3D‐morphology reconstruction of nanoscale phase‐separation in polymer memory blends

In many organic electronic devices functionality is achieved by blending two or more materials, typically polymers or molecules, with distinctly different optical or electrical properties in a single film. The local scale morphology of such blends is vital for the device performance. Here, a simple approach to study the full 3D morphology of phase‐separated blends, taking advantage of the possibility to selectively dissolve the different components is introduced. This method is applied in combination with AFM to investigate a blend of a semiconducting and ferroelectric polymer typically used as active layer in organic ferroelectric resistive switches. It is found that the blend consists of a ferroelectric matrix with three types of embedded semiconductor domains and a thin wetting layer at the bottom electrode. Statistical analysis of the obtained images excludes the presence of a fourth type of domains. The criteria for the applicability of the presented technique are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1231–1237     

PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

Three New Polyoxygenated Steroids from Two Species of the South China Sea Gorgonian Muricella flexuosa and Menella verrucosa Brundin

Three new polyoxygenated steroids, muricesteroid ( 1 ), and menellsteroids A ( 2 ) and B ( 3 ), were isolated from two species of the South China Sea gorgonian Muricella flexuosa and Menella verrucosa Brundin , respectively. The structures of these new compounds were elucidated on the basis of extensive spectroscopic analysis, chemical methods and comparison with known related compounds.     

Characterization and Computation of Canonical Tight Windows for Gabor Frames

Let (\gnm)_{n,m ? \Zst}(\gnm)_{n,m\in\Zst} be a Gabor frame for \LtR\LtR for given window gg. We show that the window \ho = \SQI g\ho=\SQI g that generates the canonically associated tight Gabor frame minimizes ||g-h||\|g-h\| among all windows hh generating a normalized tight Gabor frame. We present and prove versions of this result in the time domain, the frequency domain, the time-frequency domain, and the Zak transform domain, where in each domain the canonical \ho\ho is expressed using functional calculus for Gabor frame operators. Furthermore, we derive a Wiener--Levy type theorem for rationally oversampled Gabor frames. Finally, a Newton-type method for a fast numerical calculation of \ho\ho is presented. We analyze the convergence behavior of this method and demonstrate the efficiency of the proposed algorithm by some numerical examples.     

Anomale änderungen physikalischer Eigenschaften beim heterogenen Zerfall übersättigter Fe-Ni-Cu-Legierungen

Zusammenfassung Einige charakteristische ?nderungen physikalischer Werkstoffeigenschaften beim heterogenen Zerfall übers?ttigter Mischkristalle werden am Beispiel der fl?chenzentrierten Eisen-Nickel-Kupfer-Legierungen beschrieben. Bei der Behandlung des Einflusses der Ausscheidungsvorg?nge auf die Rekristallisationserscheinungen tritt die Bedeutung des übers?ttigungsgrades der zerfallenden festen L?sung für den Ablauf dieser Zustands?nderungen besonders klar zutage. Kritische Stadien der Ausscheidung und der Koagulation der heterogenen Phasen sind bei diesen Legierungen für die Erzeugung besonders hochwertiger magnetischer Eigenschaften verantwortlich. Der vorliegende Bericht wurde von Herrn Prof., Dr. Wo. Ostwald angeregt. Für das diesem Arbeitsgebiet entgegengebrachte Interesse m?chte ich Herrn Prof. Ostwald meinen besten Dank aussprechen.     

Radiochemical proton activation analysis for the determination of cadmium and lead in sediment reference materials

Proton activation analysis was used for the determination of cadmium and lead in three sediment reference materials. The method is based on the^111,112Cd(p, xn)¹¹¹ In and the^206,207,208Pb(p, xn)²⁰⁶Bi reactions.¹¹¹In and²⁰⁶Bi were chemically separated by anion exchange. The results obtained were taken into account for the certification of the materials and are in the excellent agreement with the certified values.     

Modulation of the distance dependence of paramagnetic relaxation enhancements by CSA × DSA cross-correlation

Paramagnetic metal ions with fast-relaxing electronic spin and anisotropic susceptibility tensor provide a rich source of structural information that can be derived from pseudo-contact shifts, residual dipolar couplings, dipole-dipole Curie spin cross-correlation, and paramagnetic relaxation enhancements. The present study draws attention to a cross-correlation effect between nuclear relaxation due to anisotropic chemical shielding (CSA) and due to the anisotropic dipolar shielding (DSA) caused by the electronic Curie spin. This CSA x DSA cross-correlation contribution seems to have been overlooked in previous interpretations of paramagnetic relaxation enhancements. It is shown to be sufficiently large to compromise the 1/r6 distance dependence usually assumed. The effect cannot experimentally be separated from auto-correlated DSA relaxation. It can increase or decrease the observed paramagnetic relaxation enhancement. Under certain conditions, the effect can dominate the entire paramagnetic relaxation, resulting in nuclear resonances narrower than in the absence of the paramagnetic center. CSAxDSA cross-correlation becomes important when paramagnetic relaxation is predominantly due to the Curie rather than the Solomon mechanism. Therefore the effect is most pronounced for relaxation by metal ions with large magnetic susceptibility and fast-relaxing electron spin. It most strongly affects paramagnetic enhancements of transverse relaxation in macromolecules and of longitudinal relaxation in small molecules.