pH- and concentration-programmable electrodialytic buffer generator.

We have presented in a companion paper a suppressor-based electrodialytic buffer generator (EBG) that can produce programmable pH gradients. Here we demonstrate a three-electrode EBG. In this three-compartment flow-through device, the central compartment is separated from the outer compartments with a cation-exchange membrane (CEM) and an anion-exchange membrane (AEM), respectively. One platinum electrode is disposed in each compartment. The flows through each compartment are independent. With appropriate solutions in each compartment, independent potentials are applied to the CEM and AEM electrodes with respect to the grounded central electrode. The CEM current and the AEM current can be independently manipulated to generate buffers with variable concentration and pH in the central compartment. Both the CEM and AEM currents can be positive or negative. For the CEM, a positive current (i(cat)(in)) indicates that cations are coming in from the CEM channel to the center. A negative current (i(cat)(out)) takes cations out of the center to the CEM channel. Similarly for the AEM, currents governing anion transport into the center channel from the AEM channel (AEM electrode negative) or the reverse (AEM electrode positive) are respectively denoted by i(an)(in) or i(an)(out). Most examples herein involve inward ion transport, referred to as the additive mode. Depending on whether i(cat)(in) <i(an)(in) or i(cat)(in) > i(an)(in), H(+)/O(2) and OH(-)/H(2) are respectively produced at the central electrode to maintain electroneutrality. Any gas formed is subsequently removed by a gas removal device. The pH of the central channel effluent is related to the ratio of the currents through the two membranes, while the generated concentration is controlled by the absolute value of the currents. The buffer concentration and pH can be varied in a controlled predictable manner. A pH span of 3-12 was attained and a phosphate buffer concentration up to 140 mM was generated. We demonstrate a variety of combined pH/concentration gradients from a mixture of ethylenediamine, citrate, and phosphate by manipulating i(cat)(in), which controls introduction of the ethylenediammonium ion, and i(an)(in), which controls the introduction of citrate and phosphate ions. We also demonstrate an additive-subtractive mode of operation where both inward and outward currents are used to add one type of ion while removing another type of ion to reproducibly generate pH/concentration gradients.