LC Separation and Online MS Characterization of Saturated and Unsaturated Alginic Acid Oligomers

We report the complete separation and characterization by online high-performance liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) of fully saturated alginic acid (AA) oligosaccharides from DP1 to beyond DP23, obtained by a chemical process, and unsaturated oligomers from DP1 to DP10, produced by lyase treatment. A series of negatively charged species of different m/z ratio are seen for each oligosaccharide. Smaller AA species, from DP1 to DP4, mainly furnish [M–H]^? anions whereas the DP5 to DP9-10 oligomers predominantly exist as the 2- charge state. The AA oligomers from DP10 to DP17 are mainly represented by the [M–3H]^3? anions whereas species from DP18 to DP23 are characterized by the 4? charge state. Online LC-ESI-MS enabled separation and simultaneous characterization of complex saturated and unsaturated AA oligomer mixtures without previous sample treatment, in particular extensive removal of salts to obtain species compatible with ESI-MS.     

On the Positive Parts of Second Order Symmetric Pseudodifferential Operators

Using microlocalization, the positive and the negative parts for a class of second order formally self-adjoint pseudodifferential operators are constructed.      

Strength vs. toughness optimization of microstructured composites

Aim of this paper is to present a new fractal approach linking the macroscopic mechanical properties of micro- and nano-structured materials with the main parameters: composition, grain size and structural dimension, as well as contiguity and mean free path. Assuming the key role played by the interfaces, the proposed fractal energy approach unifies the influences of all the above parameters, through the introduction of a fractal structural parameter (FSP), which represents an extension of the Gurland’s structural parameter. This modeling approach is assessed through an extensive comparison with experimental data on poly crystalline diamond (PCD) and WC–Co alloys. The results clearly show that the theoretical fractal predictions are in a fairly good agreement with the experiments on both hardness and toughness. This new synthetic parameter is thus proposed to investigate, design and optimize new micro- and nano-grained materials. Eventually, FSP-based optimization maps are developed, that allow to design new materials with high hardness and toughness.     

Urea Unfolding of Opsin in Phospholipid Bicelles†

Opsin is the unstable apo‐protein of the light‐activated G protein‐coupled receptor rhodopsin. We investigated the stability of bovine opsin, solubilized in 1,2‐dimyristoyl‐sn‐glycero‐3‐phosphocholine (DMPC)/detergent bicelles, against urea‐induced unfolding. A single irreversible protein unfolding transition was observed from changes in intrinsic tryptophan fluorescence and far‐UV circular dichroism. This unfolding transition correlated with loss of protein activity. Changes in tertiary structure, as indicated by fluorescence measurements, were concomitant with an approximate 50% reduction in α‐helical content of opsin, indicating that global unfolding had been induced by urea. The urea concentration at the midpoint of unfolding was dependent on the lipid/detergent environment, occurring at approximately 1.2 m urea in DMPC/1,2‐dihexanoyl‐sn‐glycero‐3‐phosphocholine bicelles, while being significantly stabilized to approximately 3.5 m urea in DMPC/3‐[(cholamidopropyl)dimethylammonio]‐1‐propanesulfonate bicelles. These findings demonstrate that interactions with the surrounding lipids and detergent are highly influential in the unfolding of membrane protein structure. The urea/bicelle system offers the possibility for a more detailed understanding of the structural changes that take place upon irreversible unfolding of opsin.     

3-Quasi-Sasakian manifolds

We correct the results in section 6 of [B. Cappelletti Montano, A. De Nicola, G. Dileo, 3-Quasi-Sasakian manifolds, Ann. Global Anal. Geom. 33 (2008), 397–409], concerning the corrected energy of the Reeb distribution of a compact 3-quasi-Sasakian manifold. The results are slightly different than what was originally claimed and they are obtained by using results in [B. Cappelletti Montano, A. De Nicola, G. Dileo, The geometry of a 3-quasi-Sasakian manifold, Int. J. Math., to appear, arXiv:0801.1818], where the geometry of these manifolds is more deeply investigated. The online version of the original article can be found under doi:.     

On the shape factor of interaction laws for a non-local approximation of the Sobolev norm and the total variation

We consider the family of non-local and non-convex functionals introduced by H. Brézis and H.-M. Nguyen in a recent paper. These functionals Gamma-converge to a multiple of the Sobolev norm or the total variation, depending on a summability exponent, but the exact values of the constants are unknown in many cases.We describe a new approach to the Gamma-convergence result that leads in some special cases to the exact value of the constants, and to the existence of smooth recovery families.     

Total synthesis of (−)-dictyostatin, a microtubule-stabilising anticancer macrolide of marine sponge origin

An efficient convergent synthesis of the anticancer marine macrolide (−)-dictyostatin is described that proceeds in 4.6% yield over 27 steps. Most of the stereocentres were configured using substrate control, making use of a common building block to install the C12-C14 and C20-C22 stereotriads, with a lactate boron aldol reaction employed to construct a C4-C10 β-ketophosphonate as utilised in the pivotal Still-Gennari HWE coupling step with a fully elaborated C11-C26 aldehyde. Following introduction of the (2Z,4E)-dienoate, a modified Yamaguchi macrolactonisation and deprotection delivered the requisite 22-membered macrocyclic lactone.