An approach to triquinane synthesis using the Pauson-Khand reaction

Tricyclic skeletons have been generated from acyclic enyne precursors by using an intramolecular Pauson-Khand reaction in combination with aldol, Michael and alkylation reactions.     

A new insight into the understanding of the collapsed form of poly(N-isopropylacrylamide) molecules

Possible collapsed forms of poly(N-isopropylacrylamide) molecules are reviewed on the basis of first principle calculations. Various configurations and associated conformations are detailed. The calculated optimized structures exhibit different possibilities of creating networks of intra-molecular bonds of the hydrogen type. We show that the most remarkable one is able to form a local, self-saturated and well ordered helix. We also indicate in which direction the synthesis of the molecule should be oriented to improve its global behavior in term of hydrophobic/hydrophilic behavior.     

Random Classical Fidelity

We introduce a random perturbed version of the classical fidelity and we show that it converges with the same rate of decay of correlations, but not uniformly in the noise. This makes the classical fidelity unstable in the zero-noise limit.     

Latex particles bearing hydrophilic grafted hairs with controlled chain length and functionality synthesized by reversible addition–fragmentation chain transfer

A method is described for synthesizing latex particles with anchored hairs by the grafting of hydrophilic chains, synthesized by reversible addition–fragmentation chain transfer, onto functionalized latex particles. These have the potential to bind biologically active species. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1188–1195, 2003     

Likelihood and conditional likelihood inference for generalized additive mixed models for clustered data

Lin and Zhang (J. Roy. Statist. Soc. Ser. B 61 (1999) 381) proposed the generalized additive mixed model (GAMM) as a framework for analysis of correlated data, where normally distributed random effects are used to account for correlation in the data, and proposed to use double penalized quasi-likelihood (DPQL) to estimate the nonparametric functions in the model and marginal likelihood to estimate the smoothing parameters and variance components simultaneously. However, the normal distributional assumption for the random effects may not be realistic in many applications, and it is unclear how violation of this assumption affects ensuing inferences for GAMMs. For a particular class of GAMMs, we propose a conditional estimation procedure built on a conditional likelihood for the response given a sufficient statistic for the random effect, treating the random effect as a nuisance parameter, which thus should be robust to its distribution. In extensive simulation studies, we assess performance of this estimator under a range of conditions and use it as a basis for comparison to DPQL to evaluate the impact of violation of the normality assumption. The procedure is illustrated with application to data from the Multicenter AIDS Cohort Study (MACS).     

Fundamental reactions in TiO2 nanocrystallite aqueous solutions studied by pulse radiolysis

Reactions of the hydrated electron, H atoms, 2-propanol, and methanol radicals with the TiO₂ nano-particles have been studied either directly or by competition kinetics. The radicals were produced by radiolysis of 2-propanol, t-butanol, or methanol aqueous solutions in acid pH's. The reactions involve electron injection to the conduction band. As expected, the t-butanol radical is inert towards TiO₂ under our conditions, while the other reducing radicals react with TiO₂. The reactivity decreases in the order: e_aq⁻>H>CH₃COHCH₃>CH₂OH. Two TiO₂ nanocrystallite sizes, with average diameters of 1.0 and 4.7 nm were compared. For equal concentrations (in terms of TiO₂ molecules), the rate of electron injection shows relatively little dependency on particle size. The rates of interfacial electron transfer and transfer coefficient are also reported.