Electrokinetic characterization of poly(dimethylsiloxane) microchannels

This paper characterizes the basic electrokinetic phenomena occurring within native poly(dimethylsiloxane) (PDMS) microchannels. Using simple buffers and current measurements, current density and electroosmosis data were determined in trapezoidal, reversibly sealed PDMS/PDMS and hybrid PDMS/glass channels with a cross-sectional area of 1035.5 microm(2) and about 6 cm length. This data was then compared to that obtained in an air-thermostated 50 microm inner diameter (1963.5 microm(2) cross-sectional area) fused-silica (FS) capillary of 70 cm length. Having a pH 7.8 buffer with an ionic strength (I) of 90 mM, Ohms's law was observed in the microchannels with electric field strengths of up to about 420 V/cm, which is about twice as high as for the FS capillary. The electroosmotic mobility (micro(EO)) in PDMS and FS is shown to exhibit the same general dependences on I and pH. For all configurations tested, the experimentally determined micro(EO) values were found to correlate well with the relationship micro(EO) = a + b log(I), where a and b are coefficients that are determined via nonlinear regression analysis. Electroosmotic fluid pumping in native PDMS also follows a pH dependence that can be estimated with a model based upon the ionization of silanol. Compared to FS, however, the magnitude of the electroosmotic flow in native PDMS is 50-70% smaller over the entire pH range and is difficult to maintain at acidic pH values. Thus, the origin of the negative charge at the inner wall of PDMS, glass, and FS appears to be similar but the density is lower for PDMS than for glass and FS.     

Electrokinetic particle translocation through a nanopore

Nanoparticle electrophoretic translocation through a single nanopore induces a detectable change in the ionic current, which enables the nanopore-based sensing for various bio-analytical applications. In this study, a transient continuum-based model is developed for the first time to investigate the electrokinetic particle translocation through a nanopore by solving the Nernst-Planck equations for the ionic concentrations, the Poisson equation for the electric potential and the Navier-Stokes equations for the flow field using an arbitrary Lagrangian-Eulerian (ALE) method. When the applied electric field is relatively low, a current blockade is expected. In addition, the particle could be trapped at the entrance of the nanopore when the electrical double layer (EDL) adjacent to the charged particle is relatively thick. When the electric field imposed is relatively high, the particle can always pass through the nanopore by electrophoresis. However, a current enhancement is predicted if the EDL of the particle is relatively thick. The obtained numerical results qualitatively agree with the existing experimental results. It is also found that the initial orientation of the particle could significantly affect the particle translocation and the ionic current through a nanopore. Furthermore, a relatively high electric field tends to align the particle with its longest axis parallel to the local electric field. However, the particle's initial lateral offset from the centerline of the nanopore acts as a minor effect.     

Electrokinetic generation of temporally and spatially stable concentration gradients in microchannels

Generating stable microscale concentration gradients is key to numerous biological and chemical analyses. Microfluidic systems offer the ability to maintain laminar fluid diffusion interfaces ideal for the production of temporally stable concentration gradients. Previous efforts have focused on pressure driven flows and have relied on networks of branching channels to create streams of varying concentrations which can subsequently be combined to form the desired gradients. In this study, we numerically and experimentally demonstrate a novel electrokinetic technique which utilizes applied voltages and surface charge heterogeneity in simpler channel geometries to control and manipulate microscale concentration gradients without the need for parallel lamination. Flow rates ranged from 30 to 460 nl min(-1) for Peclet numbers between 70 and 1100. Spatial stability of 0.6 mm or greater was obtained for a wide range of gradient shapes and magnitudes over lateral dimensions of 400-450 microm. Sensitivity analysis determined that this technique is largely independent of channel depth and species electrophoretic mobility, however channel width and the diffusion coefficient of the analyte are critical. It was concluded that by adjusting applied voltages and/or channel width, this approach to concentration gradient generation can be adapted to a wide range of applications.     

Electrokinetic particle translocation through a nanopore containing a floating electrode

Electrokinetic particle translocation through a nanopore containing a floating electrode is investigated by solving a continuum model, composed of the coupled Poisson-Nernst-Planck (PNP) equations for the ionic mass transport and the modified Stokes equations for the flow field. Two effects due to the presence of the floating electrode, the induced-charge electroosmosis (ICEO) and the particle-floating electrode electrostatic interaction, could significantly affect the electrokinetic mobility of DNA nanoparticles. When the electrical double layers (EDLs) of the DNA nanoparticle and the floating electrode are not overlapped, the particle-floating electrode electrostatic interaction becomes negligible. As a result, the DNA nanoparticle could be trapped near the floating electrode arising from the induced-charge electroosmosis when the applied electric field is relatively high. The presence of the floating electrode attracts more ions inside the nanopore resulting in an increase in the ionic current flowing through the nanopore; however, it has a limited effect on the deviation of the current from its base current when the particle is far from the pore.     

Continuous particle separation in spiral microchannels using Dean flows and differential migration

Microparticle separation and concentration based on size has become indispensable in many biomedical and environmental applications. In this paper we describe a passive microfluidic device with spiral microchannel geometry for complete separation of particles. The design takes advantage of the inertial lift and viscous drag forces acting on particles of various sizes to achieve differential migration, and hence separation, of microparticles. The dominant inertial forces and the Dean rotation force due to the spiral microchannel geometry cause the larger particles to occupy a single equilibrium position near the inner microchannel wall. The smaller particles migrate to the outer half of the channel under the influence of Dean forces resulting in the formation of two distinct particle streams which are collected in two separate outputs. This is the first demonstration that takes advantage of the dual role of Dean forces for focusing larger particles in a single equilibrium position and transposing the smaller particles from the inner half to the outer half of the microchannel cross-section. The 5-loop spiral microchannel 100 microm wide and 50 microm high was used to successfully demonstrate a complete separation of 7.32 microm and 1.9 microm particles at Dean number De = 0.47. Analytical analysis supporting the experiments and models is also presented. The simple planar structure of the separator offers simple fabrication and makes it ideal for integration with on-chip microfluidic systems, such as micro total analysis systems (muTAS) or lab-on-a-chip (LOC) for continuous filtration and separation applications.     

Synthetic entry into the secoisoquinoline alkaloids

Several analogs of secoisoquinolinc alkaloids bearing a dimethylaminoethyl side chain and a benzilic, or reduced benzilic group were synthesized. Two independent methods based on the intermediacy of 1,3-dithians and O-benzoylated cyanohydrins as acyl anion equivalents were used.     

A convenient entry into diruthenium chemistry

In boiling toluene, diphenylacetylene is readily displaced from the dimetallocycle [Ru₂(CO)(μ-CO) {μ-C(O)C₂Ph₂} (η-C₅H₅)₂] by a variety of reagents (P(OMe)₃, SO₂, R₂CN₂, Ph₂PCH₂) to produce [Ru₂(CO){P(OMe)₃}(μ-CO)₂ - (η-C₅H₅)₂] or [Ru₂(CO)₂(μ-CO)(μ-L)(η-C₅H₅)₂] (L  SO₂, CR₂, CH₂) in high yield.     

A concise entry into nonsymmetrical alkyl polyamines

The synthesis of nonsymmetrical polyamines (PAs) has, up to now, been problematic due to lengthy synthetic procedures, lack of regioselectivity, and very poor atom economy. An innovative synthetic protocol for nonsymmetrical PAs using a modified Ugi reaction ( N-split Ugi) which simplifies the synthesis of these tricky compounds is described. We believe that this new synthesis may open the door for the generation of new and pharmacologically active PAs.     

Polydimethylsiloxane-LiNbO3 surface acoustic wave micropump devices for fluid control into microchannels

This paper presents prototypical microfluidic devices made by hybrid microchannels based on piezoelectric LiNbO(3) and polydimethylsiloxane. This system enables withdrawing micropumping by acoustic radiation in microchannels. The withdrawing configuration, integrated on chip, is here quantitatively investigated for the first time, and found to be related to the formation and coalescence dynamics of droplets within the microchannel, primed by surface acoustic waves. The growth dynamics of droplets is governed by the water diffusion on LiNbO(3), determining the advancement of the fluid front. Observed velocities are up to 2.6 mm s(-1) for 30 dBm signals applied to the interdigital transducer, corresponding to tens of nl s(-1), and the micropumping dynamics is described by a model taking into account an acoustic power exponentially decaying upon travelling along the microchannel. This straighforward and flexible micropumping approach is particularly promising for the withdrawing of liquids in lab-on-chip devices performing cycling transport of fluids and biochemical reactions.     

Modeling the flow of fluid/particle mixtures in microchannels: encapsulating nanoparticles within monodisperse droplets

We develop a hybrid computational approach for simulating mixtures of binary fluids and mobile, submicron particles. The model couples a lattice Boltzmann method for the binary fluid with a Brownian dynamics model for the particles. The particles can exhibit preferential wetting interactions with the different components of the fluid. As an illustration of the method, we carry out simulations in two dimensions to compare the spinodal decomposition of a pure binary fluid with the phase separation of binary blends that contain either fixed or mobile particles. We then isolate conditions where the flow of a binary fluid/particle mixture past surfaces with well-defined asperities leads to the formation of monodisperse droplets, which encapsulate the nanoparticles. The findings provide guidelines for creating multiphase emulsions with well-controlled morphologies.     

Nanosecond electric pulse-induced calcium entry into chromaffin cells

Electrically excitable bovine adrenal chromaffin cells were exposed to nanosecond duration electric pulses at field intensities ranging from 2 MV/m to 8 MV/m and intracellular calcium levels ([Ca(2+)](i)) monitored in real time by fluorescence imaging of cells loaded with Calcium Green. A single 4 ns, 8 MV/m pulse produced a rapid, short-lived increase in [Ca(2+)](i), with the magnitude of the calcium response depending on the intensity of the electric field. Multiple pulses failed to produce a greater calcium response than a single pulse, and a short refractory period was required between pulses before another maximal increase in [Ca(2+)](i) could be triggered. The pulse-induced rise in [Ca(2+)](i) was not affected by depleting intracellular calcium stores with caffeine or thapsigargin but was completely prevented by the presence of EGTA, Co(2+), or the L-type calcium channel blocker nitrendipine in the extracellular medium. Thus, a single nanosecond pulse is sufficient to elicit a rise in [Ca(2+)](i) that involves entry of calcium via L-type calcium channels.     

A novel short convergent entry into himbacine derivatives

[reaction: see text]. The IMDA reaction of 9 leads with good stereoselectivity to exo-adduct 10b. The functionalized ABC-ring core in 10 is well suited for the convergent synthesis of analogues of himbacine, a naturally occurring M2 selective muscarine receptor antagonist, as illustrated with the further synthesis of the dehydro-derivative 5.     

An entry route into non-aqueous plutonyl coordination chemistry

The Pu(VI) molecular complex, [PuO(2)Cl(2)(thf)(2)]2, is prepared by addition of a HCl/Et(2)O solution to a suspension of PuO(2)CO(3) in thf, yielding the first example of a precursor suitable for investigation of the non-aqueous chemistry of the plutonyl dioxo cation under inert atmospheric conditions.     

An enantioselective entry into the strychnos alkaloid skeleton

A tryptophan derivative is used for the first time as a chiral precursor of Strychnos alkaloid skeleta. Removal of the extra carbon is presented and discussed.     

Single particle confocal fluorescence spectroscopy in microchannels: dependence of burst width and burst area distributions on particle size and flow rate.

This article presents a non-invasive, optical technique for measuring particulate flow within microfluidic channels. Confocal fluorescence detection is used to probe single fluorescently labeled microspheres (200-930 nm diameter) passing through a focused laser beam at a variety of flow rates (100 - 1000 nL/min). Simple statistical methods are subsequently used to investigate the resulting fluorescence bursts and generate single-particle burst width and burst area distributions. Analysis of such distributions demonstrates that the average burst width and burst area decrease as particle size increases. In addition, both burst width and burst area (for a given particle size) are observed to decrease as volumetric flow rate is increased. The dependence of such distributions on particle size is proposed as a potential route to sizing single particles and molecules in microfluidic systems.