Performance of laterally elongated pillar array columns in capillary electrochromatography mode

In the present study, cylindrical and laterally elongated pillar array columns were investigated for use in capillary electrochromatography. Minimal theoretical plate heights of H = 1.90 and 1.46 μm (in absence of sidewall effect) were obtained for coumarin C440 under unretained conditions for cylindrical and rectangular (laterally elongated, aspect ratio 4) pillar array columns, respectively. By comparing dispersion at the entire channel width to that at the central zone only, it appears that sidewall related dispersion significantly contributes to overall dispersion. A 40% reduction of the plate height was observed by taking into account only the central channel zone. A kinetic plot analysis was performed to evaluate the potential of the studied geometries by considering a maximum operating voltage of 20 kV as limiting parameter. It was demonstrated that rectangular radially elongated pillars produce a higher efficiency than cylindrical pillars and other microfabricated column structures for microchip capillary electrochromatography previously studied.     

Diffusioosmotic flow in rectangular microchannels

The diffusioosmosis of an electrolyte solution inside a uniformly charged rectangular channel at steady locally developed conditions is the subject of this study. Utilizing a finite element based numerical procedure, we try to estimate the errors incurred by modeling the actual rectangular geometry of typical microchannels as a slit. We demonstrate that the flow pattern and direction are generally dependent upon the width‐to‐height ratio of the channel. Such a finding, besides showing the ineffectiveness of the slit geometry in representing a rectangular channel of small aspect ratio, informs us of another mechanism of controlling the diffusioosmotic flow. Inspections of the mean velocity reveal that, although it drastically grows by increasing the aspect ratio at smaller values of this parameter, no significant change is observed when the aspect ratio is 5 or higher. The same trend is observed when EDL is shrunk and is considered as a basis for the introduction of a slip‐like velocity, similar to the concept of the Helmholtz–Smoluchowski electroosmotic velocity, which will be of high practical importance when dealing with a micronsized channel. Because of its significance, an expression is presented for this slip velocity utilizing the curve fitting of the results, assuming a typical Peclet number.     

Optimisation of a microfluidic analysis chamber for the placement of microelectrodes

The behaviour of droplets entering a microfluidic chamber designed to house microelectrode detectors for real time analysis of clinical microdialysate is described. We have designed an analysis chamber to collect the droplets produced by multiphase flows of oil and artificial cerebral spinal fluid. The coalescence chamber creates a constant aqueous environment ideal for the placement of microelectrodes avoiding the contamination of the microelectrode surface by oil. A stream of alternating light and dark coloured droplets were filmed as they passed through the chamber using a high speed camera. Image analysis of these videos shows the colour change evolution at each point along the chamber length. The flow in the chamber was simulated using the general solution for Poiseuille flow in a rectangular chamber. It is shown that on the centre line the velocity profile is very close to parabolic, and an expression is presented for the ratio between this centre line velocity and the mean flow velocity as a function of channel aspect ratio. If this aspect ratio of width/height is 2, the ratio of flow velocities closely matches that of Poiseuille flow in a circular tube, with implications for connections between microfluidic channels and connection tubing. The droplets are well mixed as the surface tension at the interface with the oil dominates the viscous forces. However once the droplet coalesces with the solution held in the chamber, the no-slip condition at the walls allows Poiseuille flow to take over. The meniscus at the back of the droplet continues to mix the droplet and acts as a piston until the meniscus stops moving. We have found that the no-slip conditions at the walls of the chamber, create a banding effect which records the history of previous drops. The optimal position for sensors is to be placed at the plane of droplet coalescence ideally at the centre of the channel, where there is an abrupt concentration change leading to a response time ?16 ms, the compressed frame rate of the video. Further away from this point the response time and sensitivity decrease due to convective dispersion.     

General theory for flow optimisation of split-flow thin fractionation

Recently, magnetic split-flow thin (SPLITT) fractionation has been developed to separate macromolecules, colloids, cells and particles. However, the previous theory, developed for an infinitely long channel, needs to be improved to consider the flow transit regimes at both inlet and outlet. In this paper, we describe a new approach to optimising flow-rates for particle separation which considers the effect of flow transit region. Surprisingly, the critical particle migration velocities derived by the present theory are identical to the previous simplified theory. Therefore, the previous simplified theory may have wider application than might have been expected. As a test of our theory, a numerical simulation based on solving Navier-Stokes equations has also been carried out for a magnetic SPLITT device. The trajectory of a particle with the critical migration velocity is exactly as expected by our theory. Following experimental validation, this work will facilitate the design of new SPLITT fractionation systems with smaller aspect ratio.     

Structure-transport analysis for particulate packings in trapezoidal microchip separation channels

This article investigates the efficiency of particulate beds confined in quadrilateral microchannels by analyzing the three-dimensional fluid flow velocity field and accompanying hydrodynamic dispersion with quantitative numerical simulation methods. Random-close packings of uniform, solid (impermeable), spherical particles of diameter d(p) were generated by a modified Jodrey-Tory algorithm in eighteen different conduits with quadratic, rectangular, or trapezoidal cross-section at an average bed porosity (interparticle void fraction) of epsilon = 0.48. Velocity fields were calculated by the lattice Boltzmann method, and axial hydrodynamic dispersion of an inert tracer was simulated at Péclet numbers Pe = u(av)d(p)/D(m) (where u(av) is the average fluid flow velocity through a packing and D(m) the bulk molecular diffusion coefficient) from Pe = 5 to Pe = 30 by a Lagrangian particle-tracking method. All conduits had a cross-sectional area of 100d(p)(2) and a length of 1200d(p), translating to around 10(5) particles per packing. We present lateral porosity distribution functions and analyze fluid flow profiles and velocity distribution functions with respect to the base angle and the aspect ratio of the lateral dimensions of the different conduits. We demonstrate significant differences between the top and bottom parts of trapezoidal packings in their lateral porosity and velocity distribution functions, and show that these differences increase with decreasing base angle and increasing base-aspect ratio of a trapezoidal conduit, i.e., with increasing deviation from regular rectangular geometry. Efficiencies are investigated in terms of the axial hydrodynamic dispersion coefficients as a function of the base angle and base-aspect ratio of the conduits. The presented data support the conclusion that the efficiency of particulate beds in trapezoidal microchannels strongly depends on the lateral dimensions of the conduit and that cross-sectional designs based on large side-aspect-ratio rectangles with limited deviations from orthogonality are favorable.     

Bacterial transport in porous media: New aspects of the mathematical model

Transport of bacteria is an important aspect from scientific, industrial and environmental point of view. In this work, a one-dimensional mathematical model based on linear equilibrium adsorption of bacteria has been developed to predict bacterial transport through porous media. This model is more realistic than existing models because of its coupling both physicochemical and biological phenomena. Two important biological phenomena, the growth and decay of bacterial cells and chemotactic/chemotaxis of bacteria along with physicochemical properties have been adequately incorporated which are quite new aspects in our model. In agreement with experimental study by [D.K. Powelson, R.J. Simpson, C.P. Gerba, J. Environ. Qual. 19 (1990) 396], model simulations indicated that enhancement of breakthrough occurs due to increase in flow velocity, cell concentration, substrate concentration, respectively. It has also been found that chemo tactic has a significant effect on bacterial transport, especially under conditions of considerable substrate gradient and at low pore velocity. The importance of threshold concentration of captured cells (σ₀) on bacterial transport has also been identified which is also a new aspect in our model.     

Field-flow fractionation in microfluidic channels of low aspect ratio

The shape of the steady-state three-dimensional flow velocity profile established in carrier liquid flowing inside the rectangular cross-sectional channel for field-flow fractionation should be taken into account to optimize the separation. The central parts of this profile in the planes parallel to the main channel walls are flat with almost identical flow velocities which drop down to zero at the side walls. The separated species transported by the flow in the close-to-side walls regions move with lower average velocities compared to the species transported in the central part of the channel and are undesirably broadened. The hydrodynamic splitting of the carrier liquid at the entry of the channel where the sample is injected only into the central part of the channel eliminates the excessive zone broadening. The aspect ratio of the breadth to the thickness of the channel ratio can thus be reduced. The effect of various aspect ratios on the shape of the flow velocity profile is calculated and the results are used to optimize the aspect ratio of microfluidic channels. The experiments carried out by microthermal field-flow fractionation confirmed that the aspect ratio cannot be reduced to a value of 1, proposed by other authors.     

Fluorescence photobleaching to evaluate flow velocity and hydrodynamic dispersion in nanoslits

Velocity measurement is a key issue when studying flows below the micron scale, due to the lack of sensitivity of conventional detection techniques. We present an approach based on fluorescence photobleaching to evaluate flow velocity at the nanoscale by direct visualization. Solutions containing a fluorescent dye are injected into nanoslits. A photobleached line, created through laser beam illumination, moves through the channel due to the fluid flow. The velocity and effective diffusion coefficient are calculated from the temporal data of the line position and width respectively. The measurable velocity range is only limited by the diffusion rate of the fluorescent dye for low velocities and by the apparition of Taylor dispersion for high velocities. By controlling the pressure drop and measuring the velocity, we determine the fluid viscosity. The photobleached line spreads in time due to molecular diffusion and Taylor hydrodynamic dispersion. By taking into account the finite spatial and temporal extensions of the bleaching under flow, we determine the effective diffusion coefficient, which we find to be in good agreement with the expression of the two dimensional Taylor-Aris dispersion coefficient. Finally we analyze and discuss the role of the finite width of the rectangular slit on hydrodynamic dispersion.     

A simple and efficient approach for calculating permeability coefficients and HETP for rectangular columns

There had been little progress in development of the theoretical basis of rectangular chromatography columns until Spangler made great progress by using a more exact model than Golay's. Unfortunately, there was a deficiency in his calculations, which led to a conclusion inconsistent with the previous theories. In this paper, a simpler formula with defined variables was first established to calculate the mean permeability coefficient for a rectangular GC column. A formula was also established to calculate the height equivalent to a theoretical plate (HETP) for a rectangular column based on this work and the correction of Spangler's theory. By comparing both our predictions and Spangler's predictions with Golay's, respectively, we could demonstrate that our theory is more exact. Further, one parameter (A) was found to be not monotonous. This finding leads to the conclusion that the square column has the highest performance among all the rectangular-shaped columns used for chromatography, and that a width/depth ratio of around three is desirable if the column is used for mixing reactants in lab-on-a-chip systems, instead of for chromatography. The conclusions are applicable not only for gas but also for liquid chromatography columns.     

Comparison of intermolecular interaction energies from SAPT and DFT including empirical dispersion contributions

The dispersion correction based on damped atom-atom long-range interaction contributions has been tested for an extended S22 database of intermolecular complexes using density functional theory (DFT) and symmetry adapted perturbation theory (SAPT) to account for the remaining interaction energy contributions. In the case of DFT, the dispersion correction of Grimme (J. Comput. Chem. 2006, 27, 1787) was used, while for SAPT, another damping function has been developed that has been optimized particularly for the database. It is found that both approaches yield about the same accuracy for the mixed-type complexes, while the DFT plus dispersion method performs better for the hydrogen-bridged systems and the SAPT plus dispersion approach is better for the dispersion-dominated complexes if compared with coupled cluster singles-doubles with perturbative triples interaction energies as a reference.     

Low-frequency velocity correlation spectrum of fluid in a rectangular microcapillary

In addition to the fast correlation for local stochastic motion, the velocity correlation function in a fluid enclosed within the pore boundaries features a slow long time-tail decay. At late times, the flow approaches that of an incompressible fluid. Here, we consider the motion of a viscous fluid, at constant temperature, in a rectangular semipermeable channel. The fluid is driven through the rectangular capillary by a uniform main pressure gradient. Tiny pressure gradients are allowed perpendicular to the main flux. We solve numerically the three-dimensional Navier-Stokes equations for the velocity field to obtain the steady solution. We then set and solve the Langevin equation for the fluid velocity. We report hydrodynamic fluctuations for the center-line velocity together with the corresponding relaxation times as a function of the size of the observing region and the Reynolds number. The effective diffusion coefficient for the fluid in the microchannel is also estimated (Deff = 1.43 x 10(-10) m2.s-1 for Re = 2), which is in accordance with measurements reported for a similar system (Stepisnik, J.; Callaghan, P. T. Physica B 2000, 292, 296-301; Stepisnik, J.; Callaghan, P. T. Magn. Reson. Imaging 2001, 19, 469-472).     

Dispersion Stability Evaluated by Experimental Design

The stability of paraffin and hydrocarbon oil dispersions stabilized by nonionic surfactants has been systematically evaluated. Using experimental design, the influence of the following parameters on dispersion stability was studied: surfactant concentration, shear rate, shear time and temperature of homogenisation. The experiments were evaluated with respect to particle size and particle migration velocity by a scanning optical analysis technique. This scanning technique monitors physical variations in a dispersion as a function of time and the technique is well suited for evaluation of dispersion stability. It was found that the only factor examined affecting particle migration velocity in a significant way was the surfactant concentration. A pronounced maximum in creaming rate was obtained at around 10 wt% surfactant both for the paraffin dispersions (suspensions at room temperature) and for the hydrocarbon oil emulsions. This surfactant-induced instability is explained as depletion flocculation caused by elongated surfactant micelles or by small oil-containing aggregates formed as microemulsion droplets during the emulsification process.     

Method to predict the bandwidth of elution profile under the linear gradient elution in reversed‐phase HPLC

Solute migration in a chromatographic column is an important consideration when designing batch or continuous chromatographic separation processes. Most design methods for the chromatographic processes are based on the equilibrium theory which concerns only the migration velocity of the solute. However, in real cases, it is important to predict the zone spreading which occurs by axial dispersion and mass transfer resistance. To predict the actual solute profiles in the column or effluent stream, numerical methods to solve nonlinear partial differential equations have been used. However, these methods involve much time and expense. In this work, two different rate factors are considered to predict the characteristics of the solute profiles. The first is solute migration velocity and the second is the zone spreading rate. The zone spreading rate can be estimated by the apparent axial dispersion coefficient which is obtained from the height of the equivalent theoretical plate in particular. Four benzene derivatives (benzene, toluene, p‐xylene, and acetophenone) were used as model solutes, and two mobile phase systems, water/methanol and water/ACN, were used in RP‐HPLC. The bandwidths and retention times of the solutes were predicted under several linear gradient conditions. The predicted and experimental bandwidths and retention times showed good agreement.     

Lock-exchange experiments with an autocatalytic reaction front

A viscous lock-exchange gravity current corresponds to the reciprocal exchange of two fluids of different densities in a horizontal channel. The resulting front between the two fluids spreads as the square root of time, with a diffusion coefficient reflecting the buoyancy, viscosity, and geometrical configuration of the current. On the other hand, an autocatalytic reaction front between a reactant and a product may propagate as a solitary wave, namely, at a constant velocity and with a stationary concentration profile, resulting from the balance between molecular diffusion and chemical reaction. In most systems, the fluid left behind the front has a different density leading to a lock-exchange configuration. We revisit, with a chemical reaction, the classical situation of lock-exchange. We present an experimental analysis of buoyancy effects on the shape and the velocity of the iodate arsenous acid autocatalytic reaction fronts, propagating in horizontal rectangular channels and for a wide range of aspect ratios (1/3 to 20) and cylindrical tubes. We do observe stationary-shaped fronts, spanning the height of the cell and propagating along the cell axis. Our data support the contention that the front velocity and its extension are linked to each other and that their variations scale with a single variable involving the diffusion coefficient of the lock-exchange in the absence of chemical reaction. This analysis is supported by results obtained with lattice Bathnagar-Gross-Krook (BGK) simulations Jarrige et al. [Phys. Rev. E 81, 06631 (2010)], in other geometries (like in 2D simulations by Rongy et al. [J. Chem. Phys. 127, 114710 (2007)] and experiments in cylindrical tubes by Pojman et al. [J. Phys. Chem. 95, 1299 (1991)]), and for another chemical reaction Schuszter et al. [Phys. Rev. E 79, 016216 (2009)].     

Electron paramagnetic resonance line shifts and line shape changes due to heisenberg spin exchange and dipole-dipole interactions of nitroxide free radicals in liquids 8. Further experimental and theoretical efforts to separate the effects of the two interactions

The work in part 6 of this series (J. Phys. Chem. A 2009, 113, 4930), addressing the task of separating the effects of Heisenberg spin exchange (HSE) and dipole-dipole interactions (DD) on electron paramagnetic resonance (EPR) spectra of nitroxide spin probes in solution, is extended experimentally and theoretically. Comprehensive measurements of perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (pDT) in squalane, a viscous alkane, paying special attention to lower temperatures and lower concentrations, were carried out in an attempt to focus on DD, the lesser understood of the two interactions. Theoretically, the analysis has been extended to include the recent comprehensive treatment by Salikhov (Appl. Magn. Reson. 2010, 38, 237). In dilute solutions, both interactions (1) introduce a dispersion component, (2) broaden the lines, and (3) shift the lines. DD introduces a dispersion component proportional to the concentration and of opposite sign to that of HSE. Equations relating the EPR spectral parameters to the rate constants due to HSE and DD have been derived. By employing nonlinear least-squares fitting of theoretical spectra to a simple analytical function and the proposed equations, the contributions of the two interactions to items 1-3 may be quantified and compared with the same parameters obtained by fitting experimental spectra. This comparison supports the theory in its broad predictions; however, at low temperatures, the DD contribution to the experimental dispersion amplitude does not increase linearly with concentration. We are unable to deduce whether this discrepancy is due to inadequate analysis of the experimental data or an incomplete theory. A new key aspect of the more comprehensive theory is that there is enough information in the experimental spectra to find items 1-3 due to both interactions; however, in principle, appeal must be made to a model of molecular diffusion to separate the two. The permanent diffusion model is used to illustrate the separation in this work. In practice, because the effects of DD are dominated by HSE, negligible error is incurred by using the model-independent extreme DD limit of the spectral density functions, which means that DD and HSE may be separated without appealing to a particular model.     

Structure and stability of supramolecular crown ether complexes

Despite the fact that the complexation of ammonium cations with ionophores like crown ethers plays an important role in biological and industrial processes, there is still a lack of theoretical methods to reproduce or even predict the host–guest complex structures or their thermodynamic stabilities in an accurate manner. Hence, the development of ionophores has often relied on a trial‐and‐error approach and the synthetic efforts associated with this have been enormous, so far. Therefore, theoretical methods for the reliable prediction of binding affinities of crown ether derivatives with ammonium ions would be an indispensable tool for the rational design of new receptors with tailored properties. Here, we suggest a computationally efficient but still accurate theoretical approach. It is tested for a model system consisting of 18‐crown‐6 ether and an ammonium cation, but is invented for application to much larger complexes. The accuracy of various approximate quantum‐chemical methods, based on density functional theory (DFT) and many‐body perturbation theory, is evaluated against the gold standard CCSD(T) in the basis set limit as internal reference. An important aspect is the consideration of dispersion interactions in DFT methods, for which the dispersion‐correction by Grimme was employed. For all selected methods, the basis‐set dependence of calculated interaction energies was investigated. © 2015 Wiley Periodicals, Inc.     

Spectral properties of Nd-doped BiB_3O_6 crystal

Transparent Nd : BiB3O6 crystal has been grown by top-seeded method. The refraction indices of the crystal were measured and the parameters of chromatic dispersion were fitted. The room temperature absorption spectra of the crystal have been measured and compared with that of 0.2 mol/L NdCI3 solution. According to Judd-Ofelt (JO) theory, the spectral strength parameters Ω2 = 0.1776×10-20 cm2, Ω4 = 0.1282×10-20 cm2 and Ω6 = 0.1357×10-20 cm2 of Nd3+ ion were fitted. The radiative transition probabilities AJ,(?), oscillator strengths fJ,(?), radiative lifetime T and the branching ratio β(?) have all been calculated. Based on these parameters, the properties and application perspective are discussed.     

Numerical simulation of nanofluids for improved cooling efficiency in a 3D copper microchannel heat sink (MCHS)

In this paper, laminar nanofluid flow in 3D copper microchannel heat sink (MCHS) with rectangular cross section, and a constant heat flux, has been treated numerically using the computational fluid dynamics software (FLUENT). Results for the temperature and velocity distributions in the investigated MCHS are presented. In addition, experimental and numerical values are compared in terms of friction factors, convective heat transfer coefficients, wall temperature and pressure drops, for various particle volume concentrations and Reynolds numbers. The numerical results show that enhancing the heat flux has a very weak effect on the heat transfer coefficient for pure water, but an appreciable effect for the case of a nanofluid. For all considered volume fractions, the sink friction factor decreases by increasing the Reynolds number and slightly increases by increasing the volume fractions, and, with increasing the volume fractions and the Reynolds number, the pressure drop increases.     

A post-Hartree-Fock model of intermolecular interactions: inclusion of higher-order corrections

We have previously demonstrated that the dipole moment of the exchange hole can be used to derive intermolecular C(6) dispersion coefficients [J. Chem. Phys. 122, 154104 (2005)]. This was subsequently the basis for a novel post-Hartree-Fock model of intermolecular interactions [J. Chem. Phys. 123, 024101 (2005)]. In the present work, the model is extended to include higher-order dispersion coefficients C(8) and C(10). The extended model performs very well for prediction of intermonomer separations and binding energies of 45 van der Waals complexes. In particular, it performs twice as well as basis-set extrapolated MP2 theory for dispersion-bound complexes, with minimal computational cost.