Effects of structure on the performance of latex nanoparticles as a pseudostationary phase in electrokinetic chromatography.

The fundamental relationships between the structure and chemistry of latex nanoparticles synthesized by reversible addition fragmentation chain transfer (RAFT) controlled living polymerization and their subsequent performance as pseudostationary phases (PSP) are reported in this paper. RAFT enables the rational optimization of latex nanoparticle pseudostationary phases and control of the behavior of the PSP. Nanoparticles comprised of amphiphilic diblock copolymers of 2-acrylamido-2-methylpropane sulfonic acid-derived ionic/hydrophilic blocks and butyl- ethyl- or methyl-acrylate-derived hydrophobic blocks were synthesized in two sizes. The mobility, methylene selectivity, and efficiency of each of the six pseudostationary phases are reported, as well as the relationship between monomer quantity and NP size. Linear solvation energy relationships are reported and compared to SDS micelles and previous nanoparticle pseudostationary phases. The solvation characteristics and selectivity of nanoparticle pseudostationary phases is shown to be affected primarily by the structure of the hydrophobic copolymer block. Butyl acrylate nanoparticles 17 nm in diameter are found to provide the best overall separation performance with over 500 thousand theoretical plates generated in 6 min separations.

Synthesis and characterization of [Zn(acetate)2(amine)x] compounds (x = 1 or 2) and their use as precursors to ZnO.

As an obvious candidate for a p-type dopant in ZnO, nitrogen remains elusive in this role. Nitrogen containing precursors are a potential means to incorporate nitrogen during MOCVD growth. One class of nitrogen-containing precursors are zinc acetate amines, yet, they have received little attention. The synthesis and single crystal X-ray structure of [Zn(acetate)2(en)], and the synthesis of [Zn(acetate)2(en)2], [Zn(acetate)2(benzylamine)2], [Zn(acetate)2(butylamine)2], [Zn(acetate)2(NH3)2], and [Zn(acetate)2(tris)2], where en = ethylenediamine and tris = (tris[hydroxymethyl]aminomethane) are reported. The compounds were characterized by thermogravimetric analysis and pyrolyzed in air and inert gas to yield ZnO. These compounds are useful single source precursors to ZnO bulk powders by alkali precipitation and ZnO thin films by spray pyrolysis. The amine bound to the zinc influences the ZnO crystal size and shape and acts as a nitrogen donor for preparing nitrogen-doped ZnO during alkali precipitation. Thin films of ZnO prepared by spray pyrolysis using the precursors had a (100) preferred orientation and measured n-type to intrinsic conductivity.

RAFT polymerized nanoparticles: influences of shell and core chemistries on performance for electrokinetic chromatography.

The performance and solvation characteristics of two novel latex nanoparticle (NP) pseudo-stationary phases (PSPs) for EKC are determined and compared to those of previously reported micellar, polymeric, and NP materials. The new NPs have shells composed of strongly acidic poly(AMPS) as opposed to the poly(acrylic acid) shell of the prior NP, and have varied hydrophobic core chemistry of either poly(butyl acrylate) or poly(ethyl acrylate). The NPs poly(AMPS) shell shows only minor changes in mobility and selectivity between pH 4.9 and 9.4, allowing adjustment of pH to influence and optimize separation performance. All of the NP phases have significantly different solvation characteristics and selectivity relative to SDS micelles. The selectivity and solvent character are similar for NPs with poly(butyl acrylate) cores and different shells, but vary significantly between NPs with poly(butyl acrylate) versus poly(ethyl acrylate) cores. NPs with poly(butyl acrylate) cores are among the least cohesive PSPs reported to date, while the NP with poly(ethyl acrylate) core is among the most cohesive. The results demonstrate that PSPs with unique selectivity can be generated by altering the chemistry of the hydrophobic core.