A mathematical model is developed to study the combined influences of electromagnetohydrodynamic forces in controlling the fluid flow through parallel plate rectangular microchannels. The electric double layer (EDL) effects are modelled by employing the classical Poisson–Boltzmann equation. The governing fluid flow equations are subsequently solved, in an effort to obtain closed form expressions depicting the variations in the overall flow rate as a function of various influencing system parameters. It is revealed that, with the aid of a relatively low-magnitude magnetic field, a substantial augmentation in the volumetric flow rates can be achieved. However, with magnetic fields of higher strengths, strongly opposing volumetric forces might offset any further possibilities of flow rate augmentation. Certain critical non-dimensional parameters are also identified, which can play significant roles in the overall flow augmentation mechanism.

The development and characterization of a microanalytical subsystem comprising silicon-micromachined first- and second-dimension separation columns and a silicon-micromachined thermal modulator (μTM) for comprehensive two-dimensional (i.e., μGC × μGC) separations are described. The first dimension consists of two series-coupled 3.1 cm × 3.1 cm μcolumn chips with etched channels 3 m long and 250 μm × 140 μm in cross section, wall-coated with a poly(dimethylsiloxane) (PDMS) stationary phase. The second dimension consists of a 1.2 cm × 1.2 cm μcolumn chip with an etched channel 0.5 m long and 46 μm × 150 μm in cross section wall-coated with either a trigonal tricationic room-temperature ionic liquid (RTIL) or a commercial poly(trifluoropropylmethyl siloxane) (OV-215) stationary phase. The two-stage, cryogen-free μTM consists of a Si chip containing two series-coupled, square spiral channels 4.2 cm and 2.8 cm long and 250 μm × 140 μm in cross section wall-coated with PDMS. Conventional injection methods and flame ionization detection were used. Temperature-ramped separations of a simple alkane mixture using the RTIL-coated second-dimension ((2)D) μcolumn produced reasonably good peak shapes and modulation numbers; however, strong retention of polar compounds on the RTIL-coated (2)D μcolumn led to excessively broad peaks with low (2)D resolution. Substituting OV-215 as the (2)D μcolumn stationary phase markedly improved the performance, and a structured 22 min chromatogram of a 36-component mixture spanning a vapor pressure range of 0.027 to 13 kPa was generated with modulated peak fwhm (full width at half-maximum) values ranging from 90 to 643 ms and modulation numbers of 1-6.

Rapid, comprehensive two-dimensional gas chromatographic (GC × GC) separations by use of a microfabricated midpoint thermal modulator (μTM) are demonstrated, and the effects of various μTM design and operating parameters on performance are characterized. The two-stage μTM chip consists of two interconnected spiral etched-Si microchannels (4.2 and 2.8 cm long) with a cross section of 250 × 140 μm(2), an anodically bonded Pyrex cap, and a cross-linked wall coating of poly(dimethylsiloxane) (PDMS). Integrated heaters provide rapid, sequential heating of each μTM stage, while a proximate, underlying thermoelectric cooler provides continual cooling. The first-dimension column used for GC × GC separations was a 6 m long, 250 μm i.d. capillary with a PDMS stationary phase, and the second-dimension column was a 0.5 m long, 100 μm i.d. capillary with a poly(ethylene glycol) phase. Using sets of five to seven volatile test compounds (boiling point ≤174 °C), the effects of the minimum (T(min)) and maximum (T(max)) modulation temperature, stage heating lag/offset (O(s)), modulation period (P(M)), and volumetric flow rate (F) on the quality of the separations were evaluated with respect to several performance metrics. Best results were obtained with a T(min) = -20 °C, T(max) = 210 °C, O(s) = 600 ms, P(M) = 6 s, and F = 0.9 mL/min. Replicate modulated peak areas and retention times were reproducible to <5%. A structured nine-component GC × GC chromatogram was produced, and a 21 component separation was achieved in <3 min. The potential for creating portable μGC × μGC systems is discussed.

Comprehensive two-dimensional gas chromatography (GC×GC) with a temperature-programmed microfabricated thermal modulator (μTM) is demonstrated. The 0.78 cm(2), 2-stage μTM chip with integrated heaters and a PDMS coated microchannel was placed in thermal contact with a solid-state thermoelectric cooler and mounted on top of a bench scale GC. It was fluidically coupled through heated interconnects to an upstream first-dimension ((1)D) PDMS-coated capillary column and a downstream uncoated capillary or second-dimension ((2)D) PEG-coated capillary. A mixture of n-alkanes C6-C10 was separated isothermally and the full-width-at-half-maximum (fwhm) values of the modulated peaks were assessed as a function of the computer-controlled minimum and maximum stage temperatures of μTM, Tmin and Tmax, respectively. With Tmin and Tmax fixed at -25 and 100°C, respectively, modulated peaks of C6 and C7 had fwhm values<53 ms while the modulated peaks of C10 had a fwhm value of 1.3s, due to inefficient re-mobilization. With Tmin and Tmax fixed at 0 and 210°C, respectively, the fwhm value for the modulated C10 peaks decreased to 67 ms, but C6 and C7 exhibited massive breakthrough. By programming Tmin from -25 to 0°C and Tmax from 100 to 220°C, the C6 and C7 peaks had fwhm values≤50 ms, and the fwhm for C10 peaks remained<95 ms. Using the latter conditions for the GC×GC separation of a sample of unleaded gasoline yielded resolution similar to that reported with a commercial thermal modulator. Replacing the PDMS phase in the μTM with a trigonal-tricationic room temperature ionic liquid eliminated the bleed observed with the PDMS, but also reduced the capacity for several test compounds. Regardless, the demonstrated capability to independently temperature program this low resource μTM enhances its versatility and its promise for use in bench-scale GC×GC systems.

We describe first results from a micro-analytical subsystem that integrates a detector comprising a polymer-coated micro-optofluidic ring resonator (μOFRR) chip with a microfabricated separation module capable of performing thermally modulated comprehensive two-dimensional gas chromatographic separations (μGC ×μGC) of volatile organic compound (VOC) mixtures. The 2 × 2 cm μOFRR chip consists of a hollow, contoured SiO(x) cylinder (250 μm i.d.; 1.2 μm wall thickness) grown from a Si substrate, and integrated optical and fluidic interconnection features. By coupling to a 1550 nm tunable laser and photodetector via an optical fiber taper, whispering gallery mode (WGM) resonances were generated within the μOFRR wall, and shifts in the WGM wavelength caused by transient sorption of eluting vapors into the PDMS film lining the μOFRR cylinder were monitored. Isothermal separations of a simple alkane mixture using a PDMS coated 1st-dimension ((1)D) μcolumn and an OV-215-coated 2nd-dimension ((2)D) μcolumn confirmed that efficient μGC ×μGC-μOFRR analyses could be performed and that responses were dominated by film-swelling. Subsequent tests with more diverse VOC mixtures demonstrated that the modulated peak width and the VOC sensitivity were inversely proportional to the vapor pressure of the analyte. Modulated peaks as narrow as 120 ms and limits of detection in the low-ng range were achieved. Structured contour plots generated with the μOFRR and a reference FID were comparable.

The present paper aims to develop a theoretical model to highlight the influences of the near-wall interaction potentials and the consequent migrative fluxes on the size-based separation of macromolecules in microchannels subject to combined electromagnetohydrodynamic influences. It is established that the speed of traverse and the extent of spreading (dispersion) of the macromolecular bands is effectively determined on the basis of the macromolecular size relative to the channel height and the extent of near-wall interactions. It is demonstrated that because of the near-wall effects, macromolecular pairs with less disparities in sizes give rise to higher values of resolution.

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Fast efficient chromatography is important in order to resolve the individual components of complex biological mixtures. Classically, thermal effects that decrease chromatographic efficiency accompany both HPLC and SFC. In