Rate Enhancement of the Radical 1,2-Acyloxy Shift (Surzur–Tanner Rearrangement) by Complexation with Lewis Acids

New prospects for synthetic applications are offered by the 1,2-acyloxy shift of β-(acyloxy)alkyl radicals, which proceeds with high yields under Lewis acidic conditions [Eq. (1)]. With the exception of cyclizations, this is the first Lewis acid mediated acceleration of a radical rearrangement.     

Dynamic acoustoelastic testing of weakly pre-loaded unconsolidated water-saturated glass beads

Dynamic acoustoelastic testing is applied to weakly pre-loaded unconsolidated water-saturated glass beads. The gravitational acceleration produces, on the probed beads, a static stress of order 130 Pa, thus the granular medium is close to the jamming transition. A low-frequency (LF) acoustic wave gently disturbs the medium, inducing successively slight expansion and compaction of the granular packing expected to modulate the number of contacts between beads. Ultrasound (US) pulses are emitted simultaneously to dynamically detect the induced modification of the granular skeleton. US propagation velocity and attenuation both increase when the LF pressure increases. The quadratic nonlinear elastic parameter β, related to the pressure dependence of US propagation velocity, was measured in the range 60-530 if water-saturated glass beads are considered as an effective medium. A dynamic modification of US scattering induced by beads is proposed to modulate US attenuation. Complex hysteretic behaviors and tension-compression asymmetry are also observed and analyzed by time-domain and spectral analyses. Furthermore acoustic nonlinearities are measured in cases of quasi-static and dynamic variations of the LF wave amplitude, providing quantitatively similar acoustic nonlinearities but qualitatively different.     

Experimental evidence of simultaneous multi-resonance noise reduction using an absorber with essential nonlinearity under two excitation frequencies

The addition of an essentially nonlinear membrane absorber to a linear vibroacoustic system with multiple resonances is studied experimentally, using quasiperiodic excitation. An extended experimental dataset of the system response is analyzed under steady-state excitation at two frequencies. Thresholds between low and high damping states within the system and associated noise reduction are observed and quantified thanks to frequency conversion and RMS efficiency indicators. Following previous numerical results, it is shown that the membrane NES (Nonlinear Energy Sink) acts simultaneously and efficiently on two acoustic resonances. In all cases, the introduction of energy at a second excitation frequency appears favorable to lower the frequency conversion threshold and to lower the noise within the system. In particular, a simultaneous control of two one-to-one resonances by the NES is observed. Exploration of energy conversion in the two excitation amplitudes plane advocates for a linear dependence of the frequency conversion thresholds on the two excitation amplitudes.     

Effectiveness of multilayer viscoelastic insulators to prevent occurrences of brake squeal: A numerical study

The purpose of this publication is to give an overview of the actual role of multi-layered viscoelastic parts, so called “shims”, to prevent squeal noises of automotive brake systems. Since shear stress is usually used to damp thin structures in their bending modes it is commonly believed to be the largest underwent by shims. To check this assumption and considering that stresses underwent by shims cannot be measured experimentally, the authors have computed them with the help of a detailed and realistic finite element model. Contrary to what shims manufacturers say, this study exhibits the fact that shims are almost uniquely solicited in their normal direction in brake systems. Secondly, the study focuses on the added damping and stiffening induced by the viscoelastic materials. In order to take into account these materials, a realistic frequency dependent viscoelastic behavior has been integrated in the simulations. Finally, the study shows certains eigenmodes for which the viscoelastic behavior of the shims reveals instabilities that would not exist without it. It is shown that this is due to coalescence phenomenon.     

Polyimide-based microfluidic devices

This paper describes the development of polyimide-based microfluidic devices. A layer transfer and lamination technique is used to fabricate flexible microfluidic channels in various shapes and with a wide range of dimensions. High bond strengths can be achieved by cure cycle adaptation and surface treatment of the polyimide layers prior to bonding. The polyimide microchannels can be combined with metallization layers to fabricate electrodes inside and outside channels. The resulting devices can be used for flexible fluidic and electrical connectors, implantable fluid delivery devices, microelectrodes with embedded fluidic channels, chip-based flow cytometry and for a great variety of other applications in medical, chemical or biological research.     

Highly stereoselective radical cyclization of haloacetals controlled by the acetal center

A systematic investigation of radical haloacetal cyclizations (Ueno-Stork reaction) where the acetal center is the unique stereogenic element is reported. This highly diastereoselective reaction can be used for the preparation of polysubstituted tetrahydrofurans and gamma-lactones. We report herein the full experimental details of reactions where up to three new chiral centers are created. To demonstrate the potential of this approach, short syntheses of (+)-eldanolide and of tricyclic acetals related to biologically active lignans have been achieved.     

Simulation of electron spin resonance spectra by fast fourier transform: A Novel Method of Calculating Spectra to Include Isotopic Substitution,Superhyperfine Coupling,Instrument Time Constant and Modulation Broadening in

A computer program is described for the rapid calculation of solution and polycrystalline electron spin resonance spectra of systems containing one unpaired electron. The calculation time is virtually independent of the number of e.s.r. transitions considered, e.g., morphamquat radical cation (3025 lines) requires 4.5 s. Second-order corrections and line-width anisotropy can be included in the simulation. The graphical output may be matched to the output of any e.s.r. spectrometer. Instrumental parameters, e.g. modulation amplitude and time constant, are accounted for in the calculation of the simulated spectrum which enables exact comparison between experimental and simulated spectra. To accommodate mixtures of paramagnetic species, a spectrum addition facility is provided; the output may be presented as an absorption or as any derivative. Spectra originating from isotopically substituted molecules may be calculated routinely and quickly, without the necessity for prior calculation of the relative contributions of the various combinations of isotopic nuclei.Several examples are given, illustrating the usefulness of this program in extracting spectral information under most experimental conditions.     

Self-assembly of highly luminescent lanthanide complexes promoted by pyridine-tetrazolate ligands

Two tridentate pyridine-tetrazolate ligands (H(2)pytz and H(2)pytzc), analogues of the well-known dipicolinate (H(2)dpa) ligand, have been synthesized in a straightforward manner and used for lanthanide(III) coordination. The structures of the resulting tris-ligand complexes were determined in solution ((1)H-NMR), where they remain undissociated, as well as in the solid state (X-ray diffraction). The solubility of these anionic complexes can be easily tuned by changing the countercation. The bis-tetrazolate-pyridine ligand H(2)pytz sensitizes very efficiently both the visible and near-IR emission of the lanthanides, with unusually high luminescence quantum yields in solid state (61% and 65% for Eu and Tb, respectively, and 0.21% for Nd) and in water (63% for Tb and 18% for Eu). Furthermore, the absorption window of the complexes is significantly extended towards the visible region up to 330 nm. The results show that the bis-tetrazolate-pyridine ligand provides a very attractive alternative to the classic dipicolinate ligand.