75 research outputs found
Heterogeneous glycosylation and methylation of the Aeromonas caviae flagellin
Bacterial swimming is mediated by the rotation of a flagellar filament. Many bacteria are now known to be able to O-glycosylate their flagellins, the proteins that make up the flagellar filament. For bacteria that use nonulosonic acid sugars such as pseudaminic acid, this glycosylation process is essential for the formation of a functional flagellum. However, the specific role of glycosylation remains elusive. Aeromonas caviae is a model for this process as it has a genetically simple glycosylation system. Here, we investigated the localization of the glycans on the A. caviae flagellum filament. Using mass spectrometry it was revealed that pseudaminic acid O-glycosylation was heterogeneous with no serine or threonine sites that were constantly glycosylated. Site-directed mutagenesis of particular glycosylation sites in most cases resulted in strains that had reduced motility and produced less detectable flagellin on Western blots. For flagellin O-linked glycosylation, there is no known consensus sequence, although hydrophobic amino acids have been suggested to play a role. We, therefore, performed site-directed mutagenesis of isoleucine or leucine residues flanking the sites of glycosylation and demonstrated a reduction in motility and the amount of flagellin present in the cells, indicating a role for these hydrophobic amino acids in the flagellin glycosylation process
Experimental and theoretical near edge x ray absorption fine structure studies of NO
Experimental near edge x ray absorption fine structure NEXAFS spectra of the nitrosonium NO ion are presented and theoretically analyzed. While neutral NO has an open shell, the cation is a closed shell species, which for NEXAFS leads to the simplicity of a closed shell spectrum. Compared to neutral NO, the electrons in the cation experience a stronger Coulomb potential, which introduces a shift of the ionization potential towards higher energies, a depletion of intensity in a large interval above the amp; 960; amp; 8727; resonance, and a shift of the amp; 963; amp; 8727; resonance from the continuum to below the ionization threshold. NEXAFS features at the nitrogen and oxygen K edges of NO are compared, as well as NEXAFS features at the nitrogen edges of the isoelectronic closed shell species NO , N2, and N2
Selective gating to vibrational modes through resonant X ray scattering
The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X ray scattering RIXS study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X ray excitation to different core excited potential energy surfaces PESs will act as spatial gates to selectively probe the particular ground state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra high resolution RIXS measurements for gas phase water with state of the art simulation
A study of the water molecule using frequency control over nuclear dynamics in resonant X ray scattering
In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X ray scattering RIXS spectra of H 2O, D 2O and HDO. We demonstrate that electronically elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X ray frequency across core excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied system
Ultrafast dissociation features in RIXS spectra of the water molecule
In this combined theoretical and experimental study we report on an analysis of the resonant inelastic X ray scattering RIXS spectra of gas phase water via the lowest dissociative core excited state 1s amp; 8722;1O4a11 amp; 12297;. We focus on the spectral feature near the dissociation limit of the electronic ground state. We show that the narrow atomic like peak consists of the overlapping contribution from the RIXS channels back to the ground state and to the first valence excited state 1b amp; 8722;114a11 amp; 12297; of the molecule. The spectral feature has signatures of ultrafast dissociation UFD in the core excited state, as we show by means of ab initio calculations and time dependent nuclear wave packet simulations. We show that the electronically elastic RIXS channel gives substantial contribution to the atomic like resonance due to the strong bond length dependence of the magnitude and orientation of the transition dipole moment. By studying the RIXS for an excitation energy scan over the core excited state resonance, we can understand and single out the molecular and atomic like contributions in the decay to the lowest valence excited state. Our study is complemented by a theoretical discussion of RIXS in the case of isotopically substituted water HDO and D2O where the nuclear dynamics is significantly affected by the heavier fragments mas
Efeito do tipo de ramo e do regime de luz fornecido à planta matriz no estabelecimento in vitro de araçazeiro cv. "Irapuã"
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