13C NMR spectroscopy of new amino protective groups

The ¹³C data of several new amino protecting groups of the urethane structure are reported. The speeds of acidolytic cleavage are correlated with the ¹³C parameters.     

Interactions intramoleculaires. XXI—Constantes de couplage et interactions gauches avec un groupement t-butyle (molécules cyclohexaniques deutériées)

Different isotopic modifications of deuterated products of 1-t-butlyl-4-methoxycarbonyl cyclohexene (d₄-3,3,6,6), cis- and trans-3-methyl-4-cyanocyclohexene (d₃-3,6,6), cis- and trans-3-methyl-4-cyanocyclohexene (d₃,6,6), cis- and trans-3-t-butyl-4-methoxycarbonylcyclohexene (d₃,-3,6,6) are shown by nuclear magnetic resonance spectral analysis. By comparison of ³J and ⁴J coupling constants of model molecules and molecules with large gauche interactions, we obtain proof that the latter are in a chair conformation with moderate cycle deformations.     

Quantification of Auger depth profiles by means of Rutherford backscattering spectrometry

Conclusion Due to their complementary character, AES and RBS can give a very rich set of information when they are combined for profiling thin films. The interpretation of data is easier and more accurate when a same simulated structure is fitted successively to the RBS and AES data.

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Quantifizierung von Auger-Tiefenprofilen mit Hilfe der Rutherford-Rückstreu-Spektrometrie

     

Double beta decay of <Superscript>150</Superscript>Nd to the First 0<Superscript>+</Superscript> excited state of <Superscript>150</Superscript>Sm

Two neutrino double beta decay of ¹⁵⁰Nd to the first 0⁺ excited state in ¹⁵⁰Sm is investigated with the 400 cm³ low-background HPGe detector. Data analysis for 11320.5 h shows the excess of events at 333.9 and 406.5 keV. This makes it possible to estimate the half-life of the investigated process as [1.4 _?0.2 ^+.04 (stat)±0.3(syst)]×10²⁰yr.     

<Emphasis Type="Bold">(Ba,Sr)TiO</Emphasis><Subscript>3</Subscript> thin films grown by pulsed laser deposition with low dielectric loss at microwave frequencies

We report a method for producing BST films with consistently high figures of merit for tunable microwave applications. (Ba_1-x,Sr_x)TiO₃ (x=0.4, target doped with 1% W) thin films have been deposited using pulsed laser deposition onto (100)MgO substrates. Films were deposited at low partial pressures of oxygen (50 mTorr) at a substrate temperature of 730 °C. An analysis of the X-ray diffraction data indicates that the film has a nearly cubic structure, with the overall lattice parameter enlarged relative to the bulk material due to the presence of oxygen vacancies. A post-deposition anneal of the film in flowing oxygen (1000 °C for 6 h) resulted in a decrease in the lattice parameter while remaining nearly cubic. An analysis of the microwave dielectric properties (1–20 GHz) showed that the annealed film exhibited about 10% tunability for an applied bias field of 67 kV/cm with a dielectric Q(1/tan)>600. Investigation of the films by time-resolved confocal scanning optical microscopy (CSOM) has revealed that there is an out-of-plane polarization at zero applied field (E_DC=0). The results show that the paraelectric response is relatively insensitive to applied field, while the ferroelectric response is correlated with the growth of in-plane nanodomains. We find these results to be consistent with a large number of studies that show that strain-relief is of paramount importance if ferroelectric films are to be developed as microwave circuit components. PACS 81.15.Fg; 85.50.-n     

Interlaboratory study of a liquid chromatography method for erythromycin: determination of uncertainty

Erythromycin is a mixture of macrolide antibiotics produced by Saccharopolyspora erythreas during fermentation. A new method for the analysis of erythromycin by liquid chromatography has previously been developed. It makes use of an Astec C18 polymeric column. After validation in one laboratory, the method was now validated in an interlaboratory study. Validation studies are commonly used to test the fitness of the analytical method prior to its use for routine quality testing. The data derived in the interlaboratory study can be used to make an uncertainty statement as well. The relationship between validation and uncertainty statement is not clear for many analysts and there is a need to show how the existing data, derived during validation, can be used in practice. Eight laboratories participated in this interlaboratory study. The set-up allowed the determination of the repeatability variance, s(2)r and the between-laboratory variance, s(2)L. Combination of s(2)r and s(2)L results in the reproducibility variance s(2)R. It has been shown how these data can be used in future by a single laboratory that wants to make an uncertainty statement concerning the same analysis.     

Bioactive peptides grafted silicone dressings: A simple and specific method

The need for bioactive dressings increases with the population aging and the prevalence of chronic diseases. In contrast, there are very few dressings on the market which are designed to display a chosen bioactivity. In this context, we investigated the surface-functionalization of silicone wound dressing with bioactive peptides. One of the challenges was to avoid multistep grafting reactions involving catalysts, solvents or toxic reagents, which are not suitable for the fabrication of medical devices at an industrial scale. In the other hand, a covalent bonding was necessary to avoid the loss of the biological effect by progressive removal of the peptide in biological fluids generated by the wound. To solve these limitations, we developed a strategy allowing an easy and direct functionalization of silicone. This strategy relies on hybrid silylated bioactive peptides, which chemoselectively react with plasma-activated silicone surfaces. We synthesized three hybrid peptides with wound healing properties, which were grafted on commercially available silicone dressings Cerederm^® and Mepitel^®. Grafted dressings were evaluated in vitro and enabled a quicker scare recovery and extracellular matrix deposition with human dermal fibroblasts. These results were confirmed by in vivo studies showing an enhanced wound-healing of the pig skin. By this simple method, we transformed inert dressing into bioactive dressing which showed properties of wound healing.     

Selective Coordination of Gallium(III), Zinc(II), and Copper(II) by an Asymmetric Dinucleating Ligand: A Model for Metallophosphatases

Complexation studies of the dinucleating ligand H₃L (H₃L=2‐{[bis(pyridin‐2‐ylmethyl)amino]methyl}‐6‐{[bis(6‐pivaloylamidopyridin‐2‐ylmethyl)amino]methyl}‐4‐methylphenol), with metal‐binding sites A and B, which both provide four donors to a metal ion; a tertiary amine; two pyridines (substituted with amide hydrogen‐bond donors in site B), and a bridging phenolate, with Zn^II, Cu^II, and Ga^III are reported. The titration of H₃L with the three metal ions in solution was monitored by NMR spectroscopy or EPR and UV/Vis/near‐IR spectroscopy, as well as by ESI‐MS to analyze the selectivity of the two metal‐ion sites A and B of this model ligand for metallophosphatases; the spectroscopic assignments are supported by X‐ray crystallography results. The first Zn^II ion coordinates to site A with unsubstituted pyridine donors and, upon addition of a second equivalent of Zn^II, this coordinates to the sterically less accessible site B. From a similar titration with Ga^III, it emerges that only a mononuclear complex is obtained, with the Ga^III center coordinated to site A. When one equivalent of Ga^III is reacted with the mononuclear Zn^II complex, Zn^II is forced by Ga^III to exchange the site; this results in a dinuclear complex with Ga^III in site A and Zn^II in site B. With Cu^II, two isomers are observed: one with and the other without a bridging phenolate; these differ significantly in their spectroscopic and magnetic properties.     

Azaphilic versus Carbophilic Coupling at CN Bonds: Key Steps in Titanium‐Assisted Multicomponent Reactions

Consecutive C‐ and N‐arylation of N‐heterocyclic nitriles is mediated by titanium(IV) alkoxides. The carbo‐ and azaphilic arylation step may be separated by choosing the order in which the two equivalents of aryl transfer reagent are added. In the course of this transformation, the ancillary N‐heterocycle acts as both a directing anchor group and electron reservoir. In the selectivity‐determining step, the selectivity is governed by a choice between (direct) C‐ and Ti‐arylation; the latter opens up a reaction pathway that allows further migration to the nitrogen atom. The isolation of metal‐containing aggregates from the reaction mixture and computational studies gave insights into the reaction mechanism. Subsequently, a multicomponent one‐pot protocol was devised to rapidly access complex quaternary carbon centers.