Self-adaptive inexact proximal point methods

We propose a class of self-adaptive proximal point methods suitable for degenerate optimization problems where multiple minimizers may exist, or where the Hessian may be singular at a local minimizer. If the proximal regularization parameter has the form where η∈[0,2) and β>0 is a constant, we obtain convergence to the set of minimizers that is linear for η=0 and β sufficiently small, superlinear for η∈(0,1), and at least quadratic for η∈[1,2). Two different acceptance criteria for an approximate solution to the proximal problem are analyzed. These criteria are expressed in terms of the gradient of the proximal function, the gradient of the original function, and the iteration difference. With either acceptance criterion, the convergence results are analogous to those of the exact iterates. Preliminary numerical results are presented using some ill-conditioned CUTE test problems. This material is based upon work supported by the National Science Foundation under Grant Nos. 0203270, 0619080, and 0620286.     

Dependence of enantioselectivity on the ligand/metal ratio in the asymmetric Michael addition of indole to benzylidene malonates: electronic influence of substrates

Simple bis(oxazoline) ligands, especially azabis(oxazolines), can promote the copper(II)-catalyzed Michael addition of indoles to benzylidene malonates with up to >99 % ee (ee=enantiomeric excess), provided that the ligand/metal ratio is tuned meticulously with particular regard to the electronic properties of the substrate. Despite a common paradigm followed in many asymmetric catalyses, an excess of chiral ligand is not always beneficial. In fact any excess of ligand has to be avoided to reach excellent enantioselectivities when electron-rich benzylidene malonates are used. On the contrary, malonates carrying an electron-withdrawing group require an excess of ligand for an optimum ee value. A correlation of optical yields versus the sigma(I) values of several para substituents shows a sigmoid trajectory. In the presence of an additive, such as triflate, the significance of the ligand/metal ratio vanishes and very good enantioselectivities are achieved at any rate--no matter whether electron-donating or withdrawing substituents are present.     

Frequency tunable single-line pulsed first-overtone carbon monoxide laser

Tunable single-line first-overtone (FO) CO lasing on wavelengths from 2.7 up to 4.2 μm corresponding to overtone vibrational transitions from 13→11 up to 38→36 on 413 ro-vibrational lines was experimentally obtained. A parametric study of energetic and spectral characteristics of the single-line FO CO laser was carried out. Energy distribution over ro-vibrational lines was measured. The maximum specific output energy (SOE) came up to 3 J/l Amagat, with single-line output efficiency being up to 0.6%. For the first time, a multi-quantum theoretical model was used to describe the tunable single-line FO CO laser. This multi-quantum approach demonstrated better agreement between theoretical calculations and observed experimental data for laser output as a function of vibrational quantum numbers.     

Poly[N‐(10‐oxo‐2‐vinylanthracen‐9(10H)‐ylidene)cyanamide] as a novel cathode material for li‐organic batteries

Redox‐active polymers draw significant attention as active material in secondary batteries during the last decade. A new anthraquinone‐based redox‐active monomer was designed, which electrochemical behavior was tailored by mono‐modification of one keto group. The monomer exhibits two one‐electron redox reactions and has a low molar mass, resulting in a high theoretical capacity of 207 mAh/g. The polymerization of the monomer was optimized by variation of solvent and initiator. Moreover, the electrochemical behavior was studied using cyclic voltammetry and the polymer was used as active material in a composite electrode in lithium organic batteries. The polymer reveals a cell potential of 2.3 V and a promising capacity of 137 mAh/g. During the first 100 cycles, the capacity drops to 85% of the initial value. The influence of the charging speed on the charging/discharging properties of the batteries was further investigated. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2517–2523     

Synthesis and physical properties of highly branched perfluorinated polymers from AB and AB2 monomers

Highly branched perfluorinated aromatic polyether copolymers were prepared from the polycondensation of the AB₂ monomer, 3,5‐bis[(pentafluorobenzyl)oxy]benzyl alcohol with a variety of fluoroaryl and alkyl bromide AB comonomers. The structures and comonomer distribution of the resulting polymers were characterized in detail. ¹H NMR data from kinetic trials illustrated that perfluoroaryl AB comonomer distribution correlated to AB comonomer sterics. ¹⁹F NMR data revealed that fluorinated AB monomers and 3‐bromo‐1‐propanol AB monomers were distributed within the AB₂ polymer backbone, while longer alkyl bromide AB monomers, 6‐bromo‐1‐hexanol, were mostly distributed along hyperbranched polymer chain ends. In general, as AB comonomer incorporation increased for nonsterically hindered copolymers, thermal decomposition onset increased and glass transition temperatures decreased. The combined data demonstrated the effect of comonomer distribution and sterics on physical properties of AB₂‐based polymer systems. The resulting materials were used to cast thin polymer films for measurement of contact angle, which were shown to be directly related to comonomer content. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1880–1894     

Untersuchung von Fetten und Oelen

Ohne Zusammenfassung     

A theorem and a question about epicomplete archimedean lattice-ordered groups

An archimedean ?-group is called epicomplete (or universally σ-complete, or sequentially inextensible) if it is divisible, σ-complete and laterally σ-complete. Various characterizations of such G are known in case the G have weak order units. The “theorem” of the title is a characterization of such G which have no weak order unit; it involves the requirement that G have a certain kind of representation. The “question” of the title is whether every epicomplete G has such a representation.     

C. fumago chloroperoxidase is also a dehaloperoxidase: oxidative dehalogenation of halophenols

We have examined the H2O2-dependent oxidative dehalogenation of 2,4,6-trihalophenols and p-halophenols catalyzed by Caldariomyces fumago chloroperoxidase (CCPO). CCPO is significantly more robust than other peroxidases and can function under harsher reaction conditions, and so its ability to dehalogenate halophenols could lead to its use as a bioremediation catalyst for aromatic dehalogenation reactions. Optimal catalysis occurred under acidic conditions (100 mM potassium phosphate solution, pH 3.0). UV-visible absorption spectroscopy, high-performance liquid chromatography, and gas chromatography/mass spectrometry clearly identified the oxidized reaction product for CCPO-catalyzed dehalogenation of 2,4,6-trihalophenols as the corresponding 2,6-dihalo-1,4-benzoquinones. This reaction has previously been reported for two His-ligated heme-containing peroxidases (see Osborne, R. L.; Taylor, L. O.; Han, K. P.; Ely, B.; Dawson, J. H. Biochem. Biophys. Res. Commun. 2004, 324, 1194-1198), but this is the first example of a Cys-ligated heme-containing peroxidase functioning as a dehaloperoxidase. The relative catalytic efficiency (turnover number) of CCPO reported herein is comparable to that of horseradish peroxidase (Ferrari, R. P.; Laurenti, E.; Trotta, F. J. Biol. Inorg. Chem. 1965, 4, 232-237). The mechanism of dehalogenation has been probed using p-halophenols as substrates. Here the major product is a dimer with 1,4-benzoquinone as the minor product. An electron-transfer mechanism is proposed that accounts for the products formed from both the 2,4,6-trihalo- and p-halophenols. Finally, we note that this is the first case of a peroxidase known primarily for its halogenation ability being shown to also dehalogenate substrates.     

Poly(2‐vinyl pyridine)‐block‐Poly(ethylene oxide) Featuring a Furan Group at the Block Junction—Synthesis and Functionalization

Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross‐linkable nanostructured materials via Diels–Alder reactions. Here, the use of FGE for the mid‐chain functionalization of a P2VP‐b‐PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP₆₈‐FGE‐b‐PEO₃₉₀, which can be subsequently addressed in Diels–Alder reactions using maleimide‐functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero‐grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP₆₈‐FGE‐b‐PEO₃₉₀, a powerful tool for selective functionalization reactions, including the modification of surfaces.

     

Survey of Plasmonic Nanoparticles: From Synthesis to Application

The unique properties of plasmonic nanostructures have fuelled research based on the tremendous amount of potential applications. Their tailor‐made assemblies in combination with the tunable size and morphology of the initial building blocks allow for the creation of materials with a desired optical response. In this respect, it is crucial to synthesize nanoparticles with a defined shape that are at the core of such developments. Moreover, the interaction of individual nanoparticles with an incident electromagnetic field cannot only be influenced by their structure, but in fact, also by their spatial arrangement to each other. To harvest such opportunities, a profound theoretical understanding of these interactions is required as well as concise strategies to create such ordered assemblies. A quantitative evaluation of their optical properties can only be conducted when discrete structures of high uniformity can be achieved. As a consequence, separation steps have to be applied in order to obtain materials of high purity and uniformity. This also allows for an easier structural characterization of the nanoparticles and their assembled superstructures. In this progress report, an overview about the current development in this field of research is provided.