The measurement of trace elements in human nails and nail clippings using portable X-ray fluorescence: A review

A variety of biomarkers are available for the assessment of human exposure to, and absorption of, trace elements. The measurement of trace elements in nail or nail clippings offers some benefits relative to other body sites. Typically, concentrations of elements are assessed in clippings, using high precision methods such as inductively coupled plasma mass spectrometry or instrumental neutron activation analysis. Over the last decade, portable X-ray fluorescence (pXRF) has emerged as a novel method with potential advantages for the measurement of trace elements in nail and nail clippings. This review paper examines early developments and recent work in the use of pXRF to measure elements such as As, Se, Mn, Zn, Cr, Pb, and Hg in nails and nail clippings. While initial pXRF studies were limited to the use of nail phantoms and nail clipping phantoms, more recent work has applied the pXRF method with real nail clippings and nails. Results have been promising, but a number of issues have emerged requiring additional attention. These relate to the analysis of X-ray spectra, selection of X-ray beam for excitation, method validation and normalization, and practical aspects of study design. With consideration of these issues, pXRF offers significant potential to provide a straightforward, economical, and rapid measurement approach to help improve our understanding of trace element exposure and related health outcomes.     

Signal-processing techniques for low signal-to-noise ratio laser Doppler velocimetry signals

A variety of methods have been developed to obtain acurate frequency estimates from laser Doppler velocimetry (LDV) signals. Rapid scanning and fiber optic LDV systems require robust methods for extracting accurate frequency estimates with computational efficiency from data with poor signal-to-noise ratios. These methods typically fall into two general categories, time domain parametric techniques and frequency domain techniques. The frequency domain approach is initiated by transforming the Doppler bursts into the frequency domain using the fast Fourier transform (FFT). From this basic transformation a variety of interpolation procedures (parabolic, Gaussian, and centroid fits) have been developed to optimize the frequency estimation accuracy. The time domain approaches are derived from the parametric form of a sinusoid. The estimation of constants in this relationship is performed to satisfy specific constraints, typically a minimization of a variance expression. A comparison of these techniques is presented using simulated signals and additive Gaussian and Poisson white noise. The statistical bias and random errors for each method are presented from 200 signal simulations at each condition. Frequency estimation via the FFT with zero-padding and a Gaussian interpolation scheme was found to produce the lowest bias and random errors.List of symbols A(z) eigenfilter or characteristic polynomial - a _{m + 1} eigenvector - f frequency, Hz - f normalized frequency f = f/f _s - _d Doppler frequency estimate - f _i frequency of FFT spectral bin - f ^s sampling frequency - N number of sample points in data set - P _i ith power spectral line from PSD - r _xx (i) autocorrelation coefficient for time lag i - R_{Mn + 1} autocorrelation matrix of order M+1 - T sampling period - f spectral resolution for FFT, f = 1/N t - t sampling interval     

An experimental study of a turbulent wing-body junction and wake flow

Extensive measurements were conducted in an incompressible turbulent flow around the wing-body junction formed by a 3∶2 semi-elliptic nose/NACA 0020 tail section and a flat plate. Mean and fluctuating velocity measurements were performed adjacent to the wing and up to 11.56 chord lengths downstream. The appendage far wake region was subjected to an adverse pressure gradient. The authors' results show that the characteristic horseshoe vortex flow structure is elliptically shaped, with ? (W)/?Y forming the primary component of the streamwise vorticity. The streamwise development of the flow distortions and vorticity distributions is highly dependent on the geometry-induced pressure gradients and resulting flow skewing directions. The primary goal of this research was to determine the effects of the approach boundary layer characteristics on the junction flow. To accomplish this goal, the authors' results were compared to several other junction flow data sets obtained using the same body shape. The trailing vortex leg flow structure was found to scale on T. A parameter known as the momentum deficit factor (MDF = (Re _T)² (θ/T)) was found to correlate the observed trends in mean flow distortion magnitudes and vorticity distribution. Changes in δ/T were seen to affect the distribution of u′, with lower ratios producing well defined local turbulence maxima. Increased thinning of the boundary layer near the appendage was also observed for small values of δ/T.     

Mapping the spatial overlap of excitons in a photosynthetic complex via coherent nonlinear frequency generation

We experimentally demonstrate a nonlinear spectroscopic method that is sensitive to exciton-exciton interactions in a Frenkel exciton system. Spatial overlap of one-exciton wavefunctions leads to coupling between them, resulting in two-exciton eigenstates that have the character of many single-exciton pairs. The mixed character of the two-exciton wavefunctions gives rise to a four-wave-mixing nonlinear frequency generation signal. When only part of the linear excitation spectrum of the complex is excited with three spectrally tailored pulses with separate spatial directions, a frequency-shifted third-order nonlinear signal emerges in the phase-matched direction. We employ the nonlinear response function formalism to show that the emergence of the signal is mediated by and carries information about the two-exciton eigenstates of the system. We report experimental results for nonlinear frequency generation in the Fenna-Matthews-Olson (FMO) photosynthetic pigment-protein complex. Our theoretical analysis of the signal from FMO confirms that the emergence of the frequency-shifted signal is due to the interaction of spatially overlapped excitons. In this method, the signal intensity is directly measured in the frequency domain and does not require scanning of pulse delays or signal phase retrieval. The wavefunctions of the two-exciton states contain information about the spatial overlap of excitons and can be helpful in identifying coupling strengths and relaxation pathways. We propose this method as a facile experimental means of studying exciton correlations in systems with complicated electronic structures.     

Pure optical dephasing dynamics in semiconducting single-walled carbon nanotubes

We report a detailed study of ultrafast exciton dephasing processes in semiconducting single-walled carbon nanotubes employing a sample highly enriched in a single tube species, the (6,5) tube. Systematic measurements of femtosecond pump-probe, two-pulse photon echo, and three-pulse photon echo peak shift over a broad range of excitation intensities and lattice temperature (from 4.4 to 292 K) enable us to quantify the timescales of pure optical dephasing (T(2)(*)), along with exciton-exciton and exciton-phonon scattering, environmental effects as well as spectral diffusion. While the exciton dephasing time (T(2)) increases from 205 fs at room temperature to 320 fs at 70 K, we found that further decrease of the lattice temperature leads to a shortening of the T(2) times. This complex temperature dependence was found to arise from an enhanced relaxation of exciton population at lattice temperatures below 80 K. By quantitatively accounting the contribution from the population relaxation, the corresponding pure optical dephasing times increase monotonically from 225 fs at room temperature to 508 fs at 4.4 K. We further found that below 180 K, the pure dephasing rate (1/T(2)(*)) scales linearly with temperature with a slope of 6.7 ± 0.6 μeV/K, which suggests dephasing arising from one-phonon scattering (i.e., acoustic phonons). In view of the large dynamic disorder of the surrounding environment, the origin of the long room temperature pure dephasing time is proposed to result from reduced strength of exciton-phonon coupling by motional narrowing over nuclear fluctuations. This consideration further suggests the occurrence of remarkable initial exciton delocalization and makes nanotubes ideal to study many-body effects in spatially confined systems.     

Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass

The neutral muonic helium atom (4)Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of (4)Heμ with molecular hydrogen, (4)Heμ + H(2) → (4)HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k(Heμ), are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for k(Heμ) are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for k(Heμ) on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H(2) and Mu + H(2) reactions in a novel study of kinetic isotope effects for the H + H(2) reactions over a factor of 36.1 in isotopic mass of the atomic reactant.