Gold Nanoparticles as Effective ion Traps in Poly(dimethylsiloxane) Cross-Linked by Metal-Ligand Coordination

At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl₂-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl⁻ counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl⁻ counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems.     

Applicability of medium-size basis sets in calculations of molecular dynamic polarisabilities

Static and dynamic average polarisabilities and polarisability anisotropies of seven linear non-polar and polar molecules are calculated within the CCS, CC2, and CC3 approximations using a range of medium-sized basis sets: the polarised LPol-n (n = ds, dl, fs, fl), the aug-pc-n (n = 1, 2), the def2-SVPD, and -TZVPD basis sets. Reference values are obtained using a hierarchy of Dunning's (d-)aug-cc-pVXZ (X = D, T, Q, 5) basis sets. The results are discussed together with the available CCSD values in terms of basis set and correlation method errors, and their ratio. Detailed analysis shows that already the def2-SVPD basis set can be used in CCS polarisability calculations. When affordable, the slightly larger aug-pc-1 basis set is recommended, as it leads to significant reduction of basis set error. The def2-TZVPD, LPol-ds, and aug-pc-2 basis sets are optimal choice within the CC2 approximation, with the latter allowing to approach the CC2 basis set limit. The LPol-ds, -dl, and def2-TZVPD sets outperform the aug-cc-pVTZ set in average polarisability CCSD calculations, with the def2-TZVPD being competitive to other reduced-size sets also in determination of polarisability anisotropy. The aug-pc-2 basis is a particularly attractive choice for CCSD, giving the accuracy of aug-cc-pVQZ at a significantly reduced computational cost. The polarisability anisotropy is shown to be more computationally demanding than the average polarisability, in particular with respect to the accuracy of the correlation method and an accurate evaluation of this property requires at least the CCSD model.     

Bestimmung von T-2-Toxin in pflanzlichen Nahrungsmitteln

Zusammenfassung Ein Verfahren zur quantitativen Bestimmung von T-2-Toxin in verschimmeltem Reis bzw. Mais durch Extraktion, dünnschicht-chromatographische Trennung und Fluorescenzintensitätsmessung der mit H₂SO₄ behandelten DC-Platte wird vorgestellt. Fluorescenzabsorptions- und Fluorescenzemissionsspektrum werden angegeben. Die Abhängigkeit der Mycotoxinkonzentration von der Fluorescenzintensität wird durch eine Gleichung beschrieben. Die analytische Detektion von T-2-Toxin läßt sich durch ein 4-(p-Nitrobenzyl)pyridin-Derivat und dessen Absorptionsspektrum bestätigen. Versuche mit zugesetztem T-2-Toxin zeigten einen Analysenfehler von weniger als 10%.

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Determination of T-2-toxin in vegetable foodstuffs1. T-2-toxin in mouldy rice and maize

Summary A procedure is described for the determination of T-2 toxin in extracts from mouldy rice and maize by thin-layer chromatography (TLC) and subsequent fluorescence intensity measurement of the H₂SO₄-treated TLC plates. The fluorescence absorption and emission spectra are presented. The dependence of the concentration of the mycotoxin on fluorescence intensity is described by an equation. The detection of T-2 toxin can be confirmed by colour reaction with 4-(p-nitrobenzyl)pyridine yielding a blue derivative. Experiments with added toxin revealed an analytical error smaller than 10%.

     

Generation of quaternary stereocenters by asymmetric Michael reactions: enamine regiochemistry as configuration switch

Regioselective enamine formation from cyclic β‐diketones 1 is obtained by the appropriate choice of activating agent: Brønsted acid catalyzed condensation gives endocyclic enamines 3 as the thermodynamically favored products. Activation with Lewis acid BF₃ ? OEt₂ affords betaines 8 as intermediate products, which can be reacted with L ‐valine diethylamide ( 2 ) to preferentially furnish exocyclic enamines 4 as kinetic products. Derivatives with quaternary stereocenters were accessible from both isomeric enamines by using asymmetric, copper(II )‐catalyzed Michael reactions at ambient temperature. Both regioisomers afford the triketones 7 with the same constitution but bearing the opposite absolute configuration at the quaternary stereocenter. Thus, both enantiomers of the product are prepared by using the same chiral auxiliary derived from L ‐valine.     

Killing three birds with one stone--simultaneous operando EPR/UV-vis/Raman spectroscopy for monitoring catalytic reactions

For the first time, three operando methods, namely EPR, UV-vis and laser-Raman spectroscopy have been applied in parallel on the same V/TiO2 catalyst and under identical reaction conditions during oxidative dehydrogenation of propane to elucidate structure-reactivity relationships in status operandi.