Selective linkage detection of O‐sialoglycan isomers by negative electrospray ionization ion trap tandem mass spectrometry

Sialylated O‐linked oligosaccharides are involved in many biological processes, such as cell‐cell interactions, cell‐substance adhesion, and virus‐host interactions. These activities depend on their structure, which is frequently determined by tandem mass spectrometry. However, these spectra are frequently analyzer‐dependent, which makes it difficult to develop widely applicable analytical methods. In order to deepen the origin of this behavior, two couples of isomers of sialylated O‐linked oligosaccharides, NeuAcα2‐3Galβ1‐3GalNAc‐ol/Galβ1‐3(NeuAcα2‐6)GalNAc‐ol and NeuGcα2‐3Galβ1‐3GalNAc‐ol/Galβ1‐3(NeuGcα2‐6)GalNAc‐ol, were analyzed by liquid chromatography/negative electrospray ionization ion trap tandem mass spectrometry (LC/ESI(?)‐MSⁿ) using both an ion trap and a triple quadrupole mass spectrometer. Results clearly showed that while ions obtained in the triple quadrupole instrument fitted very well with the standard fragmentation routes, in the ion trap several intense ions could not be explained by these rules, specially a fragment at m/z 597. Furthermore, this ion was observed in the mass spectrum of those isomers that sialic acid binds to GalNAc by an α2‐6 linkage. From the MS³ spectrum of this ion an unexpected structure was deduced, and it led to propose alternative fragmentation pathways. Molecular mechanics calculations suggested that the found atypical route could be promoted by a hydrogen bond located only in α2‐6‐linked oligosaccharides. It has also been demonstrated that this process follows a slow kinetic, explaining why it cannot be observed using an ion beam‐type mass analyzer. In conclusion, ion traps seem to be more appropriate than triple quadrupoles to develop a reliable analytical method to distinguish between isomeric O‐linked glycans. Copyright © 2010 John Wiley & Sons, Ltd.     

Decay widths of the spin-2 partners of the <Emphasis Type="Italic">X</Emphasis>(3872)

We consider the X(3872) resonance as a \(J^\mathrm{{PC}}=1^{++}\) \(D\bar{D}^*\) hadronic molecule. According to heavy quark spin symmetry, there will exist a partner with quantum numbers \(2^{++}\), \(X_{2}\), which would be a \(D^*\bar{D}^*\) loosely bound state. The \(X_{2}\) is expected to decay dominantly into \(D\bar{D}\), \(D\bar{D}^*\) and \(\bar{D} D^*\) in d-wave. In this work, we calculate the decay widths of the \(X_{2}\) resonance into the above channels, as well as those of its bottom partner, \(X_{b2}\), the mass of which comes from assuming heavy flavor symmetry for the contact terms. We find partial widths of the \(X_{2}\) and \(X_{b2}\) of the order of a few MeV. Finally, we also study the radiative \(X_2\rightarrow D\bar{D}^{*}\gamma \) and \(X_{b2} \rightarrow \bar{B} B^{*}\gamma \) decays. These decay modes are more sensitive to the long-distance structure of the resonances and to the \(D\bar{D}^{*}\) or \(B\bar{B}^{*}\) final state interaction.     

Titanium Dioxide/Electrolyte Solution Interface: Electron Transfer Phenomena

Electron transfer between a titanium dioxide/electrolyte solution interface has been studied. As found by other researchers of similar interfaces (TiO(2)- and ZnO-electrolyte solution), a slow consumption of OH(-) ions takes place in this type of interface. A theoretical model has been developed for calculating the change in the Fermi energy of both electrolyte solution and semiconductor, showing that ion consumption from the solution is favoured by the decrease of the difference between their Fermi energies. A kinetic constant (upsilon) is found to characterise the consumption process, its value increasing with electrolyte and semiconductor mass concentrations. Furthermore, this process may be used to estimate the point of zero charge of a titanium dioxide colloidal dispersion. Copyright 2000 Academic Press.     

Differences in voice quality between men and women: Use of the long-term average spectrum (LTAS)

The goal of this study was to determine if there are acoustical differences between male and female voices, and if there are, where exactly do these differences lie. Extended speech samples were used. The recorded readings of a text by 31 women and by 24 men were analyzed by means of the Long-term Spectrum (LTAS), extracting the amplitude values (in decibels) at intervals of 160 Hz over a range of 8 kHz. The results showed a significant difference between genders, as well as an interaction of gender and frequency level. The female voice showed greater levels of aspiration noise, located in the spectral regions corresponding to the third formant, which causes the female voice to have a more “breathy” quality than the male voice. The lower spectral tilt in the women's voices is another consequence of this presence of greater aspiration noise.     

S = -1 meson-baryon scattering in coupled-channel unitarized Chiral Perturbation Theory

The s-wave meson-baryon scattering amplitude is analyzed for the strangeness S = -1 and isospin I = 0 sector in a Bethe-Salpeter coupled-channel formalism incorporating Chiral Symmetry. Four two-body channels have been considered: , , , . The needed two-particle irreducible matrix amplitude is taken from lowest-order Chiral Perturbation Theory in a relativistic formalism. Off-shell behaviour is parameterized in terms of low-energy constants, which outnumber those assumed in previous works and provide a better fit to the data. The position of the complex poles in the second Riemann sheet of the scattering amplitude determines masses and widths of the and resonances which compare well with accepted numbers.Received: 30 September 2002, Published online: 22 October 2003PACS: 11.10.St Bound and unstable states; Bethe-Salpeter equations - 11.30.Rd Chiral symmetries - 11.80.Et Partial-wave analysis - 13.75.Lb Meson-meson interactionsE. Ruiz Arriola: Spokesperson     

Structure factor scaling in colloidal charge heteroaggregation

The structure factor, S(q), of a system composed of a 1:1 mixture of oppositely charged colloids undergoing heteroaggregation is studied by Browninan dynamics simulations. A peak develops in S(q) at low wave vectors, which can be scaled for different times to overlap using the scaling of spinodal decomposition, as shown for DLCA. The same master function is obtained for different interaction ranges. The origin of the peak can be traced back to a depletion layer of clusters surrounding every aggregate. At those long distances, cluster-cluster interaction is negligible and the aggregation is diffusion limitted, as deduced from the evolution of peak position, and the S(q) scaling at different interaction ranges. The interaction is, nevertheless, strong enough to affect the internal cluster structure.     

Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.