Methods for the structural investigation of xanthones: Part II. Location of hydroxyl groups by ultraviolet and visible spectroscopy1

Ultraviolet spectral shifts in presence of certain additives may be used to determine the hydroxylation pattern of xanthones. Thus, 3-hydroxyxanthones are characterized by an intense band around 355 nm which appears in presence of sodium hydroxide, o- and p-Dihydroxyxanthones decompose in presence of this reagent, the reaction rate depending on the position of the substituents. While the spectra of 1-and 2-hydroxyxanthones do not suffer modification in presence of sodium acetate, 3- and 4-hydroxy groups produce typical shifts which are dependent on the presence of additional oxygen functions. The spectra of 1-hydroxy-, as well as of o-dihydroxyxanthones, are affected by the addition of aluminum chloride. 1- and 4-Hydroxy groups with unsubstituted p-positions may be detected and distinguished through the visible spectrum (350–750 nm) of the reaction product of the xanthone with 2,6-dichlorobenzoquinone chloroimide (Gibbs test). Relatively acidic hydroxyls give rise to two maxima in this region. Two maxima, even if of different relative intensity, are also obtained with o- and p-dihydroxy-, as well as with o- and p-hydroxyallylxanthones.     

Monolayer properties of uronic acid bicatenary derivatives at the air-water interface: effect of hydroxyl group stereochemistry evidenced by experimental and computational approaches

By screening uronic acid-based surfactant interfacial properties, the effect of the hydroxyl group stereochemistry (OH-4) on the conformation of bicatenary (disubstituted) derivatives at the air-water interface has been evidenced by experimental and computational approaches. Physical and optical properties of a monolayer characterized by Langmuir film balance, Brewster angle microscopy, and ellipsometry at 20 °C reveal that the derivative of glucuronate (C(14/14)-GlcA) forms a more expanded monolayer, and shows a transition state under compression, in the opposite to that of galacturonate (C(14/14)-GalA). Both films are very mechanically resistant (compression modulus > 300 mN m(-1)) and stable (collapse pressure exceeding 60 mN m(-1)), while that of C(14/14)-GalA exhibits a very high compression modulus up to 600 mN m(-1) like films in the solid state. Computational approaches provide single and assembly molecular models that corroborate the molecule expansion degree and interactions data from experimental results. Differences in the molecular conformation and film behaviours of uronic acid bicatenary derivatives at the air-water interface are attributed to the intra-H-bonding formation, which is more favourable with an OH-4 in the axial (C(14/14)-GalA) than in the equatorial position (C(14/14)-GlcA).     

Quantitative mass spectrometry for bacterial protein toxins--a sensitive, specific, high-throughput tool for detection and diagnosis

Matrix-assisted laser-desorption time-of-flight (MALDI-TOF) mass spectrometry (MS) is a valuable high-throughput tool for peptide analysis. Liquid chromatography electrospray ionization (LC-ESI) tandem-MS provides sensitive and specific quantification of small molecules and peptides. The high analytic power of MS coupled with high-specificity substrates is ideally suited for detection and quantification of bacterial enzymatic activities. As specific examples of the MS applications in disease diagnosis and select agent detection, we describe recent advances in the analyses of two high profile protein toxin groups, the Bacillus anthracis toxins and the Clostridium botulinum neurotoxins. The two binary toxins produced by B. anthracis consist of protective antigen (PA) which combines with lethal factor (LF) and edema factor (EF), forming lethal toxin and edema toxin respectively. LF is a zinc-dependent endoprotease which hydrolyzes specific proteins involved in inflammation and immunity. EF is an adenylyl cyclase which converts ATP to cyclic-AMP. Toxin-specific enzyme activity for a strategically designed substrate, amplifies reaction products which are detected by MALDI-TOF-MS and LC-ESI-MS/MS. Pre-concentration/purification with toxin specific monoclonal antibodies provides additional specificity. These combined technologies have achieved high specificity, ultrasensitive detection and quantification of the anthrax toxins. We also describe potential applications to diseases of high public health impact, including Clostridium difficile glucosylating toxins and the Bordetella pertussis adenylyl cyclase.     

FT-infrared band analysis and temperature programmed dessorption for the Y,L and ferrierite zeolites

With the aim to qualifying and quantifying the acidity of the Y, L and ferrierite zeolites, an infrared band analysis of pyridine adsorption and programmed temperature dessorption measurements were carried out to a set of nine samples of the Y, L and ferrierite zeolites. The infrared spectra before and after the pyridine adsorption process had revealed that the ferrierite zeolite shows, almost in the totality, Br?nsted acid sites. The Y and L zeolites present, also, significative concentrations of Br?nsted and Lewis acid sites. These facts allow to conclude that zeolite ferrierite is the strongest acid zeolite among these three types.     

d-xylose-based bolaamphiphiles: Synthesis and influence of the spacer nature on their interfacial and membrane properties

A two-step synthesis, with good yields, of d-xylose-based bolaamphiphiles is described. The monolayer properties, the adsorption behavior and membrane destabilization properties of two bolaamphiphiles differing by their spacers (presence or absence of one double bond) were studied. The presence of one unsaturation has no influence on the interfacial organization at low compression but impairs the stability of the monolayer at high compression. Saturated and unsaturated molecules are suggested to adopt a loop structure at the interface at low compression. The higher degree of freedom of the saturated hydrophobic spacer does not affect the initial diffusion step of the bolaform from the subphase to the interface but greatly slows the arrangement step at the interface. However, once at the interface, their surface-active properties are similar. The higher flexibility of the saturated analogue spacer also greatly increases its lipid vesicle destabilizing property. Its rearrangement within the lipid bilayer is in favour of the formation of inverted phases, facilitating membrane fusion.     

Simulation-based comparison of noise effects in wavelength modulation spectroscopy and direct absorption TDLAS

A simulative investigation of noise effects in wavelength modulation spectroscopy (WMS) and direct absorption diode laser absorption spectroscopy is presented. Special attention is paid to the impact of quantization noise of the analog-to-digital conversion (ADC) of the photodetector signal in the two detection schemes with the goal of estimating the necessary ADC resolution for each technique. With laser relative intensity noise (RIN), photodetector shot noise and thermal amplifier noise included, the strategies used for noise reduction in direct and wavelength modulation spectroscopy are compared by simulating two respective systems. Results show that because of the combined effects of dithering by RIN and signal averaging, the resolutions required for the direct absorption setup are only slightly higher than for the WMS setup. Only for small contributions of RIN an increase in resolution will significantly improve signal quality in the direct scheme.     

Influence of electrode separation on ion density in the vacuum arc

The density of singly ionized chromium shortly before and after forced extinction of vacuum arcs between chromium-copper electrodes was measured by laser-induced fluorescence for 2- and 10-mm contact gaps and currents between 200 A and 1 kA. In all cases studied, the ion density was constant before ramping down to the current and decayed exponentially after current zero. The ion density at current zero was found to be lower and to decay faster for a short gap than for a longer one, clearly indicating the effect of the contact separation on the charge carrier density. The variation of the time constant for the ion density decay with contact separation is closely analogous to the influence of contact separation on the recovery time of a switch gap. Furthermore, the recovery of dielectric strength of a chromium-copper gap proceeds on the same timescale as the decay of the density of singly ionized chromium. Both of these findings confirm that the ion density has a strong impact on the recovery of a vacuum gap     

An effective algorithm to get linking numbers of 3-manifolds

Summary A colored triangulation of a 3-manifoldM ³ is a decomposition into tetrahedra so that each vertex of them receive one of the colors 0, 1, 2, 3 in such a way that each tetrahedron has four differently colored vertices. From the combinatorics of the dual of a colored triangulation forM ³ we provide an easy algorithm to get a special kind of intersection matrix; from this matrix and from the torsion coefficients of the firstZ-homology group ofM ³ we provide a formula which yields its linking numbers.     

On the vertex group of n-manifolds

In this paper we obtain the decomposition of the vertex group of n-manifolds, extending the one given by Kauffman and Lins for dimension 3 and solving the related conjecture. The result is obtained in the more general category of gems: the vertex group of a gem , representing an n-manifold M, is the free product of n copies of the fundamental group of M and a free group F of rank N–n, where N is the number of n-residues of . In particular, for crystallizations FZ and consequently the vertex group is an invariant of M.