Identification of selenium species in urine by ion-pairing HPLC–ICP–MS using laboratory-synthesized standards

This study focused on the detection/identification of possible selenium metabolites in human urine. Organoselenium compounds not commercially unavailable were synthesized and characterized by electrospray mass spectrometry. Separation of selenomethionine, methylselenomethionine, trimethylselonium, selenoethionine, and selenoadenosylmethionine was achieved by ion-pairing HPLC with a mobile phase of 2 mmol L^–1 hexanesulfonic acid, 0.4% acetic acid, 0.2% triethanolamine (pH 2.5), and 5% methanol. The column effluent was introduced on-line to inductively coupled plasma–mass spectrometry for selenium-specific detection (⁷⁷Se and ⁷⁸Se). For selenium speciation in urine, solid-phase extraction was carried out using C₁₈ cartridges modified with hexanesulfonic acid. Selective retention of cationic species was observed from acidified urine (perchloric acid, pH 2.0). After elution with methanol, evaporation, and dissolution in the mobile phase, the sample was introduced to the HPLC–ICP–MS system and the chromatographic peaks were assigned by adding standards. The species identified in urine were selenomethionine, trimethylselonium ion, and selenoadenosylmethionine. The last species was detected for the first time and our results suggest that selenomethionine might enter the metabolic pathway of its sulfur analog in the activated methylation cycle.Kazimierz Wrobel and Katarzyna Wrobel are on the leave from the Institute of Scientific Research, University of Guanajuato, L. de Retana No. 5, 36000 Guanajuato, Gto., Mexico     

Pulsed fluorescence measurements of trapped molecular ions with zero background detection

Sensitive methods have been developed to measure laser-induced fluorescence from trapped ions by reducing the detection of background scattering to zero levels during the laser excitation pulse. The laser beam diameter has been reduced to approximately 150 microm to eliminate scattering on trap apertures and the resulting laser-ion interaction is limited to a volume of approximately 10(-5) cm which is approximately 0.03-0.15 of the total ion cloud volume depending on experimental conditions. The detection optics collected fluorescence only from within the solid angle defined by laser-ion interaction volume. Rhodamine 640 and Alexa Fluor 350 ions, commonly used as fluorescence resonance energy transfer (FRET) fluorophores, were generated in the gas phase by using electrospray ionization and injected into a radiofrequency Paul trap where they were stored and exposed to Nd:YAG laser pulses at 532 and 355 nm for times up to 10 m. Fluorescence emitted by these ions was investigated for several trap q(z) values and ion cloud temperatures. Analysis of photon statistics indicated an average of approximately 10 photons were incident on the PMT detector per 15 ns pulse for approximately 10(3) trapped ions in the interaction volume. Fluorescence measurements displayed a dependence on trapped ion number which were consistent with calculations of the space charge limited ion density. To investigate the quantitative capability of these fluorescence techniques, the laser-induced fragmentation of trapped Alexa Fluor 350 ions was measured and compared with a rate equation model of the dynamics. Decay of the fluorescence signal as well as the parent ion number compared closely with quantitative predictions of the photofragmentation model.     

A new tri-orthogonal strategy for peptide cyclization

A solid phase tri-orthogonal protection/cleavage strategy that uses acidic, basic, and neutral conditions is described. Strategically protected alpha-azido-gamma-9-fluorenylmethyl-L-glutamate (1) and alpha-azido-epsilon-N-Fmoc-L-lysine (2) were incorporated into growing peptides on Wang resin using a novel azide protection strategy. These residues, separated by 1-3 monomers, were deprotected at the side chains and cyclized via lactam formation. The N-terminus was further functionalized to extend the chain. This method represents a straightforward protocol for peptide cyclization on solid support.     

Intramolecular azide-diene cycloadditions. An approach to fused bicyclic 3-pyrrolines based on a one-pot nitrene-diene cycloaddition equivalent.

Cyclization of heterosubstituted ω-azidodienes 11 provides fused bicyclic 3-pyrrolines 12 in one operation. These pyrrolines are potentially useful intermediates for natural products synthesis, as illustrated by further functionalization.     

Direct observation of molecular rotation-translation coupling by far-infrared spectroscopy

The differences between the far-infrared absorption of liquid (+)3-methylcyclohexanone and the racemic mixture are interpreted as supporting evidence for the direct observation of rotation-translation coupling.     

Surface oxides on porous carbon

Wet oxidation of BPL porous carbon by H₂O₂ and HNO₃ changes the pore structure and also increases the concentration of surface oxides. KOH uptake is increased by oxidation and is seen to be dependent on KOH concentration and to a lesser extent on inert electrolyte concentration. Enthalpy of immersion measurements have allowed the estimation of the enthalpy of hydration of the surface oxides and the enthalpy of neutralization of the easily accessible acid oxides.     

Finite-size scaling and the renormalization group

Renormalization group calculations ind = 4 andd = 4 – are performed for a system of finite size. A form of mean-field theory is used which yields a rounded transition for a finite system, and this allows a sensible expansion in fluctuations. A combination of Ewald and Poisson sum techniques is used to produce explicit numerical results for the specific heat ind = 4 which, with the setting of two nonuniversal metrical factors and the fourth-order coupling constant may be compared with simulations. The numerical visibility of logarithmic corrections is investigated. The universal scaling function for the specific heat to relativeO() is also evaluated numerically.     

“Statistical” symmetry with applications to phase transitions

Hermann proposed that mesomorphic media should be classified by assigning certain statistical symmetry groups to each possible partially ordered array. Two translational groups introduced were called superordinate and subordinate. We find that the average density in such a partially ordered medium has the superordinate symmetry ₁, while the pair correlation function has the subordinate symmetry ₂. A complete listing is made of all compatible combinations of ₁ and ₂ in two and three dimensions. This leads to more possible symmetries than Hermann obtained, e.g., also to nonstoichiometric crystals. The order parameter space for the systems is found to be the quotient space ₁/₂. In most cases it is identical to the order parameter space of low-dimensionalXY spin systems. The Landau free energy is expanded as functional of the two-particle correlation functionK; the translation group is found to be ₁×₂. A Landau mean-field theory can then be carried out by expanding the system free energy into a series of invariants of the active irreducible representations ofK and mapping the free energy onto that for anXY planar spin system. We predict novel critical behavior for transitions between mesomorphic phases and go nogo selection rules for continuous transitions. We give the structure factors for X-ray scattering so changes in all such phase transitions are observable. The statistical symmetry groups, which describe point and translational symmetries of the mesophases, are classified. Proposals are made to include quasi-long-range or topological order in the classification scheme.This work supported in part by National Science Foundation (Division of International Programs), the PSC-BHE—Faculty Research Award CUNY and Deutsche Forschungsgemeinschaft.     

Matchings and radon transforms in lattices. I. Consistent lattices

An element in a lattice is join-irreducible if x=ab implies x=a or x=b. A meet-irreducible is a join-irreducible in the order dual. A lattice is consistent if for every element x and every join-irreducible j, the element xj is a join-irreducible in the upper interval [x, î]. We prove that in a finite consistent lattice, the incidence matrix of meet-irreducibles versus join-irreducibles has rank the number of join-irreducibles. Since modular lattices and their order duals are consistent, this settles a conjecture of Rival on matchings in modular lattices.     

The ground state energy of a Bose gas with Coulomb interaction

LetH _N be the 2N particle Hamiltonian $$\begin{array}{*{20}c} {H_N = \sum\limits_{i = 1}^{2N} {( - \Delta _\iota ) + \sum\limits_{i< j = 1}^N {\left| {x_i - x_j } \right|^{ - 1} + } \sum\limits_{i< j = 1}^N {\left| {x_{i + N} - x_{j + N} } \right|^{ - 1} } } } \\ { - \sum\limits_{i,j< j = 1}^N {\left| {x_i - x_{j + N} } \right|^{ - 1} ,} } \\ \end{array} $$ whereΔ _i is the Laplacian in the variablex _i ∈?³, 1≦i≦2N. The operatorH _N is assumed to act on wave functionsΨ(x ₁, ...,x _N ;x _N+1, ...,x _2N ) which are symmetric in the variables (x ₁, ...,x _N ) and (x _N+1, ...,x _2N ). SupposeΨ is supported in a setΛ ^2N , whereΛ is a cube in ?³. It is shown that if a normalized wave functionΨ can be written as a product of two wave functions $$\psi (x_1 ,...,x_N ;x_{N + 1} ,...,x_{2N} ) = \psi _1 (x_2 ,...,x_N )\psi _2 (x_{N + 1} ,...,x_{2N} ),$$ and the density of particles inΛ is constant, then 〈Ψ|H _N |Ψ〉≧?CN ^7/5 for some universal constantC.