Secondary electrospray ionization (SESI) of ambient vapors for explosive detection at concentrations below parts per trillion

We determine the sensitivity of several commercial atmospheric pressure ionization mass spectrometers towards ambient vapors, ionized by contact with an electrospray of acidified or ammoniated solvent, a technique often referred to as secondary electrospray ionization (SESI). Although a record limit of detection of 0.2 × 10⁻¹² atmospheres (0.2 ppt) is found for explosives such as PETN and 0.4 ppt for TNT (without preconcentration), this still implies the need for some 10⁸–10⁹ vapor molecules/s for positive identification of explosives. This extremely inefficient use of sample is partly due to low charging probability (∼10⁻⁴), finite ion transmission, and counting probability in the mass spectrometer (1/10 in quadrupoles), and a variable combination of duty cycle and background noise responsible typically for a 10³ factor loss of useful signal.     

Suspensions of biological tissues in alkaline medium for the determination of copper, manganese and cobalt by electrothermal atomic absorption spectrometry

Electrothermal atomic absorption spectrometry was applied to the determination of copper, manganese and cobalt in biological tissues of which small amounts are available only. The samples (10 mg of mice tissue) were suspended in 1 mL of water containing tetramethylammonium hydroxide, Triton X-100 and silicone antifoam. The sample was homogenized by heating to 60 °C for 5 min, submitted to dilution if necessary, and injected into the atomizer. Wall atomization was used for Cu and Mn, and platform atomization for Co. Calibration was carried out using aqueous standards for copper and manganese determination. The determination of cobalt suffered from a matrix effect and, in this case, calibration was enabled by using a suspension of a cobalt-free muscle sample. The detection limits are 25, 20 and 62 ng?g^?1. The results obtained for five certified reference materials demonstrated the reliability of the procedures for the determination of the three analytes in normal and dystrophic mice tissue.     

Enhancement of cyanide photocatalytic degradation using sol–gel ZnO sensitized with cobalt phthalocyanine

In this work, the photodegradation of cyanide in aqueous suspension was used to determine the photocatalytic activity of sol–gel prepared ZnO which was impregnated with the Co (II) phthalocyanine (CoPc), as sensitizer. The prepared catalyst was characterized by Scanning Electron Microscopy (SEM) with Energy Dispersed Spectroscopy (EDS) detector, X-Ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FT-IR) and Diffuse UV–Vis Reflectance spectroscopy. Specific surface area was calculated from nitrogen adsorption isotherm using BET method. Compared with commercial ZnO and TiO₂ Degussa P25 photocatalysts, the sol–gel prepared ZnO catalyst sensitized with cobalt phthalocyanine showed the highest activities for degradation of cyanide in aqueous solution under visible light irradiation.     

Automated sample treatment with the injection of large sample volumes for the determination of contaminants and metabolites in urine

This work reports the development of a simple and automated method for the quantitative determination of several contaminants (triazine, phenylurea, and phenoxyacid herbicides; carbamate insecticides and industrial chemicals) and their metabolites in human urine with a simplified sample treatment. The method is based on the online coupling of an extraction column with RP LC separation–UV detection; this coupling enabled fast online cleanup of the urine samples, efficiently eliminating matrix components and providing appropriate selectivity for the determination of such compounds. The variables affecting the automated method were optimized: sorbent type, washing solvent and time, and the sample volume injected. The optimized sample treatment reported here allowed the direct injection of large volumes of urine (1500 μL) into the online system as a way to improve the sensitivity of the method; limits of detection in the 1–10 ng/mL range were achieved for an injected volume of 1500 μL of urine, precision being 10% or better at a concentration level of 20 ng/mL. The online configuration proposed has advantages such as automation (all the steps involved in the analysis – injection of the urine, sample cleanup, analyte enrichment, separation and detection – are carried out automatically) with high precision and sensitivity, reducing manual sample manipulation to freezing and sample filtration.     

Democracy functions and optimal embeddings for approximation spaces

We prove optimal embeddings for nonlinear approximation spaces $\mathcal{A}^{\alpha}_q$ , in terms of weighted Lorentz sequence spaces, with the weights depending on the democracy functions of the basis. As applications we recover known embeddings for N-term wavelet approximation in L ^p , Orlicz, and Lorentz norms. We also study the ??greedy classes?? ${\mathcal{G}_{q}^{\alpha}}$ introduced by Gribonval and Nielsen, obtaining new counterexamples which show that ${\mathcal{G}_{q}^{\alpha}}\not=\mathcal{A}^{\alpha}_q$ for most non-democratic unconditional bases.     

Ligand-modification effects on the reactivity, solubility, and stability of organometallic tantalum complexes in water

Tantalum complexes [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NMe(2))=CH)py}] (4) and [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NH(2))=CH)py}] (5), which contain modified alkoxide pincer ligands, were synthesized from the reactions of [TaCp*Me{κ(3)-N,O,O-(OCH(2))(OCH)py}] (Cp* = η(5)-C(5)Me(5)) with HC≡CCH(2)NMe(2) and HC≡CCH(2)NH(2), respectively. The reactions of [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(Ph)=CH)py}] (2) and [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(SiMe(3))=CH)py}] (3) with triflic acid (1:2 molar ratio) rendered the corresponding bis-triflate derivatives [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(OCHC(Ph)=CH(2))py}] (6) and [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(OCHC(SiMe(3))=CH(2))py}] (7), respectively. Complex 4 reacted with triflic acid in a 1:2 molar ratio to selectively yield the water-soluble cationic complex [TaCp*(OTf){κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NHMe(2))=CH)py}]OTf (8). Compound 8 reacted with water to afford the hydrolyzed complex [TaCp*(OH)(H(2)O){κ(3)-N,O,O-(OCH(2))(OCHC(CH(2)NHMe(2))=CH(2))py}](OTf)(2) (9). Protonation of compound 8 with triflic acid gave the new tantalum compound [TaCp*(OTf){κ(4)-C,N,O,O-(OCH(2))(HOCHC(CH(2)NHMe(2))=CH)py}](OTf)(2) (10), which afforded the corresponding protonolysis derivative [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(HOCHC(CH(2)NHMe(2))=CH(2))py}](OTf) (11) in solution. Complex 8 reacted with CNtBu and potassium 2-isocyanoacetate to give the corresponding iminoacyl derivatives 12 and 13, respectively. The molecular structures of complexes 5, 7, and 10 were established by single-crystal X-ray diffraction studies.     

Determination of 5-nitroimidazoles and metabolites in environmental samples by micellar electrokinetic chromatography

A method based on micellar electrokinetic chromatography (MEKC) with UV detection has been developed for the determination of nine 5-nitroimidazoles (5-NDZs), including metabolites in river water samples. Due to the relative insensitivity of UV detection in MEKC, a solid-phase extraction (SPE) method has been proposed that preconcentrates water samples fiftyfold and cleans them up off-line. An on-line preconcentration approach based on sweeping and the use of an extended light path fused-silica capillary (64.5?cm?×?50?μm i.d., 56?cm effective length) was also found to improve the sensitivity of the method. Separation was carried out in <21?min using 20?mM phosphate buffer (pH 6.5) and 150?mM SDS as the background electrolyte (BGE). The temperature of the capillary was kept constant at 20°C, a voltage of 25?kV was applied (normal mode), and a detected wavelength of 320?nm was utilized. Hydrodynamic injection (50?mbar for 15?s) of the samples, which were dissolved in 20?mM phosphate (pH 6.5), was employed. The limits of detection were lower than 1.1?μg?L(-1). Recoveries of >80% from spiked river water samples were obtained for most of the analytes at three different concentration levels with acceptable precision. This method could provide an efficient and economical alternative to the use of chromatographic methods to monitor nitroimidazole residues, thus supplementing the relatively few methods available for the analysis of these compounds in environmental samples.     

Functional Magnetic Resonance Imaging Data Analysis by Autoregressive Estimator

The autoregressive (AR) estimator, a non-parametric method, is used to analyze functional magnetic resonance imaging (fMRI) data. The same method has been used, with success, in several other time series data analysis. It uses exclusively the available experimental data points to estimate the most plausible power spectra compatible with the experimental data and there is no need to make any assumption about non-measured points. The time series, obtained from fMRI block paradigm data, is analyzed by the AR method to determine the brain active regions involved in the processing of a given stimulus. This method is considerably more reliable than the fast Fourier transform or the parametric methods. The time series corresponding to each image pixel is analyzed using the AR estimator and the corresponding poles are obtained. The pole distribution gives the shape of power spectra, and the pixels with poles at the stimulation frequency are considered as the active regions. The method was applied in simulated and real data, its superiority is shown by the receiver operating characteristic curves which were obtained using the simulated data.     

Role of the longitudinal piston error in a tiled-grating compressor in second and high-order harmonic generation

In this work, we study the limitations for overcoming the longitudinal piston error in a femtosecond tiled-grating compressor using nonlinear measurements like second harmonic generation. In particular, we observe the influence of this error when developing high-power laser experiments such as high-order harmonic generation. The generation of nonlinear processes with femtosecond pulses compressed in tiled-grating systems is studied. Special attention is paid to the role of the longitudinal piston error which is the most difficult to overcome in the compressor alignment. A complex spatio-temporal structure is expected to appear due to that misalignment. Both second harmonic generation in nonlinear crystals and high-order harmonic generation in gases are studied and a strong dependence with piston error is found, thus leading to a sub-micron modulation in the generated signal. In particular, the high sensitivity of the high-order harmonics to the longitudinal position allows one to use this processes for the accurate alignment of the compressor to few tens of nanometers.     

LC‐DAD/ESI‐MS/MS study of phenolic compounds in ash (Fraxinus excelsior L. and F. americana L.) heartwood. Effect of toasting intensity at cooperage

The phenolic composition of heartwood extracts from Fraxinus excelsior L. and F. americana L., both before and after toasting in cooperage, was studied using LC‐DAD/ESI‐MS/MS. Low‐molecular weight (LMW) phenolic compounds, secoiridoids, phenylethanoid glycosides, dilignols and oligolignols compounds were detected, and 48 were identified, or tentatively characterized, on the basis of their retention time, UV/Vis and MS spectra, and MS fragmentation patterns. Some LMW phenolic compounds like protocatechuic acid and aldehyde, hydroxytyrosol and tyrosol, were unlike to those for oak wood, while ellagic and gallic acid were not found. The toasting of wood resulted in a progressive increase in lignin degradation products with regard to toasting intensity. The levels of some of these compounds in medium‐toasted ash woods were much higher than those normally detected in toasted oak, highlighting vanillin levels, thus a more pronounced vanilla character can be expected when using toasted ash wood in the aging wines. Moreover, in seasoned wood, we found a great variety of phenolic compounds which had not been found in oak wood, especially oleuropein, ligstroside and olivil, along with verbascoside and isoverbascoside in F. excelsior, and oleoside in F. americana. Toasting mainly provoked their degradation, thus in medium‐toasted wood, only four of them were detected. This resulted in a minor differentiation between toasted ash and oak woods. The absence of tannins in ash wood, which are very important in oak wood, is another peculiar characteristic that should be taken into account when considering its use in cooperage. Copyright © 2012 John Wiley & Sons, Ltd.