Synthesis and characterization of core–shell SiO2@(Er3+,Yb3+):Lu2O3

We synthesized crystalline Erbium Er³⁺ and Ytterbium Yb³⁺ codoped -Lu₂O₃ nanolayers on SiO₂ microspheres using the modified Pechini method. Two different kinds of precursors, nitrates and chlorides, have been used leading to a layer-to-layer morphology and necklaces structures, respectively. In both cases, the size of nanocrystallites constituting the optical active layer is around 5 nm. We performed X-ray powder diffraction to confirm the cubic crystalline structure of the sesquioxides layer. High resolution transmission electron microscopy analyses corroborate the crystalline nature of the layer. The optical emission of Er³⁺ in the visible range has been recorded.     

Bioinspired pressure actuated adhesive system

We developed a dry synthetic adhesive system inspired by gecko feet adhesion that can switch reversibly from adhesion to non-adhesion with applied pressure as external stimulus. Micropatterned polydimethylsiloxane (PDMS) surfaces with pillars of 30 μm length and 10 μm diameter were fabricated using photolithography and moulding. Adhesion properties were determined with a flat probe as a function of preload. For low and moderate applied compressive preloads, measured adhesion was 7.5 times greater than on flat controls whereas for high applied preloads adhesion dropped to very low values. In situ imaging shows that the increased preload caused the pillars to deform by bending and/or buckling and to lose their adhesive contact. The elasticity of PDMS aids the pillar recovery to the upright position upon removal of preload enabling repeatability of the switch.     

Effect of stereoregularity and solvent upon molecular motion and structure of stereoregular poly(methyl methacrylates) in solution. 13C and 1H n.m.r. relaxation study

Spin-lattice relaxation times T₁ of ¹³C and ¹H nuclei, as well as nuclear Overhauser enhancement (NOE) values of stereoregular poly(methyl methacrylates) (PMMA) in CD₃CN and CDCl₃ were measured. Analysis of these data has shown that the mobility of PMMA in solution is affected by stereoregularity of PMMA and by solvent. Comparison of ¹³C and ¹H n.m.r. relaxation data has further shown that the solvent affects also the local conformational structure of stereoregular PMMA in solution; this conclusion is supported by preliminary measurements of infra-red spectra. Based on this finding, the effect of solvent upon formation of the ordered structure of the so-called stereocomplex of PMMA is discussed.     

Transition behavior and phase segregation in TDI polyurethanes

Prior studies of two series of segmented polyurethanes based on 2, 4 toluene cliisocyanate (2, 4 TDI) or 2, 8 TDI, butanediol, and a 1000 molecular weight polytetramethyleneoxide (PTMO-1000) soft segment revealed a rapid increase in soft segment glass transition temperature (T_g) with increasing urethane content in the 2, 4 TDI series. The change in T_g couldbe correlated with estimates of hard segment-soft segment phase mixing obtained by infrared analysis of the urethane NH and carbonyl bands. In the present paper, the infrared data have been reevaluated using improved procedures for resolving the carbonyl band into H-bonded and nonbonded components, and the relation between the estimated extent of phase mixing and T_g has been reexamined. The transition behavior in an extensive series of related polymers has also been determined, including 2, 4 TDI arid 2, 6 TDI samples with PTMO2000 as well as polybutyleneadipate (PBA-1000 and PBA-2000) soft segments. The results indicate the effectiveness, of increased soft segment molecular weight in promoting phase segregation, imply that much greater phase mixing occurs in polyester than polyether samples, suggest that anchoring the ends of the soft segments has only a small effect on T_g, and provide some evidence that H-bonding not only increases T_g but can also impede soft segment crystallization.     

Reaktion von Acetophenonmonomethyl‐ und ‐dimethylhydrazonen mit dem Vilsmeier‐Reagenz; Bildung von Pyrazol‐4‐carbiminiumsalzen: ein Beitrag zum Mechanismus

Reactions of Acetophenonmonomethyl‐ and ‐dimethylhydrazones with the Vilsmeier‐Reagent; Formation of Pyrazol‐4‐carbiminium Salts: A Contribution to the Mechanism Kira discovered the formation of ( 4e ) N,N‐Dimethyl‐N‐[1,3‐diphenylpyrazol‐4‐ylmethylen]ammonium perchlorat by the reaction from acetophenonphenylhydrazone 1e with the Vilsmeier‐Reagent 2 . On the example of the Acetophenonmonomethylhydrazone 1a we represent the mechanism of this reaction. 1a reacts with the Vilsmeier‐Reagent 2 firstly to 3a (scheme 1). 3a is formylated in the secondary step by 2 on the methyl group of the acetophenon part followed of a ring conclusion to the pyrazol 4a containing a carbiminium group in position 4 as substituent. 3a doesN′t react to 6a directly. Hydrolysis of 4a gives 5a . We found moreover, that acetophenondimethylhydrazones 8 react with 2 to 4 , too (scheme 2, eq 2). But here the proton of the methylamino group in 1 is occupied by the methyl group in 8 . Therefore, the reaction starts in this case with an attack on the methyl group of the acetophenon part followed of the ringconclusion to the intermediate 6 accompanied of the eli‐mination of the methyl group. In the last step the not isolated pyrazol 6 is formylated by 2 in 4‐position to 4 . In a secondary reaction from 8 with 2 the compounds 9 are formed (scheme 2, eq. 3). 9 are intermediates in the reaction from 8 to 4 only in a small extent.     

Enzymatic esterification of glycerol III. Lipase-catalyzed synthesis of regioisomerically pure 1,3-sn-diacylglycerols and 1 (3)-rac-monoacylglycerols derived from unsaturated fatty acids

Lipases that display high regioselectivities and broad substrate tolerance were used as catalysts for the efficient esterification of glycerol under the conditions of irreversible acyl transfer. A variety of unsaturated fatty acids, such as oleic, linoleic, erucic, ricinolic, hydroxystearic and coriolic acid, were used for this purpose in the form of their vinyl esters. Suitable biocatalysts were chosen on the basis of systematic screening experiments regarding their regioselectivities (RE) and substrate tolerances. Distinct differences were found and expressed in numerical RE values as a measure for differences of these biocatalysts as being specific, selective, and nonspecific. Based on these experiments, a variety of molecules were synthesized on a preparative scale (>150 mmol) in good yield (ca.85%) and with high regioisomerical purities (>95% RE).     

Synthesis of 2-Substituted 2-Arylmalonates via Tricarbonylchromium Complexes

Tricarbonylchromium complexes 1 react with monosubstituted malonic acid esters 2 in DMSO at room temperature in the presence of KOtBu to give the complexes 3 . After oxidative demetalation, the appropriate aryl derivatives 4 are obtained in moderate to good overall yields. Diastereoselective arylations of chirally modified malonates such as 5a–c were studied. The stereoselectivity was highest for the products 6c/6c ′ (80:20) with (−)-8-phenylmenthol as alcohol component in the malonate 5 .     

New aspects of transversal1H-NMR relaxation in natural rubber vulcanizates

Summary Structure and dynamics of unfilled and carbon black filled natural rubber vulcanizates were investigated by means of transversal¹H-NMR-relaxation. A simple theoretical model including different motions in polymer network was extended by the discussion of an anisotropy parameter of segmental motion not only for the intercrosslink chains but also for the dangling ends. It makes characterization of the filling state of the network possible to approximate. The effect of increasing correlation times _f of the fast anisotropic local motion with reduction of the molecular mass of intercrosslink chains which was observed, but not cleared up in previous investigation is evidently smaller by using this modified model in accordance with the expectation of a local motion. The determined values of M_c are in good agreement with the results of fits by using the unmodified relaxation function.¹³C-NMR-spectra and stress-strain-experiments are leading in most cases to similar results, especially for M_c.