The high-speed GC separation and MS characterization of lime oil and lemon oil samples using programmable column selectivity and time-of-flight mass spectrometry is described. The volatile essential oils are separated on a series-coupled (tandem) column ensemble consisting of a polar trifluoropropylmethyl polysiloxane column and a nonpolar 5% phenyl dimethyl polysiloxane column. Both columns are 7 m long. A 50 degrees C/min linear temperature ramp from 50 to 200 degrees C is used, giving an analysis time of approximately 2.5 min. A time-of-flight MS with time array detection and automated peak finding and characterization software was used to identify 50 components in lime oil samples and 25 components in lemon oil samples. Despite numerous cases of extensive peak overlap, spectral deconvolution software was very successful in the characterization of most overlapping peaks. For cases where a more complete chromatographic separation is desirable, the tandem column ensemble is operated in the first-column stop-flow mode to enhance the separation of selected overlapping clusters of peaks. A valve between the junction point of the tandem column ensemble and a source of carrier gas at the GC inlet pressure is opened for 2-5-s intervals to stop the flow of carrier gas in the first column. This is used to increase the separation of target component groups that overlap in the ensemble chromatogram without first-column stop-flow operation. This procedure is used to isolate the peak for limonene, the largest peak in the analytical-ion chromatogram of both the lime and lemon oil samples.

A pneumatically actuated valve is used to connect the junction point of a series-coupled column ensemble to a ballast chamber containing carrier gas at the ensemble inlet pressure in order to periodically stop the carrier gas flow in the first column. When the valve is opened, mixture components, which have migrated across the column junction, are accelerated toward a time-of-flight mass spectrometer that is used as an ensemble detector. Mixture components, which are still in the first column, are frozen in position. This allows for the insertion of time windows into the ensemble chromatogram that can aid in the separation of some overlapping component peaks. The capillary column ensemble (0.18-mm i.d. x 0.18-microm film thickness) consists of a 7.0-m length of polar, (trifluoropropyl)methyl polysiloxane column followed by a 7.0-m length of nonpolar dimethyl polysiloxane column. A flame ionization detector located at the column junction point is used to monitor a portion of the effluent from the first column in order to determine the valve timing sequence needed to enhance the separation of component pairs that are separated by the first column but coelute from the column ensemble. When one of the components of a targeted pair has crossed the junction but the other component is still in the first column, the valve is opened, typically for 1-5 s. The stop-flow system is used to enhance the separation of a mixture containing some common essential oil components and a mixture containing some common pesticides.

A computer-driven pressure controller is used to deliver pressure pulses to the junction point of two series-coupled columns using different stationary-phase chemistries. The column ensemble consists of a trifluoropropylmethyl polysiloxane column followed by a dimethyl polysiloxane column. Each pressure pulse causes a differential change in the carrier gas velocities in the two columns, which lasts for the duration of the pulse. A pressure pulse is used to selectively increase the separation of a component pair that is separated by the first column but coelutes from the series-coupled ensemble. If both components are on the same column when the pulse is applied, a small change in the ensemble separation occurs. If one component of the pair is on the first column and the other component is on the second column, a pressure pulse can result in a much larger change in the ensemble separation for the component pair. A model with a spreadsheet algorithm is used to predict the effects of a pressure pulse on the trajectories of component bands on the column ensemble. The effect of the initiation time of a pressure pulse is investigated for a two-component mixture that coelutes from the column ensemble. For the case where the entire pressure pulse occurs when one of the components is on the first column and the other component is on the second column, the peak separation from the ensemble increases nearly linearly with the product of the pressure pulse amplitude and the pulse duration. Peak shape artifacts are observed if the pressure pulse occurs when a solute band is migrating across the column junction point.

Lubricant-infused surfaces (LISs) and slippery liquid-infused porous surfaces (SLIPSs) have shown remarkable success in repelling low-surface-tension fluids. The atomically smooth, defect-free slippery surface leads to reduced droplet pinning and omniphobicity. However, the presence of a lubricant introduces liquid–liquid interactions with the working fluid. The commonly utilized lubricants for LISs and SLIPSs, although immiscible with water, show various degrees of miscibility with organic polar and nonpolar working fluids. Here, we rigorously investigate the extent of miscibility by considering a wide range of liquid–vapor surface tensions (12–73 mN/m) and different categories of lubricants having a range of viscosities (5–2700 cSt). Using high-fidelity analytical chemistry techniques including X-ray photoelectron spectroscopy, nuclear magnetic resonance, thermogravimetric analysis, and two-dimensional gas chromatography, we quantify lubricant miscibility to parts per billion accuracy. Furthermore, we quantify lubricant concentrations in the collected condensate obtained from prolonged condensation experiments with ethanol and hexane to delineate mixing and shear-based lubricant drainage mechanisms and to predict the lifetime of LISs and SLIPSs. Our work not only elucidates the effect of lubricant properties on miscibility with various fluids but also develops guidelines for developing stable and robust LISs and SLIPSs.

SummaryA series-coupled ensemble of two capillary GC columns of different selectivity with an adjustable pressure at the column junction point is used to obtain tunable selectivity for high-speed GC and GC/ TOFMS. An electronic pressure controller with a 0.1-psi step size is used to obtain numerous computer-selected unique selectivities. System configurations for conventional, atmospheric-pressure outlet operation with flame ionization detection and for vacuum-outlet operation with photoionization detection are described for GC-only experiments. Polydimethylsiloxane is used as the non-polar column and polyethylene glycol (atmospheric outlet) or triflouropropylpolysiloxane (vacuum outlet) is used as the polar column. For GC/ TOFMS experiments, 5% phenyl polydimethylsiloxane was used as the non-polar column, and polyethylene glycol was used as the polar column. The time-of-flight mass spectrometer can acquire up to 500 complete mass spectra per second. Since spectral continuity is achieved across the entire chromatographic peak profile, severely overlapping peaks can be spectrally deconvoluted for high-speed characterization of completely unknown mixtures. For mixture components with significantly different fragmentation patterns, spectral deconvolution can be achieved for chromatographic peak separations of as little as 6.0 ms. This can result is very large peak capacity for time compressed (not completely resolved) chromatograms. The use of columns with tunable selectivity allows for precise peak-position control, which can result in more efficient utilization of available peak capacity and thus further time compression of chromatograms. The limits of tunability and deconvolution are tested for near co-elutions of different classes of hydrocarbon compounds as well as for more multi-functional mixtures.