Enantioseparation of Dioxopromethazine Hydrochloride in Urine with Liquid-Liquid Extraction by CE-ECL Detection

Capillary electrophoresis coupled with electrochemiluminescence detection was developed for the separation and determination of dioxopromethazine hydrochloride (DPZ) enantiomers. Performance parameters of the proposed method were evaluated. An improved separation of DPZ enantiomers could be achieved after adding boric acid to buffer. The enantiomers were completely separated with running buffer of 16.5 mM beta-CD in 25 mM tris-H3PO4-40 mM H3BO3 at pH 2.5. The proposed method was successfully applied to the separation and determination of DPZ enantiomers in human urine with a liquid-liquid extraction procedure.

Electrochemical Detection of Hydrazine Based on Electrospun Palladium Nanoparticle/Carbon Nanofibers

In this work, we developed an electrochemical method for the detection of hydrazine based oil palladium nanoparticle/carbon nanofibers (Pd/CNFs). Pd/CNFs were prepared by electrospinning technique and subsequent thermal treatments. The electrocatalytic behaviors of Pd/CNFs modified glassy carbon electrode (Pd/CNF-GCE) for hydrazine oxidation were evaluated by cyclic voltammetry (CV), an obvious and well-defined oxidation peak appeared at -0.32 V (vs. Ag/AgCl). The mechanism of the oxidation of hydrazine at Pd/CNF-GCE was also studied, which demonstrated an irreversible diffusion-controlled electrode process and a four-electron transfer involved in the overall reaction. Furthermore, the wide linear range, low detection limit, good reproducibility and excellent storage stability were obtained utilizing differential pulse voltammetry (DPV).

Simple and rapid voltammetric determination of morphine at electrochemically pretreated glassy carbon electrodes

A simple and rapid method for morphine detection has been described based on electrochemical pretreatment of glassy carbon electrode (GCE) which was treated by anodic oxidation at 1.75 V, following potential cycling in the potential range from 0 V to 1.0 V vs. Ag vertical bar AgCl reference electrode. The sensitivity for morphine detection was improved greatly and the detection limit was 0.2 mu M. The reproducibility of the voltammetric measurements was usually less than 3% RSD for six replicate measurements. Moreover, this method could readily discriminate morphine from codeine. And an electrochemical detection of morphine in spiked urine sample was succeeded with satisfactory results.

Gold nanoparticle-based near-infrared fluorescent detection of biological thiols in human plasma

In this work, a new fluorescent method for sensitive detection of biological thiols in human plasma was developed using a near-infrared (NIR) fluorescent dye, FR 730. The sensing approach was based on the strong affinity of thiols to gold and highly efficient fluorescent quenching ability of gold nanoparticles (Au NPs). In the presence of thiols, the NIR fluorescence would enhance dramatically due to desorption of FR 730 from the surfaces of Au NPs, which allowed the analysis of thiol-containing amino acids in a very simple approach. The size of Au NPs was found to affect the fluorescent assay and the best response for cysteine detection was achieved when using Au NPs with the diameter of 24 nm, where a linear range of 2.5 x 10(-8) M to 4.0 x 10(-6) M and a detection limit of as low as 10 nM was obtained. This method also demonstrated a high selectivity to thiol-containing amino acids due to the strong affinity of thiols to gold.

Successful establishment of MEKC with electrochemiluminescence detection based on one functionalized ionic liquid

Herein, one water-soluble functionalized ionic liquid, 1-butyl-3-methylimidazolium dodecyl sulfate ([BMIm(+)][C12H25SO4-]), was designed and its superiorities either used as supporting electrolytes or as additives for successful establishment of MEKC with electrochemiluminescence (ECL) detection (MEKC-ECL) method were investigated. Compared with the common supporting electrolytes such as phosphate solution, 1-butyl-3-methylimidazolium dodecyl sulfate solution used as running buffers led to greatly enhanced ECL intensities and column efficiencies for negative targets, a little increase for neutral-charge ones while maintained nearly unchanged for positive ones due to the electrostatic forces between the large cation BMIm(+) and the solutes and the hydrophobic interactions resulting from the large anion C12H25SO4.

Surface modification of poly(dimethylsiloxane) microchips using a double-chained cationic surfactant for efficiently resolving fluorescent dye adsorption

This paper described a double-chained cationic surfactant, didodecyldimethylammonium bromide (DDAB). for dynamic surface modification of poly(dimethylsiloxane) (PDMS) microchips to reduce the fluorescent dyes adsorption onto the microchannel. When DDAB with a high concentration was present as the dynamic modification reagent in the running and sample buffer, it not only reversed the direction of electroosmotic flow, but also efficiently suppressed fluorescent dyes pyronine Y (PY) or rhodamine 8 (RB) adsorption onto the chip surface. In addition, vesicles formed by DDAB in the buffer with higher surface charge density and electrophoretic mobility could provide wider migration window and potential for the separation of compounds with similar hydrophobicity. Factors affecting modification, such as pH and concentrations of the buffer, DDAB concentration in the buffer were investigated. Compared with commonly used single-chained cetyltrimethylammonium bromide, DDAB provided a better modification performance.

Solid-state electrochemiluminescence sensor based on the Nafion/poly(sodium 4-styrene sulfonate) composite film

An effective electrochemiluminescence (ECL) sensor based on Nafion/poly(sodium 4-styrene sulfonate) (PSS) composite film-modified ITO electrode was developed. The Nafion/PSS/Ru composite film was characterized by atomic force microscopy, UV-vis absorbance spectroscopy and electrochemical experiments. The Nafion/PSS composite film could effectively immobilize tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) via ion-exchange and electrostatic interaction. The ECL behavior of Ru(bpy)(3)(2+) immobilized in Nafion/PSS composite film was investigated using tripropylamine (TPA) as an analyte. The detection limit (S/N = 3) for TPA at the Nafion/PSS/Ru composite-modified electrode was estimated to be 3.0 nM, which is 3 orders of magnitude lower than that obtained at the Nafion/Ru modified electrode. The Nafion/PSS/Ru composite film-modified indium tin oxide (ITO) electrode also exhibited good ECL stability. In addition, this kind of immobilization approach was simple, effective, and timesaving.

Formation of [Ru(bpy)(3)](2+)-containing microstructures induced by electrostatic assembly and their application in solid-state detection of electrochemiluminescence

Tris(2,2'-bipyridine)ruthenium(II) ((Ru(bpy)(3)](2+)) is one of the most extensively studied and used electrochemiluminescent (ECL) compounds owing to its superior properties, which include high sensitivity and stability under moderate conditions in aqueous solution. In this paper we present a simple method for the preparation of [Ru(bpy)(3)](2+)-containing microstructures based on electrostatic assembly The formation of such micro-structures occurs in a single process by direct mixing of aqueous solutions of [Ru(bpy)(3)]Cl-2 and K-3[Fe(CN)(6)] at room temperature. The electrostatic interactions between [Ru(bpy)(3)]Cl-2 cations and [Fe(CN)(6)](3-) anions cause them to assemble into the resulting microstructures. Both the molar ratio and concentration of reactants were found to have strong influences on the formation of these microstructures. Most importantly, the resulting [Ru(bpy)(3)](2+)- containing microstructures exhibit excellent ECL behavior and, therefore, hold great promise for solid-state ECL detection in capillary electrophoresis (CE) or CE microchips.

A DNA nanomachine induced by single-walled carbon nanotubes on gold surface

Single-walled carbon nanotubes (SWNTs) can selectively induce human telomeric i-motif DNA formation at pH 7.0. Based on this property, we design a DNA nanomachine induced by SWNTs on gold surface. The motor DNA is human telomeric G-quadruplex DNA. The reversible hybridization between the motor DNA and its complementary human telomeric i-motif DNA can be modulated by SWNTs without changing solution pH. Up to now, to our knowledge, there is no report to show that a DNA nanomachine is induced by SWNTs or a DNA nanomachine can detect i-motif formation at pH 7.0. Our work may provide a new concept for designing an SWNT-induced DNA nanomachine and for the detection of i-motif DNA structure at pH 7.0. DNA hybridization, conformational transition and i-motif formation have been characterized on surface or in solution by fluorescence confocal microscopy, circular dichroism, DNA melting and gel electrophoresis. The folding and unfolding kinetics of the DNA nanomachine on gold surface were studied by Fourier transform-surface plasmon resonance (FT-SPR). All these results indicate that SWNTs can induce the DNA nanomachine to work efficiently and reversibly.

Luminescent supramolecular microstructures containing Ru(bpy)(3)(2+): Solution-based self-assembly preparation and solid-state electrochemiluminescence detection application

In this correspondence, we report on the first preparation of novel, robust Ru(bpy)(3)(2+)-containing supramolecular microstructures via a solution-based self-assembly strategy, carried out by directly mixing H2PtCl6 and Ru(bpy)(3)Cl-2 aqueous solutions at room temperature. It reveals that both the molar ratio and concentration of reactants have a heavy influence on the morphologies of such microstructures. The electrochemical behavior of the Ru(bpy)(3)(2+) components contained in the solid film of the microstructures formed on the electrode surface is also studied and found to exhibit a diffusion-controlled voltammetric feature. Most importantly, such microstructures exhibit excellent electrochemiluminescence (ECL) behaviors and therefore hold great promise as new luminescent materials for solid-state ECL detection in capillary electrophoresis (CE) or CE microchip.

Electrochemiluminescence sensor based on partial sulfonation of polystyrene with carbon nanotubes

Herein, homogenously partial sulfonation of polystyrene (PSP) was performed. An effective electrochemiluminescence (ECL) sensor based on PSP with carbon nanotube (CNTs) composite film was developed. Cyclic voltammetry and electrochemical impendence spectroscopy were applied to characterize this composite film. The PSP was used as an immobilization matrix to entrap the ECL reagent Ru(bpy)(3)(2+) due to the electrostatic interactions between sulfonic acid groups and Ru(bpy)(3)(2+) cations. The introduction of CNTs into PSP acted not only as a conducting pathway to accelerate the electron transfer but also as a proper matrix to immobilize Ru(bpy)(3)(2+) on the electrode by hydrophobic interaction. Furthermore, the results indicated the ECL intensity produced at this composite film was over 3-fold compared with that of the pure PSP film due to the electrocatalytic activity of the CNTs. Such a sensor was verified by the sensitive determinations of 2-(dibutylamino)ethanol and tripropylamine.

Ionic liquids as selectors for the enhanced detection of proteins

Herein, we report an approach for protein detection enhanced by ionic liquid (IL) selectors in capillary electrophoresis (CE), with avidin as a model protein. Hydrophilic ILs were added into the running buffer of CE and acted as selectors for sample injection, enriching the positive target and excluding the negative from the capillary. When using 3% (v/v) IL selector, the detection sensitivity of avidin was improved by over one order of magnitude, while the interference from protein adsorption was effectively avoided, even in an uncoated capillary. The electrochemiluminescence method was initially used for IL-based CE with low noise that was independent of the IL concentration, making ILs almost transparent as additives in the electrophoresis buffer.

A novel sensitive solid-state electrochemiluminescence sensor material: Ru(bpy)(2+)(3) doped SiO2@MWNTs coaxial nanocable

A simple, large scale, and one-step process for the preparation of tris(2,2'-bipyridyl)ruthenium(I) (Ru(bpy)(3)(2+)) doped SiO2@carbon nanotubes (MVNTs) coaxial nanocable used for an ultrasensitive electrochemiluminescence (ECL) is presented for the first time. More importantly, a directly coated as-formed functional material on ITO electrode surface exhibits excellent ECL behavior, good stability, and high sensitivity in the presence of tripropylamine (TPA). This novel functional material will find potential applications in biosensor, electrophoresis and electroanalysis.

Adaptive recognition of small molecules by nucleic acid aptamers through a label-free approach

We report a novel label-free method for the investigation of the adaptive recognition of small molecules by nucleic acid aptamers using capillary electrophoresis analysis. Cocaine and argininamide were chosen as model molecules, and the two corresponding DNA aptamers were used. These single-strand DNAs folded into their specific secondary structures, which were mainly responsible for the binding of the target molecules with high affinity and specificity. For molecular recognition, the nucleic acid structures then underwent additional conformational changes, while keeping the target molecules stabilized by intermolecular hydrogen bonds. The intrinsic chemical and physical properties of the target molecules enabled them to act as indicators for adaptive binding. Thus any labeling or modification of the aptamers or target molecules were made obsolete. This label-free method for aptamer-based molecular recognition was also successfully applied to biological fluids and therefore indicates that this approach is a promising tool for bioanalysis.

Lung alveolar proteomics of bronchoalveolar lavage from a pulmonary alveolar proteinosis patient using high-resolution FTICR mass spectrometry

High-resolution Fourier transform ion cyclotron resonance (FTICR) mass spectrometry was developed and applied to the proteome analysis of bronchoalveolar lavage fluid (BALF) from a patient with pulmonary alveolar proteinosis. With use of 1-D and 2-D gel electrophoresis, surfactant protein A (SP-A) and other surfactant-related lung alveolar proteins were efficiently separated and identified by matrix-assisted laser desorption/ionization FTICR mass spectrometry . Low molecular mass BALF proteins were separated using a gradient 2-D gel. An efficient extraction/precipitation system was developed and used for the enrichment of surfactant proteins. The result of the BALF proteome analysis show the presence of several isoforms of SP-A, in which an N-non-glycosylierte form and several proline hydroxylations were identified. Furthermore, a number of protein spots were found to contain a mixture of proteins unresolved by 2-D gel electrophoresis, illustrating the feasibility of high-resolution mass spectrometry to provide identifications of proteins that remain unseparated in 2-D gels even upon extended pH gradients.