Scaling law analysis of electrohydrodynamics and dielectrophoresis for isomotive dielectrophoresis microfluidic devices

Isomotive dielectrophoresis (isoDEP) is a unique DEP geometrical configuration where the gradient of the field-squared () is constant. IsoDEP analyzes polarizable particles based on their magnitude and direction of translation. Particle translation is a function of the polarizability of both the particles and suspending medium, the particles’ size and shape, and the frequency of the electric field. However, other electrokinetics act on the particles simultaneously, including electrothermal hydrodynamics. Hence, to maximize the DEP force relative to over electrokinetic forces, design parameters such as microchannel geometry, fabrication materials, and applied electric field must be properly tuned. In this work, scaling law analyses were developed to derive design rules, relative to particle diameter, to reduce unwanted electrothermal hydrodynamics relative to DEP-induced particle translation. For a particle suspended in 10 mS/m media, if the channel width and height are below ten particle diameters, the electrothermal-driven flow is reduced by ∼500 times compared to a channel that is 250 particles diameters in width and height. Replacing glass with silicon as the device's underlying substrate for an insulative-based isoDEP reduces the electrothermal induced flow approximately 20 times less.     

Direct electrochemistry and electrocatalysis of heme-protein based on N,N-dimethylformamide film electrode

The heme-protein including myoglobin (Mb), hemoglobin (Hb) and horseradish peroxidase (HRP) were immobilized on normal graphite electrode by using N,N-dimethylformamide (DMF). The proteins undergo direct electron-transfer reactions. The current is linearly dependent on the scan rate, indicating that the direct electrochemistry of heme-protein in that case is a surface-controlled electrode process. The E°s are linearly dependent on solution pH (redox-Bohr effect), indicating that the electron transfer was proton-coupled. Ultraviolet-visible (UV-vis) and reflection-absorption infrared (RAIR) spectra suggest that the conformation of proteins in the presence of DMF are little different from that proteins alone the conformation changes reversibly in the range of pH 3.0-10.0. The catalytic activity of proteins were examined by hydrogen peroxide and nitrite.     

Opportunities and challenges of thin-film boron-doped diamond electrochemistry for valuable resources recovery from waste: Organic,inorganic, and volatile product electrosynthesis

Thin-film boron-doped diamond (BDD) electrochemistry has made a tremendous progress in electrochemical synthesis/recovery of high-added value products from aqueous and gaseous waste streams. The distinguished electrochemical characteristic of this electrode has made this material emerging and successfully used in electrosynthetic transformations, besides its destructive and powerful performance in disinfection and detoxification of wastewaters. Organic electrosynthesis is achieved by the oxyl radical oxidation formed at BDD, peroxo compounds electrosynthesis is attained by oxidation of corresponding anions at the BDD surface, whereas electrochemical conversion of SO₂, CO₂, NO₃^?, and NH₃ to value-added products occurs by BDD cathodic reduction process. There are still some challenges needed to address for seamless scale-up and translation into application of this future technology.     

Direct electrochemistry of glucose oxidase based on its direct immobilization on carbon ionic liquid electrode and glucose sensing

Direct electrochemistry of glucose oxidase (GOx) has been achieved by its direct immobilization on carbon ionic liquid electrode (CILE) with a conductive hydrophobic ionic liquid, 1-butyl pyridinium hexafluophosphate ([BuPy][PF₆]) as binder for the first time. A pair of reversible peaks is exhibited on GOx/CILE by cyclic voltammetry. The peak-to-peak potential separation (ΔE_P) of immobilized GOx is 0.056 V in 0.067 M phosphate buffer solution (pH 6.98) with scan rate of 0.1 V/s. The average surface coverage and the apparent Michaelis–Menten constant are 6.69 × 10⁻¹¹ mol·cm⁻² and 2.47 μM. GOx/CILE shows excellent electrocatalytic activity towards glucose determination in the range of 0.1–800 μM with detection limit of 0.03 μM (S/N = 3). The biosensor has been successfully applied to the determination of glucose in human plasma with the average recoveries between 95.0% and 102.5% for three times determination. The direct electrochemistry of GOx on CILE is achieved without the help of any supporting film or any electron mediator. GOx/CILE is inexpensive, stable, repeatable and easy to be fabricated.     

Separation/preconcentration and determination of vanadium with dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) and electrothermal atomic absorption spectrometry

A novel dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) for separation/preconcentration of ultra trace amount of vanadium and its determination with the electrothermal atomic absorption spectrometry (ETAAS) was developed. The DLLME-SFO behavior of vanadium (V) using N-benzoyl-N-phenylhydroxylamine (BPHA) as complexing agent was systematically investigated. The factors influencing the complex formation and extraction by DLLME-SFO method were optimized. Under the optimized conditions: 100 μL, 200 μL and 25 mL of extraction solvent (1-undecanol), disperser solvent (acetone) and sample volume, respectively, an enrichment factor of 184, a detection limit (based on 3S_b/m) of 7 ng L⁻¹ and a relative standard deviation of 4.6% (at 500 ng L⁻¹) were obtained. The calibration graph using the preconcentration system for vanadium was linear from 20 to 1000 ng L⁻¹ with a correlation coefficient of 0.9996. The method was successfully applied for the determination of vanadium in water and parsley.     

Electrochemical,fluorescence, and UV detection for HPLC analysis of various cysteine derivatives

Electrochemical (ECD), fluorescence (FLD), and UV spectrophotometric (UVD) detection were used to monitor various S-alk(en)yl-L -cysteines and their corresponding sulfoxide isomers following pre-column derivatization with o-phthaldialdehyde-tert-butylthiol and separation by reversed-phase HPLC. Recording of hydrodynamic voltammograms, FLD stop-flow scanning, and on-line captured UV spectra were methods used for establishing optimal detector settings which were defined as a compromise between favorable selectivity and high sensitivity. Optimal detector settings were found at: (A) 750 mV vs. Ag/AgCl for ECD; (B) excitation at 230 nm and emission at 420 nm for FLD; and (C) 337 nm for UVD. Various aspects of detector practicability such as selectivity, baseline disturbances due to excessive reagent, scanning possibilities, as well as detection limits were evaluated and compared. Minimal detectable amounts of the compounds were in the range of 130-160 fmol for ECD, and 2.5-3.5 pmol and 13-16 pmol for FLD and UVD. In addition, the possibilities and benefits of detector coupling were examined.     

Electrochemical study and flow injection analysis of paracetamol in pharmaceutical formulations based on screen-printed electrodes and carbon nanotubes

Acetaminophenol or paracetamol is one of the most commonly used analgesics in pharmaceutical formulations. Acetaminophen is electroactive and voltammetric mechanistic studies for the electrode processes of the acetaminophenol/N-acetyl-p-quinoneimine redox system are presented. Carbon nanotubes modified screen-printed electrodes with enhanced electron transfer properties are used for the study of the electrochemical-chemical oxidation mechanism of paracetamol at pH 2.0.Quantitative analysis of paracetamol by using its oxidation process (in a Britton-Robinson buffer solution pH 10.0) at +0.20 V (vs. an Ag pseudoreference electrode) on an untreated screen-printed carbon electrode (SPCE) was carried out. Thus, a cyclic voltammetric based reproducible determination of acetaminophen (R.S.D., 2.2%) in the range 2.5 × 10⁻⁶ M to 1 × 10⁻³ M, was obtained. However, when SPCEs are used as amperometric detectors coupled to a flow injection analysis (FIA) system, the detection limit achieved for paracetamol was 1 × 10⁻⁷ M, one order of magnitude lower than that obtained by voltammetric analysis. The repeatability of the amperometric detection with the same SPCE is 2% for 15 successive injections of 10⁻⁵ M acetaminophen and do not present any memory effect.Finally, the applicability of using screen-printed carbon electrodes for the electrochemical detection of paracetamol (i.e. for quality control analysis) was demonstrated by using two commercial pharmaceutical products.     

A microextraction procedure based on a task‐specific ionic liquid for the separation and preconcentration of lead ions from red lipstick and pine leaves

First, the extraction and preconcentration of ultratrace amounts of lead(II) ions was performed using microliter volumes of a task‐specific ionic liquid. The remarkable properties of ionic liquids were added to the advantages of microextraction procedure. The ionic liquid used was trioctylmethylammonium thiosalicylate, which formed a lead thiolate complex due to the chelating effect of the ortho‐positioned carboxylate relative to thiol functionality. So, trioctylmethylammonium thiosalicylate played the roles of both chelating agent and extraction solvent simultaneously. Hence, there is no need to use a ligand. The main parameters affecting the efficiency of the method were investigated and optimized. Under optimized conditions, this approach showed a linear range of 2.0–24.0 ng/mL with a detection limit of 0.0010 ng/mL. The proposed method was applied to the extraction and preconcentration of lead from red lipstick and pine leaves samples prior to electrothermal atomic absorption spectroscopic determination.     

Electrochemical derivatization‐capillary electrophoresis‐contactless conductivity detection: A versatile strategy for simultaneous determination of cationic,anionic, and neutral analytes

The simultaneous determination of cationic, anionic, and neutral analytes in a real sample was demonstrated by coupling electrochemical (EC) derivatization with counter‐EOF CE‐C⁴D. An EC flow cell was used to oxidize alcohols from an antiseptic mouthwash sample into carboxylic acids at a platinum electrode in acid medium. The carboxylates formed in the derivatization process and other sample ingredients, such as benzoate, saccharinate, and sodium ions, were separated in counter‐flow mode and detected in one run in Tris‐HCl buffer, pH 8.6. Fewer than 5 min were needed to complete each analysis with the automated flow system comprising solenoid pumps for the management of solutions. Insights into the electrochemistry of benzoic acid, present in the sample matrix, were also gained by EC‐CE‐C⁴D; more specifically, by applying potentials higher than 1.47 V to the platinum electrode, some formiate and minute amounts of salicylate were detected.     

Rapid identification and high sensitive detection of cancer cells on the gold nanoparticle interface by combined contact angle and electrochemical measurements

In this study, we have proposed a novel strategy for the rapid identification and high sensitive detection of different kinds of cancer cells by means of electrochemical and contact angle measurements. A simple, unlabeled method based on the functionalized Au nanoparticles (GNPs) modified interface has been utilized to distinguish the different cancer cells, including lung cancer cells, liver cancer cells, drug sensitive leukemia K562/B.W cells and drug resistant leukemia K562/ADM cells. The relevant results indicate that under optimal conditions, this method can provide the quantitative determination of cancer cells, with a detection limit of ∼10³ cells mL⁻¹. Our observations demonstrate that the difference in the hydrophilic properties for target cellular surfaces and in the uptake efficiency of the anticancer drug daunorubicin for different cancer cells could be readily chosen as the elements of cancer identification and sensitive detection. This raises the possibility to advance the promising clinic diagnosis and monitoring of tumors with the aim of successful chemotherapy of human cancers.     

Amperometric determination of cyanides at the low ppb level by automated preconcentration based on gas diffusion coupled to sequential injection analysis

A simple, sensitive method for determining free cyanides is described. The assay is based on automated gas diffusion of the analyte using sequential injection analysis (SIA) coupled to amperometric detection on a silver working electrode. The effects of varying several parameters affecting the analytical procedure (including the flow rates of the donor and acceptor streams, the concentrations of the reagents and the sample volumes) were studied. The validity and quality of the method were also assessed, by examining its linearity, limits of detection and quantitation, precision, selectivity to potentially interfering substances. Its sensitivity can be enhanced by applying a simple preconcentration step, following which limits of detection were found to be 0.05-0.12 μg L⁻¹. Application of the proposed assay to the analysis of tap, mineral and table water samples spiked at concentrations ranging from 1 to 10 μg L⁻¹ CN⁻, yielded satisfactory recoveries (88-112%).     

Two coordination polymers based on semicarbazone Schiff base and azide: synthesis,crystal structure,electrochemistry, magnetic properties and biological activity

[Mn(L)(μ_1,1–N₃)₂]_{2 n} [Mn(H₂O)₂(μ_1,1–N₃)₂] _n (1) and [Cd(HL)(μ_1,1–N₃)₂] _n (2) have been synthesized from HL (HL: pyridine-2-carbaldehyde semicarbazone) and azide ligands, characterized by FT-IR, UV–vis spectroscopy and X-ray crystallography. Single crystal X-ray diffraction revealed that 1 is a coordination polymer consisting of two infinite 1-D chains: chain A with [Mn(L)(μ_1,1–N₃)₂]_{2 n} and chain B with [Mn(H₂O)₂(μ_1,1–N₃)₂] _n . In both chains, Mn centers are connected via two double end-on (EO) azide bridges. 2 is a coordination polymer consisting of a 1-D infinite chain, where Cd centers are connected via two double EO azide bridges. The electrochemistry of HL, 1 and 2 were studied by cyclic voltammetry. Magnetic susceptibility measurements indicate bulk ferromagnetic coupling for 1 below 5?K. Antimicrobial activities of both compounds 1 and 2 were greater than HL, with the strongest effect for 2 consistent with its larger radius and electronegativity of Cd(II) ions.     

In situ and online monitoring of hydrodynamic flow profiles in microfluidic channels based upon microelectrochemistry: concept, theory, and validation.

Herein, we propose a method for reconstructing any plausible macroscopic hydrodynamic flow profile occurring locally within a rectangular microfluidic channel. The method is based on experimental currents measured at single or double microband electrodes embedded in one channel wall. A perfectly adequate quasiconformal mapping of spatial coordinates introduced in our previous work [Electrochem. Commun. 2004, 6, 1123] and an exponentially expanding time grid, initially proposed [J. Electroanal. Chem. 2003, 557, 75] in conjunction with the solution of the corresponding variational problem approached by the Ritz method are used for the numerical reconstruction of flow profiles. Herein, the concept of the method is presented and developed theoretically and its validity is tested on the basis of the use of pseudoexperimental currents emulated by simulation of the diffusion-convection problem in a channel flow cell, to which a random Gaussian current noise is added. The flow profiles reconstructed by our method compare successfully with those introduced a priori into the simulations, even when these include significant distortions compared with either classical Poiseuille or electro-osmotic flows.     

阳离子表面活性剂溶液的临界胶束浓度及扩散系数

在无探针分子条件下用循环伏安法(CV)研究了DTAB,TTAB,CTAB,OTAB水溶液体系胶束在玻碳电极(GCE)上的电化学行为,并用电位阶跃计时库仑法(CC)测定了胶束的扩散系数,进而得到第一与第二CMC,该方法简捷、快速、准确。对离子型表面活性剂的第二CMC提供了新的测定方法。     

Simultaneous analysis of six cardiovascular drugs by capillary electrophoresis coupled with electrochemical and electrochemiluminescence detection,using a chemometrical optimization approach

CE coupled with dual electrochemical (EC) and electrochemiluminescence (ECL) detection was optimized for simultaneous analysis of six cardiovascular drugs (alprenolol, propafenone, acebutolol, verapamil, atenolol and metoprolol) via central composite design. Following this study, three critical electrophoretic factors governing the CE separation were investigated: Tris‐H₃PO₄ buffer concentration, buffer pH value and separation voltage. A modified chromatographic response was adopted for evaluating CE separation quality. Optimum conditions were achieved using Tris‐H₃PO₄ buffer 35.6 mM (pH 2.3) separated at 13.9 kV, which was employed experimentally and led to the successful simultaneous separation of the above six drugs. The good agreement of the chromatographic response was observed between predicted data and actual experimental results using these optimized conditions (RSD=3.75%). The proposed method was validated for linearity, repeatability and sensitivity, and subsequently successfully applied to determine six basic drugs in urine samples.     

Numerical analysis of the thermal effect on electroosmotic flow and electrokinetic mass transport in microchannels

Joule heating is present in electrokinetically driven flow and mass transport in microfluidic systems. Nowadays, there is a trend of replacing costly glass-based microfluidic systems by the disposable, cheap polymer-based microfluidic systems. Due to poor thermal conductivity of polymer materials, the thermal management of the polymer-based microfluidic systems may become a problem. In this study, numerical analysis is presented for transient temperature development due to Joule heating and its effect on the electroosmotic flow (EOF) and mass species transport in microchannels. The proposed model includes the coupling Poisson-Boltzmann (P-B) equation, the modified Navier-Stokes (N-S) equations, the conjugate energy equation, and the mass species transport equation. The results show that the time development for both the electroosmotic flow field and the Joule heating induced temperature field are less than 1 s. The Joule heating induced temperature field is strongly dependent on channel size, electrolyte concentration, and applied electric field strength. The simulations reveal that the presence of the Joule heating can result in significantly different characteristics of the electroosmotic flow and electrokinetic mass transport in microchannels.     

A continuous approach for the determination of Cr(VI) in sediment and soil based on the coupling of microwave-assisted water extraction, preconcentration, derivatization and photometric detection

A dynamic system for the continuous leaching of Cr(VI) from sediment and soil based on both microwave assistance and iterative change of the flow direction of the extractant through the sample cell has been developed. The microwave-assisted extractor has been coupled to a photometric detector through a flow injection interface in order to develop a fully automated method. The Cr(VI) extracted was monitored after derivatization with 1,5-diphenylcarbazide. Two approaches are proposed which differ in the inclusion of a preconcentration minicolumn packed with a strong anion exchange resin. A 0.04 M ammonium buffer solution was used as extractant and 0.2 g of sample—river sediment spiked with 50 and 5 μg g⁻¹ for the method without preconcentration (method A) and with preconcentration (method B)—was subjected to 8-14 min of 300 W microwave-assisted extraction. The within-laboratory reproducibility and repeatability were 2.6 and 1.9 for method A, and 4.0 and 2.6 for method B. The proposed methods have been compared with the reference EPA method 3060/7196.     

Direct electrochemistry of glucose oxidase entrapped in nano gold particles-ionic liquid-N,N-dimethylformamide composite film on glassy carbon electrode and glucose sensing

The direct electrochemistry of glucose oxidase (GOD) entrapped in nano gold particles (NAs)-N,N-dimethylformamide (DMF)-1-butyl-3-methylimidazolium hexafluophosphate (BMIMPF₆) composite film on a glassy carbon electrode (NAs-DMF-GOD (BMIMPF₆)/GC) has been investigated for first time. The immobilized GOD exhibits a pair of well-defined reversible peaks in 0.050 M pH 5 phosphate solutions (PS), resulting from the redox of flavin adenine dinucleotide (FAD) in GOD. The peak currents are three times as large as those of GOD-NAs-DMF film coated GC electrode (i.e. NAs-DMF-GOD (water)/GC). In addition, the NAs-DMF-GOD (BMIMPF₆) composite material has higher thermal stability than NAs-DMF-GOD (water). Results show that ionic liquid BMIMPF₆, DMF and NAs are requisite for GOD to exhibit a pair of stable and reversible peaks. Without any of them, the peaks of GOD become small and unstable. Upon the addition of glucose, the peak currents of GOD decrease and a new cathodic peak occurs at −0.8 V (versus SCE), which corresponds to the reduction of hydrogen peroxide (H₂O₂) generated by the catalytic oxidation of glucose. The peak current of the new cathodic peak and the glucose concentration show a linear relationship in the ranges of 1.0 × 10⁻⁷ to 1.0 × 10⁻⁶ M and 2.0 × 10⁻⁶ to 2.0 × 10⁻⁵ M. The kinetic parameter I_max of H₂O₂ is estimated to be 1.19 × 10⁻⁶ A and the apparent K_m (Michaelis-Menten constant) for the enzymatic reaction is 3.49 μM. This method has been successfully applied to the determination of glucose in human plasma and beer samples, and the average recoveries are 97.2% and 99%, respectively.     

Glucose biosensor based on the layer-by-layer self-assembling of glucose oxidase and chitosan derivatives on a thiolated gold surface

This work examines in deep the analytical performance of an example of “first-generation” microdevices: capillary electrophoresis microchip (CE) with end-channel electrochemical detection (ED). A hydroquinone and arbutin separation strategically chosen as route involving pharmaceutical-clinical testing, public safety and food control scenes was carried out. The reproducibility of the unpinched electrokinetic protocol was carefully studied and the technical possibility of working indiscriminately and/or sequentially with both simple cross-injectors was also demonstrated using a real sample (R.S.D.'s less than 7%). The robustness of the injection protocol allowed checking the state of the microchip/detector coupling and following the extraction efficiency of the analyte from real sample. Separation variables such as pH, ionic strength and, separation voltage were also carefully assayed and optimized. Analyte screening was performed using borate buffer (pH 9, 60 mM) in less than 180 s in the samples studied improving dramatically the analysis times used for the same analytes on a conventional scale (15 min), with good precision (R.S.D.'s ranging 5-10%), accuracy (recoveries ranging 90-110%) and acceptable resolution (Rs ≥ 1.0).In addition, the excellent analytical performance of the overall analytical method indicated the quality of the whole analytical microsystem and allowed to introduce the definition of robustness for methodologies developed into the “lab-on-a-chip” scene.     

Flow analysis based on a pulsed flow of solution: theory, instrumentation and applications

The increased demands placed on solution propulsion by programmed flow systems, such as sequential injection analysis, lab-on-value technology, bead injection and multi-commutation, has highlighted the inability of many conventional pumps to generate a smooth, consistent flow. A number of researchers have examined ways to overcome the inadvertent, uncontrolled pulsation caused by the mechanical aciton of peristaltic pumps. In contrast, we have developed instruments that exploit the characteristics of a reproducible pulsed flow of solution. In this paper, we discuss our instrumental approaches and some applications that have benefited from the use of a reproducible pulsed flow rather than the traditional linear flow approach. To place our approach in the context of the continuously developing field of flow analysis, an overview of other programmed flow systems is also presented.