Phosphorus-31 nuclear magnetic resonance spectroscopy ( (31)P NMR) was used to differentiate virgin coconut oil (VCO) from refined, bleached, deodorized coconut oil (RCO). Monoglycerides (MGs), diglycerides (DGs), sterols, and free fatty acids (FFAs) in VCO and RCO were converted into dioxaphospholane derivatives and analyzed by (31)P NMR. On the average, 1-MG was found to be higher in VCO (0.027%) than RCO (0.019%). 2-MG was not detected in any of the samples down to a detection limit of 0.014%. On the average, total DGs were lower in VCO (1.55%) than RCO (4.10%). When plotted in terms of the ratio [1,2-DG/total DGs] versus total DGs, VCO and RCO samples grouped separately. Total sterols were higher in VCO (0.096%) compared with RCO (0.032%), and the FFA content was 8 times higher in VCO than RCO (0.127% vs 0.015%). FFA determination by (31)P NMR and titration gave comparable results. Principal components analysis shows that the 1,2-DG, 1,3-DG, and FFAs are the most important parameters for differentiating VCO from RCO.

Lab-in-a-drop, using ultrasonic levitation, has been actively investigated for the last two decades. Benefits include lack of contact between solutions and an apparatus and a lack of sample cross-contamination. Understanding and controlling mixing in the levitated drop is necessary for using an acoustically levitated drop as a microreactor, particularly for studying kinetics. A pulsed electrostatic delivery system enables addition and mixing of a desired-volume droplet with the levitated drop. Measurement of mixing kinetics is obtained by high-speed video monitoring of a titration reaction. Drop heterogeneity is visualized as 370 nl of 0.25 M KOH (pH: 13.4) was added to 3.7 μL of 0.058 M HCl (pH: 1.24). Spontaneous mixing time is about 2 s. Following droplet impact, the mixed drop orbits the levitator axis at about 5 Hz during homogenization. The video's green channel (maximum response near 540 nm) shows the color change due to phenolphthalein absorption. While mixing is at least an order of magnitude faster in the levitated drop compared with three-dimensional diffusion, modulation of the acoustic waveform near the surface acoustic wave resonance frequency of the levitated drop does not substantially reduce mixing time.

The electrochemical interfacial properties of a well-ordered self-assembled monolayer (SAM) of 1-undecanethiol (UDT) on evaporated gold surface have been investigated by electrochemical impedance spectroscopy (EIS) in electrolytes without a redox couple. Using a constant-phase element (CPE) series resistance model, prolonged incubation times (up to 120 h) show decreasing monolayer capacitance approaching the theoretical value for 1-undecanethiol. Using the CPE exponent α as a measure of ideality, it was found that the monolayer approaches an ideal dielectric (α = 0.992) under prolonged incubation, which is attributed to the reduction of pinholes and defects in the monolayer during coalescence and annealing of SAM chains. The SAMs behave as insulators until a critical potential, Vc, is exceeded in both cathodic and anodic regimes, where electrolyte ions are believed to penetrate the monolayers. Using a Randles circuit model for these cases, the variation of the capacitance and charge transfer resistance with applied dc potential shows decreased permeability to ionic species with prolonged incubation time. The EIS data show that UDT (methylene chain length n = 10), incubated for 120 h, forms a monolayer whose critical voltage range extends from −0.3 to 0.5 V versus Ag/AgCl, previously attained only for alkanethiol at n = 15. At low frequencies where ion diffusion occurs, almost pure capacitive phase (−89 deg) was attained with lengthy incubation.

Levitated drops show potential as microreactors, especially when radicals are present as reactants or products. Solid/liquid interfaces are absent or minimized, avoiding adsorption and interfacial reaction of conventional microfluidics. We report amperometric detection in an acoustically levitated drop with simultaneous ballistic addition of reactant. A gold microelectrode sensor was fabricated with a lithographic process; active electrode area was defined by a photosensitive polyimide mask. The microdisk gold working electrode of radius 19 μm was characterized using ferrocenemethanol in aqueous buffer. Using cyclic voltammetry, the electrochemically active surface area was estimated by combining a recessed microdisk electrode model with the Randles-Sevcik equation. Computer-controlled ballistic introduction of reactant droplets into the levitated drop was developed. Chronoamperometric measurements of ferrocyanide added ballistically demonstrate electrochemical monitoring using the microfabricated electrode in a levitated drop. Although concentration increases with time due to drop evaporation, the extent of concentration is predictable with a linear evaporation model. Comparison of diffusion-limited currents in pendant and levitated drops show that convection arising from acoustic levitation causes an enhancement of diffusion-limited current on the order of 16%.

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