A simple high pH liquid chromatography-tandem mass spectrometry method for basic compounds: application to ephedrines in doping control analysis

Solvent systems for use with LC-MS often result in a compromise between chromatographic performance and mass spectrometric detection, exemplified here by a LC-MS/MS method development for the analysis of ephedrines in doping control. Ephedrines, frequently found in therapeutic and nutritional preparations, are among the most commonly administered doping agents in competitive sport. Improved separation of these hydrophilic, basic compounds, some of which are diastereoisomers, is achieved in reversed-phase LC by the use of a high pH mobile phase in order to suppress analyte ionisation, and thus alter their polarity, resulting in reduced peak tailing and enhanced retention. However, when coupled to an ESI-MS detector, this eluent composition generated a non-linear and poorly reproducible signal. APCI yielded greater stability and reproducibility and is here presented as an ion source for the analysis of basic compounds under conditions that suppress their ionisation. Errors as large as 49.3% were observed with ESI, compared with 15.4% generated using APCI, for pseudoephedrine over the calibration range (25-400 μg/mL) in urine with a simple dilution and injection of samples. These data highlight the importance of suitable MS conditions for stable performance, necessary for accurate quantification, without undue compromise to the LC separation.     

Quantum transport in mesoscopic 3He films: experimental study of the interference of bulk and boundary scattering

We discuss the mass transport of a degenerate Fermi liquid ^{3}He film over a rough surface, and the film momentum relaxation time, in the framework of theoretical predictions. In the mesoscopic regime, the anomalous temperature dependence of the relaxation time is explained in terms of the interference between elastic boundary scattering and inelastic quasiparticle-quasiparticle scattering within the film. We exploit a quasiclassical treatment of quantum size effects in the film in which the surface roughness, whose power spectrum is experimentally determined, is mapped into an effective disorder potential within a film of uniform thickness. Confirmation is provided by the introduction of elastic scattering centers within the film. The improved understanding of surface roughness scattering may impact on enhancing the conductivity in thin metallic films.     

Synthesis and Study of Electrochemically Grown Salts of Organic II-Donors

Abstract

The effects of purity and crystal perfection on the properties of (TMTSF)₂ClO₄ are examined via SEM's and transition temperatures. Careful electrochemical techniques using gradient sublimed TMTSF starting material and short term oxidation result in high quality crystals. Preliminary work on HMTSF salts of PF ^? ₆ and AsF^? ₆ is also reported.     

Characterization of [2Fe–2S]‐Cluster‐Bridged Protein Complexes and Reaction Intermediates by use of Native Mass Spectrometric Methods

Many iron–sulfur proteins involved in cluster trafficking form [2Fe–2S]‐cluster‐bridged complexes that are often challenging to characterize because of the inherent instability of the cluster at the interface. Herein, we illustrate the use of fast, online buffer exchange coupled to a native mass spectrometry (OBE nMS) method to characterize [2Fe–2S]‐cluster‐bridged proteins and their transient cluster‐transfer intermediates. The use of this mechanistic and protein‐characterization tool is demonstrated with holo glutaredoxin 5 (GLRX5) homodimer and holo GLRX5:BolA‐like protein 3 (BOLA3) heterodimer. Using the OBE nMS method, cluster‐transfer reactions between the holo‐dimers and apo‐ferredoxin (FDX2) are monitored, and intermediate [2Fe–2S] species, such as (FDX2:GLRX5:[2Fe–2S]:GSH) and (FDX2:BOLA3:GLRX5:[2Fe–2S]:GSH) are detected. The OBE nMS method is a robust technique for characterizing iron–sulfur‐cluster‐bridged protein complexes and transient iron–sulfur‐cluster transfer intermediates.     

Singular solutions of elliptic equations involving nonlinear gradient terms on perturbations of the ball

In this article we obtain positive singular solutions of

(1)$?\mathrm{\Delta }u=|\mathrm{?}u{|}^p\text{ in }\mathrm{\Omega },u=0\text{ on }?\mathrm{\Omega },$

where Ω is a small $C^2$ perturbation of the unit ball in ${\mathbb{R}}^N$. For $\frac{N}{N?1}<p<2$ we prove that if Ω is a sufficiently small $C^2$ perturbation of the unit ball there exists a singular positive weak solution u of (1). In the case of $p>2$ we prove a similar result but now the positive weak solution u is contained in $C^{0,\frac{p?2}{p?1}}(\stackrel{￣}{\mathrm{\Omega }})$ and yet is not in $C^{0,\frac{p?2}{p?1}+\epsilon }(\stackrel{￣}{\mathrm{\Omega }})$ for any $\epsilon >0$.     

The Critical Dimension for a Fourth Order Elliptic Problem with Singular Nonlinearity

We study the regularity of the extremal solution of the semilinear biharmonic equation ${{\Delta^2} u=\frac{\lambda}{(1-u)^2}}We study the regularity of the extremal solution of the semilinear biharmonic equation D² u=\fracl(1-u)²{{\Delta^2} u=\frac{\lambda}{(1-u)^2}}, which models a simple micro-electromechanical system (MEMS) device on a ball B ì \mathbbR^N{B\subset{\mathbb{R}}^N}, under Dirichlet boundary conditions u=?_n u=0{u=\partial_\nu u=0} on ?B{\partial B}. We complete here the results of Lin and Yang [14] regarding the identification of a “pull-in voltage” λ* > 0 such that a stable classical solution u _λ with 0 < u _λ < 1 exists for l ? (0,l^*){\lambda\in (0,\lambda^*)}, while there is none of any kind when λ > λ*. Our main result asserts that the extremal solution u_l^*{u_{\lambda^*}} is regular (sup_B u_l^* < 1 ){({\rm sup}_B u_{\lambda^*} <1 )} provided N \leqq 8{N \leqq 8} while u_l^*{u_{\lambda^*}} is singular (sup_B u_l^* = 1){({\rm sup}_B u_{\lambda^*} =1)} for N \geqq 9{N \geqq 9}, in which case 1-C₀|x|^4/3 \leqq u_l^* (x) \leqq 1-|x|^4/3{1-C_0|x|^{4/3} \leqq u_{\lambda^*} (x) \leqq 1-|x|^{4/3}} on the unit ball, where C₀:=(\fracl^*[`(l)])<sup>\frac</sup>13{C_0:=\left(\frac{\lambda^*}{\overline{\lambda}}\right)^\frac{1}{3}} and [`(l)]: = \frac89(N-\frac23)(N- \frac83){\bar{\lambda}:= \frac{8}{9}\left(N-\frac{2}{3}\right)\left(N- \frac{8}{3}\right)}.     

Phonon driven proton transfer in crystals with short strong hydrogen bonds

Recent work on understanding why protons migrate with increasing temperature in short, strong hydrogen bonds is extended here to three more organic, crystalline systems. Inelastic neutron scattering and density functional theory based simulations are used to investigate structure, vibrations, and dynamics of these systems as functions of temperature. The mechanism determined in a previous work on urea phosphoric acid of low frequency vibrations stabilizing average crystal structures, in which the potential energy well of the hydrogen bond has its minimum shifted towards the center of the bond, is found to be valid here. The new feature of the N-H...O hydrogen bonds studied in this work is that the proton is transferred from the donor atom to the acceptor atom. Molecular dynamics simulations show that in an intermediate temperature regime, in which the proton is not completely transferred, the proton is bistable, jumping from one side of the hydrogen bond to the other. In the case of 3,5-pyridine dicarboxylic acid, which has been studied in most detail, specific phonons are identified, which influence the potential energy surface of the proton in the short, strong hydrogen bond.     

A comparison of adaptive procedures for rapid and reliable threshold assessment and training in naive listeners

In psychoacoustic studies there is often a need to assess performance indices quickly and reliably. The aim of this study was to establish a quick and reliable procedure for evaluating thresholds in backward masking and frequency discrimination tasks. Based on simulations, four procedures likely to produce the best results were selected, and data collected from 20 naive adult listeners on each. Each procedure used one of two adaptive methods (staircase or maximum-likelihood estimation, each targeting the 79% correct point on the psychometric function) and two response paradigms (3-interval, 2-alternative forced-choice AXB or 3-interval; 3-alternative forced-choice oddball). All procedures yielded statistically equivalent threshold estimates in both backward masking and frequency discrimination, with a trend to lower thresholds for oddball procedures in frequency discrimination. Oddball procedures were both more efficient and more reliable (test-retest) in backward masking, but all four procedures were equally efficient and reliable in frequency discrimination. Fitted psychometric functions yielded similar thresholds to averaging over reversals in staircase procedures. Learning was observed across threshold-assessment blocks and experimental sessions. In four additional groups, each of ten listeners, trained on the different procedures, no differences in performance improvement or rate of learning were observed, suggesting that learning is independent of procedure.     

Stages of homogeneous nucleation in solid isotopic helium mixtures

We have made pressure and NMR measurements during the evolution of phase separation in solid helium isotopic mixtures. Our observations indicate clearly all three stages of the homogeneous nucleation-growth process: (1) creation of nucleation sites; (2) growth of the new-phase component at these nucleation sites; and (3) coarsening: the dissolution of subcritical droplets with the consequent further late-stage growth of the supercritical droplets. The time exponent for the coarsening, a=1/3, is consistent with the conserved order parameter Lifshitz-Slezov evaporation-condensation mechanism.     

Perception of multiple electrode stimulus patterns: implications for design of an electrotactile speech processor

Identification of multiple-electrode stimulus patterns was evaluated in nine adult subjects, to assess the feasibility of providing additional speech information through the tactual display of an electrotactile speech processor. Absolute identification scores decreased from 97.8% for single electrodes, to 61.9% for electrode pairs, and, to 31.8% for electrode triplets. Although input information increased with paired-and triple-electrode stimuli, information transmission scores were not significantly increased for either electrode pairs (2.99 bits) or triplets (2.84 bits) as compared with single electrodes (2.84 bits). These results suggest that speech coding strategies using stimulus patterns of electrode pairs or triplets would provide little improvement beyond that found for the present single-electrode scheme. However, higher absolute identification scores (73.6%), and an increase in information transmission to 3.88 bits, were recorded for test stimuli containing all combinations of paired and single electrodes. Based on this finding, two stimulus sets using a restricted number of combinations of paired and single electrodes were evaluated. The two stimulus sets simulated the spatial patterns of paired and single electrodes arising from use of alternative speech coding schemes to increase consonant voicing information. Results for the two stimulus sets showed higher electrode identification scores (79.7% and 90.4%), as compared with paired-electrode stimuli. Although electrode identification score was not as high as for single electrodes, information transmission was increased to 3.31 bits for the VF2 stimulus set. Analysis of the responses also showed that scores for identification of simulated voicing information conveyed by the two stimulus sets were 99.4 and 90.4% correct.(ABSTRACT TRUNCATED AT 250 WORDS)