Quantification of myo‐inositol, 1,5‐anhydro‐ D‐sorbitol,and D‐chiro‐inositol using high‐performance liquid chromatography with electrochemical detection in very small volume clinical samples

Inositol is a six‐carbon sugar alcohol and is one of nine biologically significant isomers of hexahydroxycyclohexane. Myo‐inositol is the primary biologically active form and is present in higher concentrations in the fetus and newborn than in adults. It is currently being examined for the prevention of retinopathy of prematurity in newborn preterm infants. A robust method for quantifying myo‐inositol (MI), D ‐chiro‐inositol (DCI) and 1,5‐anhydro‐ D ‐sorbitol (ADS) in very small‐volume (25 μL) urine, blood serum and/or plasma samples was developed. Using a multiple‐column, multiple mobile phase liquid chromatographic system with electrochemical detection, the method was validated with respect to (a) selectivity, (b) accuracy/recovery, (c) precision/reproducibility, (d) sensitivity, (e) stability and (f) ruggedness. The standard curve was linear and ranged from 0.5 to 30 mg/L for each of the three analytes. Above‐mentioned performance measures were within acceptable limits described in the Food and Drug Administration's Guidance for Industry: Bioanalytical Method Validation. The method was validated using blood serum and plasma collected using four common anticoagulants, and also by quantifying the accuracy and sensitivity of MI measured in simulated urine samples recovered from preterm infant diaper systems. The method performs satisfactorily measuring the three most common inositol isomers on 25 μL clinical samples of serum, plasma, milk, and/or urine. Similar performance is seen testing larger volume samples of infant formulas and infant formula ingredients. MI, ADS and DCI may be accurately tested in urine samples collected from five different preterm infant diapers if the urine volume is greater than 2–5 mL. Copyright © 2015 John Wiley & Sons, Ltd.     

On the Dual Phosphorescence of Xanthone and Chromone in Glassy Hydrocarbon Hosts

Trace quantities of hydrogen‐bonding impurities in otherwise highly purified and dried glassy hydrocarbon matrices at 77 K can modify the relative triplet state energy levels, and hence the photophysical properties of two aromatic ketones, xanthone and chromone, to the extent that the intrinsic spectroscopic properties are obscured. The intrinsic spectroscopic properties of each are revealed in multicrystalline n‐alkane Shpol'skii matrices, and also can be observed in rigorously purified and dried hydrocarbon glasses at 77 K. The extreme sensitivity to stoichiometric, and even substoichiometric quantities of hydrogen‐bonding impurities arises from the near‐degeneracy of the two lowest‐lying triplet states, and the sensitive nature of the n→π* blueshift phenomena to specific hydrogen‐bonding interactions.     

Effective Relative Permeabilities and Capillary Pressure for One-Dimensional Heterogeneous Media

The paper presents an analytical construction of effective two-phase parameters for one-dimensional heterogeneous porous media, and studies their properties. We base the computation of effective parameters on analytical solutions for steady-state saturation distributions. Special care has to be taken with respect to saturation and pressure discontinuities at the interface between different rocks. The ensuing effective relative permeabilities and effective capillary pressure will be functions of rate, flow direction, fluid viscosities, and spatial scale of the heterogeneities.The applicability of the effective parameters in dynamic displacement situations is studied by comparing fine-gridded simulations in heterogeneous media with simulations in their homogeneous (effective) counterparts. Performance is quite satisfactory, even with strong fronts present. Also, we report computations studying the applicability of capillary limit parameters outside the strict limit.     

Analytic and numerical solutions in the theory of elastic plates

ABSTRACT

Numerical approximations of the solution of a boundary value problem when an exact solution is not available can be constructed by means of a variety of methods. In this paper, we present a technique that is based on the integral representation of the solution of an elliptic problem and the properties of the associated layer potentials. The procedure is illustrated in application to the mathematical model of bending of plates with transverse shear deformation in a finite domain, in the presence of Dirichlet, Neumann, and Robin conditions prescribed on the boundary.     

A shell model for tyre belt vibrations

We present a new formulation for the prediction of tyre belt vibrations in the frequency range 0-500 Hz. Our representation includes the effects of belt width, curvature and anisotropy, and also explicitly models the tyre sidewalls. Many of the associated numerical parameters are fixed by physical considerations; the remainder require empirical input. A systematic and general approach to this problem is developed, and illustrated for the specific example of a Goodyear Wrangler tyre. The resulting predictions for the radial response to radial forcing show good correspondence with experiment up to 300 Hz, and satisfactory agreement up to 1 kHz.     

Laser Ablation Molecular Isotopic Spectrometry: Parameter influence on boron isotope measurements

Laser Ablation Molecular Isotopic Spectrometry (LAMIS) was recently reported for optical isotopic analysis of condensed samples in ambient air and at ambient pressure. LAMIS utilizes molecular emissions which exhibit larger isotopic spectral shits than in atomic transitions. For boron monoxide ¹⁰BO and ¹¹BO, the isotopic shifts extend from 114 cm⁻¹ (0.74 nm) to 145–238 cm⁻¹ (5–8 nm) at the B²Σ⁺ (v = 0) → X²Σ⁺ (v = 2) and A²Π_i (v = 0) → X²Σ⁺ (v = 3) transitions, respectively. These molecular isotopic shifts are over two orders of magnitude larger than the maximum isotopic shift of approximately 0.6 cm⁻¹ in atomic boron. This paper describes how boron isotope abundance can be quantitatively determined using LAMIS and how atomic, ionic, and molecular optical emission develops in a plasma emanating from laser ablation of solid samples with various boron isotopic composition. We demonstrate that requirements for spectral resolution of the measurement system can be significantly relaxed when the isotopic abundance ratio is determined using chemometric analysis of spectra. Sensitivity can be improved by using a second slightly delayed laser pulse arriving into an expanding plume created by the first ablation pulse.     

Adsorption kinetics of alkanethiol-capped gold nanoparticles at the hexane–water interface

The pendant drop technique was used to characterize the adsorption behavior of n-dodecane-1-thiol and n-hexane-1-thiol-capped gold nanoparticles at the hexane–water interface. The adsorption process was studied by analyzing the dynamic interfacial tension versus nanoparticle concentration, both at early times and at later stages (i.e., immediately after the interface between the fluids is made and once equilibrium has been established). A series of gold colloids were made using nanoparticles ranging in size from 1.60 to 2.85 nm dissolved in hexane for the interfacial tension analysis. Following free diffusion of nanoparticles from the bulk hexane phase, adsorption leads to ordering and rearrangement of the nanoparticles at the interface and formation of a dense monolayer. With increasing interfacial coverage, the diffusion-controlled adsorption for the nanoparticles at the interface was found to change to an interaction-controlled assembly and the presence of an adsorption barrier was experimentally verified. At the same bulk concentration, different sizes of n-dodecane-1-thiol nanoparticles showed different absorption behavior at the interface, in agreement with the findings of Kutuzov et al. (Phys Chem Chem Phys 9:6351–6358, 2007). The experiments additionally demonstrated the important role played by the capping agent. At the same concentration, gold nanoparticles stabilized by n-hexane-1-thiol exhibited greater surface activity than gold nanoparticles of the same size stabilized by n-dodecane-1-thiol. These findings contribute to the design of useful supra-colloidal structures by the self-assembly of alkane-thiol-capped gold nanoparticles at liquid–liquid interfaces.     

In situ measurements of the spectral emittance of coal ash deposits

The spectral emittance of deposits left by bituminous and sub-bituminous coals under oxidizing conditions have been measured in situ. Pulverized coal is injected into a down-fired entrained-flow reactor. Ash accumulates on a probe in the reactor effluent and radiation emitted by the ash layer is recorded using a Fourier transform infrared (FTIR) spectrometer. Values for the spectral emissive power emitted by the ash and the surface temperature of the ash are extracted from these data. These results are then used to calculate the spectral emittance of the deposit. The spectral emittances of ash deposits formed by burning Illinois #6 (bituminous) coal and Powder River Basin (sub-bituminous) coal were measured between 3000 and 500 wavenumbers. The spectral emittance of the deposit left by the bituminous coal has a constant value of approximately 0.46 between 3000 and 2400 wavenumbers. Between 2200 and 1200 wavenumbers, the spectral emittance of the deposit increases from approximately 0.47 to approximately 0.61. Between 1200 and 500 wavenumbers, the spectral emittance is relatively constant at 0.61. The spectral emittance of the deposit left by the sub-bituminous coal is also relatively constant between 3000 and 2400 wavenumbers at a value of 0.29. Between 2200 and 500 wavenumbers, the spectral emittance of deposits from the sub-bituminous coal increases from approximately 0.29 to 0.55. Differences between these spectral emittance measurements and those measured ex situ illustrate the importance of making in situ measurements. Band emittances were calculated using the measured spectral emittances, and band emittances of the deposits are reported as functions of temperature.