Measurement of the K(L) charge asymmetry

We present a measurement of the charge asymmetry delta(L) in the mode K(L)-->pi(+/-)e(-/+)nu based on 298 x 10(6) analyzed decays. We measure a value of delta(L) = [3322+/-58(stat)+/-47(syst)]x10(-6), in good agreement with previous measurements and 2.4 times more precise than the current best published result. The result is used to place more stringent limits on CPT and DeltaS = DeltaQ violation in the neutral kaon system.     

On-substrate Enzymatic Reaction to Determine Acetylcholinesterase Activity in Whole Blood by Paper Spray Mass Spectrometry

Currently, all assays measuring acetylcholinesterase (AChE) activity following a suspected nerve agent exposure leverage methodologies that fail to identify the agent. This limits the overall effectiveness and ability to administer proper countermeasures. As such, there is an urgent need to identify novel, rapid, and more comprehensive approaches to establish AChE activity, including identification of the toxicant. Paper spray mass spectrometry was used to monitor the activity of acetylcholinesterase, both in-solution and on modified hydrophobic paper surface. Hydrophobic paper surfaces were prepared using vaporized trichloro(3,3,3-trifluoropropyl)silane. In both approaches, mixtures of diluted human whole blood with and without VX were mixed with a non-endogenous AChE specific substrate, 1,1-dimethyl-4-acetylthiomethylpiperidinium (MATP+). Formation of the cleaved MATP+ product was monitored over time and compared to MATP+ to determine relative AChE activity. This on-substrate assay was effective at determining AChE activity and identifying the toxicant; however, determination of AChE activity in-solution proceeded at a slower rate. The on-substrate assay serves as a pioneering example of an enzymatic reaction occurring on the surface of a paper spray ionization ticket. This work broadens the range of applications relating to paper spray ionization-based clinical diagnostic assays.

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Uncertainty in most probable number calculations for microbiological assays

Microbiological assays commonly use incubations of multiple tubes in a dilution series, and microorganism concentration is read as a most probable number (MPN) in standard tables for the observed pattern of positive tubes. Published MPN tables differ, sometimes substantially, because of use of approximate MPN calculation procedures, different rounding conventions in the results, and different methods of calculating confidence or credible intervals. We conclude that the first 2 issues can now be resolved by using recently developed exact MPN calculation methods and by reporting rounding conventions in standard tables. The third issue is not amenable to complete resolution, especially if credible interval (as opposed to confidence interval) limits are desired--as we think they most often are. In that case, Bayesian statistics are called for and the analyst must provide a distribution of concentration that was presumed to be true before the assay was performed. This is mathematically combined with the assay data, resulting in a posterior concentration distribution. These distributions may then be used to quantify the uncertainty in the MPN estimate, and the best approach is to use the highest posterior density regions of these distributions. If based on diffuse prior information (positing that, prior to an assay being performed, all positive concentrations are equally likely), then established procedures might be used to calculate the limits and publish them in standard tables. In the event that this prior assumption is held to be not satisfactory, we show results for an empirical Bayes procedure, with a Poisson prior distribution, giving credible interval widths much narrower than in the other cases examined.     

Cluster Complexes of Polythioether Macrocycles: The Synthesis and Molecular Structures of Ru6(CO)13(cis-SCH2 CHMe(CH2SCH2CHMe)2CH2)(μ6-C) and Ru6(CO)13(trans-SCH2 CHMe(CH2SCH2CHMe)2CH2)(μ6-C)

The reaction of a mixture of cis-3,7,11-trimethyl-1,5,9-trithiacyclododecane, cis-Me₃12S3, 1 and trans-3,7,11-trimethyl-l,5,9-trithiacyclododecane, trans-Me₃12S3, 2, with Ru₆(CO)₁₇(μ ₆-C), 3, yielded three new cluster compounds Ru₆(CO)₁₃(μ-η³-cis-SCH₂CHMe(CH₂SCH₂CHMe)₂CH₂)(μ ₆-C) 4, and two isomers of Ru₆(CO)₁₃(μ-η³-cis-SCH₂CHMe(CH₂SCH₂CHMe)₂CH₂)(μ ₆-C) 5a and 5b. The molecular structures of 4 and 5b were established by single crystal X-ray diffraction analyses. In both complexes, the macrocycles have adopted tridentate coordination with one of the sulfur atoms in a bridging position. Two carbonyl ligands occupy bridging positions in each compound. Crystal Data for 4·Me₂CO: space group=P2₁/n, a=11.295(1) Å, b=17.547(3) Å, c=20.318(3) Å, β=93.71(1)°, Z=4, 2900 reflections, R=0.025. Crystal Data for 5b·1.5 C₆H₆: space group=Pbca, a=31.8900(8) Å, b=23.4330(6) Å, c=21.6240(4) Å, Z=16, 12163 reflections, R=0.040.     

PHOTCHEMICAL DEGRADATION OF FLAVINS—III. HYDROXYETHYL AND FORMYLMETHYL ANALOGS OF RIBOFLAVIN*

Abstract— The anaerobic photolysis of the flavins containing hydroxyethyl and formythmethyl side-chains in place of the ribityl group of riboflavin has been studied employing spectro-photmetry, thin-layer chromatography and other mehtods. Both flavins are shown to decompose, in part, directly to lumichrome. Acetaldehyde arises from the hudoxyethyl by the flavin nucleus as has been observed previously for riboflavin. The side-chain of the hydroxyethylflavin, is shown to be oxidized to the formylmethyl group. Formylmethylflavin is converted in part to lumichrome and unknown products from the side-chain and in part to a reduced flavin. Formaldehyde could not be detected among the products. Possible mechanisms are discussed briefly.     

White-light emission from magic-sized cadmium selenide nanocrystals

Magic-sized cadmium selenide (CdSe) nanocrystals have been pyrolytically synthesized. These ultra-small nanocrystals exhibit broadband emission (420-710 nm) that covers most of the visible spectrum while not suffering from self absorption. This behavior is a direct result of the extremely narrow size distribution and unusually large Stokes shift (40-50 nm). The intrinsic properties of these ultra-small nanocrystals make them an ideal material for applications in solid state lighting and also the perfect platform to study the molecule-to-nanocrystal transition.     

Ternary VO-ligand-surface complexes on boehmite and noncrystalline aluminosilicates

Electron spin resonance (ESR) spectroscopy was used to characterize the ligand environment of VO²⁺ absorbed on boehmite and noncrystalline aluminosilicates. Boehmite possessed a relatively low capacity to chemisorb VO²⁺ at discrete sites at low pH, a fact attributed to the chemical inactivity of the dominant (020) surfaces of the mineral. The chemisorbed cation is rigidly bound by one or two surface oxyanions. Chemisorption on allophane produced slightly different ESR parameters for VO²⁺, a possible consequence of the participation of silanol groups in the metal-surface bond. Evidence for ternary surface complexes was seen upon the addition of phosphate to the VO²⁺-surface complexes, with changes occurring in the ESR spectrum of bound VO²⁺. Oxalate also appeared to perturb the ligand environment of sorbed VO²⁺, but other anionic species had little or no effect. The experimental results point to the coadsorption of a vanadyl-phosphate complex, in which both the VO²⁺ and the PO₄³⁻ are chemisorbed to surface Al atoms. The ESR spectra of VO²⁺ in model phosphate compounds are used to establish the effect of PO₄³⁻ coordination with VO²⁺ on the spectral parameters.