Mass spectrometry study of PRL‐3 phosphatase inactivation by disulfide bond formation and cysteine into glycine conversion

The Phosphatase of Regenerating Liver‐3 (PRL‐3) is a cysteine‐based phosphatase (CBP) that is highly over‐expressed in liver metastasis in colorectal cancer and suspected to be involved in the progression from tumor to metastasis. During substrate‐specificity studies based on the screening of PRL‐3 phosphatase activity on several phosphorylated synthetic peptides, we observed a decrease in activity depending on sample aging and storage conditions. By liquid chromatography combined with selective alkylation and mass spectrometry, we found two main PRL‐3 inactivation pathways: a disulfide bond formation between the catalytic C104 and C49, blocking the enzyme in an inactive oxidized form, or the conversion of the catalytic C104 into glycine. We also found that the disulfide formation and the cysteine into glycine conversion are catalyzed by cations present in the sample after protein purification through a nickel column. By adding a cation chelator such as EDTA and de‐oxygenating the sample with argon, PRL‐3 phosphatase activity was preserved. These findings suggest that PRL‐3, like other CBPs, is sensitive to inactivation by catalytic cysteine oxidation and this has implications for future studies of its activity and specificity. Copyright © 2009 John Wiley & Sons, Ltd.     

Isotope dilution method for the assay of rotenone in olive oil and river waters by liquid chromatography/multiple reaction monitoring tandem mass spectrometry

A new approach for the assay of rotenone (1) by isotope dilution mass spectrometry is presented. The extreme toxicity of rotenone, a natural phytodrug with insecticidal and piscicidal activity, recently banned by national and international environmental protection agencies, calls for the development of sensitive and accurate methods of analyses. Accordingly, the proposed protocol is based on the availability of the labeled internal standard rotenone‐d₃ (3) which can be conveniently prepared by consecutive and specific mono‐O‐demethylation, and remethylation with methyl iodide‐d₃. The sensitivity of the method is confirmed by the very low limit of detection (LOD) and quantitation (LOQ) values achieved in the assay of 1 in two distinct fortified matrices, and is further supported by the observed accuracy values. Copyright © 2009 John Wiley & Sons, Ltd.     

Neuromelanins Isolated from Different Regions of the Human Brain Exhibit a Common Surface Photoionization Threshold

Neuromelanin isolated from the premotor cortex, cerebellum, putamen, globus pallidus and corpus callosum of the human brain is studied by scanning probe and photoelectron emission microscopies and the results are compared with previously published work on neuromelanin from the substantia nigra. Scanning electron microscopy reveals common structure for all neuromelanins. All exhibit spherical entities of diameters between 200 and 400 nm, composed of smaller spherical substructures, ∼30 nm in diameter. These features are similar to that observed for many melanin systems including Sepia cuttlefish, bovine eye, and human eye and hair melanosomes. Photoelectron microscopy images were collected for all neuromelanins at specific wavelengths of ultraviolet light between 248 and 413 nm, using the spontaneous emission output from the Duke free electron laser. Analysis of the data establishes a common threshold photoionization potential for neuromelanins of 4.7 ± 0.2 eV, corresponding to an oxidation potential of −0.3 ± 0.2 V vs the normal hydrogen electrode (NHE). These results are consistent with previously reported potentials for neuromelanin from the substantia nigra of 4.5 ± 0.2 eV (−0.1 ± 0.2 V vs NHE). All neuromelanins exhibit a common low surface oxidation potential, reflecting their eumelanic component and their inability to trigger redox processes with neurotoxic effect.     

Moment based approaches to value the risk of contingent claim portfolios

In this paper we describe and apply the estimating function methodology to value the risk of asset derivative portfolios. We first implement the Li’s model based on the first four moments and then we show the limits of this model in forecasting the maximum loss of contingent claims. In addition, we show that four moments are not enough to describe the behavior of the lower percentiles of derivatives. Finally, we propose a model that considers the first six moments and we compare the performances of these models proposing a backtest analysis on several historical and truncated asset derivative portfolios.     

Polybrusselator‐type models

In this paper, the possibility for autocatalysis in polymerization reactions is explored by introducing part of a polymerization mechanism in a model known as Brusselator. It is assumed that monomer concentration is practically constant. Four possibilities are examined: (1) a first radical propagator X, which has an isomer of position of the free electron, Y, dimerizes reversibly and this dimer catalyzes the isomerization of Y to X; (2) the radical propagator X is a polymer with a critical degree of polymerization and has an isomer of position of the free electron Y. This critical radical propagator catalyzes the conversion of Y to X; (3) any radical propagator has an isomer of position of the free electron, Y, and any polymer obtained by recombination of the radicals can catalyze the conversion of Y into its corresponding isomer X; and (4) any radical propagator with a critical degree of polymerization can catalyze the conversion of Y into its corresponding isomer. Isomorphism equations are obtained in all mechanisms, which implies the possibility of limit cycle oscillations (Brusselator model). © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 617–623, 2008     

Spectral analysis of finite Markov chains with spherical symmetries

We generalize the classical Fourier analysis of Gelfand pairs to the setting of groups acting not transitively on a set X. We use this analysis to determine the spectrum of several random walks on graphs. Moreover, as byproduct, we show that, for a new urn diffusion model, the cut-off phenomenon holds.     

Markov bases and subbases for bounded contingency tables

In this paper we study the computation of Markov bases for contingency tables whose cell entries have an upper bound. It is known that in this case one has to compute universal Gröbner bases, and this is often infeasible also in small- and medium-sized problems. Here we focus on bounded two-way contingency tables under independence model. We show that when these bounds on cells are positive the set of basic moves of all 2 × 2 minors connects all tables with given margins. We also give some results about bounded incomplete table and we conclude with an open problem on the necessary and sufficient condition on the set of structural zeros so that the set of basic moves of all 2 × 2 minors connects all incomplete contingency tables with given positive margins.     

Affine Kähler hypersurfaces satisfying certain conditions on the curvature tensor

The notion of affine Kähler immersions has been recently introduced by Nomizu-Pinkall-Podestà ([N-Pi-Po]). This work is aimed at giving some results towards the classification of non degenerate affine Kähler hypersurfaces with symmetric and parallel Ricci tensor; this problem generalizes the classical results due to Nomizu-Smyth ([N-S]) in the theory of Kählerian hypersurfaces. In a second section we deal with the case of “semisymmetric” affine Kähler immersions, when the curvature tensor R satisfies R · R = 0 and the Ricci tensor is symmetric, providing a complete classification; for affine Kähler curves we prove that the conditions above are actually equivalent to saying that the immersion is isometric for a suitable Kähler metric in C².     

Kernel Theorems for Modulation Spaces

Journal of Fourier Analysis and Applications - We deal with kernel theorems for modulation spaces. We completely characterize the continuity of a linear operator on the modulation spaces $$M^p$$...