Determination of polybrominated diphenyl ethers in human hair by gas chromatography-mass spectrometry

A rapid analytical method has been developed for the determination of polybrominated diphenyl ethers (PBDEs) in human hair. PBDEs were determined by gas chromatography with electron ionization mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). A 200 mg amount of hair samples was overnight digested in 3N HCl and then PBDEs extracted with n-hexane. After clean up of extracts in a Florisil column, PBDEs were analyzed by GC-MS. The method has been validated by spiking human hair at five concentration levels, in the range from 5 to 25 ng/g for most compounds, and PBDEs were quantified using labelled compounds as internal standards. Recoveries of PBDEs were higher than 90%, repeatability was equal or lower than 12.5%, and reproducibility lower than 14%, expressed as relative standard deviation (RSD). Limits of detection (LOD) were in the range 0.08-0.9 ng/g and limits of quantification (LOQ) were between 0.27 and 3.0 ng/g. This method was applied to the determination of PBDEs in hair samples from 16 individuals and 5 PBDE congeners were detected in most of the samples. BDE-209 was the dominant compound found, followed by BDE-47, BDE-99, BDE-100, and BDE-190. BDE-209 was found in 12 out of 16 hair samples, and the total levels of PBDEs ranged from 1.4 to 19.9 ng/g.     

Chaotic parameters and their role in quantifying noise in the output signals from UV, TGA and DSC apparatus

Two fractal dimensions and the Liapunov exponent (LE) have been applied to detect noisy output signals from UV spectrophotometer (UV), thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) apparatus of 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid ([emim][EtSO₄]). The data collected from these three pieces of equipment were classified before calculating LE, regularization (RD) and box dimensions (BD). The RD and LE are able individually to detect and quantify noisy output signals with a mean error value less than 5% in all cases tested. Given that the LE can be calculated using a really simple method, this chaotic parameter has been selected as the most suitable to detect noise of signals from these apparatus.     

Convergent and Asymptotic Methods for Second-order Difference Equations with a Large Parameter

We consider the second-order linear difference equation \(y(n+2)-2a y(n+1)-\Lambda ^2 y(n)=g(n)y(n)+f(n)y(n+1)\), where \(\Lambda \) is a large complex parameter, \(a\ge 0\) and g and f are sequences of complex numbers. Two methods are proposed to find the asymptotic behavior for large \(\vert \Lambda \vert \) of the solutions of this equation: (i) an iterative method based on a fixed point method and (ii) a discrete version of Olver’s method for second-order linear differential equations. Both methods provide an asymptotic expansion of every solution of this equation. The expansion given by the first method is also convergent and may be applied to nonlinear problems. Bounds for the remainders are also given. We illustrate the accuracy of both methods for the modified Bessel functions and the associated Legendre functions of the first kind.     

Ramsey fringes in an electric-field-tunable quantum dot system

We report on Ramsey fringes measured in a single InGaAs/GaAs quantum dot two-level system. We are able to control the transition energy of the system by Stark effect tuning. In combination with double pulse excitation this allows for a voltage controlled preparation of the phase and the occupancy of the two-level system. For long pulse delay times we observe extremely narrow fringes with spectral width below the homogeneous linewidth of the system. Implications on quantum information processing are discussed.     

Estimated communication range of social sounds used by bottlenose dolphins (Tursiops truncatus)

Bottlenose dolphins, Tursiops truncatus, exhibit flexible associations in which the compositions of groups change frequently. We investigated the potential distances over which female dolphins and their dependent calves could remain in acoustic contact. We quantified the propagation of sounds in the frequency range of typical dolphin whistles in shallow water areas and channels of Sarasota Bay, Florida. Our results indicated that detection range was noise limited as opposed to being limited by hearing sensitivity. Sounds were attenuated to a greater extent in areas with seagrass than any other habitat. Estimates of active space of whistles showed that in seagrass shallow water areas, low-frequency whistles (7-13 kHz) with a 165 dB source level could be heard by dolphins at 487 m. In shallow areas with a mud bottom, all whistle frequency components of the same whistle could be heard by dolphins travel up to 2 km. In channels, high-frequency whistles (13-19 kHz) could be detectable potentially over a much longer distance (> 20 km). Our findings indicate that the communication range of social sounds likely exceeds the mean separation distances between females and their calves. Ecological pressures might play an important role in determining the separation distances within communication range.     

Electrospray mass spectrometry of a series of mixed nitrido 99gTc- heterocomplexes conjugated with bioactive molecules

Electrospray ionization mass spectrometry (ESI-MS) was successfully employed for the identification of six nitrido technetium mixed ligand complexes with a general formula of [99gTc(N)(O,S-BID)(PNP)], where PNP represents a heterodiphosphine and O,S-BID represents a simple dianionic bidentate ligand (compounds 1-3) or a more sophisticated N-substituted O,S-cysteine framework conjugated with a bio- active molecule (BAM) (compounds 4-6). In spite of similar coordination spheres exhibited by all the complexes investigated, simple co-ordination compounds 1-3 displayed collisionally-induced fragmentation processes (MSn) different from those observed in biomolecule-containing compounds 4-6. In the latter, more decomposition channels were observed. This behavior is likely to be associated with some additional intramolecular contacts of the biomolecule (or part of the biomolecule) with pendant group(s) incorporated in the PNP-co-ligand. This view is further supported by the observations arising from both in vitro binding affinity experiments and nuclear magnetic resonance investigations. The presence of cationized forms for all compounds 1-6 and the practical lack of the [2M + Na]+ species for biomolecule-containing compounds 4-6 provided further evidence of a subtly different structural conformation.     

Analytic Approximations for a Singularly Perturbed Convection—Diffusion Problem with Discontinuous Data in a Half-Infinite Strip

We consider a singularly perturbed convection—diffusion equation, –u+v u=0, defined on a half-infinite strip, (x,y)(0,)×(0,1) with a discontinuous Dirichlet boundary condition: u(x,0)=1, u(x,1)=u(0,y)=0. Asymptotic expansions of the solution are obtained from an integral representation in two limits: (a) as the singular parameter 0⁺ (with fixed distance r to the discontinuity point of the boundary condition) and (b) as that distance r0⁺ (with fixed ). It is shown that the first term of the expansion at =0 contains an error function or a combination of error functions. This term characterizes the effect of discontinuities on the -behavior of the solution and its derivatives in the boundary or internal layers. On the other hand, near the point of discontinuity of the boundary condition, the solution u(x,y) is approximated by a linear function of the polar angle at the point of discontinuity (0,0).     

Influence of preparation and storage conditions on photoluminescence of porous silicon powder with embedded Si nanocrystals

The time changes of photoluminescence (PL) characteristics of porous silicon (porSi) powder during storing in different ambients have been reported. A porous silicon material with embedded Si nanocrystals of size of few nanometers was prepared by an electrochemical method from 10 to 20 Ωcm p-type Si wafers, and both constant and pulse current anodization regimes were used. A powder with a submicron average particle size was obtained by simple mechanical lift-off of the porous layer followed by additional manual milling. The air, hexane, and water as storage media were used, and modification by a nonionic surfactant (undecylenic acid) of the porSi surface was applied in the latter case. Dependence of PL characteristics on preparation and storage conditions was then studied. A remarkable blue shift of a position of PL maximum was observed in time for porSi powders in each storage media. In water suspension a many-fold build-up (10–30) of PL intensity in a time scale of few days was accompanied by an observed blue shift. Photoluminescence time behavior of porSi powders was described by a known mechanism of the change of porSi PL from free exciton emission of Si nanocrystals to luminescence of localized oxidized states on the Si nanocrystal surface.