Scenery reconstruction on finite abelian groups

We consider the question of when a random walk on a finite abelian group with a given step distribution can be used to reconstruct a binary labeling of the elements of the group, up to a shift. Matzinger and Lember (2006) give a sufficient condition for reconstructability on cycles. While, as we show, this condition is not in general necessary, our main result is that it is necessary when the length of the cycle is prime and larger than 5, and the step distribution has only rational probabilities. We extend this result to other abelian groups.     

An application-based characterization of dynamical distance geometry problems

The dynamical distance geometry problem (dynDGP) is the problem of finding a realization in a Euclidean space of a weighted undirected graph G representing an animation by relative distances, so that the distances between realized vertices are as close as possible to the edge weights. In the dynDGP, the vertex set of the graph G is the set product of V, representing certain objects, and T, representing time as a sequence of discrete steps. We suppose moreover that distance information is given together with the priority of every distance value. The dynDGP is a special class of the DGP where the dynamics of the problem comes to play an important role. In this work, we propose an application-based characterization of dynDGP instances, where the main criteria are the presence or absence of a skeletal structure, and the rigidity of such a skeletal structure. Examples of considered applications include: multi-robot coordination, crowd simulations, and human motion retargeting.     

Generation of onions and nanotubes of GaS and GaSe through laser and thermally induced exfoliation

Although theoretical calculations have predicted that layered GaS and GaSe should form nanotube and related structures, they have not been prepared experimentally to date. We have carried out laser irradiation as well as thermal treatment of GaS and GaSe to cause exfoliation, which yielded onionlike structures and nanotubes by the rolling of the exfoliated sheets.     

Tracking excited state dynamics with coherent control: automated limiting of population transfer in LDS750

Closed loop automated pulse shaping experiments are conducted to investigate population transfer in solutions of the laser dye LDS750 in acetonitrile and ethanol. Guided by a genetic algorithm, the optical phases of broadband noncollinear parametric amplifier pulses are modulated by a micromachined deformable mirror to minimize sample fluorescence. The objectives were to test if nonlinearly chirped pulses could reduce population transfer below levels attained by their linearly chirped analogues, and if so, whether the resulting pulse shapes could be rationalized in terms of the photoinduced molecular dynamics. We further aimed to discover how the optimal solutions depend on the pulse fluence, and on the nature of the solvent. Using frequency resolved optical gating, the optimal field is shown to consist of a transform limited blue portion, which promotes population to the excited state, and a negatively chirped red tail, which follows the Stokes shifting of the excited density and dumps it back down to the ground state through stimulated emission. This is verified by comparing the optimal group delay dispersion with multichannel transient absorption data collected in acetonitrile. The optimal pulse shape was not significantly affected by variation of pulse fluence or by the change of solvent for the two polar liquids investigated. These results are discussed in terms of accumulated insights concerning the photophysics of LDS750 and the capabilities of our learning feedback scheme for quantum control.     

Enantioselective synthesis of 2-amino-4-(nitromethyl)-4H-chromene-3-carbonitriles from 2-iminochromenes

A series of medicinally important 2-amino-4-(nitromethyl)-4H-chromene-3-carbonitriles were synthesized using enantioselective conjugate addition of nitromethane to 2-iminochromenes. The reactions were performed using L8-Cu (II) catalytic system and moderate to good enantioselectivities (62–88%) and yields (66–96%) were obtained.     

Risk analysis under progressive type II censoring with binomial claim numbers

This paper presents a model of actuarial loss events that follow a progressive censoring scheme. Loss events are modelled according to this scheme regarding the claim number and size. Claim events at random time points are assumed to happen progressively in a given period due to each of an m number of claims that occur due to hazardous events, while a fixed number of n claims are anticipated to take place in total. Distribution of the resulting total loss amount is derived, and according to its properties, some risk management issues about reserves and solvency are discussed.     

trans-Bis(ethanolamine-N,O)bis(saccharinato-N)copper(II)

In the title complex, [Cu(C₇H₄NO₃S)₂(C₂H₇NO)₂], the Cu^II centre lies on an inversion centre and exhibits octahedral coordination, with the two ethano­lamine (Hea) and two saccharinate [sac; anionic 1,2-benziso­thia­zol-3(2H)-one 1,1-dioxide] ligands in a trans configuration. The bidentate Hea ligands bridge axial and equatorial positions and the sac anions occupy equatorial sites around the distorted octahedral copper(II) centre [Cu—O = 2.3263 (16), Cu—N_Hea = 1.9923 (16) and Cu—N_sac = 2.1776 (16) Å].     

Switch chemistry at cryogenic conditions: quantum tunnelling under electric fields

While the influence of intramolecular electric fields is a known feature in enzymes, the use of oriented external electric fields (EEF) to enhance or inhibit molecular reactivity is a promising topic still in its infancy. Herein we will explore computationally the effects that EEF can provoke in simple molecules close to the absolute zero, where quantum tunnelling (QT) is the sole mechanistic option. We studied three exemplary systems, each one with different reactivity features and known QT kinetics: π bond-shifting in pentalene, Cope rearrangement in semibullvalene, and cycloreversion of diazabicyclohexadiene. The kinetics of these cases depend both on the field strength and its direction, usually giving subtle but remarkable changes. However, for the cycloreversion, which suffers large changes on the dipole through the reaction, we also observed striking results. Between the effects caused by the EEF on the QT we observed an inversion of the Arrhenius equation, deactivation of the molecular fluxionality, and stabilization or instantaneous decomposition of the system. All these effects may well be achieved, literally, at the flick of a switch.

Adding an external electric field to reactions driven by quantum mechanical tunneling brings a whole new dimension to the idea of switch chemistry.