SynopsisThe grafting of methyl methacrylate (MMA) onto polybutadiene (PB) latexes prepared by seeded emulsion polymerization at 50°C was investigated as a function of: (a) initiator concentration used in the secondary polymerization, (b) monomer-to-polymer ratio, (c) the specific surface area of the seed latex, and (d) the degree of conversion. The thin Layer chromatography/flame ionization detection (TLC/FID) technique was used to determine the proportion of graft copolymer in the core/shell latex. It was found that grafting PMMA onto PB depended upon the concentration of initiator, decreasing as the concentration was increased. The amount of grafting increased with increasing specific surface area of the seed latex, while the molecular weight of the acetone-soluble graft copolymer decreased. The amount of graft copolymer was found to decrease concurrently with increasing monomer-to-polymer ratio and degree of conversion. These results suggest a hydrogen abstraction mechanism in the formation of graft PB-PMMA through a chain transfer process.
Photoionization with attosecond pulses populates hole states in the photoion. Superpositions of hole states represent ideal candidates for time-dependent spectroscopy, for example via pump-probe studies. The challenge consists in identifying pulses that create coherent superpositions of hole states while satisfying practical constraints. Here, we employ quantum optimal control to maximize the degree of coherence between these hole states. To this end, we introduce a derivative-free optimization method with sequential parametrization update (SPA optimization). We demonstrate the versatility and computational efficiency of SPA optimization for photoionization in argon by maximizing the coherence between the 3s and 3p 0 hole states using shaped attosecond pulses. We show that it is possible to maximize the hole coherence while simultaneously prescribing the ratio of the final hole state populations.
Controlled transport of surface-functionalized magnetic beads in a liquid medium is a central requirement for the handling of captured biomolecular targets in microfluidic lab-onchip biosensors. Here, the influence of the physiological liquid medium on the transport characteristics of functionalized magnetic particles and on the functionality of the coupled protein is studied. These aspects are theoretically modeled and experimentally investigated for prototype superparamagnetic beads, surfacefunctionalized with green fluorescent protein immersed in buffer solution with different concentrations of a surfactant. The model reports on the tunability of the steady-state particle substrate separation distance to prevent their surface sticking via the choice of surfactant concentration. Experimental and theoretical average velocities are discussed for a ratchet-like particle motion induced by a dynamic external field superposed on a static locally varying magnetic field landscape. The developed model and experiment may serve as a basis for quantitative forecasts on the functionality of magnetic particle transport-based lab-on-chip devices.
The particle morphology and percent grafting were investigated as a function of the crosslink density of the seed latex in two systems of core/shell latexes of polybutadiene/polymethyl methacrylate (PB/PMMA) and styrene–butadiene rubber/polymethyl methacrylate (SBR/PMMA) prepared by seeded emulsion polymerization at 50°C. The thin layer chromatography/flame ionization detection (TLC/FID) technique was used to characterize the grafting efficiency of the core/shell latexes. The percent grafting of the shell polymer was found to decrease with increasing the crosslink density of the core material. The particle morphology and precent grafting were also investigated as a function of composition and structure of the core material in four core/shell latex systems: polybutadiene/styrene–acrylonitrile copolymer (PB/SAN), (styrene‐butadiene) random copolymer/styrene acrylonitrile copolymer (S:B/SAN), polystyrene : polybutadiene/styrene‐acrylonitrile copolymer (PS:PB/SAN) and Kraton/styrene‐acrylonitrile copolymer (Kraton/SAN), which were prepared by direct emulsification for the seed followed by emulsion polymerization at 70°C for the shell polymer. Grafting and crosslinking of the core material were found to be competitive reactions depending on the microstructure of the seed latex.
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