Chemically Treated Silver Electrodes for the Determination of Cysteine

 This paper describes the use of Ag/Ag₂S and Ag/AgI ion-selective electrodes by means of chemical pretreatment of a silver wire or tube for the determination of cysteine (RSH) in batch and flow injection analysis (FIA). Received December 15, 2000. Revision July 11, 2001.     

Acetone,butanone, pentanone,hexanone and heptanone in the headspace of aqueous solution and urine studied by selected ion flow tube mass spectrometry

Urine is commonly analysed in clinical practice by a variety of liquid‐phase techniques to check for excessive ketone bodies, proteins and salts to name just a few compounds. However, little work has been carried out to measure the volatile compounds emitted by urine since these do not yet have an established role in clinical diagnosis. There is, however, a growing body of evidence that these volatile compounds can be indicators of adverse physiological conditions and disease and with the advent of sensitive gas‐phase analytical methods they can be quickly quantified in urine headspace and potentially provide valuable support for clinical diagnosis. Thus, we are developing selected ion flow tube mass spectrometry, SIFT‐MS, for the real‐time analysis of urine headspace, ultimately to support rapid diagnosis in the clinical environment. In this paper we focus on volatile ketones in the headspace of aqueous solutions and urine donated by three healthy volunteers. Using SIFT‐MS, we have unambiguously quantified in urine headspace acetone, by far the most abundant ketone, butanone, pentanone, hexanone and heptanone using NO⁺ precursor ions. Further to this, we have determined the Henry's Law coefficients, HLC, for these ketones in aqueous solution to allow the liquid‐phase concentrations in urine to be estimated from headspace levels of their vapours. In addition, the influence of the addition of physiological amounts of dissolved urea, sodium chloride and hydrochloric acid on the partitioning of these ketones between the aqueous phase and gas phase has been investigated and found to be small, which gives greater credence to the use of the HLC obtained using aqueous solutions for the estimation of ketone concentrations in urine. Finally, parallel measurements of the levels of acetone in exhaled breath and urine headspace have been obtained and shown to be very similar, which gives support to the previous deduction from breath analysis that acetone is a truly systemic compound. Copyright © 2009 John Wiley & Sons, Ltd.     

Transition between Airy1 and Airy2 processes and TASEP fluctuations

We consider the totally asymmetric simple exclusion process, a model in the KPZ universality class. We focus on the fluctuations of particle positions, starting with certain deterministic initial conditions. For large time t, one has regions with constant and linearly decreasing density. The fluctuations on these two regions are given by the Airy₁ and Airy₂ processes, whose one‐point distributions are the GOE and GUE Tracy‐Widom distributions of random matrix theory. In this paper we analyze the transition region between these two regimes and obtain the transition process. Its one‐point distribution is a new interpolation between GOE and GUE edge distributions. © 2007 Wiley Periodicals, Inc.     

Coordination of imidazoles by Cu(II) and Zn(II) as studied by NMR relaxometry, EPR, far-FTIR vibrational spectroscopy and ab initio calculations: effect of methyl substitution

Synthetic imidazole ligands are typically substituted at the N(1) ((1)-Im) position while natural imidazole ligands are substituted at the C(4) ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl(2) and ZnCl(2) and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D(4h) [CuL(4)X(2)] complexes with CuCl(2) whereas the methylated imidazoles form pseudotetrahedral C(2v) complexes instead of the usual octahedral O(h) [ZnIm(6)](2+) complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position.     

Tverberg’s Theorem and Graph Coloring

The topological Tverberg theorem has been generalized in several directions by setting extra restrictions on the Tverberg partitions. Restricted Tverberg partitions, defined by the idea that certain points cannot be in the same part, are encoded with graphs. When two points are adjacent in the graph, they are not in the same part. If the restrictions are too harsh, then the topological Tverberg theorem fails. The colored Tverberg theorem corresponds to graphs constructed as disjoint unions of small complete graphs. Hell studied the case of paths and cycles. In graph theory these partitions are usually viewed as graph colorings. As explored by Aharoni, Haxell, Meshulam and others there are fundamental connections between several notions of graph colorings and topological combinatorics. For ordinary graph colorings it is enough to require that the number of colors q satisfy q>Δ, where Δ is the maximal degree of the graph. It was proven by the first author using equivariant topology that if q>Δ ² then the topological Tverberg theorem still works. It is conjectured that q>KΔ is also enough for some constant K, and in this paper we prove a fixed-parameter version of that conjecture. The required topological connectivity results are proven with shellability, which also strengthens some previous partial results where the topological connectivity was proven with the nerve lemma.     

Free Energy Fluctuations for Directed Polymers in Random Media in 1 + 1 Dimension

We consider two models for directed polymers in space‐time independent random media (the O'Connell‐Yor semidiscrete directed polymer and the continuum directed random polymer) at positive temperature and prove their KPZ universality via asymptotic analysis of exact Fredholm determinant formulas for the Laplace transform of their partition functions. In particular, we show that for large time τ, the probability distributions for the free energy fluctuations, when rescaled by τ^1/3, converges to the GUE Tracy‐Widom distribution. We also consider the effect of boundary perturbations to the quenched random media on the limiting free energy statistics. For the semidiscrete directed polymer, when the drifts of a finite number of the Brownian motions forming the quenched random media are critically tuned, the statistics are instead governed by the limiting Baik–Ben Arous–Péché distributions from spiked random matrix theory. For the continuum polymer, the boundary perturbations correspond to choosing the initial data for the stochastic heat equation from a particular class, and likewise for its logarithm—the Kardar‐Parisi‐Zhang equation. The Laplace transform formula we prove can be inverted to give the one‐point probability distribution of the solution to these stochastic PDEs for the class of initial data. © 2014 Wiley Periodicals, Inc.     

Synthesis of 2′-Iodo Analogues of β-Rhodomycins1

Abstract

10-O-(R/S)Tetrahydropyranosyl-β-rhodomycinone (5a,b) was prepared via 7,9-O-phenylboronyl-β-rhodomycinone (3) from β-rhodomycinone (1). Glycosidation of 5a,b with 3,4-di-O-acetyl-1,5-anhydro-2,6-dideoxy-L-arabino-hex-1-enitol (3,4-di-O-acetyl-L-rhamnal) (6) and 3,4-di-O-acetyl-1,5-anhydro-2,6-dideoxy-L-lyxo-hex-1-enitol (3,4-di-O-acetyl-L-fucal) (7) using N-iodosuccinimide gave the corresponding 7-O-glycosyl-β-rhodomycinones 8a,b, 9a,b and 10a,b, 11a,b. After cleavage of the THP-ether and O-deacetylation 7-O-(2,6-dideoxy-2-iodo-α-L-manno-hexopyranosyl)-β-rhodomycinone (14) and 7-O-(2,6-dideoxy-2-iodo-α-L-talo-hexopyranosyl)-β-rhodomycinone (16) were obtained.