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.

Electron doping and phonon scattering in Ti1+xS2 thermoelectric compounds

Bulk polycrystalline samples in the series Ti1+xS2 (x = 0 to 0.05) were prepared using high temperature synthesis from the elements and spark plasma sintering. X-ray structure analysis shows that the lattice constant c expands as titanium intercalates between TiS2 slabs. For x=0, a Seebeck coefficient close to -300 μV/K is observed for the first time in TiS2 compounds. The decrease in electrical resistivity and Seebeck coefficient that occurs upon Ti intercalation (Ti off stoichiometry) supports the view that charge carrier transfer to the Ti 3d band takes place and the carrier concentration increases. At the same time, the thermal conductivity is reduced by phonon scattering due to structural disorder induced by Ti intercalation. Optimum ZT values of 0.14 and 0.48 at 300K and 700K, respectively, are obtained for x=0.025.

A high frequency boundary element method for scattering by a class of nonconvex obstacles

In this paper we propose and analyse a hybrid numerical-asymptotic boundary element method for the solution of problems of high frequency acoustic scattering by a class of sound-soft nonconvex polygons. The approximation space is enriched with carefully chosen oscillatory basis functions; these are selected via a study of the high frequency asymptotic behaviour of the solution. We demonstrate via a rigorous error analysis, supported by numerical examples, that to achieve any desired accuracy it is sufficient for the number of degrees of freedom to grow only in proportion to the logarithm of the frequency as the frequency increases, in contrast to the at least linear growth required by conventional methods. This appears to be the first such numerical analysis result for any problem of scattering by a nonconvex obstacle. Our analysis is based on new frequency-explicit bounds on the normal derivative of the solution on the boundary and on its analytic continuation into the complex plane.

A frequency-independent boundary element method for scattering by two-dimensional screens and apertures

We propose and analyse a hybrid numerical–asymptotic hp boundary element method (BEM) for time-harmonic scattering of an incident plane wave by an arbitrary collinear array of sound-soft two-dimensional screens. Our method uses an approximation space enriched with oscillatory basis functions, chosen to capture the high-frequency asymptotics of the solution. We provide a rigorous frequency-explicit error analysis which proves that the method converges exponentially as the number of degrees of freedom N increases, and that to achieve any desired accuracy it is sufficient to increase N in proportion to the square of the logarithm of the frequency as the frequency increases (standard BEMs require N to increase at least linearly with frequency to retain accuracy). Our numerical results suggest that fixed accuracy can in fact be achieved at arbitrarily high frequencies with a frequency-independent computational cost, when the oscillatory integrals required for implementation are computed using Filon quadrature. We also show how our method can be applied to the complementary ‘breakwater’ problem of propagation through an aperture in an infinite sound-hard screen.

Aerosol scattering and absorption during the EUCAARI-LONGREX flights of the Facility for Airborne Atmospheric Measurements (FAAM) BAe-146: can measurements and models agree?

Scattering and absorption by aerosol in anthropogenically perturbed air masses over Europe has been measured using instrumentation flown on the UK’s BAe-146-301 large Atmospheric Research Aircraft (ARA) operated by the Facility for Airborne Atmospheric Measurements (FAAM) on 14 flights during the EUCAARI-LONGREX campaign in May 2008. The geographical and temporal variations of the derived shortwave optical properties of aerosol are presented. Values of single scattering albedo of dry aerosol at 550 nm varied considerably from 0.86 to near unity, with a campaign average of 0.93 ± 0.03. Dry aerosol optical depths ranged from 0.030 ± 0.009 to 0.24 ± 0.07. An optical properties closure study comparing calculations from composition data and Mie scattering code with the measured properties is presented. Agreement to within measurement uncertainties of 30% can be achieved for both scattering and absorption,but the latter is shown to be sensitive to the refractive indices chosen for organic aerosols, and to a lesser extent black carbon, as well as being highly dependent on the accuracy of the absorption measurements. Agreement with the measured absorption can be achieved either if organic carbon is assumed to be weakly absorbing, or if the organic aerosol is purely scattering and the absorption measurement is an overestimate due to the presence of large amounts of organic carbon. Refractive indices could not be inferred conclusively due to this uncertainty, despite the enhancement in methodology compared to previous studies that derived from the use of the black carbon measurements. Hygroscopic growth curves derived from the wet nephelometer indicate moderate water uptake by the aerosol with a campaign mean f (RH) value (ratio in scattering) of 1.5 (range from 1.23 to 1.63) at 80% relative humidity. This value is qualitatively consistent with the major chemical components of the aerosol measured by the aerosol mass spectrometer, which are primarily mixed organics and nitrate and some sulphate.

Acoustic scattering : high frequency boundary element methods and unified transform methods

We describe some recent advances in the numerical solution of acoustic scattering problems. A major focus of the paper is the efficient solution of high frequency scattering problems via hybrid numerical-asymptotic boundary element methods. We also make connections to the unified transform method due to A. S. Fokas and co-authors, analysing particular instances of this method, proposed by J. A. De-Santo and co-authors, for problems of acoustic scattering by diffraction gratings.

Rayleigh scattering by hexagonal ice crystals and the interpretation of dual-polarisation radar measurements

Dual-polarisation radar measurements provide valuable information about the shapes and orientations of atmospheric ice particles. For quantitative interpretation of these data in the Rayleigh regime, common practice is to approximate the true ice crystal shape with that of a spheroid. Calculations using the discrete dipole approximation for a wide range of crystal aspect ratios demonstrate that approximating hexagonal plates as spheroids leads to significant errors in the predicted differential reflectivity, by as much as 1.5 dB. An empirical modification of the shape factors in Gans's spheroid theory was made using the numerical data. The resulting simple expressions, like Gans's theory, can be applied to crystals in any desired orientation, illuminated by an arbitrarily polarised wave, but are much more accurate for hexagonal particles. Calculations of the scattering from more complex branched and dendritic crystals indicate that these may be accurately modelled using the new expression, but with a reduced permittivity dependent on the volume of ice relative to an enclosing hexagonal prism.

New insights into the compressibility and high-pressure stability of Ni(CN)2: a combined study of neutron diffraction, Raman spectroscopy, and inelastic neutron scattering

Nickel cyanide is a layered material showing markedly anisotropic behaviour. High-pressure neutron diffraction measurements show that at pressures up to 20.1 kbar, compressibility is much higher in the direction perpendicular to the layers, c, than in the plane of the strongly chemically bonded metal-cyanide sheets. Detailed examination of the behaviour of the tetragonal lattice parameters, a and c, as a function of pressure reveal regions in which large changes in slope occur, for example, in c(P) at 1 kbar. The experimental pressure dependence of the volume data is fitted to a bulk modulus, B0, of 1050 (20) kbar over the pressure range 0–1 kbar, and to 124 (2) kbar over the range 1–20.1 kbar. Raman spectroscopy measurements yield additional information on how the structure and bonding in the Ni(CN)2 layers change with pressure and show that a phase change occurs at about 1 kbar. The new high-pressure phase, (Phase PII), has ordered cyanide groups with sheets of D4h symmetry containing Ni(CN)4 and Ni(NC)4 groups. The Raman spectrum of phase PII closely resembles that of the related layered compound, Cu1/2Ni1/2(CN)2, which has previously been shown to contain ordered C≡N groups. The phase change, PI to PII, is also observed in inelastic neutron scattering studies which show significant changes occurring in the phonon spectra as the pressure is raised from 0.3 to 1.5 kbar. These changes reflect the large reduction in the interlayer spacing which occurs as Phase PI transforms to Phase PII and the consequent increase in difficulty for out-of-plane atomic motions. Unlike other cyanide materials e.g. Zn(CN)2 and Ag3Co(CN)6, which show an amorphization and/or a decomposition at much lower pressures (~100 kbar), Ni(CN)2 can be recovered after pressurising to 200 kbar, albeit in a more ordered form.

Internal nanoparticle structure of temperature-responsive self-assembled PNIPAM-b-PEG-b-PNIPAM triblock copolymers in aqueous solutions: NMR, SANS and light scattering studies

In this study we report detailed information on the internal structure of PNIPAM-b-PEG-b-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-b-PEG-b-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solid-like particles and chain network with a mesh size of 1-3 nm are present; nanoparticles formed from PNIPAM-b-PEG-b-PNIPAM copolymers have non-uniform structure with “frozen” areas interconnected by single chains in Gaussian conformation. SANS data with deuterated “invisible” PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation.

Modified section method for laser-welding of ill-fitting cp Ti and Ni-Cr alloy one-piece cast implant-supported frameworks

P>This study aimed to verify the effect of modified section method and laser-welding on the accuracy of fit of ill-fitting commercially pure titanium (cp Ti) and Ni-Cr alloy one-piece cast frameworks. Two sets of similar implant-supported frameworks were constructed. Both groups of six 3-unit implant-supported fixed partial dentures were cast as one-piece [I: Ni-Cr (control) and II: cp Ti] and evaluated for passive fitting in an optical microscope with both screws tightened and with only one screw tightened. All frameworks were then sectioned in the diagonal axis at the pontic region (III: Ni-Cr and IV: cp Ti). Sectioned frameworks were positioned in the matrix (10-Ncm torque) and laser-welded. Passive fitting was evaluated for the second time. Data were submitted to anova and Tukey-Kramer honestly significant difference tests (P < 0 center dot 05). With both screws tightened, one-piece cp Ti group II showed significantly higher misfit values (27 center dot 57 +/- 5 center dot 06 mu m) than other groups (I: 11 center dot 19 +/- 2 center dot 54 mu m, III: 12 center dot 88 +/- 2 center dot 93 mu m, IV: 13 center dot 77 +/- 1 center dot 51 mu m) (P < 0 center dot 05). In the single-screw-tightened test, with readings on the opposite side to the tightened side, Ni-Cr cast as one-piece (I: 58 center dot 66 +/- 14 center dot 30 mu m) was significantly different from cp Ti group after diagonal section (IV: 27 center dot 51 +/- 8 center dot 28 mu m) (P < 0 center dot 05). On the tightened side, no significant differences were found between groups (P > 0 center dot 05). Results showed that diagonally sectioning ill-fitting cp Ti frameworks lowers misfit levels of prosthetic implant-supported frameworks and also improves passivity levels of the same frameworks when compared to one-piece cast structures.

Recurrent sores by ill-fitting dentures and intra-oral squamous cell carcinoma in smokers

Objectives: To examine whether denture use and recurrent sores caused by ill-fitting dentures are associated with intra-oral squamous cell carcinoma (IO-SCC) in individuals exposed to tobacco. Methods: We conducted a hospital-based case-control study. The study population comprised 124 patients with IO-SCC and the same number of controls (individually paired according to gender and age) recruited from outpatient units of the same hospital. Conditional logistic regression analysis assessed the effect of denture use and recurrent oral sores by ill-fitting dentures, adjusted by covariates on the lifetime exposure to alcohol and tobacco, socioeconomic standings, and dietary patterns. Results: The use of dentures showed no association with IO-SCC [adjusted odds ratio (OR) 1.40, 95 percent confidence interval 0.51-3.87, P = 0.513] in an assessment controlled by socioeconomic position, lifetime exposure to alcohol and tobacco, and dietary patterns. However, the report of recurrent sores caused by ill-fitting dentures showed significant association with the disease (adjusted OR 4.58, 95 percent confidence interval 1.52-13.76, P = 0.007). Conclusions: The association between recurrent oral sores caused by ill-fitting dentures and squamous cell carcinoma of the mouth in smokers is in agreement with the hypothesis that the chronic physical irritation of oral mucosa contributes to the topical carcinogenic effect of tobacco, which must be taken into careful consideration in the planning of dental services for adults and the elderly.

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.