5,627 research outputs found

    Effects of Vacuum Fluctuation Suppression on Atomic Decay Rates

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    The use of atomic decay rates as a probe of sub-vacuum phenomena will be studied. Because electromagnetic vacuum fluctuations are essential for radiative decay of excited atomic states, decay rates can serve as a measure of the suppression of vacuum fluctuation in non-classical states, such as squeezed vacuum states. In such states the renormalized expectation value of the square of the electric field or the energy density can be periodically negative, representing suppression of vacuum fluctuations. We explore the extent to which atomic decays can be used to measure the mean squared electric field or energy density. We consider a scheme in which atoms in an excited state transit a closed cavity whose lowest mode contains photons in a non-classical state. The change in the decay probability of the atom in the cavity due to the non-classical state can, under certain circumstances, serve as a measure of the mean squared electric field or energy density in the cavity. We derive a quantum inequality bound on the decrease in this probability. We also show that the decrease in decay rate can sometimes be a measure of negative energy density or negative squared electric field. We make some estimates of the magnitude of this effect, which indicate that an experimental test might be possible.Comment: 19 pages, 3 figure

    Whole-blood thiopurine S-methyltransferase activity with genotype concordance: a new, simplified phenotyping assay.

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    BackgroundWe have developed a new thiopurine S-methyltransferase (TPMT) phenotyping method that measures TPMT activity in whole blood. To evaluate this assay, we compared it with conventional TPMT phenotyping, which uses a red blood cell (RBC) lysate and genotyping for analysis of common TPMT mutations.MethodsWhole-blood and RBC lysates were prepared from 402 patients' samples received for routine analysis. The TPMT activity of lysates was determined using 6-thioguanine as substrate with high-performance liquid chromatographic (HPLC) analysis and fluorimetric detection. DNA was extracted from buffy coats using phenol-chloroform extraction. A multiplex amplification refractory mutation system (ARMS) strategy was used to screen for the common TPMT mutations TPMT*2 and TPMT*3 (TPMT*3A, TPMT*3C and TPMT*3D).ResultsTPMT activities were higher in the whole-blood (mean TPMT activity 51 nmol 6-MTG/gHb/h) compared with the RBC lysate (37 nmol 6-MTG/gHb/h). Overall, concordance with TPMT genotypic analysis was 97% for both the new whole-blood and standard RBC lysate methods. Between low TPMT activity and heterozygotes, both phenotypic methods gave a concordance of 79%.ConclusionUsing multiplex ARMS testing for TPMT*2 and 3*C mutations to define the cut-off between low and normal TPMT activity, we have demonstrated that the new whole-blood TPMT phenotyping method performs as well as the conventional RBC lysate assay. This new method overcomes the need to prepare a RBC lysate, a process which is time consuming and increases analytical variation. The resulting assay is better suited to a regional or national TPMT phenotyping service

    Copper-catalyzed asymmetric oxidation of sulfides

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    Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee)

    Asymmetric oxidation of sulfides

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    This review discusses synthesis of enantiopure sulfoxides through the asymmetric oxidation of prochiral sulfides. The use of metal complexes to promote asymmetric sulfoxidation is described in detail, with a particular emphasis on the synthesis of biologically active sulfoxides. The use of non-metal-based systems, such as oxaziridines, chiral hydroperoxides and peracids, as well as enzyme-catalyzed sulfoxidations is also examined
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