Synthesis of an ent-halimanolide from ent-halimic acid

An efficient synthesis of ent-halimanolide 2 (15,16-epoxy-12-oxo-ent-halima- 5(10),13(16),14-trien-18,2beta-olide), from ent-halimic acid has been achieved, corroborating the structure of the natural compound and establishing its absolute configuration.     

Microhydration of protonated glycine: an ab initio family tree

The incremental hydration of the glycine cation is investigated using an ab initio approach fully correcting for basis set superposition errors and explicitly incorporating electron-correlation effects. Structures with zero to four surrounding water molecules have been determined. It is demonstrated that the successive aggregates follow a Darwinian family tree, the most stable complexes systematically belonging to the same branch of the tree. In strong contrast with neutral glycine, the direct hydrogen bonding to the glycine cation is favored over bridging water structures. The agreement between experimental and theoretical hydration enthalpies and Gibbs free energies is impressive, as ab initio estimates almost systematically fit the experimental error bars. For GlyH(+)-(H2O) and GlyH(+)-(H2O)3, we show that two structures are generated by the experimental setup. The present approach also resolves most of the previous theory/experiment discrepancies and provides patterns for the evolution of the vibrational spectra: a decrease of the hydrogen-bond stretching frequency indicating second-shell water molecules. Additionally, the impact of bulk solvent solvation is investigated, as four discrete water molecules still do not fully hydrate the protonated glycine.     

Diastereoselective synthesis of delta-aminoacids through domino Ireland-Claisen rearrangement and Michael addition

A novel domino reaction--stereoselective Ireland-Claisen rearrangement and asymmetric Michael addition--is described. A protocol starting from Baylis-Hillman adducts 3a-f using chiral lithium amide affords optically active gamma-substituted delta-amino acids 4a-f with high diastereoselectivities and enantioselectivities. The acid can be isolated easily from large-scale reactions and transformed to 2,3-disubstituted piperidines 11 or 2-substituted nipecotic acid derivates 12.     

Hydration, charge, size, and shape characteristics of peptides from their CZE analyses

A CZE model is presented for peptide characterization on the basis of well-established physicochemical equations. The effective mobility is used as basic data in the model to estimate relevant peptide properties such as, for instance, hydration, net and total electrical charge numbers, hydrodynamic size and shape, particle average orientation, and pH-microenvironment from the charge regulation phenomenon. Therefore 102 experimental effective mobilities of different peptides are studied and discussed in relation to previous work. An equation for the estimation of peptide hydration as a function of ionizing, polar, and non-polar amino acid residues is included in the model. It is also shown that the shape-orientation factor of peptides may be either lower or higher than one, and its value depends on a complex interplay among total charge number, molar mass, hydration, and amino acid sequence.     

Three‐dimensional hydrogen‐bonded framework in bis(melamin‐1‐ium) naphthalene‐1,5‐disulfonate melamine pentahydrate

Crystals of the title compound, 2C₃H₇N₆⁺·C₁₀H₆O₆S₂²⁻·C₃H₆N₆·5H₂O, are built up of neutral 2,4,6‐triamino‐1,3,5‐triazine (melamine), singly protonated melaminium cations, naphthalene‐1,5‐disulfonate dianions and water molecules. Two independent anions lie across centres of inversion in the space group P. The melamine molecules are connected by N—H...N hydrogen bonds into two different one‐dimensional polymers almost parallel to the (010) plane, forming a stacking structure along the b axis. The centrosymmetric naphthalene‐1,5‐disulfonate anions interact with water molecules via O—H...O hydrogen bonds, forming layers parallel to the (001) plane. The cations and anions are connected by N—H...O and O—H...N hydrogen bonds to form a three‐dimensional supramolecular framework.     

The critical hyperbola for a Hamiltonian elliptic system with weights

In this paper we look for existence results for nontrivial solutions to the system,

Nontrivial compact blow-up sets of smaller dimension

We provide examples of solutions to parabolic problems with nontrivial blow-up sets of dimension strictly smaller than the space dimension. To this end we just consider different diffusion operators in different variables, for example, or . For both equations, we prove that there exists a solution that blows up in the segment .

     

The Neumann problem for nonlocal nonlinear diffusion equations

We study nonlocal diffusion models of the form

Refined asymptotic expansions for nonlocal diffusion equations

We study the asymptotic behavior for solutions to nonlocal diffusion models of the form u _t = J * u – u in the whole with an initial condition u(x, 0) = u ₀(x). Under suitable hypotheses on J (involving its Fourier transform) and u ₀, it is proved an expansion of the form

Single-shot fast spin-echo diffusion tensor imaging of the lumbar spine at 1.5 and 3 T

Diffusion tensor imaging (DTI) of the lumbar spine could improve diagnostic specificity. The purpose of this work was to determine the feasibility of and to validate DTI with single-shot fast spin-echo (SSFSE) for lumbar intervertebral discs at 1.5 and 3 T. Six normal volunteers were scanned with DTI-SSFSE using an eight- and a three-b-value protocol at 1.5 and 3 T, respectively. Apparent diffusion coefficient (ADC) values were computed and validated based on those obtained at 1.5 T from corresponding diffusion tensor scans using line scan diffusion imaging (LSDI), a technique that has been previously validated for use in the spine. Pearson correlation coefficients for LSDI and DTI-SSFSE ADC values were .88 and .89 for 1.5 and 3 T, respectively, with good quantitative agreement according to the Bland-Altman method. Results indicate that DTI-SSFSE is a candidate as a clinical sequence for obtaining diffusion tensor images of the lumbar intervertebral discs with scan times shorter than 4 min.