Analysis of estrogens in environmental waters using polymer monolith in-polyether ether ketone tube solid-phase microextraction combined with high-performance liquid chromatography

A simple, rapid and sensitive on-line method for simultaneous determination of four endocrine disruptors (17 beta-estradiol, estriol, bisphenol A and 17 alpha-ethinylestradiol) in environmental waters was developed by coupling in-tube solid-phase microextraction (SPME) to high-performance liquid chromatography (HPLC) with fluorescence detection (FLD). A poly(acrylamide-vinylpyridine-NAP-methylene bisacrylamide) monolith, synthesized inside a polyether ether ketone (PEEK) tube, was selected as the extraction medium. To achieve optimum extraction performance, several parameters were investigated, including extraction flow-rate, extraction time, and pH value, inorganic salt and organic solvent content of the sample matrix. By simply filtered with nylon membrane filter and adjusting the pH of samples to 6.0 with phosphoric acid, the sample solution then could be directly injected into the device for extraction. Low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method were achieved in the range of 0.006-0.10 ng/mL and 0.02-0.35 ng/mL from spiked lake waters, respectively. The calibration curves of four endocrine disruptors showed good linearity ranging from quantification limits to 50 ng/mL with a linear coefficient R-2 value above 0.9913. Good method reproducibility was also found by intra- and inter-day precisions, yielding the RSDs less than 12 and 9.8%, respectively. Finally, the proposed method was successfully applied to the determination of these compounds in several environmental waters. (c) 2006 Elsevier B.V. All rights reserved.

Controlled growth of silicon nanowires by solid-liquid-solid method and their formation mechanism

High quality silicon nanowires (SiNWs) were grown directly from n-(111) silicon single crystal substrate by using Au film as a metallic catalyst. The diameter and length of the formed nanowires are 30-60 nm and from several micrometers to sereral tens of micrometers, respectively. The effects of Au film thickness, annealing temperature, growth time and N-2 gas flow rate on the formation of the nanowires were experimentally investigated. The results confirmed that the silicon nanowires with controlled diameter, length, shape and orientation can be obtained via reasonably choosing and optimizing various technical conditions. The formation process of the silicon nanowires is analyzed qualitatively based on solid-liquid-solid growth mechanism.

Effect of channel surface wettability and temperature gradients on the boiling flow pattern in a single microchannel

The objective of this paper is to investigate the effects of channel surface wettability and temperature gradients on the boiling flow pattern in a single microchannel. The test section consists of a bottom silicon substrate bonded with a top glass cover. Three consecutive parts of an inlet fluid plenum, a central microchannel and an outlet fluid plenum were etched in the silicon substrate. The central microchannel had a width of 800 mu m and a depth of 30 mu m. Acetone liquid was used as the working fluid. High outlet vapor qualities were dealt with here. The flow pattern consists of a fluid triangle (shrinkage of the liquid films) and a connected long liquid rivulet, which is generated in the central microchannel in the timescale of milliseconds. The peculiar flow pattern is formed due to the following reasons: (1) the liquid rivulet tends to have a large contact area with the top hydrophilic channel surface of the glass cover, but a smaller contact area with the bottom silicon hydrophobic surface. (2) The temperature gradient in the chip width direction at the top channel surface of the glass cover not only causes the shrinkage of the liquid films in the central microchannel upstream, but also attracts the liquid rivulet populated near the microchannel centerline. (3) The zigzag pattern is formed due to the competition between the evaporation momentum forces at the vapor-liquid interfaces and the force due to the Marangoni effect. The former causes the rivulet to deviate from the channel centerline and the latter draws the rivulet toward the channel centerline. (4) The temperature gradient along the flow direction in the central microchannel downstream causes the breakup of the rivulet to form isolated droplets there. (5) Liquid stripes inside the upstream fluid triangle were caused by the small capillary number of the liquid film, at which the large surface tension force relative to the viscous force tends to populate the liquid film locally on the top glass cover surface.

Seed bubbles stabilize flow and heat transfer in parallel microchannels

Seed bubbles are generated on microheaters located at the microchannel upstream and driven by a pulse voltage signal, to improve flow and heat transfer performance in microchannels. The present study investigates how seed bubbles stabilize flow and heat transfer in micro-boiling systems. For the forced convection flow, when heat flux at the wall surface is continuously increased, flow instability is self-sustained in microchannels with large oscillation amplitudes and long periods. Introduction of seed bubbles in time sequence improves flow and heat transfer performance significantly. Low frequency (similar to 10 Hz) seed bubbles not only decrease oscillation amplitudes of pressure drops, fluid inlet and outlet temperatures and heating surface temperatures, but also shorten oscillation cycle periods. High frequency (similar to 100 Hz or high) seed bubbles completely suppress the flow instability and the heat transfer system displays stable parameters of pressure drops, fluid inlet and outlet temperatures and heating surface temperatures. Flow visualizations show that a quasi-stable boundary interface from spheric bubble to elongated bubble is maintained in a very narrow distance range at any time. The seed bubble technique almost does not increase the pressure drop across microsystems, which is thoroughly different from those reported in the literature. The higher the seed bubble frequency, the more decreased heating surface temperatures are. A saturation seed bubble frequency of 1000-2000 Hz can be reached, at which heat transfer enhancement attains the maximum degree, inferring a complete thermal equilibrium of vapor and liquid phases in microchannels. Benefits of the seed bubble technique are the stabilization of flow and heat transfer, decreasing heating surface temperatures and improving temperature uniformity of the heating surface.

Boundary conditions at the solid-liquid surface over the multiscale channel size from nanometer to micron

The boundary condition at the solid surface is one of the important problems for the microfluidics. In this paper we study the effects of the channel sizes on the boundary conditions (BC), using the hybrid computation scheme adjoining the molecular dynamics (MD) simulations and the continuum fluid mechanics. We could reproduce the three types of boundary conditions (slip, no-slip and locking) over the multiscale channel sizes. The slip lengths are found to be mainly dependent on the interfacial parameters with the fixed apparent shear rate. The channel size has little effects on the slip lengths if the size is above a critical value within a couple of tens of molecular diameters. We explore the liquid particle distributions nearest the solid walls and found that the slip boundary condition always corresponds to the uniform liquid particle distributions parallel to the solid walls, while the no-slip or locking boundary conditions correspond to the ordered liquid structures close to the solid walls. The slip, no-slip and locking interfacial parameters yield the positive, zero and negative slip lengths respectively. The three types of boundary conditions existing in "microscale" still occur in "macroscale". However, the slip lengths weakly dependent on the channel sizes yield the real shear rates and the slip velocity relative to the solid wall traveling speed approaching those with the no-slip boundary condition when the channel size is larger than thousands of liquid molecular diameters for all of the three types of interfacial parameters, leading to the quasi-no-slip boundary conditions.

A New Criterion Number for the Boundary Conditions at the Solid/Liquid Interface in Nanoscale

A simple, but important three-atom model was proposed at the solid/liquid interface, leading to a new criterion number, lambda, governing the boundary conditions (BCs) in nanoscale. The solid wall is considered as the face-centered-cubic (fcc) structure. The fluid is the liquid argon with the well-known LJ potential. Based on the concept, the two micro-systems have the same BCs if they have The same criterion number. The degree of the locking BCs is enhanced when lambda equals to 0.757. Such critical criterion number results in the substantial epitaxial ordering and one, two, or even three liquid layers are locked by the solid wall, depending on the coupling energy scale ratio of the solid and liquid atoms. With deviation from the critical criterion number, the flow approaches the slip BCs and there are little ordering structures within the liquid. Always at the same criterion number, the degree of the slip is decreased or the locking is enhanced with increasing the coupling energy scale ratio of the solid and liquid atoms. The above analysis is well confirmed by the molecular dynamics (MD) simulation. The slip length is well correlated in terms of the new criterion number. The future work is suggested to extend the present theory for other microstructures of the solid wall atoms and quasi-LJ potentials.

Oscillation flow induced by underwater supersonic gas jets

This paper describes an experimental study on the oscillation flow characteristics of submerged supersonic gas jets issued from Laval nozzles. The flow pattern during the jet development and the jet expansion feedback phenomenon are studied using a high-speed camera and a pressure measurement system. The experimental results indicate that along the downstream distance, the jet has three flow regimes: (1) momentum jet; (2) buoyant jet; (3) plume. In the region near the nozzle exit a so-called bulge phenomenon is found. Bulging of the jet occurs many times before the more violent jet expansion feedback occurs. During the feedback process, the jet diameter can become several times that of the original one depending on the jet Mach number. The frequencies of the jet bulging and the jet expansion feedback are measured.

Non-modal instabilities of two-dimensional disturbances in plane Couette flow of a power-law fluid

Instabilities of fluid flows have traditionally been investigated by normal mode analysis, i.e. by linearizing the equations of flow and testing for unstable eigenvalues of the linearized problem. However, the results of eigenvalue analysis agree poorly in many cases with experiments, especially for shear flows. In this paper we study the instabilities of two-dimensional Couette flow of a polymeric fluid in the framework of non-modal stability theory rather than normal mode analysis. A power-law model is used to describe the polymeric liquid. We focus on the response to external excitations and initial conditions by examining the pseudospectra structures and the transient energy growths. For both Newtonian and non-Newtonian flows, the results show that there can be a rather large transient growth even though the linear operator of Couette flow has no unstable eigenvalue. The effects of non-Newtonian viscosity on the transient behaviors are examined in this study. The results show that the "shear-thinning/shear-thickening" effect increases/decreases the amplitude of responses to external excitations and initial conditions. (C) 2010 Elsevier B.V. All rights reserved.

Instabilities and transient behaviors of a liquid film flowing down a porous inclined plane

The nonmodal linear stability of a falling film over a porous inclined plane has been investigated. The base flow is driven by gravity. We use Darcy's law to describe the flow in the porous medium. A simplified one-sided model is used to describe the fluid flow. In this model, the influence of the porous layer on the flow in the film can be identified by a parameter beta. The instabilities of a falling film have traditionally been investigated by linearizing the governing equations and testing for unstable eigenvalues of the linearized problem. However, the results of eigenvalue analysis agree poorly in many cases with experiments, especially for shear flows. In the present paper, we have studied the linear stability of three-dimensional disturbances using the nonmodal stability theory. Particular attentions are paid to the transient behavior rather than the long time behavior of eigenmodes predicted by traditional normal mode analysis. The transient behaviors of the response to external excitations and the response to initial conditions are studied by examining the pseudospectral structures and the energy growth function G(t) Before we study the nonmodal stability of the system, we extend the results of long-wave analysis in previous works by examining the linear stabilities for streamwise and spanwise disturbances. Results show that the critical conditions of both the surface mode and the shear mode instabilities are dependent on beta for streamwise disturbances. However, the spanwise disturbances have no unstable eigenvalue. 2010 American Institute of Physics. [doi:10.1063/1.3455503]

Coupling of thermocapillary convection and evaporation effect in a liquid layer when the evaporating interface is open to air

The coupling mechanism of thermocapillary convection and evaporation effect in evaporating liquids was studied experimentally. The experiments were carried out to study a thin evaporating liquid layer in a rectangular test cell when the upper surface was open to air. By altering the imposed horizontal temperature differences and heights of liquid layers, the average evaporating rate and interfacial temperature profiles were measured. The flow fields were also visualized by PIV method. For comparison, the experiments were repeated by use of another two non-evaporating liquids to study the influence of evaporation effect. The results reveal evidently the role that evaporation effect plays in the coupling with thermocapillary convection.

Direct characterization of bitter acids in a crude hop extract by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

The applicability of on-line coupling of reversed-phase high-performance liquid chromatography to atmospheric pressure ionization tandem mass spectrometry for the separation and characterization of hop acids mixture from the crude extract of Humulus lupulus was investigated. The solvent system consisting of acetonitrile-aqueous formic acid was used to give proper separation of the six main hop bitter acids within 30 min. Further structural information about the components was acquired by collision-induced dissociation (CID). On the basis of analyses of the fragmentation patterns of the major alpha- and beta-bitter acids respectively, identification of the minor ones was performed using selected reaction monitoring (SRM) with a group of qualitatively relevant selected precursor-product ion transitions for each bitter acid in a single high performance liquid chromatography (HPLC) run. Using this technique, six minor hop acids, including "adprelupulone" observed for the first time in natural resources, were detected along with the six major acids. This hyphenated techniques provides potency for rapid qualitative determination of analogs and homologs in mixtures. (C) 2004 American Society for Mass Spectrometry.

Study on conical columns with different conical angles for semi-preparative liquid chromatography

The dynamic flow profiles and separation performances in conically shaped preparative liquid chromatographic columns (inlet i.d. larger than outlet i.d.) with three different angles (7, 10 and 15degrees) were studied and compared with cylindrical column of the same length and internal volume. The shapes of dynamic flow profiles were studied by on-column visualization method. The transparent chromatographic columns made of polymethyl methacrylate (PMMA), packed with C-18 bonded silica, were immerged into a cubic pool filled with glycerol to eliminate the cylindrical and conical lens effect. The flow profiles of colored iodine solution in the columns were observed clearly using cyclohexane as mobile phase since the refractive indices of C-18, column wall and the mobile phase are very close. In the conical column of 15degrees (20-7 mm i.d.) the mobile phase in the central region migrated slower than in wall region as it moved toward the column outlet, while in the conical column of 7degrees (17-11 mm i.d.) the mobile phase in the central region migrated faster than in wall region just like in cylindrical column. We found that a plug-like flow profile was generated in the conical column of 10degrees (18-9 mm i.d.) during the whole migration process. A carmine and brilliant blue mixture was used as a probe to test the separation ability of the columns. The resolutions of the two compounds on the conical column of 7, 10, 15degrees and on the cylindrical column were 0.6, 1.57, 1.29 and 0.8, respectively. (C) 2003 Elsevier B.V. All rights reserved.

Study of an electroosmotic pump for liquid delivery and its application in capillary column liquid chromatography

A packed-bed electroosmotic pump (EOP) was constructed and evaluated. The EOP consisted of three capillary columns packed in parallel, a gas-releasing device, Pt electrodes and a high-voltage power supply. The EOP could generate output pressure above 5.0 MPa and constant flow rate in the range of nl/min to a few mul/min for pure water, pure methanol, 2 mM potassium dihydrogenphosphate buffer, the buffer-methanol mixture and the pure water-methanol mixture at applied potentials less than 20 W The composition of solvent before/after pumping was quantitatively determined by using a gas chromatograph equipped with both flame ionization detector and thermal conductivity detector. It was found that there were no apparent changes in composition and relative concentrations after pumping process for a methanol-ethanol-acetonitrile mixture and a methanol-water mixture. Theoretical aspect of the EOP was discussed in detail. An capillary HPLC system consisting of the EOP, an injection valve, a 15 cm x 320 mum i.d., 5 mum Spherigel C(18) stainless steel analytical column, and an on-column UV detector was connected to evaluate the performance of the EOP. A comparative study was also carried out with a mechanical capillary HPLC pump on the same system. The results demonstrated that the reproducibility of flow rate and the pulsation-free flow property of the EOP are superior to that of mechanical pump in capillary HPLC application. (C) 2004 Elsevier B.V. All rights reserved.

Study on conical columns for semi-preparative liquid chromatography

The dynamic flow profiles and column efficiencies in conically shaped semi-preparative liquid chromatographic columns (inlet ID larger than outlet ID) with two different conical angles (7degrees and 15degrees) were studied. The dynamic flow profiles were studied by an on-column visualization method. Conical columns were compared with cylindrical column of the same length and internal volume. The results showed that the flow profile of a sample band in the conical column of 7degrees (50 mm x 17 mm --> 11 mm ID) was parabolic in shape. The sample band migrated slower in the wall region than in the central region, as in the cylindrical column (50 mm x 14 mm ID). However, the sample band in the conical column of 15degrees (50 mm x 20 mm --> 7 mm ID) migrated slower in the central region than in the wall region, resulting in a reverse parabolic flow profile, in contrast to that in cylindrical column. This indicated that a flat flow profile might be realized in a conical column with a conical angle between 7degrees and 15degrees. The conical column of 15degrees had the highest column efficiency among the three columns under the same conditions. Compared with the cylindrical column packed with identical packing material, the conical column of 15degrees had 22%-45% higher column efficiency and 11%-27% higher peak height.

An electroosmotic pump for packed capillary liquid chromatography

An electroosmotic pump (EOP) capable of generating pressure above 3 MPa and mul/min flow rate with reverse phase mobile phases of HPLC was constructed and evaluated. The pump consisted of three parallel connected fused silica capillary columns (25 cm x 320 mum I.D.) packed with 2 mum silica materials, hollow electrodes, a high voltage DC power supply, and. a liquid pressure transducer. The EOP was applied in a capillary liquid chromatographic system for mobile phase delivery instead of a mechanical pump. Standard samples containing thiourea, naphthalene, anthracene, phenanthrene and acetonitrile were separated on a 15 cm x 320 mum I.D. 5 mum Chromasil C-18 packed capillary column with acetonitrile/water as mobile phase. (C) 2003 Elsevier Science B.V. All rights reserved.