Dynamic graph generation for the shortest path problem in time expanded networks

In discrete optimization problems the progress of objects over time is frequently modeled by shortest path problems in time expanded networks, but longer time spans or finer time discretizations quickly lead to problem sizes that are intractable in practice. In convex relaxations the arising shortest paths often lie in a narrow corridor inside these networks. Motivated by this observation, we develop a general dynamic graph generation framework in order to control the networks’ sizes even for infinite time horizons. It can be applied whenever objects need to be routed through a traffic or production network with coupling capacity constraints and with a preference for early paths. Without sacrificing any information compared to the full model, it includes a few additional time steps on top of the latest arcs currently in use. This “frontier” of the graphs can be extended automatically as required by solution processes such as column generation or Lagrangian relaxation. The corresponding algorithm is efficiently implementable and linear in the arcs of the non-time-expanded network with a factor depending on the basic time offsets of these arcs. We give some bounds on the required additional size in important special cases and illustrate the benefits of this technique on real world instances of a large scale train timetabling problem.     

Fluorescence detected circular dichroism (FDCD) for supramolecular host–guest complexes

Fluorescence-detected circular dichroism (FDCD) spectroscopy is applied for the first time to supramolecular host–guest and host–protein systems and compared to the more known electronic circular dichroism (ECD). We find that FDCD can be an excellent choice for common supramolecular applications, e.g. for the detection and chirality sensing of chiral organic analytes, as well as for reaction monitoring. Our comprehensive investigations demonstrate that FDCD can be conducted in favorable circumstances at much lower concentrations than ECD measurements, even in chromophoric and auto-emissive biofluids such as blood serum, overcoming the sensitivity limitation of absorbance-based chiroptical spectroscopy. Besides, the combined use of FDCD and ECD can provide additional valuable information about the system, e.g. the chemical identity of an analyte or hidden aggregation phenomena. We believe that simultaneous FDCD- and ECD-based chiroptical characterization of emissive supramolecular systems will be of general benefit for characterizing fluorescent, chiral supramolecular systems due to the higher information content obtained by their combined use.

Fluorescence-detected circular dichroism (FDCD) spectroscopy is applied for the first time to supramolecular host–guest and host–protein systems and compared to the more known electronic circular dichroism (ECD).     

On the restriction of cross characteristic representations of 2 F 4(q) to proper subgroups

We prove that the restriction of any nontrivial representation of the Ree groups ² F ₄(q), q = 2²ⁿ⁺¹ ≥ 8 in odd characteristic to any proper subgroup is reducible. We also determine all triples (K, V, H) such that ${K \in \{^2F_4(2), ^2F_4(2)'\} }We prove that the restriction of any nontrivial representation of the Ree groups ² F ₄(q), q = 2²ⁿ⁺¹ ≥ 8 in odd characteristic to any proper subgroup is reducible. We also determine all triples (K, V, H) such that K ? {²F₄(2), ²F₄(2)￠}{K \in \{^2F_4(2), ^2F_4(2)'\} } , H is a proper subgroup of K, and V is a representation of K in odd characteristic restricting absolutely irreducibly to H.     

Visible light induced reversible extrusion of nitric oxide from a ruthenium(II) nitrosyl complex: a facile delivery of nitric oxide

The new ruthenium compound [Ru(NO)(pysiS4)]Br (3) (pysiS4 = 2,6-bis(3-triphenylsilyl-2-sulfanylphenylthiomethyl)pyridine), containing sterically bulky SiPh3 groups ortho to the thiolate donors, has been synthesized. In solution, 3 releases NO efficiently on exposure to visible light (lambda >/= 455 nm) at room temperature to afford [Ru(Br)(pysiS4)] (4). Treatment of 4 with NO yielded exclusively 3 without any metal-bound side reaction.     

Triggering of radial multichannel pseudospark switches by a pulsedhollow cathode discharge

We report on a special trigger discharge for pulsed high-power pseudospark switches. The switch used is a radial three-channel pseudospark switch. For triggering, a cylindrical trigger electrode is inserted into the hollow cathode of the main gap. This electrode acts as a hollow cathode for the dc preionization, while the hollow cathode of the main gap is the anode. A negative high-voltage pulse supplied to the trigger electrode ignites the main discharge. We report the temporal evolution of the trigger discharge observed with a fast camera. This trigger method gives an excellent current distribution among the discharge channels, as can be proven by fast photography. The switch has a delay of 220 ns and a jitter of 15 ns     

A competitive algorithm in searching for many edges in a hypergraph

We give a competitive algorithm to identify all d defective edges in a hypergraph with d unknown. Damaschke did the d=1 case for 2-graphs, Triesch extended the d=1 case to r-graphs, and Johann did the general d case for 2-graphs. So ours is the first attempt to solve the searching for defective edges problem in its full generality. Further, all the above three papers assumed d known. We give a competitive algorithm where d is unknown.     

Collagen stability: insights from NMR spectroscopic and hybrid density functional computational investigations of the effect of electronegative substituents on prolyl ring conformations

Collagen-like peptides of the type (Pro-Pro-Gly)(10) fold into stable triple helices. An electron-withdrawing substituent at the H(gamma)(3) ring position of the second proline residue stabilizes these triple helices. The aim of this study was to reveal the structural and energetic origins of this effect. The approach was to obtain experimental NMR data on model systems and to use these results to validate computational chemical analyses of these systems. The most striking effects of an electron-withdrawing substituent are on the ring pucker of the substituted proline (Pro(i)) and on the trans/cis ratio of the Xaa(i-1)-Pro(i) peptide bond. NMR experiments demonstrated that N-acetylproline methyl ester (AcProOMe) exists in both the C(gamma)-endo and C(gamma)-exo conformations (with the endo conformation slightly preferred), N-acetyl-4(R)-fluoroproline methyl ester (Ac-4R-FlpOMe) exists almost exclusively in the C(gamma)-exo conformation, and N-acetyl-4(S)-fluoroproline methyl ester (Ac-4S-FlpOMe) exists almost exclusively in the C(gamma)-endo conformation. In dioxane, the K(trans/cis) values for AcProOMe, Ac-4R-FlpOMe, and Ac-4S-FlpOMe are 3.0, 4.0, and 1.2, respectively. Density functional theory (DFT) calculations with the (hybrid) B3LYP method were in good agreement with the experimental data. Computational analysis with the natural bond orbital (NBO) paradigm shows that the pucker preference of the substituted prolyl ring is due to the gauche effect. The backbone torsional angles, phi and psi, were shown to correlate with ring pucker, which in turn correlates with the known phi and psi angles in collagen-like peptides. The difference in K(trans/cis) between AcProOMe and Ac-4R-FlpOMe is due to an n-->pi interaction associated with the Bürg-Dunitz trajectory. The decrease in K(trans/cis) for Ac-4S-FlpOMe can be explained by destabilization of the trans isomer because of unfavorable electronic and steric interactions. Analysis of the results herein along with the structures of collagen-like peptides has led to a theory that links collagen stability to the interplay between the pyrrolidine ring pucker, phi and psi torsional angles, and peptide bond trans/cis ratio of substituted proline residues.