Mono-Heteroatom Substitution for Harnessing Excited-State Structural Planarization of Dihydrodibenzo[a,c]phenazines

With the aim of generalizing the structure–properties relationship of bending heterocyclic molecules that undergo prominent photoinduced structural planarization (PISP), a series of new dihydrodibenzo[ac]phenazine derivatives in which one nitrogen atom is replaced by oxygen ( PNO ), sulfur ( PNS ), selenium ( PNSe ), or dimethylmethanediyl ( PNC ) was strategically designed and synthesized. Compounds PNO , PNS , and PNSe have significantly nonplanar geometries in the ground state, which undergo PISP to give a planarlike conformer and hence a large emission Stokes shift. A combination of femtosecond early relaxation dynamics and computational approaches established an R*→I* (intermediate)→P* sequential kinetic pattern for PNS and PNSe , whereas PNO undergoes R*→P* one-step kinetics. The polarization ability of the substituted heteroatoms, which is in the order O<S<Se, correlates with their increase in π conjugation, and hence the Stokes shift of the emission is in the order PNO < PNS < PNSe . Compound PNSe with the largest PISP barrier was shown to be a highly sensitive viscosity probe. Further evidence for heteroatom-harnessing PISP is given by PNC , in which the dimethylmethanediyl substituent lacks lone pair electrons for π extension, showing the normal emission of the bent structure. The results led to the conclusion that PISP is ubiquitous in dihydrodibenzo[ac]phenazines, for which the driving force is elongation of the π delocalization to gain stabilization in the excited state.     

Phase Transformations in Electrically Conductive Ferromagnetic Shape-Memory Alloys, Their Thermodynamics and Analysis

We derive a thermodynamically consistent general continuum-mechanical model describing mutually coupled martensitic and ferro/paramagnetic phase transformations in electrically-conductive magnetostrictive materials such as NiMnGa. We use small-strain and eddy-current approximations, yet large velocities and electric current injected through the boundary are allowed. Fully nonlinear coupling of magneto-mechanical and thermal effects is considered. The existence of energy-preserving weak solutions is proved by showing convergence of time-discrete approximations constructed by a carefully designed semi-implicit regularized scheme.     

The Oxidation of Thiols by Flavoprotein Oxidases: a Biocatalytic Route to Reactive Thiocarbonyls

Flavoprotein oxidases are a diverse class of biocatalysts, most of which catalyze the oxidation of C? O, C? N, or C? C bonds. Flavoprotein oxidases that are known to catalyze the oxidation of C? S bonds are rare, being limited to enzymes that catalyze the oxidative cleavage of thioethers. Herein, we report that various flavoprotein oxidases, previously thought to solely act on alcohols, also catalyze the oxidation of thiols to thiocarbonyls. These results highlight the versatility of enzymatic catalysis and provide a potential biocatalytic route to reactive thiocarbonyl compounds, which have a variety of applications in synthetic organic chemistry.     

Photochemistry in Real Space: Batho- and Hypsochromism in the Water Dimer

The development of chemical intuition in photochemistry faces several difficulties that result from the inadequacy of the one-particle picture, the Born–Oppenheimer approximation, and other basic ideas used to build models. It is shown herein how real-space approaches can be efficiently used to gain valuable insights in photochemistry through a simple example of red and blue shift effects: the double hypso- and bathochromic shifts in the low-lying valence excited states of (H₂O)₂. It is demonstrated that 1) the use of these techniques allows the perturbative language used in the theory of intermolecular interactions, even in the strongly interacting short-range regime, to be maintained; 2) one and only one molecule is photoexcited in each of the addressed excited states and 3) the electrostatic interaction between the in-the-cluster molecular dipoles provides a fairly intuitive rationalisation of the observed batho- and hypsochromism. The methods exploited and illustrated herein are able to maintain the individuality and properties of the interacting entities in a molecular aggregate, and thereby they allow chemical intuition in general states, at any geometry and using a broad variety of electronic structure methods to be kept and built.     

On the use of conditional expectation in portfolio selection problems

Annals of Operations Research - In this paper, we examine the use of conditional expectation, either to reduce the dimensionality of large-scale portfolio problems or to propose alternative...     

Gray codes extending quadratic matchings

Is it true that every matching in the n-dimensional hypercube can be extended to a Gray code? More than two decades have passed since Ruskey and Savage asked this question and the problem still remains open. A solution is known only in some special cases, including perfect matchings or matchings of linear size. This article shows that the answer to the Ruskey–Savage problem is affirmative for every matching of size at most . The proof is based on an inductive construction that extends balanced matchings in the completion of the hypercube by edges of into a Hamilton cycle of . On the other hand, we show that for every there is a balanced matching in of size that cannot be extended in this way.