Formic acid in deuterium and hydrogen matrices

ABSTRACT

Formic acid (HCOOH, FA) was studied experimentally, by infrared spectroscopy, in H₂ and D₂ matrices, with focus on the preparation and characterisation in these matrix media of structures containing the higher-energy (cis) conformer. The cis-FA monomer and the cis-FA^?…?N₂ complex were successfully produced by selective vibrational excitation of corresponding trans-FA based species, and vibrationally characterised. The tunneling-induced conversion of the cis-FA^?…?N₂ complex in the studied matrices into the corresponding trans-FA complex was also investigated, and the found tunnelling properties discussed, in particular in comparison with those observed for the spontaneous conversion of cis-FA monomer into trans-FA. This article constitutes the first report on the infrared spectrum of FA conformers and stability of cis-FA monomer in a D₂ matrix, and on the structure, spectroscopy and stability of the cis-FA^?…?N₂ complex in both H₂ and D₂ matrices. Different attempts to prepare the cis-FA^?…?H₂O complex in the two investigated matrices are also described in detail, both from previously in situ generated cis-FA monomer followed by thermal mobilisation and by direct selective vibrational excitation of the trans-FA-H₂O complex.     

Mechanical, rheological, fatigue, and degradation behavior of PLLA, PGLA and PDGLA as materials for vascular implants

The biggest challenge in the treatment of arterial stenosis remains the issue of optimization of stent design. Despite continuous improvement in surgical techniques and use of intensive pharmacotherapy, the results of stent coronary interventions may be unsatisfactory, and long-term interaction of a metal implant with a blood vessel results in complications such as recurrent stenosis and thrombosis. Therefore, it is necessary to search for new materials and stent designs to obtain a stent capable of restoring flow in the vessel and disappearing after fulfilling its function. Such stent must also be compatible with the vessel wall to enable regeneration of new structure of endothelium and deeper artery layers damaged during implantation. Consequently, there is ongoing search for functional solutions with minimum effects of long-term implant-tissue interaction. In light of the above, the team investigated the possibility of using biodegradable polymers already mentioned in the literature as a construction material for vascular stent. The study used three polyhydroxyacids based on lactic acid and glycolic acid: poly(l-lactide), poly(lactide-co-glycolide) and poly(d,l-lactide-co-glycolide). The research focused on assessing changes in mechanical, thermomechanical, rheological, and fatigue properties during the process of hydrolytic degradation. The analysis also covered the rate of release of degradation products. The results of the conducted tests indicate the possibility of developing a vascular stent with biodegradable polymers.     

Structured construction and simulation of nondeterministic stochastic activity networks

In this work we deal with nondeterministic stochastic activity networks (NDSANs). Their stochastic character results from activity durations, which are given by nonnegative continuous random variables. The nondeterministic behavior of an NDSAN is a consequence of its variable topology, based on two additional features. First, by associating choice probabilities with the immediate successors of an activity, some branches of execution are not always taken. Second, by allowing iterated executions of a group of activities according to predetermined probabilities, the number of times an activity is to be executed is not determined a priori. These properties lead to a wide variety of activity networks, capable of modelling many real situations in process engineering and project management. We describe a simple, recursively structured construction of NDSANs, which both provides a coherent syntactic mechanism to incorporate the two abovementioned nondeterminism features and allows the analytic formulation of completion time. This construction also directly gives rise to a recursive simulation algorithm for NDSANs, whose repeated execution produces an estimate of the probability distribution of the completion time of the network. We also report on real-world case studies, using the Komolgorov–Smirnov statistic for validation.     

Bursting synchronization in scale-free networks

Neuronal networks in some areas of the brain cortex present the scale-free property, i.e., the neuron connectivity is distributed according to a power-law, such that neurons are more likely to couple with other already well-connected ones. Neuron activity presents two timescales, a fast one related to action-potential spiking, and a slow timescale in which bursting takes place. Some pathological conditions are related with the synchronization of the bursting activity in a weak sense, meaning the adjustment of the bursting phase due to coupling. Hence it has been proposed that an externally applied time-periodic signal be applied in order to control undesirable synchronized bursting rhythms. We investigated this kind of intervention using a two-dimensional map to describe neurons with spiking–bursting activity in a scale-free network.     

Dilute Acid Hydrolysis of Wheat Straw Oligosaccharides

The dilute acid posthydrolysis of wheat straw hemicellulosic oligosaccharides obtained by autohydrolysis was evaluated. An empirical model was used to describe the effect of catalyst concentration (sulfuric acid, 0.1–4% w/w) and reaction time (0–60 min) based on data from a Doehlert experimental design. Catalyst concentration is the main variable influencing posthydrolysis performance, as both its linear and quadratic coefficients are statistically significant for the majority of the studied variables, namely, the ones related to sugar and byproducts production. Reaction time influences xylose and furan derivatives concentrations but not phenolics or acetic acid content. Catalyst concentration and reaction time interact synergistically, minimizing sugar recovery and promoting furan derivatives production. Based on the proposed models, it was possible to delimit an operational range that enables to obtain high monosaccharides recovery together with a slight decrease in inhibitors content as compared to the standard acid hydrolysis treatment. Furthermore, this is achieved with up to 70% less acid spending or considerable savings on reaction time.     

Vanishing viscosity limit for an expanding domain in space

We study the limiting behavior of viscous incompressible flows when the fluid domain is allowed to expand as the viscosity vanishes. We describe precise conditions under which the limiting flow satisfies the full space Euler equations. The argument is based on truncation and on energy estimates, following the structure of the proof of Kato's criterion for the vanishing viscosity limit. This work complements previous work by the authors, see Iftimie et al. (2009) [5], Kelliher (2008) [8].     

Optimal homotopy analysis of a chaotic HIV-1 model incorporating AIDS-related cancer cells

The studies of nonlinear models in epidemiology have generated a deep interest in gaining insight into the mechanisms that underlie AIDS-related cancers, providing us with a better understanding of cancer immunity and viral oncogenesis. In this article, we analyze an HIV-1 model incorporating the relations between three dynamical variables: cancer cells, healthy CD4 ⁺ T lymphocytes, and infected CD4 ⁺ T lymphocytes. Recent theoretical investigations indicate that these cells interactions lead to different dynamical outcomes, for instance to periodic or chaotic behavior. Firstly, we analytically prove the boundedness of the trajectories in the system’s attractor. The complexity of the coupling between the dynamical variables is quantified using observability indices. Our calculations reveal that the highest observable variable is the population of cancer cells, thus indicating that these cells could be monitored in future experiments in order to obtain time series for attractor’s reconstruction. We identify different dynamical behaviors of the system varying two biologically meaningful parameters: r ₁, representing the uncontrolled proliferation rate of cancer cells, and k ₁, denoting the immune system’s killing rate of cancer cells. The maximum Lyapunov exponent is computed to identify the chaotic regimes. Considering very recent developments in the literature related to the homotopy analysis method (HAM), we calculate the explicit series solutions of the cancer model and focus our analysis on the dynamical variable with the highest observability index. An optimal homotopy analysis approach is used to improve the computational efficiency of HAM by means of appropriate values for the convergence control parameter, which greatly accelerate the convergence of the series solution. The approximated analytical solutions are used to compute density plots, which allow us to discuss additional dynamical features of the model.     

Eliminating the Cuspidal Temperature Profile of a Non-equilibrium Chain

In 1967, Z. Rieder, J. L. Lebowitz, and E. Lieb (RLL) introduced a model of heat conduction on a crystal that became a milestone problem of non-equilibrium statistical mechanics. Along with its inability to reproduce Fourier’s law—which subsequent generalizations have been trying to amend—the RLL model is also characterized by awkward cusps at the ends of the non-equilibrium chain, an effect that has endured all these years without a satisfactory answer. In this paper, we first show that such trait stems from the insufficiency of pinning interactions between the chain and the substrate. Assuming the possibility of pinning the chain, the analysis of the temperature profile in the space of parameters reveals that for a proper combination of the border and bulk pinning values, the temperature profile may shift twice between the RLL cuspidal behavior and the expected monotonic local temperature evolution along the system, as a function of the pinning. At those inversions, the temperature profile along the chain is characterized by perfect plateaux: at the first threshold, the cumulants of the heat flux reach their maxima and the vanishing of the two-point velocity correlation function for all sites of the chain so that the system behaves similarly to a “phonon box.” On the other hand, at the second change of the temperature profile, we still have the vanishing of the two-point correlation function but only for the bulk, which explains the emergence of the temperature plateau and thwarts the reaching of the maximal values of the cumulants of the heat flux.     

Negative entropy,zero temperature and Markov chains on the interval

We consider ergodic optimization for the shift map on the modified Bernoulli space σ: [0, 1]^? → [0, 1]^?, where [0, 1] is the unit closed interval, and the potential A: [0, 1]^? → ? considered depends on the two first coordinates of [0, 1]^?. We are interested in finding stationary Markov probabilities µ_∞ on [0, 1]^? that maximize the value ∫ Adµ, among all stationary (i.e. σ-invariant) probabilities µ on [0, 1]^?. This problem correspond in Statistical Mechanics to the zero temperature case for the interaction described by the potential A. The main purpose of this paper is to show, under the hypothesis of uniqueness of the maximizing probability, a Large Deviation Principle for a family of absolutely continuous Markov probabilities µ _β which weakly converges to µ_∞. The probabilities µ _β are obtained via an information we get from a Perron operator and they satisfy a variational principle similar to the pressure in Thermodynamic Formalism. As the potential A depends only on the first two coordinates, instead of the probability µ on [0, 1]^?, we can consider its projection ν on [0, 1]². We look at the problem in both ways. If µ_∞ is the maximizing probability on [0, 1]^?, we also have that its projection ν _∞ is maximizing for A. The hypothesis about stationarity on the maximization problem can also be seen as a transhipment problem. Under the hypothesis of A being C ² and the twist condition, that is,

$\frac{{\partial ^2 A}}{{\partial x\partial y}}(x,y) \ne 0, for all (x,y) \in [0,1]^2 ,$

we show the graph property of the maximizing probability ν on [0, 1]². Moreover, the graph is monotonous. An important result we get is: the maximizing probability is unique generically in Mañé’s sense. Finally, we exhibit a separating sub-action for A.