The conundrum of pH in water nanodroplets: sensing pH in reverse micelle water pools.
In aqueous environments, acidity is arguably the most important property dictating the chemical, physical, and biological processes that can occur. However, in a variety of environments where the minuscule size limits the number of water molecules, the conventional macroscopic description of pH is no longer valid. This situation arises for any and all nanoscopically confined water including cavities in minerals, porous solids, zeolites, atmospheric aerosols, enzyme active sites, membrane channels, and biological cells and organelles.  To understand pH in these confined spaces, we have explored reverse micelles as a model system that confines water to nanoscale droplets. At the appropriate concentrations, reverse micelles form in ternary or higher order solutions of nonpolar solvent, polar solvent (usually water), and amphipathic molecules, usually surfactants or lipids. Measuring the acidity, or local density of protons, commonly known as pH, of these nanoscopic water pools in reverse micelles is challenging. First, because the volume of the water in these reverse micelles is so minute, we cannot probe its proton concentration using traditional pH meters. Second, the traditional concept of pH breaks down in a nanosystem that includes fewer than 10(7) water molecules. Third, the interpretation of results from studies attempting to measure acidity or pH in these environments is nontrivial because the conditions fall outside the accepted IUPAC definition for pH.  Researchers have developed experimental methods to measure acidity indirectly using various spectroscopic probe molecules. Most measurements of intramicellar pH have employed optical spectroscopy of organic probe molecules containing at least one labile proton coupled to electronic transitions to track pH changes in the environment. These indirect measurements of the pH reflect the local environment sensed by the probe and are complicated by the probe location within the sample and how that location affects properties such as pK(a). Thus, interpretation of the measurement in the highly heterogeneous reverse micellar environment can be challenging. Organic pH probes can often produce ambiguous acidity measurements, because the probes can readily associate with or penetrate the micellar interface. Protonation can also dramatically change the polarity of the probe and shift the probe's location within the system. As a result, researchers have developed highly charged pH-sensitive probes such as hydroxypyrene trisulfonate, vanadate or phosphate that reside in the water pool both before and after protonation. For inorganic probes researchers have used multinuclear NMR spectroscopy to directly measure conditions in the water droplet.  Regardless of the probe and method employed, reverse micellar studies include many implicit assumptions. All reported pH measurements comprise averages of molecular ensembles rather than the response of a single molecule. Experiments also represent averages of the dynamic reverse micelles over the time of the experiments. Thus the experiments report results from an average molecular position, pK(a), ionic strength, viscosity, etc. Although the exact meaning of pH in nanosized waterpools challenges scientific intuition and experimental data are non-trivial to interpret, continued experimental studies are critical to improve understanding of these nanoscopic water pools. Experimental data will allow theorists the tools to develop the models that further explore the meaning of pH in nanosized environments.
Department of Chemistry, Colorado State University, Fort Collins, 80523-1872, United States.
Debbie C
DC
Crans
Nancy E
NE
Levinger