Amination of CF3-enones with nosyloxycarbamates

CF3-enones showed a different reactivity in amination reactions with nosyloxycarbamates. 4-Oxazolines or vinyl carbamates were obtained as unique products depending on the nature of double-bond substituents and on the choice of carbamates and bases. Starting from trans-trifluoroacetyl olefins carrying a heterocyclic residue or the p-methoxyphenyl group on the double bond, a rare loss of CF3CO was observed when the aminations were performed under heterogeneous conditions using CaO as the base.     

Stereoselective uncatalyzed synthesis of 2,3-unsaturated-4-n-substituted-beta-O-glycosides by means of a new D-galactal-derived N-(mesyl)-aziridine

The reaction of the new D-galactal-derived allylic aziridine 1beta with O-nucleophiles (alcohols and monosaccharides) affords, in a high to complete beta-stereoselectivity, the corresponding 2,3-unsaturated-beta-O-glycosides bearing a beta-N-functionality at C4.     

p1,n1 salts: Self-assembled supramolecular structures sequestering racemates. Diastereomeric separation and enantiomeric enrichment of trans-chrysanthemic acid

The occurrence of p1,n1 salts can be exploited to sequester racemates; an application to technical mixtures of chrysanthemic acids (ChA) allowed the separation of trans- and cis-ChA and the recovery of the excess enantiomer of trans-ChA.     

Chemical and physical analysis for the improvement of the dry mounting method for fragile documents

Paper lamination is a widely used method to consolidate fragile documents. Previous studies have presented a new method of lamination that allows the consolidation of documents before undertaking aqueous treatments. In this method a thin Japanese paper coated with an acrylic resin is applied on the fragile document by means of a heated press. In this work we optimised the preparation of the lamination sheets as well as the working procedures, and we were able to establish that our laboratory-made specimens are chemically stable, easily reversible and permeable to aqueous solutions. The latest property is of particular importance, since it allows a subsequent aqueous deacidification even for fragile documents. The laminated paper documents were further analysed by means of colorimetry and FTIR spectroscopy before and after accelerated ageing as well as by determination of the alkali reserve left on the coated paper, in order to compare our lamination method with other commercially available lamination sheets.     

Efficient reconstruction of complex free energy landscapes by multiple walkers metadynamics

Recently, we have introduced a new method, metadynamics, which is able to sample rarely occurring transitions and to reconstruct the free energy as a function of several variables with a controlled accuracy. This method has been successfully applied in many different fields, ranging from chemistry to biophysics and ligand docking and from material science to crystal structure prediction. We present an important development that speeds up metadynamics calculations by orders of magnitude and renders the algorithm much more robust. We use multiple interacting simulations, walkers, for exploring and reconstructing the same free energy surface. Each walker contributes to the history-dependent potential that, in metadynamics, is an estimate of the free energy. We show that the error on the reconstructed free energy does not depend on the number of walkers, leading to a fully linear scaling algorithm even on inexpensive loosely coupled clusters of PCs. In addition, we show that the accuracy and stability of the method are much improved by combining it with a weighted histogram analysis. We check the validity of our new method on a realistic application.     

Structure and function of vanadium haloperoxidases

A quantum mechanics/molecular mechanics study of the resting state of the vanadium dependent chloroperoxidase from fungi Curvularia inaequalis and of the early intermediates of the halide oxidation is reported. The investigation of different protonation states indicates that the enzyme likely consists of an anionic H2VO4- vanadate moiety where one hydroxo group is in axial position. The calculations suggest that the hydrogen peroxide binding may not involve an initial protonation of the vanadate cofactor. A low free energy reactive path is found where the hydrogen peroxide directly attacks the axial hydroxo group, resulting in the formation of an hydrogen peroxide intermediate. This intermediate is promptly protonated to yield a peroxo species. The free energy barrier for the formation of the peroxo species does not depend significantly upon the protonation state of the cofactor. The most likely protonation states of the peroxo cofactor are neutral forms HVO2(O2) with a hydroxo group either H-bonded to Ser402 or coordinated to Arg360. The peroxo cofactor is also coordinated to an axial water molecule, which could be important for the stability of the peroxovanadate/His496 adduct. Our calculations strongly suggest that the halide oxidation may take place with the preliminary formation of a peroxovanadate/halogen adduct. Subsequently, the halogen reacts with the peroxo moiety yielding a hypohalogen vanadate. The most reactive protonation state of peroxovanadate is the neutral HVO2(O2) with the hydroxo group H-bonded to Ser402. The important role of Lys353 in determining the catalytic activity is also confirmed.     

Glasslike structure of globular proteins and the boson peak

Vibrational spectra of proteins and topologically disordered solids display a common anomaly at low frequencies, known as boson peak. We show that such feature in globular proteins can be deciphered in terms of an energy landscape picture, as it is for glassy systems. Exploiting the tools of Euclidean random matrix theory, we clarify the physical origin of such anomaly in terms of a mechanical instability of the system. As a natural explanation, we argue that such instability is relevant for proteins in order for their molecular functions to be optimally rooted in their structures.     

BIANCA: a genetic algorithm to solve hard combinatorial optimisation problems in engineering

The genetic algorithm BIANCA, developed for design and optimisation of composite laminates, is a multi-population genetic algorithm, capable to deal with unconstrained and constrained hard combinatorial optimisation problems in engineering. The effectiveness and robustness of BIANCA rely on the great generality and richness in the representation of the information, i.e. the structure of populations and individuals in BIANCA, and on the way the information is extensively exploited during genetic operations. Moreover, we developed proper and original strategies to treat constrained optimisation problems through the generalisation of penalisation methods. BIANCA can also treat constrained multi-objective problems based on the construction of the Pareto frontier. Therefore, BIANCA allows us to approach very general design problems for composite laminates, but also to make a step forward to the treatment of more general problems of optimisation of materials and structures. In this paper, we describe specifically the case of optimal design of composite laminates, concerning both the theoretical formulation and the numeric resolution.     

More on regular and decomposable ultrafilters in ZFC

We prove, in ZFC alone, some new results on regularity and decomposability of ultrafilters; among them: (a) If m ≥ 1 and the ultrafilter D is (_m(λ⁺ⁿ), _m(λ⁺ⁿ))‐regular, then D is κ ‐decomposable for some κ with λ ≤ κ ≤ 2^λ (Theorem 4.3(a^')). (b) If λ is a strong limit cardinal and D is (_m(λ⁺ⁿ), _m(λ⁺ⁿ))‐regular, then either D is (cf λ, cf λ)‐regular or there are arbitrarily large κ < λ for which D is κ ‐decomposable (Theorem 4.3(b)). (c) Suppose that λ is singular, λ < κ, cf κ ≠ cf λ and D is (λ⁺, κ)‐regular. Then: (i) D is either (cf λ, cf λ)‐regular, or (λ^', κ)‐regular for some λ^' < λ (Theorem 2.2). (ii) If κ is regular, then D is either (λ, κ)‐regular, or (ω, κ^')‐regular for every κ^' < κ (Corollary 6.4). (iii) If either (1) λ is a strong limit cardinal and λ^<λ < 2^κ, or (2) λ^<λ < κ, then D is either λ ‐decomposable, or (λ^', κ)‐regular for some λ^' < λ (Theorem 6.5). (d) If λ is singular, D is (μ, cf λ)‐regular and there are arbitrarily large ν < λ for which D is ν ‐decomposable, then D is κ ‐decomposable for some κ with λ ≤ κ ≤ λ^<μ (Theorem 5.1; actually, our result is stronger and involves a covering number). (e) D × D^' is (λ, μ)‐regular if and only if there is a ν such that D is (ν, μ)‐regular and D^' is (λ, ν^')‐regular for all ν^～ < ν (Proposition 7.1). We also list some problems, and furnish applications to topological spaces and to extended logics (Corollar‐ies 4.6 and 4.8) (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)