Study of the enzymatic degradation of vasostatin I and II and their precursor chromogranin A by dipeptidyl peptidase IV using high-performance liquid chromatography/electrospray mass spectrometry

The interaction of dipeptidyl peptidase IV with structurally related proteins differing in chain length, namely vasostatin I and II and their precursor protein chromogranin A, was examined using high-performance liquid chromatography in combination with electrospray mass spectrometry. Suitable analytical procedures were developed involving the use of reversed-phase high-performance liquid chromatography for purification of the enzymatic degradation products and a peptide mapping procedure for evaluating the enzymatic degradation of the large precursor protein chromogranin A. While vasostatin I was found to be a substrate for dipeptidyl peptidase IV, no N-terminal cleavage of Leu-Pro could be noted for chromogranin A. With respect to vasostatin II, N-terminal degradation was only observed after degradation in the C-terminal domain to proteins containing < or = 78 amino acids. The specificity of the N-terminal release of Leu-Pro was proved by addition of a DPP IV specific inhibitor.     

Adduct formation identification between phenyl glycidyl ether and 2'-deoxyadenosine and thymidine by chromatography, mass spectrometry and nuclear magnetic resonance spectroscopy

Thymidine and 2'-deoxyadenosine were reacted with phenyl glycidyl ether in order to study the formation of the corresponding 2'-deoxynucleoside adducts. Separation methods were elaborated using either reversed-phase high-performance liquid chromatography with photodiode-array detection, or centrifugal circular thin-layer chromatography. The adducts were isolated on a preparative scale and were fully characterized by UV spectroscopy, desorption chemical ionization and fast atom bombardment mass spectrometry and 270- and 360-MHz 1H NMR spectrometry. For thymidine the main adduct was characterized as N-3-(2-hydroxy-3-phenoxypropyl)thymidine. With 2'-deoxyadenosine, predominantly N-1-(2-hydroxy-3-phenoxypropyl)-2'-deoxyadenosine was formed. With longer reaction times, the formation of a minor amount of dialkylated 2'-deoxyadenosine was observed. These nucleoside adducts will be used as marker compounds for studies of DNA adduct formation.     

Characterization of oxygenated derivatives of isoprene related to 2-methyltetrols in Amazonian aerosols using trimethylsilylation and gas chromatography/ion trap mass spectrometry

In the present study, we have tentatively identified the structures of three oxygenated derivatives of isoprene in Amazonian rain forest aerosols as the C(5) alkene triols, 2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene. The formation of these oxygenated derivatives of isoprene can be explained by acid-catalyzed ring opening of epoxydiol derivatives of isoprene, namely, 1,2-epoxy-2-methyl-3,4-dihydroxybutane and 1,2-dihydroxy-2-methyl-3,4-epoxybutane. The structural proposals of the C(5) alkene triols were based on chemical derivatization reactions and detailed interpretation of electron and chemical ionization mass spectral data, including data obtained from first-order mass spectra, deuterium labeling of the trimethylsilyl methyl groups, and MS(2) ion trap experiments. The characterization of 2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene in forest aerosols is important from an atmospheric chemistry viewpoint in that these compounds hint at the formation of intermediate isomeric epoxydiol derivatives of isoprene and as such provide mechanistic insights into the formation of the previously reported 2-methyltetrols through photooxidation of isoprene.     

Stable carbon isotope analysis of different tissues of beef animals in relation to their diet

As part of a larger experiment, 31 young bulls, divided into three groups, were given different diets containing either C(3) plants or a combination of C(3) and C(4) plant-based feeds in three feeding periods before slaughter. Variation in the proportion of C(4) plant material in the diets was made by including or not maize or maize-derived ingredients, whereas the other dietary constituents were from C(3) plants. Analysis of stable carbon isotope ratios (delta(13)C value) was performed on different tissues taken at slaughter: blood, plasma, liver, kidney fat, hair, muscle and ruminal contents. Blood and plasma samples were also taken at the beginning of each period. A highly significant difference was found in the delta(13)C values of blood and plasma samples taken from animals that had received a diet of only C(3) plants or with 59% C(4) material for 70 days. The delta(13)C values of all different samples taken at slaughter were highly significantly different between the three feeding groups that had received diets with 0, 13.5 or 35% C(4) material for on average 137, 139 and 83 days, respectively. For the three groups, samples of hair, muscle, plasma, whole blood and liver were significantly enriched in (13)C compared with the diet (except for liver in one group), whereas kidney fat was significantly depleted. The proportion of C(4) plant material could be accurately estimated from the delta(13)C values of different tissue samples. Stable carbon analysis of different tissues from beef animals can be used to trace back diets containing variable proportions of C(3) and C(4) plant material.     

Discrete-time modified number- and time-limited vacation queues

A vast amount of literature has appeared on vacation queues. In the well-known number- and time-limited vacation policies, the server goes on vacation if the number of customers, respectively, work (time slots) served since the previous vacation reaches a specified value, or if the system becomes empty, whichever occurs first. However, in practice, the server does not always go on vacation when the system is empty if the number of customers/work to be served has not yet reached the specified amount. Therefore, we study modified number- and time-limited vacation policies, where we account for this feature. We complement our recent work on these vacation policies by considering a discrete time, instead of a continuous-time, setting. We therefore adopt a different analysis approach, which enables us to obtain similar as well as new results as compared to our previous work. The results in this paper are valid for a memoryless distribution, but also for distributions with finite support, and a mixture of geometric distributions.

     

Quasi‐local multitrace boundary integral formulations

In the context of time harmonic wave scattering by piecewise homogeneous penetrable objects, we present a new variant of the multitrace boundary integral formulation, that differs from the local multitrace approach of (Jerez‐Hanckes and Hiptmair, 2012) [13] by the presence of regularization terms involving boundary integral operators and localized at junctions i.e. points where at least three subdomains abut. We prove well‐posedness and quasioptimal convergence of conforming Galerkin discretizations for this new formulation, and present numerical results. © 2015 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 31: 2043–2062, 2015     

Factors determining the lifetime damage coefficients and the low-frequency noise in MeV proton irradiated silicon diodes

The impact of several factors, related to the doping density, the substrate type and the thermal pre-treatment on the proton radiation damage coefficients of Si diodes is discussed and verified experimentally. The diode parameters investigated are the leakage current density, the recombination lifetime and the low-frequency noise current spectral density. Proton irradiations have been performed in the energy range 10 MeV to 100 MeV and in the fluence range of 5·10⁹ to 4·10¹¹ cm⁻², typical for space applications. The obtained coefficients are compared with theoretical NIEL predictions.     

Higher‐order analogues of the Tracy‐Widom distribution and the Painlevé II hierarchy

We study Fredholm determinants related to a family of kernels that describe the edge eigenvalue behavior in unitary random matrix models with critical edge points. The kernels are natural higher‐order analogues of the Airy kernel and are built out of functions associated with the Painlevé I hierarchy. The Fredholm determinants related to those kernels are higher‐order generalizations of the Tracy‐Widom distribution. We give an explicit expression for the determinants in terms of a distinguished smooth solution to the Painlevé II hierarchy. In addition, we compute large gap asymptotics for the Fredholm determinants. © 2009 Wiley Periodicals, Inc.     

Structural characterization of chromone C-glucosides in a toxic herbal remedy

Two novel compounds, 8-C-D-glucopyranosyl-7-hydroxy-5-methylchromone-2-carboxylic acid and a 2-O'-p-coumaroyl derivative thereof, were identified in a herbal tea that caused severe vomiting in a South African patient who had taken the traditional remedy to clean his stomach. For structural characterization, electrospray (ES) ionization in combination with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS) were used, as well as UV and nuclear magnetic resonance (NMR) spectroscopy. Specific ions or neutral losses generated under conditions of ES-MS/CID/MS permitted the establishment of structural features such as the free carboxyl group, the C-hexosidic part and the p-coumaroyl group. NMR spectroscopy was necessary to support the structure of the chromone-type aglycone and the glucosidic parts. Since the compounds are structurally related to aloesin and aloeresin A, which are chemotaxonomic markers of Aloe species, and have not been previously reported, we propose that they were formed by oxidative degradation during preparation of the herbal tea from an Aloe species or during its storage.