A fluorinated selenide linker for solid-phase synthesis of n-pentenyl glycosides

[reaction: see text] A fluorine-labeled selenide linker for installing terminal isolated olefins has been synthesized in high overall yield. The resin-bound linker could be glycosylated both with glycosyl trichloroacetimidates and glycosyl fluorides. The linker did not decompose after oxidation with tBuOOH but underwent beta-elimination when it was subjected to heat. This allowed the released n-pentenyl glycoside 15 to be isolated in excellent yield and purity after filtration.     

Polarization effects on the surface chemistry of PbTiO3-supported Pt films

To demonstrate a new paradigm of dynamical control of surface structure and reactivity, we perform density functional theory calculations of the adsorption of several molecules and atoms to the surface of ultrathin Pt(100) films supported on ferroelectric PbTiO3. We show that reorienting the polarization direction of the substrate can dramatically change the chemisorption energies of CO, O, C, and N and alter the reaction pathways for dissociation of CO, O2, N2, and NO. We discuss the structural and electronic effects of a polarized substrate on the metal surface, and we suggest potential applications in tunable catalysis.     

Nonmonotonic TC trends in bi-based ferroelectric perovskite solid solutions

We use first-principles density functional theory calculations to investigate the strongly nonlinear compositional trends in ferroelectric BiBO3-PbTiO3 solid solutions for a variety of cations on the perovskite B site. We demonstrate that previously tabulated crystal chemical parameters (extracted from other Pb-based perovskite alloys [Grinberg et al., J. Appl. Phys. 98, 094111 (2005)]) permit accurate prediction of cation displacements in these new Bi-Pb alloys. We find that observed transition temperatures in these materials are well correlated with computed polarization magnitudes. The presented model for coupling between compositional variation and cation displacements explains the highly nonlinear and often nonmonotonic dependence of the Curie temperature (T(C)) on composition observed in these solid solutions.     

Recovery of spectral features readout with frequency-chirped laser fields

A data-processing technique is proposed for use with conventional frequency-chirped absorption spectroscopy to ensure accurate mapping of spectral features into time-domain signatures with arbitrarily fast readout chirp rates. This technique recovers the spectrum from a signal that is distorted owing to the fast chirp rate and therefore facilitates fast measurement of the spectral features over a broad spectral range with high resolution. Both numerical simulations and experimental results are presented.     

Determination of oxygenated and native polycyclic aromatic hydrocarbons in urban dust and diesel particulate matter standard reference materials using pressurized liquid extraction and LC–GC/MS

The objective of this study was to develop a novel analytical chemistry method, comprised of a coupled high-performance liquid chromatography–gas chromatography/mass spectrometry system (LC–GC/MS) with low detection limits and high selectivity, for the identification and determination of oxygenated polycyclic aromatic hydrocarbons (OPAHs) and polycyclic aromatic hydrocarbons (PAHs) in urban air and diesel particulate matter. The linear range of the four OPAHs, which include 9,10-anthraquinone, 4H-cyclopenta[def]phenanthrene-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, was 0.7 pg–43.3 ng with limits of detection (LODs) and limits of quantification (LOQs) on the order of 0.2–0.8 and 0.7–1.3 pg, respectively. The LODs in this study are generally lower than values reported in the literature, which can be explained by using large-volume injection. The recoveries of the OPAHs spiked onto glass fiber filters using two different pressurized liquid extraction (PLE) methods were in the ranges of 84–107 and 67–110 %, respectively. The analytical protocols were validated using the following National Institute of Standards and Technology standard reference materials: SRM 1649a (Urban Dust), SRM 1650b (Diesel Particulate Matter), and SRM 2975 (Diesel Particulate Matter, Industrial Forklift). The measured mass fractions of the OPAHs in the standard reference materials (SRMs) in this present study are higher than the values from the literature, except for benzanthrone in SRM 1649a (Urban Dust). In addition to the OPAHs, 44 PAHs could be detected and quantified from the same particulate extract used in this protocol. Using data from the literature and applying a two-sided t test at the 5 % level using Bonferroni correction, significant differences were found between the tested PLE methods for individual PAHs. However, the measured mass fractions of the PAHs were comparable, similar to, or higher than those previously reported in the literature.     

Improved efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) from the National Institute of Standards and Technology (NIST) Standard Reference Material Diesel Particulate Matter (SRM 2975) using accelerated solvent extraction

The efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) with molecular masses of 252, 276, 278, 300, and 302 Da from standard reference material diesel particulate matter (SRM 2975) has been investigated using accelerated solvent extraction (ASE) with dichloromethane, toluene, methanol, and mixtures of toluene and methanol. Extraction of SRM 2975 using toluene/methanol (9:1, v/v) at maximum instrumental settings (200 °C, 20.7 MPa, and five extraction cycles) with 30-min extraction times resulted in the following elevations of the measured concentration when compared with the certified and reference concentrations reported by the National Institute of Standards and Technology (NIST): benzo[b]fluoranthene, 46%; benzo[k]fluoranthene, 137%; benzo[e]pyrene, 103%; benzo[a]pyrene, 1,570%; perylene, 37%; indeno[1,2,3-cd]pyrene, 41%; benzo[ghi]perylene, 163%; and coronene, 361%. The concentrations of the following PAHs were comparable to the reference values assigned by NIST: indeno[1,2,3-cd]fluoranthene, dibenz[a,h]anthracene, and picene. The measured concentration of dibenzo[a,e]-pyrene was lower than the information value reported by the NIST. The measured concentrations of other highly carcinogenic PAHs (dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene) in SRM 2975 are also reported. Comparison of measurements using the optimized ASE method and using similar conditions to those applied by the NIST for the assignment of PAH concentrations in SRM 2975 indicated that the higher values obtained in the present study were associated with more complete extraction of PAHs from the diesel particulate material. Re-extraction of the particulate samples demonstrated that the deuterated internal standards were more readily recovered than the native PAHs, which may explain the lower values reported by the NIST. The analytical results obtained in the study demonstrated that the efficient extraction of PAHs from SRM 2975 is a critical requirement for the accurate determination of PAHs with high molecular masses in this standard reference material and that the optimization of extraction conditions is essential to avoid underestimation of the PAH concentrations. The requirement is especially relevant to the human carcinogen benzo[a]pyrene, which is commonly used as an indicator of the carcinogenic risk presented by PAH mixtures.     

Determination of dibenzopyrenes in standard reference materials (SRM) 1649a, 1650, and 2975 using ultrasonically assisted extraction and LC–GC–MS

A method has been developed for analysis of the highly potent polycyclic aromatic hydrocarbon (PAH) carcinogens dibenzo(a,l)pyrene, dibenzo(a,h)pyrene, and dibenzo(a,i)pyrene (molecular weight 302) present in small amounts in diesel and air particulate material. The method can also be used for analysis of the PAH benzo(a)pyrene, coronene, and perylene, for which reference and certified values are available for the standard reference materials used for validation of the method—SRM 1649a (urban dust) and SRM 2975 (diesel particulate matter). The only NIST values that have been published for these dibenzopyrene isomers in the analyzed SRM are reference values for dibenzo(a,i)pyrene and dibenzo(a,h)pyrene in SRM 1649a. The concentrations determined in the SRM were in good agreement with reported NIST-certified and reference values and other concentrations reported in the literature. Standard reference material 1650 (diesel particulate matter) was also analyzed. The method could not, however, be validated using this material because certification of SRM 1650 had expired. The method is based on ultrasonically assisted extraction of the particulate material, then silica SPE pre-separation and isolation, and, separation and detection by hyphenated LC–GC–MS. The method is relatively rapid and requires only approximately 1–5 mg SRM particulate material to identify and quantify the analytes. Low extraction recoveries for the analytes, in particular the dibenzopyrenes, when extracting diesel SRM 2975 and 1650 resulted, however, in the dibenzopyrenes being present in amounts near their limits of quantifications in these samples. The method’s limit of quantification (LOQ), based on analyses of SRM 1649a, is in the range 10–77 pg. By use of this method more than 25 potential PAH isomers with a molecular weight of 302 could be separated.