Application of cylindrical distribution functions to wide-angle X-ray scattering from oriented polymers

A systematic approach is presented for obtaining cylindrical distribution functions (CDF's) of noncrystalline polymers which have been oriented by extension. The scattering patterns and CDF's are also sharpened by the method proposed by Deas and by Ruland. Data from atactic poly(methyl methacrylate) and polystyrene are analysed by these techniques. The methods could also be usefully applied to liquid crystals.

Conformational analysis of oriented non-crystalline polymers using wide angle X-ray scattering

A procedure is presented for obtaining conformational parameters from oriented but non-crystalline polymers. This is achieved by comparison of the experimental wide angle X-ray scattering with that calculated from models but in such a way that foreknowledge of the orientation distribution function is not required. X-ray scattering intensity values for glassy isotactic poly(methylmethacrylate) are analysed by these techniques. The method could be usefully applied to other oriented molecular systems such as liquid crystalline materials.

Contact angle of a hemispherical bubble: an analytical approach

We have calculated the equilibrium shape of the axially symmetric Plateau border along which a spherical bubble contacts a flat wall, by analytically integrating Laplace’s equation in the presence of gravity, in the limit of small Plateau border sizes. This method has the advantage that it provides closed-form expressions for the positions and orientations of the Plateau border surfaces. Results are in very good overall agreement with those obtained from a numerical solution procedure, and are consistent with experimental data. In particular we find that the effect of gravity on Plateau border shape is relatively small for typical bubble sizes, leading to a widening of the Plateau border for sessile bubbles and to a narrowing for pendant bubbles. The contact angle of the bubble is found to depend even more weakly on gravity.

Synthesis and crystal structures of μ-oxido- and μ-hydroxido-bridged dinuclear iron(III) complexes with an N2O donor ligand - a theoretical study on the influence of weak forces on the Fe-O-Fe bridging angle

The synthesis and crystal structures of three nonheme di-iron(III) complexes with a tridentate N,N,O Schiff-base ligand, 2-({[2-(dimethylamino) ethyl] imino} methyl) phenol (HL), are reported. Complexes [Fe2OL2(NCO)(2)] (1a) and [Fe2OL2(SAL)(2)]center dot H2O [SAL = o-(CHO)C6H4O-] (1b) are unsupported mu-oxido-bridged dimers, and [Fe-2(OH)L-2(HCOO)(2)-(Cl)] (2) is a mu-hydroxido-bridged dimer supported by a formato bridging ligand. All complexes have been characterized by X-ray crystallography and spectroscopic analysis. Complex 1b has been reported previously; however, it has been reinvestigated to confirm the presence of a crucial water molecule in the solid state. Structural analyses show that in 1a the iron atoms are pentacoordinate with a bent Fe-O-Fe angle [142.7(2)degrees], whereas in 2 the metal centers are hexacoordinate with a normal Fe-OH-Fe bridging angle [137.9(2)degrees]. The Fe-O-Fe angles in complexes 1a and 1b differ significantly to those usually shown by (mu-oxido) Fe-III complexes. A theoretical study has been performed in order to rationalize this deviation. Moreover, the influence of the water molecule observed in the solid-state structure of 1b on the Fe-O-Fe angle is also analyzed theoretically.

Control and analysis of oriented thin films of lipid inverse bicontinuous cubic phases using grazing incidence small-angle X‑ray scattering

Lipid cubic phases are complex nanostructures that form naturally in a variety of biological systems, with applications including drug delivery and nanotemplating. Most X-ray scattering studies on lipid cubic phases have used unoriented polydomain samples as either bulk gels or suspensions of micrometer-sized cubosomes. We present a method of investigating cubic phases in a new form, as supported thin films that can be analyzed using grazing incidence small-angle X-ray scattering (GISAXS). We present GISAXS data on three lipid systems: phytantriol and two grades of monoolein (research and industrial). The use of thin films brings a number of advantages. First, the samples exhibit a high degree of uniaxial orientation about the substrate normal. Second, the new morphology allows precise control of the substrate mesophase geometry and lattice parameter using a controlled temperature and humidity environment, and we demonstrate the controllable formation of oriented diamond and gyroid inverse bicontinuous cubic along with lamellar phases. Finally, the thin film morphology allows the induction of reversible phase transitions between these mesophase structures by changes in humidity on subminute time scales, and we present timeresolved GISAXS data monitoring these transformations.

Modeling the observed proton aurora and ionospheric convection responses to changes in the IMF clock angle: 2. Persistence of ionospheric convection

We apply a numerical model of time-dependent ionospheric convection to two directly driven reconnection pulses during a 15-min interval of southward IMF on 26 November 2000. The model requires an input magnetopause reconnection rate variation, which is here derived from the observed variation in the upstream IMF clock angle, q. The reconnection rate is mapped to an ionospheric merging gap, the MLT extent of which is inferred from the Doppler-shifted Lyman-a emission on newly opened field lines, as observed by the FUV instrument on the IMAGE spacecraft. The model is used to reproduce a variety of features observed during this event: SuperDARN observations of the ionospheric convection pattern and transpolar voltage; FUV observations of the growth of patches of newly opened flux; FUVand in situ observations of the location of the Open-Closed field line Boundary (OCB) and a cusp ion step. We adopt a clock angle dependence of the magnetopause reconnection electric field, mapped to the ionosphere, of the form Enosin4(q/2) and estimate the peak value, Eno, by matching observed and modeled variations of both the latitude, LOCB, of the dayside OCB (as inferred from the equatorward edge of cusp proton emissions seen by FUV) and the transpolar voltage FPC (as derived using the mapped potential technique from SuperDARN HF radar data). This analysis also yields the time constant tOCB with which the open-closed boundary relaxes back toward its equilibrium configuration. For the case studied here, we find tOCB = 9.7 ± 1.3 min, consistent with previous inferences from the observed response of ionospheric flow to southward turnings of the IMF. The analysis confirms quantitatively the concepts of ionospheric flow excitation on which the model is based and explains some otherwise anomalous features of the cusp precipitation morphology.

Modeling the observed proton aurora and ionospheric convection responses to changes in the IMF clock angle: 1. Persistence of cusp proton aurora

We employ a numerical model of cusp ion precipitation and proton aurora emission to fit variations of the peak Doppler-shifted Lyman-a intensity observed on 26 November 2000 by the SI-12 channel of the FUV instrument on the IMAGE satellite. The major features of this event appeared in response to two brief swings of the interplanetary magnetic field (IMF) toward a southward orientation. We reproduce the observed spatial distributions of this emission on newly opened field lines by combining the proton emission model with a model of the response of ionospheric convection. The simulations are based on the observed variations of the solar wind proton temperature and concentration and the interplanetary magnetic field clock angle. They also allow for the efficiency, sampling rate, integration time and spatial resolution of the FUV instrument. The good match (correlation coefficient 0.91, significant at the 98% level) between observed and modeled variations confirms the time constant (about 4 min) for the rise and decay of the proton emissions predicted by the model for southward IMF conditions. The implications for the detection of pulsed magnetopause reconnection using proton aurora are discussed for a range of interplanetary conditions.

Energy and pitch-angle dispersions of LLBL/cusp ions seen at middle altitudes: predictions by the open magnetosphere model

Numerical simulations are presented of the ion distribution functions seen by middle-altitude spacecraft in the low-latitude boundary layer (LLBL) and cusp regions when reconnection is, or has recently been, taking place at the equatorial magnetopause. From the evolution of the distribution function with time elapsed since the field line was opened, both the observed energy/observation-time and pitch-angle/energy dispersions are well reproduced. Distribution functions showing a mixture of magnetosheath and magnetospheric ions, often thought to be a signature of the LLBL, are found on newly opened field lines as a natural consequence of the magnetopause effects on the ions and their flight times. In addition, it is shown that the extent of the source region of the magnetosheath ions that are detected by a satellite is a function of the sensitivity of the ion instrument . If the instrument one-count level is high (and/or solar-wind densities are low), the cusp ion precipitation detected comes from a localised region of the mid-latitude magnetopause (around the magnetic cusp), even though the reconnection takes place at the equatorial magnetopause. However, if the instrument sensitivity is high enough, then ions injected from a large segment of the dayside magnetosphere (in the relevant hemisphere) will be detected in the cusp. Ion precipitation classed as LLBL is shown to arise from the low-latitude magnetopause, irrespective of the instrument sensitivity. Adoption of threshold flux definitions has the same effect as instrument sensitivity in artificially restricting the apparent source region.

Non-thermal plasma observations using EISCAT: Aspect angle dependence

Recent observations with the EISCAT incoherent scatter radar have shown large rises in dayside, auroral plasma velocities (>2 km s^{−1}) over a wide range of latitudes and lasting about an hour. These are larger than the neutral thermal speed, and allow, for the first time, observations of a non-thermal plasma over a range of observing angles, revealing a clear angular dependence. The observed ion temperature anisotropy, deduced by assuming a Maxwellian line-of-sight ion velocity distribution, is at least 1.75, which exceeds the theoretical value for a bi-Maxwellian based on a realistic ion-neutral collision model. The aspect angle dependence of the signal spectra also indicates non-Maxwellian plasma.

Monitoring scan asymmetry of microwave humidity sounding channels using simultaneous all angle collocations (SAACs)

Simultaneous all angle collocations (SAACs) of microwave humidity sounders (AMSU-B and MHS) on-board polar orbiting satellites are used to estimate scan-dependent biases. This method has distinct advantages over previous methods, such as that the estimated scan-dependent biases are not influenced by diurnal differences between the edges of the scan and the biases can be estimated for both sides of the scan. We find the results are robust in the sense that biases estimated for one satellite pair can be reproduced by double differencing biases of these satellites with a third satellite. Channel 1 of these instruments shows the least bias for all satellites. Channel 2 has biases greater than 5 K, thus needs to be corrected. Channel 3 has biases of about 2 K and more and they are time varying for some of the satellites. Channel 4 has the largest bias which is about 15 K when the data are averaged for 5 years, but biases of individual months can be as large as 30 K. Channel 5 also has large and time varying biases for two of the AMSU-Bs. NOAA-15 (N15) channels are found to be affected the most, mainly due to radio frequency interference (RFI) from onboard data transmitters. Channel 4 of N15 shows the largest and time varying biases, so data of this channel should only be used with caution for climate applications. The two MHS instruments show the best agreement for all channels. Our estimates may be used to correct for scan-dependent biases of these instruments, or at least used as a guideline for excluding channels with large scan asymmetries from scientific analyses.

Evaluation of in vitro resistance of titanium and resorbable (poly-L-DL-lactic acid) fixation systems on the mandibular angle fracture

The purpose of this study was to compare, by mechanical in vitro testing, a 2.0-mm system made with poly-L-DL-lactide acid with an analogue titanium-based system. Mandible replicas were used as a substrate and uniformly sectioned on the left mandibular angle. The 4-hole plates were adapted and stabilized passively in the same site in both groups using four screws, 6.0 mm long. During the resistance-to-load test, the force was applied perpendicular to the occlusal plane at three different points: first molar at the plated side; first molar at the contralateral side; and between the central incisors. At 1 mm of displacement, no statistically significant difference was found. At 2 mm displacement, a statistically significant difference was observed when an unfavourable fracture was simulated and the load was applied in the contralateral first molar and when a favourable fracture was simulated and the load was applied between the central incisors. At the failure displacement, a statistically significant difference was observed only when the favourable fracture was simulated and the load was applied on the first molar at the plated side. In conclusion, despite more failure, the poly-L-DL-lactic acid-based system was effective.

Synchrotron X-ray imaging via ultra-small-angle scattering: principles of quantitative analysis and application in studying bone integration to synthetic grafting materials

Optimized experimental conditions for extracting accurate information at subpixel length scales from analyzer-based X-ray imaging were obtained and applied to investigate bone regeneration by means of synthetic beta-TCP grafting materials in a rat calvaria model. The results showed a 30% growth in the particulate size due to bone ongrowth/ingrowth within the critical size defect over a 1-month healing period.

Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 angstrom(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.