New Features in the Lipid A Structure of <Emphasis Type="Italic">Brucella suis</Emphasis> and <Emphasis Type="Italic">Brucella abortus</Emphasis> Lipopolysaccharide

Brucellaceae are Gram-negative bacteria that cause brucellosis, one of the most distributed worldwide zoonosis, transmitted to humans by contact with either infected animals or their products. The lipopolysaccharide exposed on the cell surface has been intensively studied and is considered a major virulence factor of Brucella. In the last years, structural studies allowed the determination of new structures in the core oligosaccharide and the O-antigen of this lipopolysaccharide. In this work, we have reinvestigated the lipid A structure isolated from B. suis and B. abortus lipopolysaccharides. A detailed study by MALDI-TOF mass spectrometry in the positive and negative ion modes of the lipid A moieties purified from both species was performed. Interestingly, a new feature was detected: the presence of a pyrophosphorylethanolamine residue substituting the backbone. LID-MS/MS analysis of some of the detected ions allowed assurance that the Lipid A structure composed by the diGlcN3N disaccharide, mainly hexa-acylated and penta-acylated, bearing one phosphate and one pyrophosphorylethanolamine residue.

Open image in new window

Graphical abstract ?

     

Pore Shape Effects on the Relative Permeability of Gas and Condensate in Three-Dimensional Pore Networks

Transport in Porous Media -     

Pore-Level Modeling of Gas and Condensate Flow in Two- and Three-Dimensional Pore Networks: Pore Size Distribution Effects on the Relative Permeability of Gas and Condensate

We present a mechanistic model of retrograde condensation processes in two- and three-dimensional capillary tube networks under gravitational forces. Condensate filling-emptying cycles in pore segments and gas connection–isolation cycles are included. With the pore-level distribution of gas and condensate in hand, we determine their corresponding relative permeabilities. Details of pore space and displacement are subsumed in pore conductances. Solving for the pressure field in each phase, we find a single effective conductance for each phase as a function of condensate saturation. Along with the effective conductance for the saturated network, the relative permeability for each phase is calculated. Our model porous media are two- and three-dimensional regular networks of pore segments with distributed size and square cross-section. With a Monte Carlo sampling we find the optimum network size to avoid size effects and then we investigate the effect of network dimensionality and pore size distribution on the relative permeabilities of gas and condensate.     

New method for sintering silica frits for capillary microcolumns

One of the main steps in the manufacture of robust and efficient packed capillary microcolumns for electro- and capillary chromatography is the generation of porous devices to retain the packed beds. Frits based on sintered silica particles have been found to give the best results in terms of mechanical resistance and efficiency. The conventional procedure to produce these kinds of frits consists in a radial heating of the packed material with either a flame or an electrical resistance, but the frits thus obtained have many drawbacks as a result of the procedure rather than the silica per se as the base material. In the present work we investigated a new approach to produce silica-based retaining devices involving the frontal exposure of a short silica-particle bed packed at the end of a capillary tube. The capillary is radially insulated and frontally exposed to the heat of a muffle oven, generating a transfer of heat that is not radial but rather throughout the capillary axis. This procedure resulted in substantial advantages: an improved radial homogeneity, a protection of the external polyimide, and a generation of extremely short (400–600 μm) frits that were highly permeable and avoided bubble formation.     

The formation of non-soluble complexes between polyethyleneimine-anions and their potential use to isolate enzymes

The aqueous solution behavior of polyethyleneimine (a synthetic cationic polymer) in the presence of anions with two or more electrical charges (citrate, phosphate, sulphate, malate, malonate and succinate) was studied by means of turbidimetry and light scattering. Polyethyleneimine forms non-soluble complexes with these anions, which behave as a pseudo-polyampholyte with an isoelectrical pH value dependent on the type of anion. The effect of pH, polymer concentration and ionic strength on the non-soluble complexes formation was examined. The complex precipitation pH range was between 3.5 and 8.0 and also depended on the type of anion. The complex formation was inhibited by the ionic strength in agreement with the electrostatic mechanism of the non-soluble complex formation. Model proteins with isoelectric pH from 1 to 10 were assayed in orden to be precipitated by these complexes. It was found that the non-soluble polyethyleneimine-anion complexes have the property to precipitate macromolecules charged with an opposite electrical charge.     

New dendronized polymers from acrylate Behera amine and their ability to produce visco-elastic structured fluids when mixed with CTAT worm-like micelles

Two new water soluble dendronized polymers (PLn) from acrylate Behera amine monomer of different molecular weights were successfully synthesized. The polymers were characterized by FTIR, NMR, GPC and DLS. Both GPC and DLS results indicated that these PLn have a remarkable tendency to form aggregates in solution that lead to apparent molecular weights that are much higher than their theoretical values, as well as large diameters in solution. However, the addition of any PLn to water did not cause any increase in viscosity up to concentrations of 1000 ppm. The possible interactions of PLn with the cationic surfactant CTAT were explored by solution rheometry. A synergistic viscosity enhancement was found by adding small amounts of dendronized PLn polymers to a CTAT solution composed of entangled worm-like micelles. The highest association tendency with CTAT was found for PL1 at the maximum polymer concentration before phase separation (i.e., 100 ppm). The solution viscosity at low-shear rates could be increased by an order of magnitude upon addition of 100 ppm of PL1 to a 20mM CTAT solution. For this mixture, the fluid obtained was highly structured and exhibited only shear thinning behavior from the smallest shear rates employed. These PL1/CTAT mixtures exhibited an improved elastic character (as determined by dynamic rheometry) that translated in a much longer value of the cross-over relaxation time and a pronounced thixotropic behavior which are indicative of a strong intermolecular interaction. In the case of the polymer with a higher theoretical molecular weight, PL2, its association with CTAT leads to an extraordinary doubling of solution viscosity with just 0.25 ppm polymer addition to a 20mM CTAT solution. However, such synergistic viscosity enhancement saturated at rather low concentrations (25 ppm) indicating an apparent lower solubility as compared to PL1, a fact that may be related to its higher molecular weight.     

Synthesis of chiral mesoporous silicas with oligo(saccharide) surfaces and their use in separation of stereoisomers

Novel chiral mesoporous silicas (SBA-15 motif) with chemically bonded oligo(saccharides) (1, 3, and 7 glucose units) were obtained through the cocondensation of organosilicon derivatives of the oligo(saccharides) and silica precursors in the presence of polymer surfactant template under mild acidic conditions. The pore order and structure of the materials prepared were characterized by transmission electron microscopy and nitrogen adsorption. The direct application of the oligo(saccharide)-grafted SBA-15 stationary phases in the HPLC separations of stereoisomers was demonstrated for the first time.     

Synthesis and ring-chain-ring tautomerism of bisoxazolidines, thiazolidinyloxazolidines, and spirothiazolidines

The synthesis of fused heterocycles such as thiazolidinyl-oxazolidine 3 is described starting from Tris·HCl. The mercaptomethyl bisoxazolidine 8 was found to convert to the corresponding thiazolidinyloxazolidine 3 and the spiro-heterocycle 4 by a ring-chain-ring tautomerism, depending on the electronic nature of the ring substituents as well as the reaction conditions. This equilibration pathway is absent in the hydroxymethyl bisoxazolidines 2. Computational studies confirm that both kinetic and thermodynamic control features play a role in the product distribution.     

A delafossite-based copper catalyst for sustainable Cl2 production by HCl oxidation

A copper catalyst based on a delafossite precursor (CuAlO(2)) displays high activity and extraordinary lifetime in the gas-phase oxidation of HCl to Cl(2), representing a cost-effective alternative to RuO(2)-based catalysts for chlorine recycling.