Scattering form factors for self-assembled network junctions

The equilibrium microstructures in microemulsions and other self-assembled systems show complex, connected shapes such as symmetric bicontinuous spongelike structures and asymmetric bicontinuous networks formed by cylinders interconnected at junctions. In microemulsions, these cylinder network microstructures may mediate the structural transition from a spherical or globular phase to the bicontinuous microstructure. To understand the structural and statistical properties of such cylinder network microstructures as measured by scattering experiments, models are needed to extract the real-space structure from the scattering data. In this paper, we calculate the scattering functions appropriate for cylinder network microstructures. We focus on such networks that contain a high density of network junctions that connect the cylindrical elements. In this limit, the network microstructure can be regarded as an assembly of randomly oriented, closed packed network junctions (i.e., the cylinder scattering contributions are neglected). Accordingly, the scattering spectrum of the network microstructure can be calculated as the product of the junction number density, the junction form factor, which describes the scattering from the surface of a single junction, and a structure factor, which describes the local correlations of different junctions due to junction interactions (including their excluded volume). This approach is applied to analyze the scattering data from a bicontinuous microemulsion with equal volumes of water and oil. In a second approach, we included the cylinder scattering contribution in the junction form factor by calculating the scattering intensity of Y junctions to which three rods with spherical cross section are attached. The respective theoretical predictions are compared with results of neutron scattering measurements on a water-in-oil microemulsion with a connected microstructure.     

Environmental Research for Art Conservation and Assessment of Indoor Conditions Surrounding Cultural Objects

This paper describes the results and conclusions of research directed towards the development and evaluation of a chemical sensor which would provide information on the quality of indoor environments surrounding cultural objects. In our case these objects were paintings housed in major European galleries and the main objective is their preservation through an improved understanding of their microenvironment. The concept was to prepare and expose test tempera paintings which would behave as dosimeters and integrate the environmental response at these locations. Artificial ageing of similar samples was performed to provide a means of calibrating the test paintings. Samples from the test paintings were compared with artificially aged samples and this enabled the sites to be ranked in terms of their suitability for exposure of cultural objects. Additionally, novel methodology involving piezoelectric sensors was designed for monitoring the relative humidity and temperature of the microenvironment of paintings. Dielectric techniques were also used for measuring the effect of relative humidity fluctuations on artists' materials and novel non-invasive dielectric techniques in the microwave region were used for the determination of their moisture content. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetics of the reaction of OH radicals with a series of esters under simulated conditions at 295 K

The rate constants of the isopropyl acetate, n-propyl acetate, isopropenyl acetate, n-propenyl acetate, n-butyl acetate, and ethyl butyrate reactions with OH radicals were determined in purified air under atmospheric conditions, at 750 torr and (295 ± 2) K. A relative rate experimental method was used; n-heptane, n-octane, and n-nonane were the reference compounds, with, respectively, rate constants for the reaction with OH of 7.12 × 10⁻¹², 8.42 × 10⁻¹², and 9.70 × 10⁻¹² molecule⁻¹ cm³s⁻¹. The following rate constants were obtained in units of 10⁻¹² molecule⁻¹ cm³s⁻¹; isopropyl acetate, (3.12 ± 0.29); n-propyl acetate, (1.97 ± 0.24); isopropenyl acetate, (62.53 ± 1.24); n-propenyl acetate, (24.57 ± 0.24); n-butyl acetate, (3.29 ± 0.35); and ethyl butyrate, (4.37 ± 0.42). Tertiary butyl acetate has a low reactivity with OH radicals (<1 × 10⁻¹² molecule⁻¹ cm³s⁻¹). © 1996 John Wiley & Sons, Inc.     

Toward high-performance computational chemistry: I. Scalable Fock matrix construction algorithms

Several parallel algorithms for Fock matrix construction are described. The algorithms calculate only the unique integrals, distribute the Fock and density matrices over the processors of a massively parallel computer, use blocking techniques to construct the distributed data structures, and use clustering techniques on each processor to maximize data reuse. Algorithms based on both square and row-blocked distributions of the Fock and density matrices are described and evaluated. Variants of the algorithms are discussed that use either triple-sort or canonical ordering of integrals, and dynamic or static task clustering schemes. The algorithms are shown to adapt to screening, with communication volume scaling down with computation costs. Modeling techniques are used to characterize algorithm performance. Given the characteristics of existing massively parallel computers, all the algorithms are shown to be highly efficient for problems of moderate size. The algorithms using the row-blocked data distribution are the most efficient. © 1996 by John Wiley & Sons, Inc.     

On determining a 1-tailed upper limit for future sample HorRat values

Two formulas were developed for use in computing 1-tailed upper limits for future HorRat values obtained from the collaborative study of materials. One formula is applicable when a future sample HorRat value H [formula: see text] is computed based on a known concentration (e.g., C = spike level and RSD(R) is the sample relative reproducibility standard deviation) and the other formula is applicable when the true concentration (C) is unknown and a future sample HorRat value [formula: see text] is computed using the sample mean (e.g., y, the collaborative study overall mean for an analyte). A Monte Carlo simulation procedure was developed using the Statistical Analysis System (SAS) software to assess the accuracy of the 2 developed formulas. Based on the degree of closeness between the simulated and calculated limits, the formulas for computing upper limits for future sample HorRat values will prove to be useful to Study Directors in determining worst case scenarios concerning a method's reproducibility precision relative to that predicted using the "Horwitz equation". We also define the current empirical HorRat limits as 1-tailed 100p% upper limits to assess the statistical consequence, in a probability sense, of their application as an analytical methods screening tool.     

Mach stem hysteresis: Experiments addressing a novel explanation of clumpy astrophysical jet emission

Recent time-series observations of shock waves in stellar jets taken with the Hubble Space Telescope reveal localized bright knots that persist over nearly 15 years. While some of these features represent shock fronts caused by variable velocities in the flow, others appear at the intersection points between distinct bow shocks. Theoretically, when the angle between two intersecting shocks exceeds a certain critical value, a third shock (Mach stem) should form. Because Mach stems form perpendicular to the direction of flow, incoming particles encounter a normal shock instead of an oblique one, which results in brighter emission at this location. To study this phenomenon in a controlled laboratory setting, we have carried out experiments on the Omega laser aimed at understanding the formation, growth, and destruction of Mach stems in the warm dense plasma regime. Our experimental results indicate how the growth rate depends upon included angle, and numerical simulations indicate that it may be possible to stabilize an already-formed Mach stem below the critical angle when certain conditions are satisfied.     

Ultralow power continuous-wave frequency conversion in hydrogenated amorphous silicon waveguides

We demonstrate wavelength conversion through nonlinear parametric processes in hydrogenated amorphous silicon (a-Si:H) with maximum conversion efficiency of -13 dB at telecommunication data rates (10 GHz) using only 15 mW of pump peak power. Conversion bandwidths as large as 150 nm (20 THz) are measured in continuous-wave regime at telecommunication wavelengths. The nonlinear refractive index of the material is determined by four-wave mixing (FWM) to be n(2)=7.43×10(-13) cm(2)/W, approximately an order of magnitude larger than that of single crystal silicon.     

Fluence Rate-Dependent Photobleaching of Intratumorally Administered Pc 4 Does not Predict Tumor Growth Delay

We examined effects of fluence rate on the photobleaching of the photosensitizer Pc 4 during photodynamic therapy (PDT) and the relationship between photobleaching and tumor response to PDT. BALB/c mice with intradermal EMT6 tumors were given 0.03 mg kg^?1 Pc 4 by intratumor injection and irradiated at 667 nm with an irradiance of 50 or 150 mW cm^?2 to a fluence of 100 J cm^?2. While no cures were attained, significant tumor growth delay was demonstrated at both irradiances compared with drug‐only controls. There was no significant difference in tumor responses to these two irradiances (P = 0.857). Fluorescence spectroscopy was used to monitor the bleaching of Pc 4 during irradiation, with more rapid bleaching with respect to fluence shown at the higher irradiance. No significant correlation was found between fluorescence photobleaching and tumor regrowth for the data interpreted as a whole. Within each treatment group, weak associations between photobleaching and outcome were observed. In the 50 mW cm^?2 group, enhanced photobleaching was associated with prolonged growth delay (P = 0.188), while at 150 mW cm^?2 this trend was reversed (P = 0.308). Thus, it appears that Pc 4 photobleaching is not a strong predictor of individual tumor response to Pc 4‐PDT under these treatment conditions.     

Photochemical oxygen consumption, oxygen evolution and spectral changes during UVA irradiation of EMT6 spheroids.

Remarkable rates of oxygen consumption are observed via microelectrode measurements immediately upon the onset of 325 nm irradiation of multicell tumor spheroids. Consumption is irradiance dependent over the range 20-200 mW cm-2, and its magnitude is comparable to that observed previously in the same system using exogenous photosensitizers. Oscillations in the oxygen concentrations suggest that oxygen is also being evolved during irradiation. Oxygen evolution is likely the result of enzymatic dissociation of hydrogen peroxide, which is formed through UV-induced photochemistry. Irradiation of spheroids at 442 and at 514 nm produces a much more modest but detectable oxygen consumption. The dynamics of oxygen concentration changes are quite different at these wavelengths, suggesting a different photochemical mechanism. In these cases, initial oxygen depletion is followed immediately by a more gradual, monotonic increase in the oxygen concentration, consistent with irreversible photobleaching. No oscillations in the oxygen concentration are detectable. At 662 nm, no oxygen consumption was observed over the range of irradiances studied. Fluorescence spectra of cells prior to irradiation include contributions from anthranilic acid and reduced nicotinamide adenine dinucleotide (NADH). During 325 nm irradiation, anthranilic acid is rapidly and irreversibly bleached, while NADH emission undergoes only modest reduction.