Variability of procedural blanks leads to greater uncertainty in assessing detection limits for the measurement of polonium-210

Low-level measurements of ²¹⁰Po using alpha spectrometry with a ²⁰⁹Po tracer have been conducted at the Environmental Research Institute of the Supervising Scientist (eriss) for many years, on samples with a range of activity concentrations spanning several orders of magnitude. These samples originated from a wide range of research and monitoring projects, and included a wide variety of traditional foods consumed by the indigenous population in Australia’s Northern Territory. Assessment of instrument blank and analyte blank data from these measurements collected over a period of 8 years was conducted. Instrumental blank data for ²¹⁰Po and ²⁰⁹Po generally followed a normal distribution, whereas analyte blank data for ²¹⁰Po followed a lognormal distribution. Instrumental blank data for ²⁰⁹Po indicated an increasing trend, indicative of a low level of polonium volatilisation from prepared sources. Lower limits of detection, including the critical limit, detection limit and quantification limit have been calculated. The critical limit ranges from 12 to 37 counts per day. Detection and quantification limits range from 0.18 to 0.33 mBq and 2.3 to 3.6 mBq for a 4-day count, with an assumed mean chemical recovery of 53 %. These limits are relatively high for alpha spectrometric techniques due to the high variability of the analyte blank signal and non-normal distribution for ²¹⁰Po. Native plant species have relatively low activity concentrations of ²¹⁰Po in their edible fruits and the amount of sample that should be used for analysis to ensure 90 % of fruit samples analysed reach the specified quantification limit was 11 g.     

A Sucrose-Based Approach to Enantiomerically Pure Glycerol Derivatives

Abstract

Taking advantage of the same configuration present at C-5 and C-5′ in sucrose, 6,6′-diprotected sucrose derivatives were transformed into enantiomerically pure glycerol derivatives. This was achieved by oxidative ring cleavage of both the glucopyranosyl ring as well as the fructofuranosyl moiety followed by reduction of the resulting tetraaldehyde and subsequent per-O-protection of the resulting pentahydroxy compound. The obtained intermediate was hydrolysed under acidic conditions to furnish two equivalents of partially protected chiral glycerol derivative per molecule of starting material. The efficiencies of sodium metaperiodate and lead tetraacetate as oxidizing agents were compared and the side reactions observed in these procedures were investigated.     

Various carbon dust particles

Nano-sized carbon dusts are suspected of having negative effects on human health. An exact characterization of such particles is necessary to understand possible toxic effects, i.e. in the lung. Observed by transmission electron microscopy (TEM), the carbon dusts are a composite of very small primary particles and larger agglomerates of these. A differentiation of the primary particles and agglomerates according to source is not possible by TEM, however, thermogravimetry investigations in synthetic air atmosphere are helpful. Standardized carbon black and graphite show a single-step oxidation behaviour, whereas ethene soot and diesel soot, for example, show more complex-reaction mechanisms. The results of ethene soot exemplarily demonstrate the oxidation mechanism. In addition to the oxidation reaction to carbon dioxide, a sintering process takes place. To confirm the oxidation mechanism, thermal behaviour of ethene soot has been simulated by kinetic modulation using a three-step reaction mechanism of n-th order. The reaction order indicates a complex mechanism for the first-reaction step. For the second and third-reaction step, a phase boundary mechanism could be suggested.     

NMR shielding tensors for density fitted local second-order Mo̸ller-Plesset perturbation theory using gauge including atomic orbitals

An efficient method for the calculation of nuclear magnetic resonance (NMR) shielding tensors is presented, which treats electron correlation at the level of second-order Mo?ller-Plesset perturbation theory. It uses spatially localized functions to span occupied and virtual molecular orbital spaces, respectively, which are expanded in a basis of gauge including atomic orbitals (GIAOs or London atomic orbitals). Doubly excited determinants are restricted to local subsets of the virtual space and pair energies with an interorbital distance beyond a certain threshold are omitted. Furthermore, density fitting is employed to factorize the electron repulsion integrals. Ordinary Gaussians are employed as fitting functions. It is shown that the errors in the resulting NMR shielding constant, introduced (i) by the local approximation and (ii) by density fitting, are very small or even negligible. The capabilities of the new program are demonstrated by calculations on some extended molecular systems, such as the cyclobutane pyrimidine dimer photolesion with adjacent nucleobases in the native intrahelical DNA double strand (ATTA sequence). Systems of that size were not accessible to correlated ab initio calculations of NMR spectra before. The presented method thus opens the door to new and interesting applications in this area.     

APPLICATIONS OF MULTICOMPONENT ASSEMBLY PROCESSES TO THE FACILE SYNTHESES OF DIVERSELY FUNCTIONALIZED NITROGEN HETEROCYCLES

Several multicomponent assembly processes have been developed for the synthesis of intermediates that may be elaborated by a variety of cyclizations to generate a diverse array of highly functionalized heterocycles from readily-available starting materials. The overall approach enables the efficient preparation of libraries of small molecules derived from fused, privileged scaffolds.