Estimation of dynamical invariants without embedding by recurrence plots

In this paper we show that two dynamical invariants, the second order Renyi entropy and the correlation dimension, can be estimated from recurrence plots (RPs) with arbitrary embedding dimension and delay. This fact is interesting as these quantities are even invariant if no embedding is used. This is an important advantage of RPs compared to other techniques of nonlinear data analysis. These estimates for the correlation dimension and entropy are robust and, moreover, can be obtained at a low numerical cost. We exemplify our results for the Rossler system, the funnel attractor and the Mackey-Glass system. In the last part of the paper we estimate dynamical invariants for data from some fluid dynamical experiments and confirm previous evidence for low dimensional chaos in this experimental system.     

Thed(7Li,p)8Li cross section nearE cm=0.61 MeV

The absolute cross sectionσ of thed(⁷Li,p)⁸Li reaction near theE _cm=0.61 MeV resonance has been measured using a⁷Li ion beam and a windowless gas target system filled with D₂ gas. The proton yield of the reaction and theβ-delayedα-activity of the residual nuclides⁸Li were observed both concurrently with the elastic scattering yield, relatingσ to the Rutherford scattering cross sectionσ _R. The resulting values,σ (fromp)=143.6±8.9 mb andσ (from⁸Li)=151±20 mb, lead to a weighted mean value ofσ=153±6 mb (x ²=2.26) including all available values andσ=146±5 mb (x ²=0.05) removing some values from the data set. The consequences for the expected flux of high-energy solar neutrinos are discussed.     

Solution of large dense complex matrix equations using a fastFourier transform (FFT)-based wavelet-like methodology

Wavelet-like transformations have been used in the past to compress dense large matrices into a sparse system. However, they generally are implemented through a finite impulse response filter realized through the formulation of Daubechies (1992). A method is proposed to use a very high order filter (namely an ideal one) and use the computationally efficient fast Fourier transform (FFT) to carry out the multiresolution analysis. The goal here is to reduce the redundancy in the system and also guarantee that the wavelet coefficients drop off much faster. Hence, the efficiency of the new procedure becomes clear for very high order filters. The advantage of the FFT-based procedure utilizing ideal filters is that it can be computationally efficient and for very large matrices may yield a sparse matrix. However, this is achieved, as well known in the literature, at the expense of robustness, which may lead to a larger reconstruction error due to the presence of the Gibb's phenomenon. Numerical examples are presented to illustrate the efficiency of this procedure as conjectured in the literature     

Stereoselective synthesis of N-aryl proline amides by biotransformation-Ugi-Smiles sequence

An efficient combination of MAO-N-catalyzed desymmetrization of cyclic meso-amines with Ugi-Smiles multicomponent chemistry produced optically pure N-aryl proline amides. This method represents the first report of a fully asymmetric Ugi-Smiles process.     

The Forgotten Pyrazines: Exploring the Dakin–West Reaction

Pyrazines are an underreported class of N-heterocycles available from nitrogen-rich biomass presenting an interesting functional alternative for current aromatics. In this work, access to pyrazines obtained from amino acids by using the 90 year old Dakin–West reaction was explored. After a qualitative screening several functional proteinogenic amino acids proved good substrates for this reaction, which were successfully scaled to multigram scale synthesis of the corresponding intermediate α-acetamido ketones. Subsequently, the conditions towards pyrazine formation using δ-amino-levulinic acid were optimized, and these were employed to synthesize a relevant set of five functional dimethylpyrazines in high purity. These pyrazines can be considered a versatile toolbox of aromatic building blocks for a wide range of applications, such as in the synthesis of polymers or metal–organic frameworks.     

Solvent crystallized syndiotactic polystyrene. Thermal and dynamic-mechanical behavior

The syndiotactic polystyrene can crystallize in different forms, depending on thermal and solvent treatments. The influence of the polymorphism on the dynamic-mechanical behavior has been analyzed. Thermogravimetric and calorimetric analysis were also carried out. The effects of phase transitions and solvent release on the relaxation phenomena were observed, and the correlations between structure and dynamic behavior allow to better understand some aspects of the polymorphism phenomena.     

In situ formation of allyl ketones via Hiyama-Nozaki reactions followed by a chromium-mediated Oppenauer oxidation

In Hiyama-Nozaki reactions of allylchromium with aldehydes the expected products are homoallylalcohols. However, oxidation products derived from these, predominantly allyl ketones, can be common side products. This can be explained by an Oppenauer-(Meerwein-Ponndorf-Verley)-type mechanism (OMPV-reaction). The amount of oxidation is strongly dependent on the substitution pattern of the reaction partners and the reaction conditions. An appropriate choice of these can lead to preferential formation of ketones instead of the alcohols. In addition to its synthetic usefulness, the oxidation-reduction equilibrium is of the utmost importance for the design of enantioselective Hiyama-Nozaki reactions because it is also a potential racemization pathway.     

A novel four-component reaction for the synthesis of functionalised dihydropyrimidines

In a multi-component reaction (MCR) of a phosphonate, nitriles, aldehydes and isocyanates, N3-functionalised dihydropyrimidines can be synthesised efficiently via a Horner-Emmons/aza Diels-Alder pathway.     

Probing the glycosidic linkage: UV and IR ion-dip spectroscopy of a lactoside

The beta(1-->4) glycosidic linkage found in lactose is a prevalent structural motif in many carbohydrates and glycoconjugates. Using UV and IR ion-dip spectroscopies to probe benzyl lactoside isolated in the gas phase, we find that the disaccharide unit adopts only a single, rigid structure. Its fully resolved infrared ion-dip spectrum is in excellent agreement with that of the global minimum structure computed ab initio. This has glycosidic torsion angles of phi(H) (H1-C1-O-C4') approximately 180 degrees and psi(H) (C1-O-C4'-H4') approximately 0 degrees which correspond to a rotation of approximately 150 degrees about the glycosidic bond compared to the accepted solution-phase conformation. We discuss the biological implications of this discovery and the generality of the strategies employed in making it.     

Engineering protein therapeutics: predictive performances of a structure-based virtual affinity maturation protocol

The implementation of a structure based virtual affinity maturation protocol and evaluation of its predictivity are presented. The in silico protocol is based on conformational sampling of the interface residues (using the Dead End Elimination/A* algorithm), followed by the estimation of the change of free energy of binding due to a point mutation, applying MM/PBSA calculations. Several implementations of the protocol have been evaluated for 173 mutations in 7 different protein complexes for which experimental data were available: the use of the Boltzamnn averaged predictor based on the free energy of binding (ΔΔG(*)) combined with the one based on its polar component only (ΔΔE(pol*)) led to the proposal of a subset of mutations out of which 45% would have successfully enhanced the binding. When focusing on those mutations that are less likely to be introduced by natural in vivo maturation methods (99 mutations with at least two base changes in the codon), the success rate is increased to 63%. In another evaluation, focusing on 56 alanine scanning mutations, the in silico protocol was able to detect 89% of the hot-spots.