Catalytic asymmetric reductive amination of aldehydes via dynamic kinetic resolution

A novel organocatalytic asymmetric reductive amination of aldehydes has been developed. Treating racemic alpha-branched aldehydes with p-anisidine and a Hantzsch ester in the presence of our previously developed phosphoric acid catalyst, TRIP, gave beta-branched secondary amines in excellent yields and enantioselectivities via an efficient dynamic kinetic resolution. The process is applicable to several different aromatic aldehydes and amines but gives slightly reduced enantiomeric ratios with aliphatic aldehydes.     

Site-selected Auger electron spectroscopy of N2O

The N 1s Auger spectra for the two nonequivalent N atoms in N2O have been measured via Auger electron-photoelectron coincidence spectroscopy. The site-selected Auger spectra are compared with the normal Auger spectrum and with accurate theoretical calculations accounting for the effects of the dynamics of the nuclei on the energy and linewidth of the Auger bands. Such effects are found to be crucial factors in determining the different band shapes in the site-selected spectra.     

Simplicity of principal eigenvalue for p-Laplace operator with singular indefinite weight

Given a connected open set and a function w ∈L^N/p(Ω) if 1 < p < N and w ∈L^r (Ω) for some r ∈(1, ∞) if p ≧ N, with we prove that the positive principal eigenvalue of the problem

From 1-homogeneous supremal functionals to difference quotients: relaxation and Γ-convergence

In this paper we consider positively 1-homogeneous supremal functionals of the type . We prove that the relaxation $\bar{F}$ is a difference quotient, that is where is a geodesic distance associated to F. Moreover we prove that the closure of the class of 1-homogeneous supremal functionals with respect to Γ-convergence is given exactly by the class of difference quotients associated to geodesic distances. This class strictly contains supremal functionals, as the class of geodesic distances strictly contains intrinsic distances. Mathematics Subject Classification (2000) 47J20, 58B20, 49J45     

A reasonably stereospecific multistep conversion of Boc-protected α-amino acids to Phth-protected β-amino acids

A method for the synthesis of β³-amino acids starting from α-amino acids is described. This conversion can be effected by an eight-step procedure which involves the transformation of the carboxylic group into an alkyne followed by a selenium-mediated conversion of the carbon-carbon triple bond to a Se-phenyl selenocarboxylate intermediate. The reactive Se-phenyl selenocarboxylate intermediates can be trapped with water, alcohols or the amine of an amino acid derivative to give β³-amino acids, β³-amino esters or mixed peptides, respectively. The whole transformations of the carboxylic group into an alkyne and of the alkyne group into β³-amino acids may not require purification of the intermediate products but a work-up and isolation procedure of crude materials.     

Regeneration of total RNA purification silica-based columns

Silica-based columns are largely used in RNA purification, allowing fast extractions and good yields of high quality nucleic acid, but their major limitation is the high cost. The reuse of such columns, although desirable, is not recommended because of residual amounts of material from the previous sample trapped in the column matrix, which might be released during further purification. Thus, recycling does need previous complete removal of any detectable RNA trace, but to date no protocol which allows decontamination and reuse is available.We report a very rapid decontamination procedure, based on treatment with warm alkaline solution containing Triton X-100, which ensures no RNA carry-over, and allows the recycling of columns without impairment of their efficiency in high-quality RNA purification even after several regeneration rounds.     

High performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry for sensitive determination of bioactive amines in donkey milk

In the present study we report on the optimization and validation of a sensitive high performance liquid chromatography atmospheric pressure chemical ionization mass spectrometry (HPLC–APCI–MS) method for the determination of 8 bioactive amines (histamine, tyramine, tryptamine, 2-phenylethylamine, cadaverine, putrescine, spermidine and spermine) in donkey milk samples. The method involves donkey milk pre-treatment to remove proteins and pre-column dansylation of the amines. HPLC in reversed phase mode has been used for bioactive amines separation and the operating condition of the APCI–MS system proved to be powerful and very efficient for peak assignment. The separation was accomplished in a short time with an excellent resolution for all the amine peaks. Quantification was carried out by monitoring the characteristic [M+H]⁺ ion of each amine derivative. The method sensitivity, linearity and repeatability were assayed with satisfactory results. The detection limits of the analysed amines ranged from 0.5 μg L⁻¹ to 15 μg L⁻¹; the highest LOD was for spermine. Also remarkably good recovery values were obtained; at the lowest spiking level (1 μg L⁻¹) the percent mean recoveries ranged from 77.7 to 109.7. Furthermore, as the investigations relate to a complex matrix as donkey milk, suitable studies on matrix effect were performed. Finally, the developed and validated method was applied to analyse 13 donkey milk samples. Among the identified bioactive amines, putrescine, spermine and spermidine proved to be the main amines in donkey milk. Their concentration levels in the present study were lower than the values determined in mature human, cow and sow milk.     

Minimizing Sequences for a Family of Functional Optimal Estimation Problems

Rates of convergence are derived for approximate solutions to optimization problems associated with the design of state estimators for nonlinear dynamic systems. Such problems consist in minimizing the functional given by the worst-case ratio between the ℒ _p -norm of the estimation error and the sum of the ℒ _p -norms of the disturbances acting on the dynamic system. The state estimator depends on an innovation function, which is searched for as a minimizer of the functional over a subset of a suitably-defined functional space. In general, no closed-form solutions are available for these optimization problems. Following the approach proposed in (Optim. Theory Appl. 134:445–466, 2007), suboptimal solutions are searched for over linear combinations of basis functions containing some parameters to be optimized. The accuracies of such suboptimal solutions are estimated in terms of the number of basis functions. The estimates hold for families of approximators used in applications, such as splines of suitable orders.     

Regression diagnostics applied in kinetic data processing: Outlier recognition and robust weighting procedures

An efficient protocol, based on advanced statistical diagnostics and robust fitting techniques applied to the least‐squares processing of kinetic data of chemical reactions, is presented and discussed. The procedure, which is aimed at obtaining highly accurate estimation of the fitting parameters, consists of the identification of the outliers that remarkably impair the fitting by means of the so‐called “leverage analysis” and some related diagnostics. This approach allows the elimination of the actually aberrant observations from the data set and/or their robust weighting to inhibit the negative effects induced on the data fitting, with consequent reduction of the bias introduced into the parameter estimates. It has been found that the proposed procedure, applied to experimental kinetic data, does yield to a significant improvement in the regression results. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 587–607, 2010     

Synthesis of enantiomerically enriched β-hydroxy selenides by catalytic asymmetric ring opening of meso-epoxides with (phenylseleno)silanes

The first example of the enantioselective ring opening of meso-epoxides by (phenylseleno)silanes using salen(Cr)complexes as catalyst is described. This desymmetrization reaction constitutes a simple and convenient approach to synthetically versatile optically active β-hydroxy selenides.