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The Role of Microenvironment Reagent Solubility on Reaction Kinetics of 4-Nitrophenol Reduction
Michael Zeevi1 with Andrew Harrison1 and Christina Tang, PhD1
1Department of Chemical and Life Science Engineering, VCU School of Engineering
Introduction: Nanoparticles are of increasing interest due to their high surface area to volume ratio, as well as that they enable fine-tuning of the reaction microenvironment. Through flash nanoprecipitation, core-shell polymer nanoreactors were formed by directed self-assembly. Using the reduction of 4-nitrophenol as a model reduction reaction, we investigated the effect of reagent solubility in the nanoreactor microenvironment’s on nanoreactor kinetics.
Methods: The standard reaction was conducted at room temperature, with a 1000-fold excess of sodium borohydride in a quartz cuvette for real-time in situ UV-Vis analysis. Reagent concentrations were varied to examine the resulting effect on the calculated reaction rate constant. Reagent solubility limits in the nanoreactor microenvironment were estimated from solubility measurements in solvents with similar Hansen solubility parameters. Ethanol was chosen to represent the hydrophilic poly(ethylene) glycol phase and chloroform was chosen to represent the hydrophobic polystyrene phase. The hydrophilic phase had a visual absorbance at nm, and thus UV-Vis spectrometry was used to determine the saturation concentration. 1H NMR analysis with chloroform-D containing an internal standard (v/v TMS 0.03%) was used to measure the reagent solubility in the hydrophobic phase.
Results: 4-nitrophenol solubility in ethanol was determined by UV-Vis spectrometry to be . The solubility in chloroform-D was determined by 1H NMR to be . When 4-nitrophenol concentration is varied independently of sodium borohydride, an inverse relationship is observed with respect to the rate constant. However, when 4-nitrophenol and sodium borohydride concentrations are varied concurrently, no change is witnessed in the rate constant above the standard reaction concentration.
Conclusions: This experiment demonstrated that the rate of reaction in polystyrene core nanoreactors is not dependent on the reagent concentrations above the standard concentration. Solubility in each phase was measured in an effort to explain this behavior. The differences in solubility observed between the hydrophobic and hydrophilic phases may serve to explain this behavior if the interior, hydrophobic phase is saturated by 4-nitrophenol at the standard concentration. Future work should include study of concentrations at lower values than the standard concentration to determine when a change in the observed rate constant occurs.
Chemical and Life Science Engineering
Nanoreactors, 4-nitrophenol reduction, polymer nanoreactors
Catalysis and Reaction Engineering | Nanoscience and Nanotechnology | Polymer Science
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