathwidth, which is a qualitatively stronger conclusion. Birmele's theorem was extended by Birmele et al. [Combinatorica 2007] who showed that every graph without k disjoint cycles of length at least t has treewidth . Our main result states that, under the additional assumption of ‐connectivity, such graphs have bounded pathwidth. In fact, they have pathwidth . Moreover, examples show that ‐connectivity is required for bounded pathwidth to hold. These results suggest the following general question: for which values of k and graphs H does every k‐connected H‐minor‐free graph have bounded pathwidth? We discuss this question and provide a few observations.     

Recurrent patterns of daily intimate partner violence and environment

Although predictors of violent relationships have been identified, we are only beginning to understand the day-to-day dynamics of domestic violence. The objective of this study was to identify commonly seen patterns and strings of consecutive days involving verbal or physical abuse, and their preceding and subsequent events. Adult women (n=20) seen in a primary care clinic who experienced violence within the past month were enrolled. Subjects completed a daily telephone assessment of household environment and marital relationship for two months using Interactive Verbal Response (IVR). Results were analyzed using orbital decomposition, an analytic technique based on symbolic dynamics, in which categorical time series data are used to identify recurrent patterns of strings and quantify their complexity. While days without abuse had varied patterns involving arguments, stress levels, daily hassles, husband's alcohol intake, and sense of closeness (27 unique patterns), days involving verbal or physical abuse included a narrower range of patterns (15 patterns for verbal and 16 patterns for physical abuse). Daily patterns appear to cluster in triplets (3 consecutive days) of activity and show nonlinearity with triplets involving verbal abuse and triplets involving physical violence. Triplets involving either verbal or physical abuse were associated with arguments and high stress, but differed in the consistency of association with hassles, alcohol intake, and closeness. Finally, physical and verbal abuse tended to self-propagate. However, days involving verbal abuse did not precede days involving physical violence. In conclusions, while patterns of violence and household environments followed a nonlinear trajectory, only a limited set of patterns were observed. Although violence led to more violence, verbal abuse did not necessarily lead to physical aggression. In fact, verbal abuse and physical violence differed in the consistency of their relationships to hassles, husband's alcohol intake, and closeness.     

Coupled Chemical Shrinkage and Consolidation: Some Benchmark Solutions

Mixtures of cement and mine waste are used as backfill in underground mines to provide support, which enables increased mineral extraction. Unlike most cemented material, the properties of mine backfill are relied upon immediately after cement is added and the material deposited underground. It is not only just the properties of the final cemented product but also the behaviour of cemented backfill during the hydration process that is important. During the hydration process, the backfill experiences chemically induced volume changes. These volume changes can lead to the development of effective stresses, which control the loads generated on barricade walls and the subsequent stability of unsupported faces. Although the processes that interact during cement hydration appear complex, the governing equation can be derived in terms of a small number of dimensionless parameter groups. The equation is simply the diffusion equation with a time-dependent source/sink term for which an analytical solution can be obtained under certain simplifying geometries. Approximate solutions can be obtained using a technique of analysis in which the mode shape of the spatial pore pressure variation is assumed. Such solutions provide benchmarks for simplified problems against which results of finite element modelling (for example) can be compared in order to confirm that the controlling mechanisms have been correctly identified.