Study of amphiphilic polyester micelles by hyper-rayleigh scattering: invertibility and phase transfer

For the first time, hyper-Rayleigh scattering (HRS) of invertible polymeric micellar structures has been measured. HRS measurements on amphiphilic invertible polyesters with alternating hydrophilic and hydrophobic fragments were carried out in solvents of differing polarity. The observed strong variation of the HRS signals is attributed to the switching behavior of the polyester micelles in the different solvents. The hyperpolarizabilities and the size of the micelles increased with decreasing polarity of the solvent. Observing the dynamics of the solubilization of an insoluble dye (malachite green) by the invertible polyester in toluene confirmed the possibility to reveal conformational changes in polyester macromolecules by HRS. In contrast to UV measurements which showed a continuous increase in absorbance and indicated overall solubilization of the dye, the HRS signals decreased after approaching a maximum value. The decrease of the HRS signals is attributed to the change of dye molecules' orientation within the micelles due to the change of polymeric conformation in toluene. The results have shown that HRS is sensitive to reorientation and ordering of the macromolecules and might become a powerful tool for studying polymer micellar structures as well as phase transfer processes at the nanoscale.     

Monolithic porous polymer stationary phases in polyimide chips for the fast high-performance liquid chromatography separation of proteins and peptides

Poly(lauryl methacrylate-co-ethylene dimethacrylate) and poly(styrene-co-divinylbenzene) stationary phases in monolithic format have been prepared by thermally initiated free radical polymerization within polyimide chips featuring channels having a cross-section of 200micromx200microm and a length of 6.8cm. These chips were then used for the separation of a mixture of proteins including ribonuclease A, myoglobin, cytochrome c, and ovalbumin, as well as peptides. The separations were monitored by UV adsorption. Both the monolithic phases based on methacrylate and on styrene chemistries enabled the rapid baseline separation of most of the test mixtures. Best performance was achieved with the styrenic monolith leading to fast baseline separation of all four proteins in less than 2.5min. The in situ monolith preparation process affords microfluidic devices exhibiting good batch-to-batch and injection-to-injection repeatability.     

Evidence of different stoichiometries for the limiting carbonate complexes across the lanthanide(III) series: a capillary electrophoresis-mass spectrometry study

The electrophoretic mobilities (mu ep,Ln) of twelve lanthanides (not Ce, Pr and Yb) were measured by CE-ICP-MS in 0.15 and 0.5 mol L(-1) Alk2 CO3 aqueous solutions for Alk+ = Li+, Na+, K+ and Cs+. In 0.5 mol L(-1) solutions, two different mu ep,Ln values were found for the light (La to Nd) and the heavy (Dy to Tm) lanthanides, which suggests two different stoichiometries for the carbonate limiting complexes. These results are consistent with a solubility study that attests the Ln(CO3)3(3-) and Ln(CO3)4(5-) stoichiometries for the heavy (small) and the light (big) lanthanides, respectively. The Alk+ counterions influence the mu ep,Ln Alk2 CO3 values, but not the overall shape of the mu ep,Ln Alk2 CO3 plots as a function of the lanthanide atomic numbers: the counterions do not modify the stoichiometries of the inner sphere complexes. The influence of the Alk+ counterions decreases in the Li+ > Na+ > K+ > Cs+ series. The K3,Ln stepwise formation constants of the Ln(CO3)3(3-) complexes slightly increase with the atomic numbers of the lanthanides while K4,Ln, the stepwise formation constants of Ln(CO3)4(5-) complexes, slightly decrease from La to Tb, and is no longer measurable for heavier lanthanides.     

Decatungstate (W10O)/Silane: A New and Promising Radical Source Under Soft Light Irradiation

The use of decatungstate in combination with silanes to generate silyl radicals under green fluorescence bulb irradiation as well as sunlight exposure is described. The mechanisms are investigated by ESR and laser flash photolysis experiments. The high potential of this reaction is evidenced here when using a decatungstate/silane/diphenyl iodonium salt combination as an initiating system for the ring opening photopolymerization of epoxides.