In Situ pH Measurements of Individual Levitated Microdroplets Using Aerosol Optical Tweezers

The pH of microscale reaction environments controls numerous physicochemical processes, requiring a real-time pH microprobe. We present highly accurate real-time pH measurements of microdroplets using aerosol optical tweezers (AOT) and analysis of the whispering gallery modes (WGMs) contained in the cavity-enhanced Raman spectra. Uncertainties ranging from ±0.03 to 0.06 in pH for picoliter droplets are obtained through averaging Raman frames acquired at 0.5 Hz over 3.3 min. The high accuracy in pH determination is achieved by combining two independent measurements uniquely provided by the AOT approach: the anion concentration ratio from the spontaneous Raman spectra, and the total solute concentration from the refractive index retrieved from WGM analysis of the stimulated cavity-enhanced Raman spectra. pH can be determined over a range of -0.36 to 0.76 using the aqueous sodium bisulfate system. This technique enables direct measurements of pH-dependent chemical and physical changes experienced by individual microparticles and exploration of the role of pH in the chemical behavior of confined microenvironments.