The rheological properties of hydrogenated castor oil crystals

The present study focuses on the rheological performance of a surfactant-rich aqueous suspension containing hydrogenated castor oil (HCO) crystals. HCO can be typically crystallized in five distinct shapes: spherically shaped, irregularly shaped, star-shaped (also called rosettes), short needles, and thick or thin fibers. The effect of the differences in shape on the rheological performance is studied, and the rheological properties are compared to the behavior of other triacylglycerol’s (TAG) suspensions. A suspension of TAG crystals usually behaves as a colloidal gel wherein a colloidal gel is defined as a network of flocs, with each floc being an aggregate of smaller subunits. All of these surfactant-rich aqueous suspensions of HCO crystals behaved according to a colloidal gel in the transient regime, independent of the studied crystal shapes, except the long thin fibers at a concentration above 0.1 wt% HCO transitioning from a heterogeneous fractal rod network to a homogeneous rod network, shifting from a colloidal gel to a glass.     

Estimation of surface desorption times in hydrophobically coated nanochannels and their effect on shear-driven and pressure-driven chromatography

The present paper provides a detailed analysis of the analyte-wall adsorption effects in nanochannels, including a random walk study of the analyte-wall collision frequency, and uses these insights to estimate wall desorption times from chromatographic experiments in nanochannels. Using coumarin dye analytes and using a methanol/water mixture buffered at pH 3 in 120-nm deep channels, the surface desorption times on naked fused-silica glass were found to be maximally of the order of 60 to 150 μs, while they were found to be on the order of 100 to 500 μs on a hydrophobically coated wall. These nonzero adsorption and desorption times lead to an additional band broadening when conducting chromatographic separations. Shear-driven flows, requiring a noncoated moving wall and a stationary coated wall, intrinsically turn out to be more prone to this effect than pressure-driven or electro-driven flows for example. The present study also shows that, interestingly, the number of analyte-wall collisions increases with the inverse of the channel depth and not with its second power, as would be expected from the Einstein–Smoluchowski relationship for molecular diffusion.     

Experimental study of the retention properties of a cyclo olefin polymer pillar array column in reversed-phase mode

Experimental measurements to study the retention capacity and band broadening under retentive conditions using micromachined non-porous pillar array columns fabricated in cyclo olefin polymer are presented. In particular, three columns with different depths but with the same pillar structure have been fabricated via hot embossing and pressure-assisted thermal bonding. Separations of a mixture of four coumarins using varying mobile phase compositions have been monitored to study the relation between the retention factor and the ratio of organic solvent in the aqueous mobile phase. Moreover, the linear relation between the retention and the surface/volume ratio predicted in theory has been observed, achieving retention factors up to k=2.5. Under the same retentive conditions, minimal reduced plate height values of h(min)=0.4 have been obtained at retention factors of k=1.2. These experimental results are compared with the case of non-porous and porous silicon pillars. Similar results for the plate heights are achieved while retention factors are higher than the non-porous silicon column and considerably smaller than the porous pillar column, given the non-porous nature of the used cyclo olefin polymer. The feasibility of using this polymer column as an alternative to the pillar array silicon columns is corroborated.     

Hydrodynamic chromatography of polystyrene microparticles in micropillar array columns

We report on the possibility to perform HDC in micropillar array columns and the potential advantages of such a system. The HDC performance of a pillar array column with pillar diameter = 5 μm and an interpillar distance of 2.5 μm has been characterized using both a low MW tracer (FITC) and differently sized polystyrene bead samples (100, 200 and 500 nm). The reduced plate height curves that were obtained for the different investigated markers all overlapped very well, and attained a minimum value of about h_min = 0.3 (reduction based on the pillar diameter), corresponding to 1.6 μm in absolute value and giving good prospects for high efficiency separations. The obtained reduced retention time values were in fair agreement with that predicted by the Di Marzio and Guttman model for a flow between flat plates, using the minimal interpillar distance as characteristic interplate distance.     

Experimental study of the depth influence on the band broadening effect in a cyclo-olefin polymer column containing an array of ordered pillars

An experimental study of a micromachined non-porous pillar array column performance under non-retentive conditions is presented. The same pillar structure has been fabricated in cyclo-olefin polymer (COP) chips with three different depths via hot embossing and pressure-assisted thermal bonding. The influence of the depth on the band broadening along with the already known contribution arising from the top and bottom cover plates has been studied. The experimental results exhibit reduced plate heights as low as 0.2, which are in agreement with the previous experimental work. Moreover, the constant values of the reduced Van Deemter expression are also in accordance with the previous studies. A more exhaustive study of the C-term band broadening is also presented, showing that comparing the space between the pillars with different open tubular rectangular channels offers a good estimation of the C-term band broadening that is obtained experimentally. These experimental results, hence, confirm that micromachined pillar array columns fabricated in COP can achieve the same performance as the ones fabricated in silicon for the presently studied pillar channel design.     

Detection enhancement in nano-channels using micro-machined silicon groove

The present paper reports on an experimental study of the possibility to use a micro-machined detection groove to enhance the detection sensitivity in flat-rectangular nano-channels for ultra-rapid liquid chromatography separations. Transversally running detection grooves with three different axial widths (respectively, 2, 4 and 6mum) and one depth (4.75mum) were tested in glass and silicon channels for the whole range of detectable fluorescein isothiocyanate isomer I, FITC, concentrations. The groove with the most square-like cross-section (i.e., 4mum wide and 4.75mum deep) yielded the best combination of detection gain and minimal additional band broadening. In a 1cm long channel, the effective plate loss caused by the 4mum wide groove would only be of the order of 20%, while the gain in S/N-ratio was of the order of a factor of 5. The detection groove concept yields larger gains in silicon channel substrates than in glass channel substrates, due to the larger stray light losses occurring in the latter.     

Ultra-rapid separation of an angiotensin mixture in nanochannels using shear-driven chromatography

The present paper reports on the separation of a mixture of fluorescein isothiocyanate-labeled angiotensin I and II peptides in a shear-driven nanochannel with a C18-coating and using an eluent consisting of 5% acetonitrile in 0.02 M aqueous phosphate buffer at pH 6.5. The flat-rectangular nanochannel in fused silica consisted of an etched structure in combination with a flat moving wall. The very fast separation kinetics that can be achieved in a nanochannel allowed to separate the angiotensin peptides in less then 0.2 s in a distance of only 1.8 mm. Plate heights as small as 0.4 microm were calculated after substraction of the injection effect.     

Hydrodynamic chromatography separations in micro- and nanopillar arrays produced using deep-UV lithography (J. Sep. Science 35'15)

DOI: 10.1002/jssc.201200076 Micro-pillar array columns with an inter-pillar spacing down to 500 nm have been designed and fabricated enabling hydrodynamic chromatography separations of fluorescently labeled polystyrene nano-particles. Injecting sub-nanoliter sized sample volumes and detecting the fluorescent signal on-chip, fluorescein, 20 and 40 nm diameter particles could be separated in less than 1.5 minutes.     

Separations using a porous-shell pillar array column on a capillary LC instrument

We investigated the achievable separation performance of a 9-cm-long and 1-mm-wide pillar array channel (volume = 0.6 μL) containing 5 μm diameter Si pillars (spacing 2.5 μm) cladded with a mesoporous silica layer with a thickness of 300 nm, when this channel is directly interfaced to a capillary LC instrument. The chip has a small footprint of only 4 cm × 4 mm and the channel consists of three lanes that are each 3 cm long and that are interconnected using low dispersion turns consisting of a narrow U-turn (10 μm), proceded and preceded by a diverging flow distributor. Measuring the band broadening within a single lane and comparing it to the total channel band broadening, the additional band broadening of the turns can be estimated to be of the order of 0.5 μm around the minimum of the van Deemter curve, and around some 1 μm (nonretained species) and 2 μm (retained species) in the C-term dominated regime. The overall performance (chip + instrument) was evaluated by conducting gradient elution separations of digests of cytochrome c and bovine serum albumin. Peak capacities up to 150 could be demonstrated, nearly completely independent of the flow rate.     

Visualization and quantification of the onset and the extent of viscous fingering in micro-pillar array columns

New experimental data of the viscous fingering (VF) process have been generated by studying the VF process in perfectly ordered pillar array columns instead of in the traditionally employed packed bed columns. A detailed quantitative analysis of the contribution of VF to the observed band broadening could be made by following the injected species bands using a fluorescence microscope equipped with a CCD-camera. For a viscosity contrast of 0.16 cP, a plate height increase of about 1 μm can be observed, while for a contrast of respectively 0.5 cP and 1 cP, additional plate height contributions of the order of 5–20 μm were observed. Citing these values is however futile without noting that they also depend extremely strongly on the injection volume of injected sample. It was found that, for a given viscosity contrast of 0.314 cP, the maximal plate height increase varied between 0.5 μm and 18 μm if the injection volume was varied between 3.0 nl and 32.7 nl. These values furthermore also strongly vary with the distance along the column axis.