Criteria to define the standard deviation for proficiency assessment for the determination of essential trace elements in serum: comparison of Z-scores based on the Horwitz function or on biological variability

A critical issue in the organisation of Proficiency Testing/External Quality Assessment Schemes is the definition of the criteria against which the performance of individual laboratories should be evaluated. Organisers of EQAS in Occupational and Environmental Laboratory Medicine (http://www.occupational-environmental-laboratory.com) collaborate to define common acceptable levels of performance. The aim of this study was to compare the Horwitz function to the Fraser’s approach. Sets of results obtained from the distribution of test materials in the Network schemes (for the measurands: copper, selenium or zinc in serum) were used to calculate Z-scores according to both approaches. Quality specifications derived from both approaches were also compared to the standard deviations obtained. Except for selenium, Horwitz criteria suggests a more stringent evaluation than Fraser criteria, the latter being very stringent as regard the participant analytical variability.     

New structural types and different oxidation levels in the family of Mn6-oxime single-molecule magnets

The synthesis and magnetic properties of three new members of a family of salicyaldoxime based [Mn6] single-molecule magnets possessing new structural types, core topologies and Mn oxidation state distributions are reported. The isostructural complexes [MnIII6O2(R-sao)6(X)2(EtOH)6] (R = Et, X = Br (1); R = Me, X = I (2)) exhibit single-molecule magnet behaviour with spin Hamiltonian parameters S = 12, g = 1.98 and D = -0.36 cm(-1) in both cases. The hexametallic cluster [MnIII4MnIV2O2(OMe)(4-)(Et-sao)6(MeOH)2].MeOH (3.MeOH) possesses a planar rod-like topology and a mixed valent [MnIV4MnIII2] core, which is unprecedented in this family of [Mn6] SMMs.     

Photochemistry and photopolymerization activity of novel perester derivatives of fluorenone: a conventional and laser flash photolysis study

The photochemistry of three novel t-butylperester derivatives of fluorenone was examined and compared with unsubstituted fluorenone and a mono-t-butylperester of benzophenone using both conventional microsecond and nanosecond laser flash photolysis. On conventional microsecond flash photolysis in 2-propanol, all four fluorenone compounds gave transient absorption in the region 300–400 nm due to a ketyl radical formed from the abstraction of a hydrogen atom from the solvent by the upper excited triplet n—π* state of the fluorenone chromophore. This assignment was confirmed by a pH-dependent study on the transient absorption spectra. The nitro-t-butylperester derivative of fluorenone gave additional absorption above 400 nm due to species associated with the nitro group. No evidence for benzoyloxy radical formation could be found in non-hydrogen-atom-donating solvents with microsecond flash photolysis which is associated with homolysis of the perester groups. On nanosecond laser flash photolysis of the fluorenone compounds at 355 nm excitation in acetonitrile and hexa-fluorobenzene, transient absorptions were observed in the region 320–640 nm due to the corresponding triplet states. All the t-butylperester derivatives showed residual absorbances at longer time delays which were tentatively assigned to the corresponding benzoyloxy radicals produced by homolysis of the perester groups. In contrast, the mono-t-butylperester of benzophenone, included for comparison only, showed very weak transient absorption in the region 320–640 nm compared with that of the strong triplet of benzophenone under the same excitation conditions. The triplet absorptions and lifetimes of the fluorenone compounds were correlated with their photopolymerization activities in bulk methylmethacrylate monomer. In oxygenated solutions, the triplet absorptions of fluorenone and benzophenone were effectively quenched; however, long-lived transient growths were observed for all the t-butylperester derivatives. The intensities of these novel transient absorptions appear to correlate with the total number of t-butylperester groups in the fluorenone molecule and tentative assignments are discussed.     

Model studies for the synthesis of galbonolide B

The construction of the fourteen membered ring present in galbonolide B 1 is reported. The 10,11-diene system present in the southern portion of has been constructed using an ester enolate rearrangement/silicon mediated fragmentation cascade, whilst the macrocycle has been synthesised following a Johnson rearrangement/mercury assisted ring closure protocol.     

Determination of As,Cd, Pb,and Hg in urine using inductively coupled plasma mass spectrometry with the direct injection high efficiency nebulizer

The application of the large-bore direct injection high efficiency nebulizer (LB-DIHEN) for the determination of arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg) in urine by inductively coupled plasma mass spectrometry (ICP-MS) is described. The LB-DIHEN is compared with the standard method using a concentric pneumatic nebulizer and cyclonic spray chamber. In addition to the toxicological significance of As, Cd, Pb, and Hg, these elements represent a cross-section of analytical issues including spectral interferences (e.g., ⁴⁰Ar³⁵Cl⁺ on ⁷⁵As⁺ and ⁹⁸Mo¹⁶O⁺ on ¹¹⁴Cd⁺) and memory effects (Hg). In this study, the low sample consumption of the LB-DIHEN is used to reduce the volume of urine needed for analysis, and to reduce the volume of final diluted sample required for analysis. Eliminating the spray chamber and reducing the dead volume of the nebulizer reduces memory effects, especially for analytes such as Hg. The Dynamic Reaction Cell (DRC) is used in this study to attenuate the background level of ArCl⁺ in spite of the increase in the solvent load and, in turn, the urine matrix (chloride) delivered to the plasma by the LB-DIHEN. This is the first report on coupling the LB-DIHEN to a standard autosampler for unattended sample analysis. The robustness of direct injection nebulization for routine analysis and the issues associated with automation of the sample introduction process are discussed. Although the figures of merit (sensitivity, limit of detection, and precision) determined for both nebulizers are slightly poorer for the LB-DIHEN than for the concentric pneumatic nebulizer, there is not a clinically significant difference between the results for both sample introduction systems. The accuracy of results is assessed using archived urine materials that are circulated by several different proficiency testing (PT) programs and external quality assessment schemes (EQAS). Results obtained using the LB-DIHEN were within the acceptable range established by a consensus pool generated using different methods, none of which are likely to be using direct injection nebulization. Internal quality control sample results obtained using the LB-DIHEN were compared to those obtained using the conventional nebulizer. Reported results were similar for both nebulizers. Thus, these results show that the LB-DIHEN is certainly feasible for the analysis of urine specimens.     

Things That are Right with the Traditional Square of Opposition

The truth conditions that Aristotle attributes to the propositions making up the traditional square of opposition have as a consequence that a particular affirmative proposition such as ‘Some A is not B’ is true if there are no Bs. Although a different convention than the modern one, this assumption remained part of centuries of work in logic that was coherent and logically fruitful.      

Synthesis,Crystal Structure,and Rotational Energy Profile of 3-Cyclopropyl-1,2,4-benzotriazine 1,4-Di-<Emphasis Type="Italic">N</Emphasis>-oxide

Abstract  

1,2,4-Benzotriazine 1,4-di-N-oxides are potent antitumor drug candidates that undergo in vivo bioreduction leading to selective DNA damage in the low oxygen (hypoxic) cells found in tumors. Tirapazamine (TPZ) is the lead compound in this family. Here we report on the synthesis, crystal structure, and conformational analysis of a new analog, 3-cyclopropyl-1,2,4-benzotriazine 1,4-di-N-oxide (3). Compound 3 (C₁₀H₁₀N₃O₂) crystallized in the monoclinic space group C2/c. Unit cell parameters for 3: a = 16.6306 (12), b = 7.799 (5), c = 16.0113 (11) ?, α = 90, β = 119.0440 (10), γ = 90, and z = 8.     

Room temperature aryl trifluoromethylation via copper-mediated oxidative cross-coupling

A method for the room temperature copper-mediated trifluoromethylation of aryl and heteroaryl boronic acids has been developed. This protocol is amenable to normal benchtop setup and reactions typically require only 1-4 h. Proceeding under mild conditions, the method tolerates a range of functional groups, allowing access to a variety of trifluoromethylarenes.