Nonlinear Isolator Dynamics at Finite Deformations: An Effective Hyperelastic,Fractional Derivative,Generalized Friction Model

In presenting a nonlinear dynamic model of a rubber vibrationisolator, the quasistatic and dynamic motion influences on theforce response are investigated within the time and frequencydomain. It is found that the dynamic stiffness at the frequency ofa harmonic displacement excitation, superimposed upon the longterm isolator response, is strongly dependent on staticprecompression, dynamic amplitude and frequency. The problems ofsimultaneously modelling the elastic, viscoelastic and frictionforces are removed by additively splitting them, modelling theelastic force response by a nonlinear, shape factor basedapproach, displaying results that agree with those of aneo-Hookean hyperelastic isolator at a long term precompression.The viscoelastic force is modeled by a fractional derivativeelement, while the friction force governs from a generalizedfriction element displaying a smoothed Coulomb force. A harmonicdisplacement excitation is shown to result in a force responsecontaining the excitation frequency and its every otherhigher-order harmonic, while using a linearized elastic forceresponse model, whereas all higher-order harmonics are present forthe fully nonlinear case. It is furthermore found that the dynamicstiffness magnitude increases with static precompression andfrequency, while decreasing with dynamic excitationamplitude – eventually increasing at the highest amplitudes due tononlinear elastic effects – with its loss angle displaying amaximum at an intermediate amplitude. Finally, the dynamicstiffness at a static precompression, using a linearized elasticforce response model, is shown to agree with the fully nonlinearmodel except at the highest dynamic amplitudes.     

A component tracking algorithm for accelerated and improved liquid chromatography-mass spectrometry method development

A method for tracking of sample components during liquid chromatography-mass spectrometry (LC-MS) method development has been proposed. The method manages to, fully automatically and without user intervention, find the chromatographic peaks in the data sets, discriminate them to sample components and track them when the separation conditions have been changed. The algorithm utilises the resolution obtained from all considered data sets and has the ability to discriminate the non informative parts. The technique has a great sensitivity even in cases where a majority of the tracked components cannot easily be spotted by means of traditional total ion chromatogram (TIC) or base peak chromatogram (BPC) representations. The method was tested on an experimental sample using six different columns and an average of 79% of the suggested sample components could be successfully tracked at a minimum area of 0.05% of the main component in the sample. 66 components with 79-92% of the total suggested component area were able to be tracked between all data sets. The method could be used to rapidly investigate selectivity during different types of separation conditions.     

Combining column generation and constraint programming to solve the tail assignment problem

Within the area of short term airline operational planning, Tail Assignment is the problem of assigning flight legs to individual identified aircraft while satisfying all operational constraints, and optimizing some objective function. In this article, we propose that Tail Assignment should be solved as part of both the short and the long term airline planning. We further present a hybrid column generation and constraint programming solution approach. This approach can be used to quickly produce solutions for operations management, and also to produce close-to-optimal solutions for long and mid term planning scenarios. We present computational results which illustrate the practical usefulness of the approach.     

Ice nucleation and phase behavior on oligo(ethylene glycol) and hydroxyl self-assembled monolayers: simulations and experiments

The nucleation and phase behavior of ultrathin D2O-ice overlayers have been studied on oligo(ethylene glycol) (OEG)-terminated and hydroxyl self-assembled monolayers (SAMs) at low temperatures in ultrahigh vacuum. Infrared reflection-absorption spectroscopy (IRAS) is used to characterize the ice overlayers, the SAMs, and the interactions occurring between the ice and the SAM surfaces. Spectral simulations, based on optical models in conjunction with Maxwell Garnett effective medium theory, point out the importance of including voids in the modeling of the ice structures, with void fractions reaching 60% in some overlayers. The kinetics of the phase transition from amorphous-like to crystalline-like ice upon isothermal annealing at 140 K is found to depend on the conformational state of the supporting OEG SAM surface. The rate is fast on the helical OEG SAMs and slow on the corresponding all-trans SAMs. This difference in kinetics is most likely due to a pronounced D2O interpenetration and binding to the all-trans segments of the ethylene glycol portion of the SAM. No such penetration and binding was observed on the helical OEG SAM.     

Speeding up MCMC by Delayed Acceptance and Data Subsampling

The complexity of the Metropolis–Hastings (MH) algorithm arises from the requirement of a likelihood evaluation for the full dataset in each iteration. One solution has been proposed to speed up the algorithm by a delayed acceptance approach where the acceptance decision proceeds in two stages. In the first stage, an estimate of the likelihood based on a random subsample determines if it is likely that the draw will be accepted and, if so, the second stage uses the full data likelihood to decide upon final acceptance. Evaluating the full data likelihood is thus avoided for draws that are unlikely to be accepted. We propose a more precise likelihood estimator that incorporates auxiliary information about the full data likelihood while only operating on a sparse set of the data. We prove that the resulting delayed acceptance MH is more efficient. The caveat of this approach is that the full dataset needs to be evaluated in the second stage. We therefore propose to substitute this evaluation by an estimate and construct a state-dependent approximation thereof to use in the first stage. This results in an algorithm that (i) can use a smaller subsample m by leveraging on recent advances in Pseudo-Marginal MH (PMMH) and (ii) is provably within O(m^{? 2}) of the true posterior.     

Enantioselective luminescence quenching of DNA light-switch [Ru(phen)2dppz]2+ by electron transfer to structural homologue [Ru(phendione)2dppz]2+

The quenching of the luminescence of [Ru(phen)(2)dppz](2+) by structural homologue [Ru(phendione)(2)dppz](2+), when both complexes are bound to DNA, has been studied for all four combinations of Delta and Lambda enantiomers. Flow linear dichroism spectroscopy (LD) indicates similar binding geometries for all the four compounds, with the dppz ligand fully intercalated between the DNA base pairs. A difference in the LD spectrum observed for the lowest-energy MLCT transition suggests that a transition, potentially related to the final localization of the excited electron to the dppz ligand in [Ru(phen)(2)dppz](2+), is overlaid by an orthogonally polarized transition in [Ru(phendione)(2)dppz](2+). This would be consistent with a low-lying LUMO of the phendione moiety of [Ru(phendione)(2)dppz](2+) that can accept the excited electron from [Ru(phen)(2)dppz](2+), thereby quenching the emission of the latter. The lifetime of excited Delta-[Ru(phen)(2)dppz](2+) is decreased moderately, from 664 to 427 ns, when bound simultaneously with the phendione complex to DNA. The 108 ns lifetime of opposite enantiomer, Lambda-[Ru(phen)(2)dppz](2+), is only shortened to 94 ns. These results are consistent with an average rate constant for electron transfer of approximately 1.10(6) s(-1) between the phenanthroline- and phendione-ruthenium complexes. At binding ratios close to saturation of DNA, the total emission of the two enantiomers is lowered equally much, but for the Lambda enantiomer, this is not paralleled by a decrease in luminescence lifetime. A binding isotherm simulation based on a generalized McGhee-von Hippel approach shows that the Delta enantiomer binds approximately 3 times stronger to DNA both for [Ru(phendione)(2)dppz](2+) and [Ru(phen)(2)dppz](2+). This explains the similar decrease in total emission, without the parallel decrease in lifetime for the Lambda enantiomer. The simulation also does not indicate any significant binding cooperativity, in contrast to the case when Delta-[Rh(phi)(2)bipy](3+) is used as quencher. The very slow electron transfer from [Ru(phen)(2)dppz](2+) to [Ru(phendione)(2)dppz](2+), compared to the case when [Rh(phi)(2)phen](3+) is the acceptor, can be explained by a much smaller driving free-energy difference.     

Rates of reaction between the nitrate radical and some unsaturated alcohols

Rate coefficients for nitrate radical gas-phase reactions with prop-2-en-l-ol (allyl alcohol), but-1-en-3-ol, and 2-methylbut-3-en-2-ol have been determined. Both absolute (fast flow discharge with diode laser detection of NO₃) and relative (batch reactor and FTIR spectroscopy) rate techniques were used to measure the rate coefficients. The rate coefficients at 294 K are: (1.3 ± 0.2) × 10⁻¹⁴, (1.2 ± 0.3) × 10 ⁻¹⁴, and (2.1 ± 0.3) × 10⁻¹⁴ cm³ molecule⁻¹ s⁻¹ for prop-2-en-1-ol, but-1-en-3-ol, and 2-methylbut-3-en-2-ol, respectively. The activation energy for reaction of NO₃ with prop-2-en-1-ol was determined to 2.8 ± 2.5 kJ mol⁻¹ in the temperature range between 273 and 363 K. The atmospheric importance of unsaturated alcohols and structure-reactivity considerations are also discussed. © 1996 John Wiley & Sons, Inc.