Elucidation of the Nucleophilic Potential of Diazocyclopentadiene

Diazocyclopentadiene reacts with benzhydrylium ions (Ar2CH+) to give 2,5-dibenzhydryl-substituted diazocyclopentadienes. The kinetics have been determined photometrically in dichloromethane under pseudo-first-order conditions using diazocyclopentadiene in excess. Plots of the second-order rate constants (log k 2) versus the electrophilicity parameters E of the benzhydrylium ions gave the nucleo­philicity parameter N = 4.84 and susceptibility s N = 1.06 for diazo­cyclopentadiene according to the correlation log k(20 °C) = s N(E + N). Diazocyclopentadiene thus has a similar nucleophilic reactivity as pyrrole. Previously reported electrophilic substitutions of diazocyclopentadiene are rationalized by these parameters and new reaction possibilities are predicted.

Multirate linearly-implicit GARK schemes

Many complex applications require the solution of initial-value problems where some components change fast, while others vary slowly. Multirate schemes apply different step sizes to resolve different components of the system, according to their dynamics, in order to achieve increased computational efficiency. The stiff components of the system, fast or slow, are best discretized with implicit base methods in order to ensure numerical stability. To this end, linearly implicit methods are particularly attractive as they solve only linear systems of equations at each step. This paper develops the Multirate GARK-ROS/ROW (MR-GARK-ROS/ROW) framework for linearly-implicit multirate time integration. The order conditions theory considers both exact and approximative Jacobians. The effectiveness of implicit multirate methods depends on the coupling between the slow and fast computations; an array of efficient coupling strategies and the resulting numerical schemes are analyzed. Multirate infinitesimal step linearly-implicit methods, that allow arbitrarily small micro-steps and offer extreme computational flexibility, are constructed. The new unifying framework includes existing multirate Rosenbrock(-W) methods as particular cases, and opens the possibility to develop new classes of highly effective linearly implicit multirate integrators.

Does Implicit Self-Reference Effect Occur by the Instantaneous Own-Name?

Self-reference effect (SRE) is defined as better recall or recognition performance when the materials that are memorized refer to the self. The SRE paradigm usually requires participants to explicitly refer items to themselves, but some researchers have found that the SRE also can occur for implicitly self-referenced items. Few studies though have investigated the effect of self-related stimuli without awareness. In this study, we presented self-related (participants’ names) or other (other’s names or nouns) stimuli for a very short time between masks and then explicitly presented subsequent trait adjectives to participants. Recognition performance showed no significant differences between the own-name and the other two conditions in Experiment 1 that had random-order conditions. On the other hand, the result of Experiment 2 that had block-order conditions and greater prime stimuli suggests that SRE can occur as a result of the instantaneous stimulus: Subjects who showed better memory performance also had relatively high recognition of the trait adjectives that they viewed after their instantaneously presented own-name. This effect would show that self-representation can be activated by self-related stimuli without awareness and that subsequent items are unconsciously referenced to that self-representation.

Automated Calibration of Farm-Sale Mixed Linear Programming Models using Bi-Level Programming

We calibrate Linear and Mixed Integer Programs with a bi-level estimator, minimizing under First-order-conditions (FOC) conditions a penalty function considering the calibration fit and deviations from given parameters. To deal with non-convexity, a heuristic generates restart points from current best-fit parameters and their means. Monte-Carlo analysis assesses the approach by drawing parameters for a model optimizing acreages under maximal crop shares, a land balance and annual plus intra-annual labour constraints; a variant comprises integer based investments. Resulting optimal solutions perturbed by white noise provide calibration targets. The approach recovers the true parameters and thus allows for systematic and automated calibration.

Kinetics of the Oxidation of Hydrogen Sulfide by Atmospheric Oxygen in an Aqueous Medium

Hydrogen sulfide is an important acid rain precursor and this led us to investigate the kinetics of its oxidation in aqueous phase by atmospheric oxygen. The kinetics was followed by measuring the depletion of oxygen in a reactor. The reaction was studied under pseudo order conditions with [H2S] in excess. The kinetics followed the rate law: -d[O2]/dt = k[S][O2]t (A) Where [S] represents the total concentration of hydrogen sulfide, [O2]t is the concentration of oxygen at time t and k is the second order rate constant. The equilibria (B - C) govern the dissolution of H2S; the sulfide ion in water forms different species: H2S K1 HS- + H+ (B) HS- K2 S2- + H+ (C) Where K1 and K2 are first and second dissociation constants of H2S. Although, H2S is present as undissociated H2S, HS- and S2- ions, nature of [H+ ] dependence of reaction rate required only HS- to be reactive and dominant. The rate law (A) on including [H+ ] dependence became Equation (D). -d[O2]/dt = k1K1[H+ ][S][O2]t / ([H+ ] 2 + K1[H+ ] + K1K2) (D) Our results indicate anthropogenic VOCs such as acetanilide, benzene, ethanol, aniline, toluene, benzamide, o-xylene, m-xylene, p-xylene and anisole to have no significant effect on the reaction rate and any observed small effect is within the uncertainty of the rate measurements.

Relaxed Optimization: How Close Is a Consumer to Satisfying First-Order Conditions?

We propose relaxing the first-order conditions in optimization to approximate rational consumer choice. We assess the magnitude of departures with a new, axiomatically-founded measure that admits multiple interpretations. Standard inequality tests of rationality for any given reference class of preferences can be conveniently re-purposed to measure goodness-of-fit with that class. Another advantage of our approach is that it is applicable in any context where the first-order approach is meaningful (e.g., convex budget sets arising from progressive taxation). We apply these ideas to shed new light on existing portfolio-choice data.

Kinetics and Mechanism of Catalyzed Oxidation of L-Cysteine by Salen Schiff Base Complexes of Co(III), Fe (III) and Cr(III)

Kinetics of oxidation of L-cysteine by new series of substituted ONNO-donor salen-type Schiff base complexes of general formula [MIII(L)Cl] (M = Co, Fe, Cr; L = Schiff base ligand) have been studied in aqueous solutions. Measurements were run at constant temperature (25º C), constant ionic strength (0.20 M), and constant pH (7.0) under pseudo-first order conditions, in which the concentration of cysteine is around two orders of magnitude greater than that of metal complex. The observed rate constant was determined by following the change in absorbance of reaction mixture at a predetermined wavelength with time. Results show that the rate of oxidation depends on the type of metal center, with Co(III) complexes were found to have the highest rates due to higher reduction potential of Co(III). The oxidation rate was also found to depend on steric factor and the electron withdrawing / releasing ability of the ligand bound to the metal ion.