Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

Local Minimizers of the Ginzburg-Landau Energy with Magnetic Field in Three Dimensions

We establish the existence of locally minimizing vortex solutions to the full Ginzburg-Landau energy in three dimensional simply-connected domains with or without the presence of an applied magnetic field. The approach is based upon the theory of weak Jacobians and applies to nonconvex sample geometries for which there exists a configuration of locally shortest line segments with endpoints on the boundary.Research partially supported by NSERC grant number 261955     

Optical absorption spectra of linear and cyclic thiophenes—selection rules manifestation

We theoretically study the size-dependent relation between absorption spectra of thiophene-based oligomers and the corresponding cyclothiophenes. In our approach based on a Frenkel exciton Hamiltonian, we demonstrate that the geometry and selection rules determine the observed relations between the spectra.     

Minimal Bar Tableaux

Motivated by recent results of Stanley, we generalize the rank of a partition λ to the rank of a shifted partition S(λ). We show that the number of bars required in a minimal bar tableau of S(λ) is max(o, e + (ℓ(λ) mod 2)), where o and e are the number of odd and even rows of λ. As a consequence we show that the irreducible projective characters of S_n vanish on certain conjugacy classes. Another corollary is a lower bound on the degree of the terms in the expansion of Schur’s Q_λ symmetric functions in terms of the power sum symmetric functions. Received November 20, 2003     

Linear Independence of q-Analogues of Certain Classical Constants

Let K be ? or an imaginary quadratic number field, and q ∈ K an integer with ¦q¦ > 1. We give a quantitative version of Σ_n≥1 a_n/(qⁿ ? 1) ? K for non-zero periodic sequences (a_n) in K of period length ≤ 2. As a corollary, we get a quantitative version of the linear independence over K of 1, the q-harmonic series, and a q-analogue of log 2. A similar result on 1, the q-harmonic series, and a q-analogue of ζ(2) is also proved. Mathematics Subject Classification (2000): 11J72, 11J82     

On a compromise social choice correspondence

This paper analyzes the compromise social choice correspondence derived from the τ-value of digraph games. Monotonicity of this correspondence is shown. A connection between several properties of social choice correspondences based on game theoretical solutions and game theoretical properties of the underlying solutions is given. Applications to several game theoretic solutions are provided.     

Pd-catalyzed one-pot coupling of allylamines, activated alkenes, and unsaturated halides (or triflate): an atom efficient synthesis of highly functionalized pyrrolidines

A Pd-catalyzed three-component assembling of highly functionalized 4-benzyl-(and allyl-)pyrrolidines was achieved based on a combination of allyl amines, gem-diactivated alkenes, and unsaturated halides (or triflate).     

Molecular dynamics and information on possible sites of interaction of intramyocellular metabolites in vivo from resolved dipolar couplings in localized H NMR spectra

Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct ¹H–¹H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized ¹H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD₀ (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD₀ from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution ¹H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D₀ (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10⁻⁴ indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10⁻⁴. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, ¹H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo ¹H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids.     

Phase modulation in dipolar-coupled A2 spin systems: effect of maximum state mixing in H NMR in vivo

Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (A_n system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this “pseudo-strong” system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time.