Stereodivergent syntheses of conduramines and aminocyclitols

[reaction: see text] The diastereomers of 6-amino-cyclohex-3-ene-1,2-diols 1 (4-deoxy-3-conduramines), key building blocks for the syntheses of a large range of natural products, have been enantioselectively prepared. Diastereoselective dihydroxylation of the compounds provided a new family of aminocyclitols 2 (deoxyinosamines). The key reactions of our syntheses are Sharpless catalytic asymmetric epoxidation, diastereoselective addition of vinylmetal reagents to the aldehydes, and ring-closing metathesis (RCM).     

Sample entropy of ECG time series of fearful flyers: preliminary results

Research within the framework of the nonlinear dynamical systems (NDS) in the field of anxiety disorders has shown that greater irregularity/complexity appears in the output from healthy systems. In this study we measured the Heart rate variability (HRV) and the sample sntropy (SampEn) of the ECG mV time series of fearful flyers (N = 15) and a matched control group (N = 15) when confronted with three combinations of feared stimuli (pictures, sounds, and pictures with sounds) as well as relaxing stimuli (pictures and sounds). Fearful flyers had lower SampEn than controls in all conditions, including baseline. Non-phobics showed significant entropy decreases from baseline in two out of three exposure conditions. No differences on HRV were found between groups, and HRV was not sensitive to condition changes. The main finding of the study is that the SampEn calculated on very short ECG mV recordings (10 to 60 seconds, easy to obtain in clinical settings) may be a useful diagnostic measure since it can distinguish fearful from non-fearful flyers.     

Generation of light in media with a random distribution of nonlinear domains

We show that the second order nonlinear generation of light, a process that it is assumed to require highly ordered materials, is also possible in structures of randomly oriented nonlinear domains. We explain theoretically why in such disordered structures the efficiency of the nonlinear generation of light grows linearly with the number of domains. Moreover, a higher degree of disorder, obtained when the dispersion is made very large, has no negative effect for the nonlinear light generation. In such conditions, light generation is shown to be equally efficient for any average size of the domains and also to grow linearly with respect to the number of domains.     

Existence, uniqueness, and convergence of the regularized primal-dual central path

In a recent work [J. Castro, J. Cuesta, Quadratic regularizations in an interior-point method for primal block-angular problems, Mathematical Programming, in press (doi:10.1007/s10107-010-0341-2)] the authors improved one of the most efficient interior-point approaches for some classes of block-angular problems. This was achieved by adding a quadratic regularization to the logarithmic barrier. This regularized barrier was shown to be self-concordant, thus fitting the general structural optimization interior-point framework. In practice, however, most codes implement primal-dual path-following algorithms. This short paper shows that the primal-dual regularized central path is well defined, i.e., it exists, it is unique, and it converges to a strictly complementary primal-dual solution.     

ChemInform Abstract: X2Y2 Isomers: Tuning Structure and Relative Stability Through Electronegativity Differences (X: H,Li, Na,F, Cl,Br, I; Y: O,S, Se,Te).

Density functional calculations on XYYX and X₂YY isomers of the X₂Y₂ species (X: H, Li, Na, F, Cl, Br, I; Y: O, S, Se, Te) show that the XYYX isomers are more stable than the X₂YY forms except for X = F and Y = S and Te, for which the F₂SS and F₂TeTe isomers are slightly more stable.     

Schatten classes of integration operators on Dirichlet spaces

We address the problem of determining membership in Schatten-Von Neumann ideals S _p of integration operators (T _g f)(z) = ∫ ₀ ^z = ∫ ₀ ^z f(ξ)g′(ξ)dξ acting on Dirichlet type spaces. We also study this problem for multiplication, Hankel and Toeplitz operators. In particular, we provide an extension of Luecking's result on Toeplitz operators [10, p. 347].     

An enumeration procedure for the assembly line balancing problem based on branching by non-decreasing idle time

In this article, we present a new exact algorithm for solving the simple assembly line balancing problem given a determined cycle time (SALBP-1). The algorithm is a station-oriented bidirectional branch-and-bound procedure based on a new enumeration strategy that explores the feasible solutions tree in a non-decreasing idle time order. The procedure uses several well-known lower bounds, dominance rules and a new logical test based on the assimilation of the feasibility problem for a given cycle time and number of stations (SALBP-F) to a maximum-flow problem.     

Synthesis of Azabicyclic Building Blocks for Daphniphyllum Alkaloid Intermediates Featuring N‐Trichloroacetyl Enamide 5‐endo‐trig Radical Cyclizations

A general procedure is reported for the synthesis of cis ring fused azapolycyclic compounds bearing an all‐carbon quaternary stereocenter at the ring fusion and an adequate functionalization for the assembly of new rings leading to advanced synthetic intermediates for Daphniphyllum alkaloid synthesis. The key carbon?carbon bond‐forming step in this approach is a radical cyclization of an N‐cycloalkenyl trichloroacetamide derivative involving a tetrasubstituted enamide to achieve polyfunctionalized lactams.     

Scaffolds for Sustained Release of Ambroxol Hydrochloride,a Pharmacological Chaperone That Increases the Activity of Misfolded β‐Glucocerebrosidase

Ambroxol is a pharmacological chaperone (PC) for Gaucher disease that increases lysosomal activity of misfolded β‐glucocerebrosidase (GCase) while displaying a safe toxicological profile. In this work, different poly(ε‐caprolactone) (PCL)‐based systems are developed to regulate the sustained release of small polar drugs in physiological environments. For this purpose, ambroxol is selected as test case since the encapsulation and release of PCs using polymeric scaffolds have not been explored yet. More specifically, ambroxol is successfully loaded in electrospun PCL microfibers, which are subsequently coated with additional PCL layers using dip‐coating or spin‐coating. The time needed to achieve 80% release of loaded ambroxol increases from ≈15 min for uncoated fibrous scaffolds to 3 days and 1 week for dip‐coated and spin‐coated systems, respectively. Furthermore, it is proven that the released drug maintains its bioactivity, protecting GCase against induced thermal denaturation.