Assessment of variance components in nonlinear mixed-effects elliptical models

The issue of assessing variance components is essential in deciding on the inclusion of random effects in the context of mixed models. In this work we discuss this problem by supposing nonlinear elliptical models for correlated data by using the score-type test proposed in Silvapulle and Silvapulle (1995). Being asymptotically equivalent to the likelihood ratio test and only requiring the estimation under the null hypothesis, this test provides a fairly easy computable alternative for assessing one-sided hypotheses in the context of the marginal model. Taking into account the possible non-normal distribution, we assume that the joint distribution of the response variable and the random effects lies in the elliptical class, which includes light-tailed and heavy-tailed distributions such as Student-t, power exponential, logistic, generalized Student-t, generalized logistic, contaminated normal, and the normal itself, among others. We compare the sensitivity of the score-type test under normal, Student-t and power exponential models for the kinetics data set discussed in Vonesh and Carter (1992) and fitted using the model presented in Russo et al. (2009). Also, a simulation study is performed to analyze the consequences of the kurtosis misspecification.

Observation of vinylidene emission in mixed phosphine/diimine complexes of Ru(II) at room temperature in solution

The mixed ruthenium(II) complexes trans-[RuCl(2)(PPh(3))(2)(bipy)] (1), trans-[RuCl(2)(PPh(3))(2)(Me(2)bipy)](2), cis-[RuCl(2)(dcype)(bipy)](3), cis-[RuCl(2)(dcype)(Me(2)bipy)](4) (PPh(3) = triphenylphosphine, dcype = 1,2-bis(dicyclohexylphosphino)ethane, bipy = 2,2'-bipyridine, Me(2)bipy = 4,4'-dimethyl-2,2'-bipyridine) were used as precursors to synthesize the associated vinylidene complexes. The complexes [RuCl(=C=CHPh)(PPh(3))(2)(bipy)]PF(6) (5), [RuCl(=C=CHPh)(PPh(3))(2)(Me(2)bipy)]PF(6) (6), [RuCl(=C=CHPh)(dcype)(bipy)]PF(6) (7), [RuCl(=C=CHPh)(dcype)(bipy)]PF(6) (8) were characterized and their spectral, electrochemical, photochemical and photophysical properties were examined. The emission assigned to the pi-pi* excited state from the vinylidene ligand is irradiation wavelength (340, 400, 430 nm) and solvent (CH(2)Cl(2), CH(3)CN, EtOH/MeOH) dependent. The cyclic voltammograms of (6) and (7) show a reversible metal oxidation peak and two successive ligand reductions in the +1.5-(-0.64) V range. The reduction of the vinylidene leads to the formation of the acetylide complex, but due the hydrogen abstraction the process is irreversible. The studies described here suggest that for practical applications such as functional materials, nonlinear optics, building blocks and supramolecular photochemistry. (C) 2011 Elsevier B.V. All rights reserved.