Cationic polymerization with boron halides. V. Synthesis of poly(isobutylene-b-styrene) and poly(styrene-b-isobutylene)

Block copolymers of isobutylene and styrene, PIB-b-PSt and PSt-b-PIB, have been prepared by a two-step synthesis involving (1) preparation of terminally chlorinated (telechelic) polyisobutylene or polystyrene “prepolymers” by using the H₂O/BCl₃ initiator system and (2) blocking from these telechelic prepolymers a second polymer segment by using an alkyaluminum, e.g., Et₂AlCl coinitiator. The telechelic polyisobutylene and polystyrene contain tertiary and benzylic chlorine termini, respectively. Block copolymer characterization included detailed selective solvent extraction procedures, coupled with GPC determinations, PMR, solubility, and intrinsic viscosity studies. The synthesis of PIB-b-PSt and PSt-b-PIB provides direct chemical evidence for the presence and position of active chlorine termini in BCl₃-coinitiated olefin polymerizations.     

Effects of hydraulic pressure on the stability and transition of wetting modes of superhydrophobic surfaces

The underlying mechanisms of stability, metastability, or instability of the Cassie-Baxter and Wenzel wetting modes and their transitions on superhydrophobic surfaces decorated with periodic micropillars are quantitatively studied in this article. Hydraulic pressure, which may be generated by the water-air interfacial tension of water droplets or external factors such as raining impact, is shown to be a key to understanding these mechanisms. A detailed transition process driven by increasing hydraulic pressure is numerically simulated. The maximum sustainable or critical pressure of the Cassie-Baxter wetting state on a pillarlike microstructural surface is formulated for the first time in a simple, unified, and precise form. This analytic result reveals the fact that reducing the microstructural scales (e.g., the pillars' diameters and spacing) is probably the most efficient measure needed to enlarge the critical pressure significantly. We also introduce a dimensionless parameter, the pillar slenderness ratio, to characterize the stability of either the Cassie-Baxter or the Wenzel wetting state and show that the energy barrier for transitioning from the Cassie-Baxter to the Wenzel wetting mode is proportional to both the slenderness ratio and the area fraction. Thus, the Cassie-Baxter wetting mode may collapse under a hydraulic pressure lower than the critical one if the slenderness ratio is improperly small. This quantitative study explains fairly well some experimental observations of contact angles that can be modeled by neither Wenzel nor Cassie-Baxter contact angles and eventually leads to our proposals for a mixed (or coexisting) wetting mode.     

The effects of media properties on the horseradish peroxidase-catalyzed fluorogenic reaction

The effects of media properties including buffers, acidity, solvents and surfactant on horseradish peroxidase-catalyzed fluorogenic reaction were investigated. The results showed that the so-called non-fluorescent hydrogen donors were in fact fluorescent. There existed an acid—base equilibrium in the fluorescent dimer product. For p -hydroxyphenylpropionic acid, a pK_a value of 8.0 for the product was obtained from its titration curve. The product fluorescence increased with higher pH, however, a longer time was needed to reach the reaction equilibrium due to the pH mismatch problem. Cationic micelles cetyltrimethylammonium bromide and cetyltrimethylammonium chloride could reduce the pH mismatch and offered a way to further increase the determination sensitivity. Finally, a micelle-enhanced flow-injection analysis of horseradish peroxidase is suggested.