Characterization of an unusual ring‐contraction degradant of the antifungal agent posaconazole

Posaconazole, a clinically useful antifungal agent, has several known oxidative degradation products involving the piperazine ring near the center of the molecule. A novel degradant was recently isolated and characterized spectroscopically as a novel ring‐contraction product incorporating a dihydroimidazolium moiety in lieu of the normally present piperazine ring. Copyright © 2012 John Wiley & Sons, Ltd.     

Estimation of signal coherence threshold and concealed spectral lines applied to detection of turbofan engine combustion noise

Combustion noise from turbofan engines has become important, as the noise from sources like the fan and jet are reduced. An aligned and un-aligned coherence technique has been developed to determine a threshold level for the coherence and thereby help to separate the coherent combustion noise source from other noise sources measured with far-field microphones. This method is compared with a statistics based coherence threshold estimation method. In addition, the un-aligned coherence procedure at the same time also reveals periodicities, spectral lines, and undamped sinusoids hidden by broadband turbofan engine noise. In calculating the coherence threshold using a statistical method, one may use either the number of independent records or a larger number corresponding to the number of overlapped records used to create the average. Using data from a turbofan engine and a simulation this paper shows that applying the Fisher z-transform to the un-aligned coherence can aid in making the proper selection of samples and produce a reasonable statistics based coherence threshold. Examples are presented showing that the underlying tonal and coherent broad band structure which is buried under random broadband noise and jet noise can be determined. The method also shows the possible presence of indirect combustion noise.     

HSQC-ADEQUATE: an investigation of data requirements

Utilizing ¹³C‐¹³C connectivity networks for the assembly of carbon skeletons from HSQC‐ADEQUATE spectra was recently reported. HSQC‐ADEQUATE data retain the resonance multiplicity information of the multiplicity‐edited GHSQC spectrum and afford a significant improvement in the signal‐to‐noise (s/n) ratio relative to the 1,1‐ADEQUATE data used in the calculation of the HSQC‐ADEQUATE spectrum by unsymmetrical indirect covariance (UIC) processing methods. The initial investigation into the computation of HSQC‐ADEQUATE correlation plots utilized overnight acquisition of the 1,1‐ADEQUATE data used for the calculation. In this communication, we report the results of an investigation of the reduction in acquisition time for the 1,1‐ADEQUATE data to take advantage of the s/n gain during the UIC processing to afford the final HSQC‐ADEQUATE correlation plot. Data acquisition times for the 1,1‐ADEQUATE spectrum can be reduced to as little as a few hours, while retaining excellent s/n ratios and all responses contained in spectra computed from overnight data acquisitions. Concatenation of multiplicity‐edited GHSQC and 1,1‐ADEQUATE data also allows the interrogation of submilligram samples with 1,1‐ADEQUATE data when using spectrometers equipped with 1.7‐mm Micro CryoProbes ?. Copyright © 2011 John Wiley & Sons, Ltd.     

Magnetic dipole response in rare earth nuclei

Experimental observations in certain rare earth nuclei have established the presence of sizeable B(M1) strength of two peak structure lying in the 5–10 MeV region. The character of the states concerned, studied within a self-consistent Random Phase Approximation using Skyrme forces, are identified to be that of proton and neutron giant spin-flip resonances. Received: 14 July 1997 / Revised version: 20 October 1997     

Generalized Viscoelastic 1-DOF Deterministic Nonlinear Oscillators

The theory of deterministic generalized viscoelastic linear and nonlinear 1-D oscillators is formulated and evaluated. Examples of viscoelastic Duffing, Mathieu, Rayleigh, Roberts and van der Pol oscillators and pendulum responses are investigated. Material behavior as well as additional effects of structural damping on oscillator performance are also considered. Computational protocols are developed and their results are discussed to determine the influence of viscoelastic and structural (Coulomb friction) damping on oscillator motion. Illustrative examples show that the inclusion of linear or nonlinear viscoelastic material properties significantly affects oscillator responses as related to amplitudes, phase shifts and energy loses when compared to equivalent elastic ones.     

Quantification of 21 metabolites of methylnaphthalenes and polycyclic aromatic hydrocarbons in human urine

Polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives, such as methylnaphthalenes (MeNs), are harmful pollutants ubiquitously present in the environment. Exposure to PAHs has been linked to a variety of adverse health effects and outcomes, including cancer. Alkyl PAHs have been proposed as petrogenic source indicators because of their relatively high abundance in unburned petroleum products. We report a method to quantify 11 urinary methylnaphthols (Me-OHNs), metabolites of 1- and 2-methylnaphthalenes, and 10 monohydroxy PAH metabolites (OH-PAHs), using automated liquid-liquid extraction and isotope dilution gas chromatography tandem mass spectrometry (GC-MS/MS). After spiking urine (1 mL) with ¹³C-labeled internal standards, the conjugated target analytes were hydrolyzed enzymatically in the presence of ascorbic acid. Then, their free species were preconcentrated into 20 % toluene in pentane, derivatized and quantified by GC-MS/MS. The 11 Me-OHNs eluted as 6 distinct chromatographic peaks, each representing 1???3 isomers. Method detection limits were 1.0? 41 pg/mL and the coefficients of variation in quality control materials were 4.7???19 %. The method was used to analyze two National Institute of Standards and Technology’s Standard Reference Materials® and samples from 30 smokers and 30 non-smokers. Geometric mean concentrations were on average 37 (Me-OHNs) and 9.0 (OH-PAHs) fold higher in smokers than in non-smokers. These findings support the usefulness of Me-OHNs as potential biomarkers of non-occupational exposure to MeNs and sources containing MeNs.

Rapid drug detection in oral samples by porous silicon assisted laser desorption/ionization mass spectrometry

The demand for analysis of oral fluid for illicit drugs has arisen with the increased adoption of roadside testing, particularly in countries where changes in legislation allow random roadside testing of drivers for the presence of a palette of illicit drugs such as methamphetamine (MA), 3,4‐methylenedioxymethamphetamine (MDMA) and Δ⁹‐tetrahydrocannabinol (THC). Oral samples are currently tested for such drugs at the roadside using an immunoassay‐based commercial test kit. Positive roadside tests are sent for confirmatory laboratory analysis, traditionally by means of gas chromatography/mass spectrometry (GC/MS). We present here an alternative rapid analysis technique, porous silicon assisted laser desorption/ionization time‐of‐flight mass spectrometry (pSi LDI‐MS), for the high‐throughput analysis of oral fluids. This technique alleviates the need for sample derivatization, requires only sub‐microliter sample volumes and allows fast analysis (of the order of seconds). In this study, the application of the technique is demonstrated with real samples from actual roadside testing. The analysis of oral samples resulted in detection of MA and MDMA with no extraction and analysis of THC after ethyl acetate extraction. We propose that, subject to miniaturization of a suitable mass spectrometer, this technique is well suited to underpin the deployment of oral fluid testing in the clinic, workplace and on the roadside. Copyright © 2009 John Wiley & Sons, Ltd.     

Application of ion-impact energy measurement to electrospray ionization mass spectrometry of proteins and protein mixtures

We have used a normal metal-insulator-superconductor (NIS) microcalorimeter to measure the impact energy of protein ions produced by electrospray ionization (ESI) in a magnetic-sector mass spectrometer (MS). We have used these measurements to resolve spectral ambiguities and to analyze protein mixtures. Energy measurement may be useful for the direct MS analysis of complex biopolymer mixtures that normally would confound ESI-MS deconvolution algorithms.     

The interdependence of physical parameters for infrared transmitting glasses

Glasses based on sulfur and selenium were carefully characterized to establish the interdependence between chemical composition and the magnitudes of physical parameters related to their use as infrared optical materials. Parameters considered in this paper are density, volume-expansion coefficient, glass-transition temperature, thermal conductivity, elastic moduli, and Poisson's ratio.