The effect of PEO block lengths on the size and stability of complex coacervate core micelles

We report on a series of polyion complexes from mixtures of poly(ethylene oxide)-block-poly(N,N-diethylaminoethylmethacrylate) (PEO-PDEAMA) and poly(ethylene oxide)-block-poly(aspartic acid) (PEO-PAsp). As expected, the micelle size, polydispersity and stability are dependant on the relative and absolute lengths of the polyelectrolyte chains. However, we also demonstrate that whilst the length of the charged polyelectrolyte blocks is important, the length of the PEO chains is an equally relevant variable in determining both the size and stability of the final micelles as well as the degree of charge neutralisation at which micellisation occurs. We also show that the kinetics of formation can result in very different stability of the final micelles.     

Photoinduced ultrafast electron transfer from CdSe quantum dots to Re-bipyridyl complexes

Ultrafast dissociation of excitons in CdSe quantum dots via electron transfer to adsorbed Re-bipyridyl complexes was demonstrated. The dissociation pathway was determined by the observation of reduced adsorbate using femtosecond IR spectroscopy. The rate of electron transfer was shown to increase at smaller QD sizes. Electron transfer time as fast as 2.3 ps was observed, faster than the exciton annihilation time in CdSe. The ultrafast charge separation in this quantum dot-adsorbate donor-acceptor complex provides a potential approach for separating multiple excitons in quantum dots.     

Numerical simulation of sedimentation of microparticles using the discrete particle method

A mathematical model has been formulated based on the combined continuous and discrete particle method for investigating the sedimentation behaviour of microparticles in aqueous suspensions, by treating the fluid phase as continuous and the particles phase as discrete, thus allowing the behaviour of individual particles to be followed and the evolution of the structure of the particle phase to be investigated as a function of time. The model takes into account most of the prevailing forces acting on individual particles including van der Waals attractive, electrostatic repulsive, gravitational, Brownian, depletion, steric, contact and drag forces. A code has also been developed based on the model. This paper reports some preliminary modelling results of mono-dispersed microparticles settling in aqueous suspensions under various conditions. The results show the short time dynamics of the fluid phase, which has a similar order of magnitude to the particle phase. Such short time dynamics could bear significance to processes such as particle aggregation when their size becomes very small. Preliminary analyses of the results have also been carried out on the evolution of particle settling based on a newly proposed parameter, local normalised volume fraction （LNVF）.     

Effects of physical aging,crystallinity, and orientation on the enzymatic degradation of poly(lactic acid)

The effects of physical aging, degree of crystallinity, and orientation of poly(lactic acid) (PLA) were studied using differential scanning calorimetry (DSC) and wide angle X-ray scattering (WAXS). The samples of PLA with 96% [L] and 4% [D] contents were prepared by injection molding. The physical aging of PLA strongly depended on time and temperature. The change of rate of physical aging was very fast initially and slowed down as time increased. The enzymatic degradation of PLA was carried out with proteinase K at 37°C at a pH value of 8.6 in a Tris/HCl buffer solution. The enzymatic degradation rate was found to decrease as a function of physical aging (i.e., excess enthalpy relaxation). The rate of enzymatic degradation of PLA decreased with the increase in crystallinity. A threshold was observed when the heat of fusion was less than 20 J/g. The weight loss of PLA with a low level of crystallinity had no apparent change during any period of testing time. The rates of enzymatic degradation of stretched and injection-molded specimens were comparable. © 1996 John Wiley & Sons, Inc.     

Pulsed laser ablation of La0.5Sr0.5CoO3

The ablation process of La_0.5Sr_0.5CoO₃ by a spatial uniform 248 nm excimer laser beam has been characterized. Ablation rates, changes in the target surface morphology and composition have been studied as a function of the laser fluence. The dependence of the ablation rate on the laser fluence has been explained by a model based on plasma absorption. The threshold fluence for complete dissociation of the surface has been determined and is found equal to 0.7 J/cm². Above this threshold, a steady-state target surface condition is obtained within 30 pulses. Below the threshold fluence, CoO nuclei form, which have a pronounced effect on the target composition and morphology. In addition, ellipsometric and reflectance spectra have been measured in the photon energy range of 1.8 to 5.0 eV.     

Regression with multiple regressor arrays

Extension of standard regression to the case of multiple regressor arrays is given via the Kronecker product. The method is illustrated using ordinary least squares regression (OLS) as well as the latent variable (LV) methods principal component regression (PCR) and partial least squares regression (PLS). Denoting the method applied to PLS as mrPLS, the latter was shown to explain as much or more variance for the first LV relative to the comparable L‐partial least squares regression (L‐PLS) model. The same relationship holds when mrPLS is compared to PLS or n‐way partial least squares (N‐PLS) and the response array is 2‐way or 3‐way, respectively, where the regressor array corresponding to the first mode of the response array is 2‐way and the second mode regressor array is an identity matrix. In a comparison with N‐PLS using fragrance data, mrPLS proved superior in a validation sense when model selection was used. Though the focus is on 2‐way regressor arrays, the method can be applied to n‐way regressors via N‐PLS. Copyright © 2007 John Wiley & Sons, Ltd.     

Evidence for the direct desorption of crown ether-metal ion complexes in liquid secondary Ionization Mass Spectrometry

The liquid secondary ionization mass spectra of crown ether solutions and crown ether solutions containing alkali metal cations were generated. Cesium cations acted as both the primary ion beam and as a competing gas-selvedge-phase reactant. The data suggest that crown ether complexes formed in the condensed phase survive intact the fast ion bombarding event and the transition into the gas phase. The data further suggest that crown ether complexes formed in the condensed phase predominate in the ion spectrum over the corresponding complexes formed in the selvedge.