New Tabu Search based global optimization methods outline of algorithms and study of efficiency

The study presents two new nonlinear global optimization routines; the Gradient Only Tabu Search (GOTS) and the Tabu Search with Powell's Algorithm (TSPA). They are based on the Tabu-Search strategy, which tries to determine the global minimum of a function by the steepest descent-mildest ascent strategy. The new algorithms are explained and their efficiency is compared with other approaches by determining the global minima of various well-known test functions with varying dimensionality. These tests show that for most tests the GOTS possesses a much faster convergence than global optimizer taken from the literature. The efficiency of the TSPA compares to the efficiency of genetic algorithms.     

Atomistic insights into the inhibition of cysteine proteases: first QM/MM calculations clarifying the stereoselectivity of epoxide-based inhibitors

Due to their important role in many diseases, cysteine proteases represent new promising drug targets. An important class of cysteine-protease inhibitors is derived from the naturally occurring compound E64, possessing an epoxysuccinyl moiety as warhead. Experimental studies show stereoselectivity concerning the inhibition potency, e.g., a trans-configured epoxide ring is essential for inhibition, and furthermore, in most cases, the ( S, S)-configured inhibitors have a higher inhibition potency than their ( R, R)-counterparts. However, the underlying effects are not fully understood. In this work, such effects are investigated by classical molecular dynamics simulations and combined quantum mechanics/molecular modeling (QM/MM) calculations for the E64c-cathepsin B complex. Our computations reveal that the hydrogen bonding network between the enzyme and the E64c (or its derivatives) determines the stereoselectivity of the subsequent ring opening reaction by governing the distance between the attacking thiolate and the attacked C2 atom of the epoxide ring. For the ( S, S)-configuration, a strong network can be realized which enables a close contact between the reacting centers, so that the irreversible step becomes very efficient. The ( R, S)-configuration ( cis-configuration) can only form networks in which the two reacting centers are so far away from each other that the irreversible step can hardly happen. The ( R, R)-configuration is in between, less optimal than the ( S, S)-configuration but much better than the ( R, S)-configuration. Exceptions where the ( R, R)-configurations shows higher potency than the ( S, S) ones are also explained.     

Physical background of the endurance limit in poly(ether ether ketone)

In this study, it is demonstrated that the apparent endurance (fatigue) limit for plasticity-controlled failure in poly(ether ether ketone) is related to an evolution of the yield stress. The increase of the yield stress has two separate causes: (a) stress- and temperature-accelerated physical aging of the amorphous phase and (b) strain hardening as a result of texture development. Yield stress evolution is monitored using thermomechanical treatments during which the material is exposed to temperature and load. The combined contributions of both temperature and applied stress to yield stress evolution (below T _g) can be effectively modeled using an effective time approach employing an Arrhenius temperature-activation as well as Eyring stress activation. Combination of the yield stress evolution with a previously developed model for plasticity-controlled failure allows prediction of time-to-failure under both static and cyclic load, quantitatively capturing the observed apparent endurance limit.     

Oxidation,Coordination, and Nickel-Mediated Deconstruction of a Highly Electron-Rich Diboron Analogue of 1,3,5-Hexatriene

The reductive coupling of an N-heterocyclic carbene (NHC) stabilized (dibromo)vinylborane yields a 1,2-divinyldiborene, which, although isoelectronic to a 1,3,5-triene, displays no extended π conjugation because of twisting of the C₂B₂C₂ chain. While this divinyldiborene coordinates to copper(I) and platinum(0) in an η²-B₂ and η⁴-C₂B₂ fashion, respectively, it undergoes a complex rearrangement to an η⁴-1,3-diborete upon complexation with nickel(0).     

Assessment of TD-DFT- and TD-HF-based approaches for the prediction of exciton coupling parameters, potential energy curves, and electronic characters of electronically excited aggregates

The reliability of linear response approaches such as time-dependent Hartree-Fock (TD-HF) and time-dependent density functional theory (TD-DFT) for the prediction of the excited state properties of 3,4;9,10-tetracarboxylic-perylene-bisimide (PBI) aggregates is investigated. A dimer model of PBI is investigated as a function of a torsional motion of the monomers, which was shown before to be an important intermolecular coordinate in these aggregates. The potential energy curves of the ground state and the two energetically lowest neutral excited and charge-transfer (CT) states were obtained with the spin-component scaling modification of the approximate coupled-cluster singles-and-doubles (SCS-CC2) method as a benchmark for dispersion corrected TD-HF and a range of TD-DFT approaches. The highly accurate SCS-CC2 results are used to assess the other, computationally less demanding methods. TD-HF predicts similar potential energy curves and transition dipole moments as SCS-CC2, as well as the correct order of neutral and CT states. This supports an exciton trapping mechanism, which was found on the basis of TD-HF data. However, the investigated TD-DFT methods provide generally the opposite character for the excited states. As a consequence, these TD-DFT results have unacceptably large errors for optical properties of these dye aggregates.     

Comparison of the electronic structure of different perylene‐based dye‐aggregates

Aggregates of functionalized polycyclic aromatic molecules like perylene derivatives differ in important optoelectronic properties such as absorption and emission spectra or exciton diffusion lengths. Although those differences are well known, it is not fully understood if they are caused by variations in the geometrical orientation of the molecules within the aggregates, variations in the electronic structures of the dye aggregates or interplay of both. As this knowledge is of interest for the development of materials with optimized functionalities, we investigate this question by comparing the electronic structures of dimer systems of representative perylene‐based chromophores. The study comprises dimers of perylene, 3,4,9,10‐perylene tetracarboxylic acid bisimide (PBI), 3,4,9,10‐perylene tetracarboxylic acid dianhydride (PTCDA), and diindeno perylene (DIP). Potential energy curves (PECs) and characters of those electronic states are investigated which determine the optoelectronic properties. The computations use the spin‐component‐scaled approximate coupled‐cluster second‐order method (SCS‐CC2), which describes electronic states of predominately neutral excited (NE) and charge transfer (CT) character equally well. Our results show that the characters of the excited states change significantly with the intermolecular orientation and often represent significant mixtures of NE and CT characters. However, PECs and electronic structures of the investigated perylene derivatives are almost independent of the substitution patterns of the perylene core indicating that the observed differences in the optoelectronic properties mainly result from the geometrical structure of the dye aggregate. It also hints at the fact that optical properties can be computed from less‐substituted model compounds if a proper aggregate geometry is chosen. © 2012 Wiley Periodicals, Inc.     

Neutron bound beta-decay: BOB

Frozen solution samples were made from gold chloride and KAu(CN)₂ solvated with TBP/xylene. The ¹⁹⁷Au M?ssbauer parameters were similar to those same species as frozen solutions or adsorbed onto activated carbon. Solvated samples from EuO dissolved in HCl or H₂SO₄ and frozen gave characteristic Eu(III) spectra. All the spectra were consistent with bonding to the TBP being through hydronium ions or water molecules.     

A New Class of Neutral Boron‐Based Diradicals Spanned by a Two‐Carbon‐Atom Bridge

A new structural class of boron‐based diradicals is prepared by Lewis base addition to and reduction of singly cyclic (alkyl)(amino)carbene (CAAC) stabilised diborylalkenes. The diradicals feature a perpendicular olefinic bridge preventing delocalization between the B(CAAC) π systems, making the coupling between the spin centres very weak. DFT calculations indicate that the compounds are ground‐state (open‐shell) singlets, with triplet states negligibly higher in energy, thus making the triplet states easily populated thermally.     

Formation of dispersive shock waves by merging and splitting Bose-Einstein condensates

The processes of merging and splitting dilute-gas Bose-Einstein condensates are studied in the nonadiabatic, high-density regime. Rich dynamics are found. Depending on the experimental parameters, uniform soliton trains containing more than ten solitons or the formation of a high-density bulge as well as dispersive shock waves are observed experimentally within merged BECs. Our numerical simulations indicate the formation of many vortex rings. In the case of splitting a BEC, the transition from sound-wave formation to dispersive shock-wave formation is studied by use of increasingly stronger splitting barriers. These experiments realize prototypical dispersive shock situations.