Isoxazolidine analogues of pseudouridine: a new class of modified nucleosides

A new class of modified C-nucleosides has been synthesized according to the 1,3-dipolar cycloaddition methodology. The obtained compounds are structurally related to natural pseudouridine, where the sugar moiety is replaced by an isoxazolidine ring. Different experimental conditions, and the effect of additives on the cycloaddition process, have been examined; the best results were obtained when the cycloaddition reaction was performed under microwave irradiation     

Intramolecular cycloadditions of alpha-allyloxycarbonylnitrones: stereoselective synthesis of 3-amino-2(5H)furanones

Treatment of furoisoxazolidines with NaH leads to functionalized 3-amino-2(5H)-furanones through a new rearrangement pattern of the isoxazolidine nucleus. This process has been usefully exploited for the synthesis of enantiomerically pure (5R)-3-alkylamino-5-methyl-2(5H)-furanones.     

On best approximation by rational and holomorphic mappings between Banach spaces

After proving a generalized version of Garkavi's theorem, we give as applications proofs of existence results on best approximation by polynomials, and fractional linear and holomorphic operators between Banach spaces. We also obtain theorems on best approximation by some types of rational functions defined in open subsets of Banach spaces. By considering a natural non-normable distance we prove that every mapping bounded on the bounded subsets of a Banach space has best approximation by polynomials of degree less than or equal to a fixed natural number n.     

Revealing carbocations in highly asynchronous concerted reactions: The ene-type reaction between dithiocarboxylic acids and alkenes

The ene-type reaction between (dithio)carboxylic acids and alkenes has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. The reaction proceeds under kinetic control and the observed differences in regioselectivity are well-explained by the relative stability of the different transition structures. In agreement with experimental observations, electron-rich alkenes lead to Markownikoff adducts while electron-poor alkenes lead to Michael adducts. In all cases the reaction proceeds through an only transition structure (one kinetic step) although a different synchronicity was observed depending on the alkene electronics. The ELF analysis of the reactions corroborates the existence of a transient carbocation (hidden intermediate) in the reactions with electron-rich alkenes. On the other hand, electron-poor alkenes proceed through a more synchronous concerted mechanism. It can be predicted that with electron-rich alkenes bearing highly donating the transient carbocations might be captured by a nucleophile.     

Symmetrization for singular semilinear elliptic equations

In this paper, we prove some comparison results for the solution to a Dirichlet problem associated with a singular elliptic equation and we study how the summability of such a solution varies depending on the summability of the datum f.     

A Weighted Isoperimetric Inequality in an Orthant

Let c, k ₁ , ..., k _N be non-negative numbers, and define a measure μ in the orthant W :?=?{x?∈??by \(d\mu = e^{c|x|^2 } x_1 ^{k_1 }\cdots x_N ^{k_N } \, dx \) . It is shown that among all measurable subsets of W with fixed μ-measure, the intersection of W with a ball centered at the origin renders the weighted perimeter relative to W a minimum. Norm inequalities in weighted Sobolev spaces and a comparison result for solutions to boundary value problems for degenerate elliptic equations are also given.     

Comprehensive and Accurate Ab Initio Energy Surface of Simple Alanine Peptides

Secondary structures for AcAla_nNH₂ (n=2–4) peptides have been analyzed by means of ab initio MP2, CCSD(T), and DFT‐B3PW91 methods using large basis sets and including implicit hydration effects and thermal corrections. In addition to the classical “pure” right‐handed 3₁₀‐ and α‐helices, left‐handed polyproline II, inverse γ‐turn, and fully extended conformations, a large number of “mixed” structures obtained by combining characteristic φ/ψ angles of each residue in every way have been found. All mixed structures are energetically accessible and can be present at significant levels in aqueous solution. Furthermore, they represent the way through which hierarchical unfolding of 3₁₀‐ and α‐helices or nonhierarchical polyproline II to fully extended transitions occur. Computational results are in qualitative agreement with the large amount of experimental data for simpler polyalanines and provide significant insight into their thermodynamic properties and how these can be modulated by interactions with solvent.     

Baobab-Fruit Shell and Fibrous Filaments Are Sources of Antioxidant Dietary Fibers

Since 2008, baobab-fruit dried pulp is listed as an ingredient on the European Union′s Novel Food Catalogue. By pulp production, 80% of the baobab fruit is discarded, forming side streams, namely, shell, fibrous filaments, and seeds. This study explored pulp and side-stream functional properties, including total dietary fiber (TDF), total antioxidant capacity (TAC), polyphenols, and water- (WHC) and oil-holding capacities (OHC), along with endocannabinoids (ECs) and N-acylethanolamines (NAEs) in pulp, seeds, and seed oil. Shell excelled in TDF (85%), followed by fibrous filaments (79%), and showed the highest soluble and direct TAC (72 ± 0.7 and 525 ± 1.0 µmol eq. Trolox/g, respectively). Pulp was the richest in polyphenols, followed by shell, fibrous filaments, and seeds. Quercetin predominated in shell (438.7 ± 2.5 µg/g); whereas epicatechin predominated in pulp (514 ± 5.7 µg/g), fibrous filaments (197.2 ± 0.1 µg/g), and seeds (120.1 ± 0.6 µg/g); followed by procyanidin B2 that accounted for 26–40% of total polyphenols in all the products. WHC and OHC ranged between 2–7 g H₂O-Oil/g, with fibrous filaments showing the highest values. ECs were not found, whereas NAEs were abundant in seed oil (2408.7 ± 11.1 ng/g). Baobab shell and fibrous filaments are sources of polyphenols and antioxidant dietary fibers, which support their use as functional food ingredients.