Development of liquid chromatographic methods for the determination of phytosterols in Standard Reference Materials containing saw palmetto

Liquid chromatographic (LC) methods using atmospheric pressure chemical ionization/mass spectrometric (APCI-MS) detection were developed for the separation and analysis of the phytosterols campesterol, cycloartenol, lupenone, lupeol, beta-sitosterol, and stigmasterol. Brassicasterol and cholesterol were also included for investigation as internal standards. The methods were used to identify and quantify the phytosterols in each of two Serenoa repens (saw palmetto) Standard Reference Materials (SRMs) developed by the National Institute of Standards and Technology (NIST). Values obtained by LC-MS were compared to those obtained using the more traditional approach of gas chromatography with flame ionization detection. This is the first reported use of LC-MS to determine phytosterols in saw palmetto dietary supplement materials.     

Calculated electronic transitions in sulfuric acid and implications for its photodissociation in the atmosphere

We have calculated electronic transitions for sulfuric acid in the ultraviolet region using a hierarchy of coupled cluster response functions and correlation consistent basis sets. Our calculations indicate that the lowest energy singlet transition occurs at 8.42 eV with an oscillator strength of 0.01. The lowest energy triplet state occurs at 8.24 eV. Thus, the cross section of sulfuric acid in the actinic region is likely to be very small and smaller than the upper limit put on this cross section by previous experimental investigations. We estimate the cross section of sulfuric acid in the atmospherically relevant Lyman-alpha region ( approximately 10.2 eV) to be approximately 6 x 10 (-17) cm (2) molecule (-1), a value approximately 30 times larger than the speculative value used in previous atmospheric simulations. We have calculated the J values for photodissociation of sulfuric acid with absorption of visible, UV, and Lyman-alpha radiation, at altitudes between 30 and 100 km. We find that the dominant photodissociation mechanism of sulfuric acid below 70 km is absorption in the visible region by OH stretching overtone transitions, whereas above 70 km, absorption of Lyman-alpha radiation by high energy Rydberg excited states is the favored mechanism. The low lying electronic transitions of sulfuric acid in the UV region do not contribute significantly to its dissociation at any altitude.     

Towards zirconium phosphonate-based microarrays for probing DNA-protein interactions: critical influence of the location of the probe anchoring groups

Terminal phosphate groups on double-stranded DNA probes bind strongly to glass substrates coated with a zirconium phosphonate monolayer, and probes immobilized in this way as microarrays can be used to detect protein targets. The sensitivity of the microarray was shown to be enhanced by the use of a polyguanine segment ((G)n , n > or = 5) as a spacer between the phosphate linker and the protein interaction domain. More importantly, the presence of phosphate linkers on both ends of the dsDNA probes leads to significant enhancement of target capture. The relevant characteristics of the different probes when bound to the surface were determined, by the original use of a combination of surface characterization techniques (XPS, AFM, and Sarfus). In this context, the location of the phosphate linkers in the duplex probes was found to result in different probe surface coverage and presentation on the surface, which affect subsequent interactions with the target protein.     

Post-primary students’ images of mathematics: findings from a survey of Irish ordinary level mathematics students

A questionnaire survey was carried out as part of a PhD research study to investigate the image of mathematics held by post-primary students in Ireland. The study focused on students in fifth year of post-primary education studying ordinary level mathematics for the Irish Leaving Certificate examination – the final examination for students in second-level or post-primary education. At the time this study was conducted, ordinary level mathematics students constituted approximately 72% of Leaving Certificate students. Students were aged between 15 and 18 years. A definition for ‘image of mathematics’ was adapted from Lim and Wilson, with image of mathematics hypothesized as comprising attitudes, beliefs, self-concept, motivation, emotions and past experiences of mathematics. A questionnaire was composed incorporating 84 fixed-response items chosen from eight pre-established scales by Aiken, Fennema and Sherman, Gourgey and Schoenfeld. This paper focuses on the findings from the questionnaire survey. Students’ images of mathematics are compared with regard to gender, type of post-primary school attended and prior mathematical achievement.     

Standard reference materials for foods and dietary supplements

Well-characterized certified reference materials are needed by laboratories in the food testing, dietary supplement, and nutrition communities to facilitate compliance with labeling laws and improve the accuracy of information provided on product labels, so that consumers can make good choices. As a result of the enactment of the Nutrition Labeling and Education Act of 1990 and the Infant Formula Act of 1980, the National Institute of Standards and Technology (NIST) worked to develop a series of food-matrix standard reference materials (SRMs) characterized for nutrient concentrations. These include SRM 1544 Fatty Acids and Cholesterol in a Frozen Diet Composite, SRM 1546 Meat Homogenate, SRM 1548a Typical Diet, SRM 1566b Oyster Tissue, SRM 1846 Infant Formula, SRM 1946 Lake Superior Fish Tissue, SRM 1947 Lake Michigan Fish Tissue, SRM 2383 Baby Food Composite, SRM 2384 Baking Chocolate, SRM 2385 Slurried Spinach, and SRM 2387 Peanut Butter. With the enactment of the Dietary Supplement Health and Education Act of 1994, NIST has been working to develop suites of dietary supplement SRMs characterized for active and marker compounds and for toxic elements and pesticides, where appropriate. An updated SRM 1588b Organics in Cod Liver Oil, a suite of ephedra-containing materials (SRMs 3240–3245), a carrot extract in oil (SRM 3276), and a suite of ginkgo-containing materials (SRMs 3246–3248) are available. Several other materials are currently in preparation. Dietary supplements are sometimes provided in forms that are food-like; for these, values may also be assigned for nutrients, for example SRM 3244 Ephedra-Containing Protein Powder. Both the food-matrix and dietary supplement reference materials are intended primarily for validation of analytical methods. They may also be used as “primary control materials” in assignment of values to in-house (secondary) control materials to confirm accuracy and to establish measurement traceability to NIST.     

Effects of masking noise on vowel and sibilant contrasts in normal-hearing speakers and postlingually deafened cochlear implant users

The role of auditory feedback in speech production was investigated by examining speakers' phonemic contrasts produced under increases in the noise to signal ratio (N/S). Seven cochlear implant users and seven normal-hearing controls pronounced utterances containing the vowels /i/, /u/, /e/ and /ae/ and the sibilants /s/ and /I/ while hearing their speech mixed with noise at seven equally spaced levels between their thresholds of detection and discomfort. Speakers' average vowel duration and SPL generally rose with increasing N/S. Average vowel contrast was initially flat or rising; at higher N/S levels, it fell. A contrast increase is interpreted as reflecting speakers' attempts to maintain clarity under degraded acoustic transmission conditions. As N/S increased, speakers could detect the extent of their phonemic contrasts less effectively, and the competing influence of economy of effort led to contrast decrements. The sibilant contrast was more vulnerable to noise; it decreased over the entire range of increasing N/S for controls and was variable for implant users. The results are interpreted as reflecting the combined influences of a clarity constraint, economy of effort and the effect of masking on achieving auditory phonemic goals-with implant users less able to increase contrasts in noise than controls.     

A chirp-compensated, injection-seeded alexandrite laser

A Q-switched alexandrite laser suitable for high-resolution spectroscopy is described which produces pulses of 35 mJ energy in a 10 MHz bandwidth, with a high-purity TEM₀₀ mode. The laser can be synchronised to external event to within 100 ns. The output pulse length is 120 ns and the repetition rate 25 Hz. The laser is injection-seeded by a Ti:sapphire laser operating around 730 nm. To preserve single-mode seeding under external triggering conditions, and to obtain small time-jitter, active cavity length control was used. In order to achieve the 10 MHz output bandwidth, intra-cavity electro-optic modulators were used to compensate for the frequency chirp. The refractive index of alexandrite was found to vary linearly with inversion density with a constant of proportionality equal to 1.6᎒^-24 cm³. In pulsed operation at 730 nm, the index change due to this effect is only partially compensated by changes due to ground state phonon relaxation.     

Identification of \mathrm{\ensuremath J^{\pi} = 19/2^+} and \mathrm{\ensuremath 23/2^+} isomeric states in 127Sb

The nucleus $\ensuremath {\rm ^{127}Sb}$ , which is on the neutron-rich periphery of the $\ensuremath \beta$ -stability region, has been populated in complex nuclear reactions involving deep-inelastic and fusion-fission processes with $\ensuremath {\rm {}^{136}Xe}$ beams incident on thick targets. The previously known isomer at 2325 keV in $\ensuremath {\rm {}^{127}Sb}$ has been assigned spin and parity $\ensuremath 23/2^+$ , based on the measured $\ensuremath \gamma$ - $\ensuremath \gamma$ angular correlations and total internal conversion coefficients. The half-life has been determined to be 234(12) ns, somewhat longer than the value reported previously. The 2194 keV state has been assigned $\ensuremath J^{\pi} = 19/2^+$ and identified as an isomer with $\ensuremath T_{1/2} = 14(1) {\rm ns}$ , decaying by two $\ensuremath E2$ branches. The observed level energies and transition strengths are compared with the predictions of a shell model calculation. Two $\ensuremath 15/2^+$ states have been identified close in energy, and their properties are discussed in terms of mixing between vibrational and three-quasiparticle configurations.     

Computational determination of effects of electric fields upon “trigger linkages” of prototypical energetic molecules

For five prototypical energetic molecules (nitrobenzene, methyl azide, methyl nitrate, nitromethane, and dimethylnitramine), we examine computationally the effects of external electric fields upon their “trigger linkage” bonds, the breaking of which is believed to play a key role in detonation initiation. The bonds are, respectively, C? NO₂, N? N₂, O? NO₂, C? NO₂, and N? NO₂. The calculations are at the B3PW91/6–31G** level. We find that fields along these bonds that reinforce the molecules' intrinsic polarities also lower their energies and increase the bonds' stretching vibration frequencies. This suggests a strengthening of the bonds. Fields in the opposite direction do the reverse. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009