The kinetics of the hydrolysis of glycidyl methacrylate derivatized dextran (dex-MA), hydroxyethyl methacrylate derivatized dextran (dex-Hema, and hydroxyethyl methacrylate (HEMA) were systematically investigated in aqueous solution in the H0/pH range of -1.8 to 10.4 at 37 degrees C. The degradation products were quantified with reversed-phase HPLC and used to calculate the residual amount of dextran-bound methacrylate esters. In all compounds the degradation reactions follow first-order kinetics, the rate constants being susceptible to both specific acid and specific base catalysis. The reaction rate constant was independent of both the dex-MA concentration and the degree of substitution. The log Kobs-pH profiles can be divided into three parts: a proton-catalyzed, a solvent-catalyzed, and a hydroxyl-catalyzed section. At high acidities, dex-HEMA and HEMA are equally stable, but about seven times less stable than dex-MA. At alkaline pH, the order of stability is HEMA > dex-MA > dex-HEMA. This demonstrates that at alkaline pH dex-HEMA is predominantly degraded by hydrolysis of the carbonate ester, whereas at low pH, hydrolysis of the methacrylate ester is the main degradation route of this compound.
In this paper, we show that water inside mesoporous cavities in zeolites can be supercooled to ca. -40°C at which point homogeneous nucleation of the water takes place. The fundamental phenomena observed here are similar to those reported earlier in for example emulsion droplets or droplets in the vapor phase. However, as these zeolite materials are widely available, they may provide an easily accessible source for studies of supercooled liquids in confinements. Next to this, it is now possible to discriminate with thermoporometry between mesoporous cavities inside the zeolite crystals, in which homogeneous nucleation takes place, and mesopores that are connected to the external surface in which heterogeneous nucleation takes place.
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