In silico screening of metal-organic frameworks in separation applications

Porous materials such as metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable potential for separating a variety of mixtures such as those relevant for CO(2) capture (CO(2)/H(2), CO(2)/CH(4), CO(2)/N(2)), CH(4)/H(2), alkanes/alkenes, and hydrocarbon isomers. There are basically two different separation technologies that can be employed: (1) a pressure swing adsorption (PSA) unit with a fixed bed of adsorbent particles, and (2) a membrane device, wherein the mixture is allowed to permeate through a micro-porous crystalline layer. In view of the vast number of MOFs, and ZIFs that have been synthesized there is a need for a systematic screening of potential candidates for any given separation task. Also of importance is to investigate how MOFs and ZIFs stack up against the more traditional zeolites such as NaX and NaY with regard to their separation characteristics. This perspective highlights the potency of molecular simulations in determining the choice of the best MOF or ZIF for a given separation task. A variety of metrics that quantify the separation performance, such as adsorption selectivity, working capacity, diffusion selectivity, and membrane permeability, are determined from a combination of Configurational-Bias Monte Carlo (CBMC) and Molecular Dynamics (MD) simulations. The practical utility of the suggested screening methodology is demonstrated by comparison with available experimental data.     

A new formulation of Kapila’s five-equation model for compressible two-fluid flow,and its numerical treatment

A new formulation of Kapila’s five-equation model for inviscid, non-heat-conducting, compressible two-fluid flow is derived, together with an appropriate numerical method. The new formulation uses flow equations based on conservation laws and exchange laws only. The two fluids exchange momentum and energy, for which exchange terms are derived from physical laws. All equations are written as a single system of equations in integral form. No equation is used to describe the topology of the two-fluid flow. Relations for the Riemann invariants of the governing equations are derived, and used in the construction of an Osher-type approximate Riemann solver. A consistent finite-volume discretization of the exchange terms is proposed. The exchange terms have distinct contributions in the cell interior and at the cell faces. For the exchange-term evaluation at the cell faces, the same Riemann solver as used for the flux evaluation is exploited. Numerical results are presented for two-fluid shock-tube and shock-bubble-interaction problems, the former also for a two-fluid mixture case. All results show good resemblance with reference results.     

Strategic control and interests,its effects on decision outcomes

Application of the model to artificial data shows that actors with strong preferences in the center have more possibilities to realize good outcomes than other actors. On the basis of an empirical application it is shown that a Nash equilibrium does not always arise after a large number of iterations unless actors have learning capabilities or are severely restricted in their strategic behavior.

In political systems and large organizations, ultimate decision makers are usually just a small subset of all actors in the social system. To arrive at acceptable decisions, decision makers have to take into account the preferences of other actors in the system. Typically preferences of more interested and more powerful actors are weighted heavier than those of less interested and powerful actors. This implies that the total leverage of an actor on the decision is determined by the combination of his power (his potential) and his interest (his willingness to mobilize his power). As the exact level of an actor's leverage is difficult to estimate for the other actors in the system, an actor is able to optimize his effects on outcomes of decisions by providing strategic informatioa

In this paper, first an analytic solution is presented for the optimization of strategic leverage in collective decision making by one single actor. In this solution, the actor makes assumptions about the leverage other actors will show in decision making. Subsequently, the actor optimizes the outcomes of decisions by manipulating the distribution of his leverage over a set of issues.

The analytic solution can be theoretically interpreted by decomposing the solution into three terms, the expected external leverage of the other actors on the issue, the evaluation of the deviance of the expected from the preferred outcome of the issue, and the restrictions on the distribution of leverage over the issues. The higher the expectation of the leverages the other actors will allocate to the issue, the less an actor is inclined to allocate leverage to the issue. The higher the evaluation of the deviance, the more an actor is inclined to allocate leverage to the issue. This is restricted, however, by the required distribution of leverages over the issues. The researcher is able to manipulate these restrictions to investigate its consequences for the outcomes.

In the next step, we investigate whether we can find a Nash equilibrium if all actors optimize their leverage simultaneously. Under certain conditions, a Nash equilibrium can be found by an iterative process in which actors update their estimates oh each other's leverages on the basis of what the other actors have shown in previous iterations.     

Lysine and arginine residues do not increase the helicity of alanine-rich peptide helices

The helix-disfavoring, versus alanine, propagation values of lysine (0.8) and arginine (1.0) residues placed centrally in an (Ala)(9) unit have been measured by (13)C NMR.     

Hydrogallierungsreaktionen mit den Monoalkinen H5C6‐C≡C‐SiMe3 und H5C6‐C≡C‐CMe3 – cis/trans‐Isomerie und Substituentenaustausch

Hydrogallation Reactions Involving the Monoalkynes H₅C₆‐C≡C‐SiMe₃ and H₅C₆‐C≡C‐CMe₃ – cis/trans Isomerisation and Substituent Exchange Phenyl‐trimethylsilylethyne, H₅C₆‐C≡C‐SiMe₃, reacted with different dialkylgallium hydrides, R₂Ga‐H (R = Me, Et, nPr, iPr, tBu), by the addition of one Ga‐H bond to its C≡C triple bond (hydrogallation). The gallium atoms attacked selectively those carbon atoms, which were also attached to trimethylsilyl groups. The cis arrangement of Ga and H across the resulting C=C double bonds resulted only for the sterically most shielded di(tert‐butyl)gallium derivative, while in all other cases spontaneous cis/trans rearrangement occurred with the quantitative formation of the trans addition products. The diethyl compound Et₂Ga‐C(SiMe₃)=C(H)‐C₆H₅ ( 2 ) gave by substituent exchange the secondary products EtGa[C(SiMe₃)=C(H)‐C₆H₅]₂ ( 7 , Z,Z) and Ga[C(SiMe₃)=C(H)‐C₆H₅]₃ ( 8 ). Interestingly, compound 8 has two alkenyl groups with a Z configuration, while the third C=C double bond has the cis arrangement of Ga and H (E configuration). The reversibility of the cis/trans isomerisation of hydrogallation products was observed for the first time. tert‐Butyl‐phenylethyne gave the simple addition product, R₂Ga(C₆H₅)=C(H)‐CMe₃ ( 9 ), only with di(n‐propyl)gallium hydride.     

Simulation of vibrational energy transfer in two-dimensional infrared spectroscopy of amide I and amide II modes in solution

Population transfer between vibrational eigenstates is important for many phenomena in chemistry. In solution, this transfer is induced by fluctuations in molecular conformation as well as in the surrounding solvent. We develop a joint electrostatic density functional theory map that allows us to connect the mixing of and thereby the relaxation between the amide I and amide II modes of the peptide building block N-methyl acetamide. This map enables us to extract a fluctuating vibrational Hamiltonian from molecular dynamics trajectories. The linear absorption spectrum, population transfer, and two-dimensional infrared spectra are then obtained from this Hamiltonian by numerical integration of the Schrodinger equation. We show that the amide I/amide II cross peaks in two-dimensional infrared spectra in principle allow one to follow the vibrational population transfer between these two modes. Our simulations of N-methyl acetamide in heavy water predict an efficient relaxation between the two modes with a time scale of 790 fs. This accounts for most of the relaxation of the amide I band in peptides, which has been observed to take place on a time scale of 450 fs in N-methyl acetamide. We therefore conclude that in polypeptides, energy transfer to the amide II mode offers the main relaxation channel for the amide I vibration.     

On the optimization of two-class work-conserving parameterized scheduling policies

Numerous scheduling policies are designed to differentiate quality of service for different applications. Service differentiation can in fact be formulated as a generalized resource allocation optimization towards the minimization of some important system characteristics. For complex scheduling policies, however, optimization can be a demanding task, due to the difficult analytical analysis of the system at hand. In this paper, we study the optimization problem in a queueing system with two traffic classes, a work-conserving parameterized scheduling policy, and an objective function that is a convex combination of either linear, convex or concave increasing functions of given performance measures of both classes. In case of linear and concave functions, we show that the optimum is always in an extreme value of the parameter. Furthermore, we prove that this is not necessarily the case for convex functions; in this case, a unique local minimum exists. This information greatly simplifies the optimization problem. We apply the framework to some interesting scheduling policies, such as Generalized Processor Sharing and semi-preemptive priority scheduling. We also show that the well-documented \(c\mu \)-rule is a special case of our framework.     

Kinetics of the reaction of methyl radical with hydroxyl radical and methanol decomposition

The CH3 + OH bimolecular reaction and the dissociation of methanol are studied theoretically at conditions relevant to combustion chemistry. Kinetics for the CH3 + OH barrierless association reaction and for the H + CH2OH and H + CH3O product channels are determined in the high-pressure limit using variable reaction coordinate transition state theory and multireference electronic structure calculations to evaluate the fragment interaction energies. The CH3 + OH --> 3CH2 + H2O abstraction reaction and the H2 + HCOH and H2 + H2CO product channels feature localized dynamical bottlenecks and are treated using variational transition state theory and QCISD(T) energies extrapolated to the complete basis set limit. The 1CH2 + H2O product channel has two dynamical regimes, featuring both an inner saddle point and an outer barrierless region, and it is shown that a microcanonical two-state model is necessary to properly describe the association rate for this reaction over a broad temperature range. Experimental channel energies for the methanol system are reevaluated using the Active Thermochemical Tables (ATcT) approach. Pressure dependent, phenomenological rate coefficients for the CH3 + OH bimolecular reaction and for methanol decomposition are determined via master equation simulations. The predicted results agree well with experimental results, including those from a companion high-temperature shock tube determination for the decomposition of methanol.