Asymmetric modular synthesis of highly functionalized medium-sized carbocycles and lactones via ring-closing metathesis of sulfoximine-substituted trienes

A modular asymmetric synthesis of medium-sized carbocycles and lactones has been developed that affords highly substituted 7-, 9-, and 11-membered rings. The key steps are (1) the highly diastereoselective synthesis of sulfoximine-substituted homoallylic alcohols from allylic sulfoximines and unsaturated as well as saturated aldehydes, (2) an E-stereoselective alkylation and hydroxyalkylation of sulfoximine-substituted alkenyllithium derivatives, (3) the esterification of sulfoximine-substituted homoallylic alcohols, and (4) the ring-closing metathesis reaction of sulfoximine-substituted trienes with the ruthenium catalyst 8. Two examples for the further synthetic elaboration of the sulfoximine-substituted carbocycles are provided. The selective cleavage of the tert-butyldimethylsilyl group of 12 in the presence of the triethylsilyl group afforded the allylic alcohol 18 which was oxidized to enone 19. A cross-coupling reaction of the sulfoximine-substituted carbocycle 9 with LiCuMe2 furnished the methyl-substituted derivative 20.     

What is the smallest possible constant in Céa’s lemma?

We consider finite element approximations of a second order elliptic problem on a bounded polytopic domain in ℝ^d with d ∈ {1, 2, 3, ...} The constant C ⩾ 1 appearing in Céa’s lemma and coming from its standard proof can be very large when the coefficients of an elliptic operator attain considerably different values. We restrict ourselves to regular families of uniform partitions and linear simplicial elements. Using a lower bound of the interpolation error and the supercloseness between the finite element solution and the Lagrange interpolant of the exact solution, we show that the ratio between discretization and interpolation errors is equal to as the discretization parameter h tends to zero. Numerical results in one and two-dimensional case illustrating this phenomenon are presented. This research was supported by Shandong Province Young Scientists Foundation of China 2005BS01008, Institutional Research Plan AV02 101 90503, and by Grant No A 1019201 of the Academy of Sciences of the Czech Republic.     

In vivo monitoring the changes of interstitial pH and FAD/NADH ratio by fluorescence spectroscopy in healing skin wounds

The aim of our study was to evaluate the changes of interstitial pH and flavin adenine dinucleotide (FAD)/reduced nicotinamide adenine dinucleotide (NADH) ratio in healing skin wounds using fluorescence spectroscopy in Sprague Dawley rats. In the experiment, excisional and incisional models of wound healing were used. The florescein as the pH-sensitive probe using excitation spectra (lambda(Em) = 535 nm) was used for the measurement of pH changes, and synchronous fluorescence spectra (Deltalambda = 60 nm) for the monitoring of FAD/NADH ratio changes were measured from the surfaces of healing wounds. Increase of interstitial pH and FAD/NADH ratio was recorded during the time interval from the 15th to the 65th minute after surgery. The decrease of pH between the 48th and the 72nd hour after surgery as well as the increase of FAD/NADH ratio between the 72nd and the 96th hour of wound healing were recorded. The results indicate that the use of fluorescence spectroscopy may be considered as a valuable tool for noninvasive in vivo monitoring of selected redox parameters in the early phases of wound healing.     

Linearized forward and inverse problems of the resonant ultrasound spectroscopy for the evaluation of thin surface layers

In this paper, linearized approximations of both the forward and the inverse problems of resonant ultrasound spectroscopy for the determination of mechanical properties of thin surface layers are presented. The linear relations between the frequency shifts induced by the deposition of the layer and the in-plane elastic coefficients of the layer are derived and inverted, the applicability range of the obtained linear model is discussed by a comparison with nonlinear models and finite element method (FEM), and an algorithm for the estimation of experimental errors in the inversely determined elastic coefficients is described. In the final part of the paper, the linearized inverse procedure is applied to evaluate elastic coefficients of a 310 nm thick diamond-like carbon layer deposited on a silicon substrate.     

Controlling the frequency of the frequency-shifted feedback fiber laser using injection-seeding technique

In this paper we describe the stabilization of the optical frequency comb (OFC) generated by the frequency-shifted feedback (FSF) erbium fiber laser. Frequency of the comb is controlled using the distributed feedback laser diode seeded into the cavity of the FSF laser. When the DFB diode is stabilized to the molecular absorption line of hydrogen cyanide frequency stabilized OFC is obtained.     

An Improved Rapid Mixing Device for Time-Resolved Electrospray Mass Spectrometry Measurements

Time series data can provide valuable insight into the complexity of biological reactions. Such information can be obtained by mass-spectrometry-based approaches that measure pre-steady-state kinetics. These methods are based on a mixing device that rapidly mixes the reactants prior to the on-line mass measurement of the transient intermediate steps. Here, we describe an improved continuous-flow mixing apparatus for real-time electrospray mass spectrometry measurements. Our setup was designed to minimize metal–solution interfaces and provide a sheath flow of nitrogen gas for generating stable and continuous spray that consequently enhances the signal-to-noise ratio. Moreover, the device was planned to enable easy mounting onto a mass spectrometer replacing the commercial electrospray ionization source. We demonstrate the performance of our apparatus by monitoring the unfolding reaction of cytochrome C, yielding improved signal-to-noise ratio and reduced experimental repeat errors.     

Numerical Approximation of a Reaction-Diffusion System with Fast Reversible Reaction

The authors consider the finite volume approximation of a reaction-diffusion system with fast reversible reaction.It is deduced from a priori estimates that the approximate solution converges to the weak solution of the reaction-diffusion problem and satisfies estimates which do not depend on the kinetic rate.It follows that the solution converges to the solution of a nonlinear diffusion problem,as the size of the volume elements and the time steps converge to zero while the kinetic rate tends to infinity.     

Absorption bleaching by stimulated emission in erbium-doped silicon-rich silicon nitride waveguides

Stimulated emission from sensitized erbium ions in silicon-rich silicon nitride is demonstrated by pump-probe measurements carried out in waveguides. A decrease in the photoinduced absorption of the probe at the wavelength of erbium emission is observed and is attributed to stimulated emission from erbium excited indirectly via localized states in the silicon nitride matrix.     

Heteroaggregation in binary mixtures of oppositely charged colloidal particles

Heteroaggregation (or heterocoagulation) rate constants have been measured in mixtures of well-characterized colloidal particles of opposite charge with multiangle static and dynamic light scattering. This technique permits routine measurements of absolute heteroaggregation rate constants, also in the presence of homoaggregation. Particularly with multiangle dynamic light scattering, one is able to estimate absolute heteroaggregation rate constants accurately in the fast aggregation regime for the first time. Heteroaggregation rate constants have also been measured over a wide range of parameters, for example, ionic strength and different surface charge densities. Amidine latex particles, sulfate latex particles, and silica particles have been used for these experiments, and they were well characterized with respect to their charging and homoaggregation behavior. It was shown that heteroaggregation rate constants of oppositely charged particles increase slowly with decreasing ionic strength, and provided the surface charge is sufficiently large, the rate constant is largely independent of the surface charge. These trends can be well described with DLVO theory without adjustable parameters.