Microwave-accelerated Claisen rearrangements of allyl tetronates and tetramates

[3,3]-Sigmatropic rearrangements of allyl tetronates and allyl tetramates to give 3-allyltetronic or -tetramic acids, respectively, proceed within 20-60 min under microwave irradiation (300 W, 130-190 °C). Consecutive (homo)sigmatropic [1,5] H-shifts such as oxa-ene reactions are promoted less effectively, which allows the isolation of Claisen intermediates of sigmatropic domino sequences, in contrast to conventional heating.     

OR and the challenge to improve the NHS: modelling for insight and improvement in in-patient flows

This paper considers efforts to improve in-patient flows, a particularly urgent issue in the National Health Service (NHS). The context is described and related to reasons why OR has been making relatively little contribution. The paper argues that large complex models may often be unnecessary and even get in the way of providing clear insight and guidance for problem owners. The importance of understanding the generic working of systems to lead to improvement, and the limitations of simply describing them, is stressed. It is demonstrated that some very simple models can be of significant practical value in understanding and managing complex systems, changing mindsets and driving collection and use of operationally valuable data. Recommendations for more effective engagement with the NHS are offered.     

Results of radius scaling experiments and analysis of neon K-shellradiation data from an inductively driven Z-pinch

The K-shell radiated energy (yield) from neon Z-pinch implosions with annular, gas-puff nozzle radii of 1, 1.75, and 2.5 cm was measured for implosion times from 50 to 300 ns while systematically keeping the implosion kinetic energy nearly constant. The implosions were driven by the Hawk inductive-storage generator at the 0.65-MA level. Initial neutral-neon density distributions from the nozzles were determined with laser interferometry. Measured yields are compared with predictions from zero-dimensional (0-D) scaling models of ideal. One-dimensional (1-D) pinch behavior to both benchmark the scaling models, and to determine their utility for predicting K-shell yields for argon implosions of 200 to >300 ns driven by corresponding currents of 4 to 9 MA, such as envisioned for the DECADE QUAD. For all three nozzles, the 0-D models correctly predict the Z-pinch mass for maximum yield. For the 1and 1.75-cm radius nozzles, the scaling models accurately match the measured yields if the ratio of initial to final radius (compression ratio) is assumed to be 8:1. For the 2.5-cm radius nozzle, the measured yields are only one-third of the predictions. Analysis of K-shell spectral measurements suggest that as much as 70% (50%) of the imploded mass is radiating in the K-shell for the 1-cm (1.75-cm) radius nozzle. That fraction is only 10% for the 2.5-cm radius nozzle. The 0-D scaling models are useful for predicting 1-D-like K-shell radiation yields (better than a factor-of-two accuracy) when a nominal (≈10:1) compression ratio is assumed. However, the compression ratio assumed in the models is only an “effective” quantity, so that further interpretations based on the 0-D analysis require additional justification. The lower-than-predicted yield for the 2.5-cm radius nozzle is associated with larger radius and not with longer implosion time, and is probably a result of two-dimensional effects     

Microwave‐assisted nucleophilic cleavage of 5,7‐dimethyl‐2‐phenyl‐1‐oxo‐lH‐pyrazolo[ 1,2‐a]pyrazol‐4‐ylium‐3‐olate to α‐phenylmalonamides

Three α‐phenylmalonamides have been prepared by the selective nucleophilic cleavage of 5,7‐dimethyl‐2‐phenyl‐1‐oxo‐1H‐pyrazolo[1,2‐a]pyrazol‐4‐ylium‐3‐olate in solventless microwave syntheses. The three weak nucleophiles employed were aniline, p‐chloroaniline and m‐toluidine. The α‐phenylmalonamides of these three aniline derivatives could not be prepared using the previously reported solvent syntheses via 3‐oxopyrazolo[1,2‐a]pyrazol‐8‐ylium‐1‐olates. All products were characterised using, infrared spectroscopy, ¹H nmr and electrospray mass spectrometry. The single crystal X‐ray structures of the starting pyrazolo‐[1,2‐a]pyrazole and α‐phenylmalon‐m‐toluidide are also reported.     

Rapid and sensitive liquid chromatography-tandem mass spectrometry for the quantitation of epirubicin and identification of metabolites in biological samples

A highly sensitive and selective liquid chromatography-mass spectrometry (LC-MS) method has been developed for the determination of epirubicin in serum and cell specimens using daunorubicin as an internal standard. Using atmospheric pressure chemical ionisation (APCI), the epirubicin metabolites were readily distinguishable by their fragmentation pattern in the mass spectrometer. Selected reaction monitoring (SRM) mode was employed for quantitation of epirubicin and the metabolites. Following extraction, chromatography was performed on a C18 column with a mobile phase consisting of water-acetonitrile-formic acid, pH 3.2, with a flow rate of 200 μl/min. The limit of detection (LOD) and the limit of quantitation (LOQ) of this method in serum were determined to be 1.0 and 2.5 ng/ml, respectively. Linearity of the method was verified over the concentration range of 2.5-2000 ng/ml, with a high correlation coefficient (R² ≥ 0.998). For the extraction procedure, an aliquot of 500 μl serum, spiked with internal standard, was extracted using a chloroform-2-isopropanol (2:1, v/v) mixture. The method has been applied to the analysis of epirubicin in cancer cell samples and the identification of known and unknown metabolites in clinical trial patient serum samples.     

Formation of the unusual alkynyl carboxamide complex, C2H5N(H)C(O)CC[Co2(CO)6]CCo3(CO)9

The reaction of the cluster complex HCC[Co₂(CO)₆]CCo₃(CO)₉ with (or without) BrCCo₃(CO)₉ under Cadiot-Chodkiewicz coupling conditions gave the unusual alkynyl carboxamide complex C₂H₅N(H)C(O)CC[Co₂(CO)₆]CCo₃(CO)₉ rather than a coupled product containing two tricobalt cluster units. Steric demands imposed by the Co₃ cluster allow attack at the least hindered alkyne carbon and stabilise the formed ynamine, so allowing subsequent CO insertion. The product has been characterised by X-ray crystallography.     

Capillary chromatographic analysis of volatile organic compounds in the indoor environment

The wide variety of volatile organic compounds found in the indoor environment can present a difficult chromatographic problem for the analyst. Capillary-column gas chromatography is required to achieve adequate separation. Thermal desorption/capillary gas chromatography/mass spectrometry is usually the preferred method for broad spectrum analysis of the volatile organics detected indoors. Cryogenic trapping is required for capillary gas chromatographic analysis of the more volatile components.     

Fluorescence Lifetime Spectroscopy of Glioblastoma Multiforme¶

Fluorescence spectroscopy of the endogenous emission of brain tumors has been researched as a potentially important method for the intraoperative localization of brain tumor margins. We investigated the use of time‐resolved, laser‐induced fluorescence spectroscopy for demarcation of primary brain tumors by studying the time‐resolved spectra of gliomas. The fluorescence of human brain samples (glioblastoma multiforme, cortex and white matter: six patients, 23 sites) was induced ex vivo with a pulsed nitrogen laser (337 nm, 3 ns). The time‐resolved spectra were detected in a 360–550 nm wavelength range using a fast digitizer and gated detection. Parameters derived from both the spectral‐ (intensities from narrow spectral bands) and the time domain (average lifetime) measured at 390 and 460 nm were used for tissue characterization. We determined that high‐grade gliomas are characterized by fluorescence lifetimes that varied with the emission wavelength (>3 ns at 390 nm, <1 ns at 460 nm) and their emission is overall longer than that of normal brain tissue. Our study demonstrates that the use of fluorescence lifetime not only improves the specificity of fluorescence measurements but also allows a more robust evaluation of data collected from brain tissue. Combined information from both the spectraland the time domain can enhance the ability of fluorescencebased techniques to diagnose and detect brain tumor margins intraoperatively.     

Magnetic, electronic, and structural characterization of nonstoichiometric iron oxides at the nanoscale

We have investigated the structural, magnetic, and electronic properties of nonstoichiometric iron oxide nanocrystals prepared by decomposition of iron(II) and iron(0) precursors in the presence of organic solvents and capping groups. The highly uniform, crystalline, and monodisperse nanocrystals that were produced enabled a full structural and compositional survey by electron microscopy and X-ray diffraction. The complex and metastable behavior of nonstoichiometric iron oxide (wüstite) at the nanoscale was studied by a combination of Mossbauer spectroscopy and magnetic characterization. Deposition from hydrocarbon solvents with subsequent self-assembly of iron oxide nanocrystals into superlattices allowed the preparation of continuous thin films suitable for electronic transport measurements.