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     

Light and heat control over secondary structure and amyloid-like fiber formation in an overcrowded-alkene-modified Trp zipper

The external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide. This photoresponsive unit undergoes a large conformational change and has two thermally stable isomers which has major influence on the secondary structure and the aggregation of the peptide, permitting the phototriggered formation of amyloid-like fibrils.     

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.     

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.     

The rational design of modified Cinchona alkaloid catalysts. Application to a new asymmetric synthesis of chiral chromanes

A new asymmetric synthesis of 2-substituted chiral chromanes has been achieved. The key step is the intramolecular conjugate addition of a phenolic nucleophile on a α,β-unsaturated ester catalyzed by Cinchona alkaloids. The high ee’s obtained with cinchonine and its derivatives have been rationalized by ab initio quantum chemistry calculations of transition state structures.     

On Producing Multiple Solutions Using Repeated Trials

The number of trials that is required by an algorithm to produce a given fraction of the problem solutions with a specified level of confidence is analyzed. The analysis indicates that the number of trials required to find a large fraction of the solutions rapidly decreases as the number of solutions obtained on each trial by an algorithm increases. In applications where multiple solutions are sought, this decrease in the number of trials could potentially offset the additional computational cost of algorithms that produce multiple solutions on a single trial. The analysis framework presented is used to compare the efficiency of a homotopy algorithm to that of a Newton method by measuring both the number of trials and the number of calculations required to obtain a specified fraction of the solutions.     

Lasing of iodine in the fullerene-oxygen-iodine system

The possibility of lasing in the fullerene-oxygen-iodine system with optical excitation of fullerene is studied. Laser radiation with an energy of 25 mJ and a pulse duration of 5–10 ms is obtained.     

Choquet-type Integral Representation of Invariant Functions for some Product Semigroups

We show that functions which are invariant for suitable product semigroups (one of which is a quasi-Poisson semigroup on a general state space) decompose into a singular eigen-function and a mixture of products of minimal eigen-functions.     

Fir laser stabilization using stark effect: Data on CH3Br and CH3Cl

Data on the influence of the Stark Effect on an optically pumped FIR laser with CH₃Cl or CH₃Br as active medium are given for various wavelengths. A very simple method for an effective FIR power stabilisation based on the Stark Effect is described. Its working is illustrated with the EPR signal of a 10% diluted DAG sphere.     

The valuations of the near hexagons related to the Witt designs S(5,6,12) and S(5,8,24)

Valuations of dense near polygons were introduced in 16 . In the present paper, we classify all valuations of the near hexagons ??₁ and ??₂, which are related to the respective Witt designs S(5,6,12) and S(5,8,24). Using these classifications, we prove that if a dense near polygon S contains a hex H isomorphic to ??₁ or ??₂, then H is classical in S. We will use this result to determine all dense near octagons that contain a hex isomorphic to ??₁ or ??₂. As a by‐product, we obtain a purely geometrical proof for the nonexistence of regular near 2d‐gons, d ≥ 4, whose parameters s, t, t_i (0 ≤ i ≤ d) satisfy (s, t₂, t₃) = (2, 1, 11) or (2, 2, 14). The nonexistence of these regular near polygons can also be shown with the aid of eigenvalue techniques. © 2005 Wiley Periodicals, Inc. J Combin Designs 14: 214–228, 2006