The sesquiterpenoid nootkatone and the absolute configuration of a di­bromo derivative

Nootkatone, or (4R,4aS,6R)‐4,4a,5,6,7,8‐hexa­hydro‐4,4a‐di­methyl‐6‐(1‐methyl­ethenyl)­naphthalen‐2(3H)‐one, C₁₅H₂₂O, a sesquiterpene with strong repellent properties against Formosan subterranean termites and other insects, has the valencene skeleton. The di­bromo derivative (1S,3R,4S,4aS,6R,8aR)‐1,3‐di­bromo‐6‐iso­propyl‐4,4a‐di­methyl‐1,2,3,4,5,6,7,8‐octa­hydro­naphthalen‐2‐one, C₁₅H₂₄Br₂O, has two independent mol­ecules in the asymmetric unit, which differ in the rotation of the iso­propyl group with respect to the main skeleton. The C—Br distances are in the range 1.950 (4)–1.960 (4) Å. Both independent molecules form zigzag chains, with very short intermolecular carbonyl–carbonyl interactions, having the perpendicular motif and O⋯C distances of 2.886 (6) and 2.898 (6) Å. These chains are flanked by intermolecular Br⋯Br interactions of distances in the range 4.067 (1)–4.218 (1) Å. The absolute configuration of the di­bromo derivative was determined, from which that of nootkatone was inferred.     

A host-guest optical sensor for aliphatic amines based on lipophilic cyclodextrin

A host-guest optical sensor for the determination of aliphatic amines as exemplified by octylamine is proposed. It is based on the reversible fluorescence enhancement of heptakis(2,6-di-O-isobutyl)-β-cyclodextrin(DOB-β-CD) hosting tetraphenylporphyrin (TPP) immobilized in poly(vinyl chloride) (PVC) membrane by aliphatic amine extracted from aqueous phase into membrane phase. The optimum membrane contained 1.15 wt % TPP, 6.15 wt % DOB-β-CD as sensing reagent and other membrane materials. The fluorescence enhancement of the membrane resulted from the formation of a stable three-component complex among DOB-β-CD, TPP, and aliphatic amines. With the optimum conditions described, the fluorescence response of the sensor to octylamine shows a good correlation with the theoretically derived equation in the range 1.0 × 10^–6 to 8.0 × 10^–4 mol/L. The response characteristics including reversibility, response time, reproducibility and lifetime and selectivity of this optical device are also discussed in detail. This sensor has also been applied for the determination of octylamine in water samples containing interferents with satisfactory recovery.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Interpretation of heart rate variability via detrended fluctuation analysis and alphabeta filter

Detrended fluctuation analysis (DFA), suitable for the analysis of nonstationary time series, has confirmed the existence of persistent long-range correlations in healthy heart rate variability data. In this paper, we present the incorporation of the alphabeta filter to DFA to determine patterns in the power-law behavior that can be found in these correlations. Well-known simulated scenarios and real data involving normal and pathological circumstances were used to evaluate this process. The results presented here suggest the existence of evolving patterns, not always following a uniform power-law behavior, that cannot be described by scaling exponents estimated using a linear procedure over two predefined ranges. Instead, the power law is observed to have a continuous variation with segment length. We also show that the study of these patterns, avoiding initial assumptions about the nature of the data, may confer advantages to DFA by revealing more clearly abnormal physiological conditions detected in congestive heart failure patients related to the existence of dominant characteristic scales.     

The polarization and dipole moment of lattice water in hydrogen bonded crystals

Dipole moments and charge distributions are calculated for the water molecules in four hydrogen bonded crystals, α and β oxalic dihydrates and the hexagonal and cubic ices.     

Relativistic effect on magnetic moments of negative muons bound to high-Z nuclei

The g factors of the negative muons bound to Zn, Cd, and Pb nuclei have been determined. The observed values after the corrections for the internal fields have shown substantial deviations from the free-muon g factor: $\text{(g}{}_{\mathrm{<mtext>free</mtext>}}\text{-g)}\text{g}{}_{\mathrm{<mtext>free</mtext>}}$ is (1.3±0.6)% for Zn, (2.2±1.4) % for Cd, and (5.0±2.2)% for Pb. These shifts are in good agreement with the relativistic binding corrections for finite-size nuclei calculated by Ford et al.     

μCF Experiments in D2 and HD Gases – Final Results

During 1994–1996, a series of μCF experiments were performed at PSI by the PSI-PNPI-IMEP-LBNL-TUM collaboration. These experiments aimed at high-precision studies of the d–μ–d fusion in D₂ and HD gases in a wide temperature range. The Gatchina ionization time projection chamber has been used to detect the dd-fusion reaction products. The main parameters of the d–μ–d fusion have been measured with high absolute precision. In this report, we present the results of the final analysis of the experimental data. The obtained results are compared with the calculations based on a recent μCF-theory. This revised version was published online in August 2006 with corrections to the Cover Date.     

Precise Measurement of Muon Capture on the Proton

The aim of the μCap experiment is a 1% measurement of the singlet capture rate Λ _S for the basic electro-weak reaction μ + p → n + ν_μ. This observable is sensitive to the weak form-factors of the nucleon, in particular to the induced pseudoscalar coupling constant g _P . It will provide a rigorous test of theoretical predictions based on the Standard Model and effective theories of QCD. The present method is based on high precision lifetime measurements of μ⁻ in hydrogen gas and the comparison with the free μ⁺ lifetime. The μ⁻ experiment will be performed in ultra-clean, deuterium-depleted H₂ gas at 10 bar. Low density compared to liquid H₂ is chosen to avoid uncertainties due to ppμ formation. A time projection chamber acts as a pure hydrogen active target. It defines the muon stop position in 3D and detects rare background reactions. Decay electrons are tracked in cylindrical wire-chambers and a scintillator array covering 75% of 4π. This revised version was published online in August 2006 with corrections to the Cover Date.