Surface modified nanoparticles and their applications for enantioselective detection, analysis, and separation of various chiral compounds.

The development of efficient enantioselective detection, analysis, and separation relies significantly on molecular interaction. In the scale of molecular interaction, nanomaterials have a significant influence on the performance of enantioselective recognitions. The use of nanomaterials for enantioselective recognition involved synthesizing new materials and immobilization techniques to produce various surface-modified nanoparticles that are either encapsulated or attached to surfaces, as well as layers and coatings. The combination of surface-modified nanomaterials and chiral selectors can improve enantioselective recognition. This review aims to offer engagement insights into the production and application of surface-modified nanomaterials to achieve sensitive and selective detection, better chiral analysis, and separation of numerous chiral compounds.

Alginate NiFe2O4 Nanoparticles Cryogel for Electrochemical Glucose Biosensor Development.

Glucose biosensors based on porous material of alginate cryogel has been developed, and the cryogel provides a large surface area for enzyme immobilization. The alginate cryogel has been supplemented with NiFe2O4 nanoparticles to improve the electron transfer for electrochemical detection. The fabrication parameters and operational conditions for the biosensor have also been optimized. The results showed that the optimum addition of NiFe2O4 nanoparticles to the alginate solution was 0.03 g/mL. The optimum operational conditions for the electrochemical detection were a cyclic voltammetry scan rate of 0.11 V/s, buffer pH of 7.0, and buffer concentration of 150 mM. The fabricated alginate NiFe2O4 nanoparticles cryogel-based glucose biosensor showed a linear response for glucose determination with a regression line of y = 18.18x + 455.28 and R² = 0.98. Furthermore, the calculated detection limit was 0.32 mM and the limit of quantification was 1.06 mM.

Enantioseparation of Selected Imidazole Drugs Using Dual Cyclodextrin-Modified Micellar Electrokinetic Chromatography.

Particular attention has been paid to capillary electrophoresis as versatile and environmentally friendly approach for enantioseparations of a wide spectrum of compounds. Cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) is a method of choice to provide effective separation toward hydrophobic and uncharged stereoisomers. The chiral discrimination of the solutes relies upon the partitioning between a given CD in the aqueous phase and micelles formed from a surfactant. Synergistic combinations of chiral selectors, surfactant, and modifier contribute to successful enantioseparations of the enantiomers. In this chapter, an application of CD-MEKC for the enantioseparation of selected imidazole drugs employing a dual CDs system is described.

Immobilized bacterial biosensor for rapid and effective monitoring of acute toxicity in water.

The use of biosensors by using microorganisms such as bacteria have short life cycles and provide other advantages. One colorimetric biosensor technique that has been developed is the use of a biosensor utilizing the incorporation of Prussian blue formation reactions mediated by E. coli bioreactors with ferricyanide. Immobilization is a method that allows the bacteria can be used for long-term without reducing its ability as bioreceptor. This study aimed to develop a novel and rapid immobilized bacterial biosensor for the detection of toxic compound in water and to evaluate their analytical performances. Immobilization of E. coli performed by trapping method using alginate material support. The bacterial suspension was mixed with sodium alginate (1:1 v/v), and the mixture was continuously dropped in CaCl2 solution to be a form of beads. The beads were used as bioreceptor to detect toxicants regarding cadmium, arsenic, mercury, chromium and lead solutions with Prussian blue as a colorimetric indicator. The linearity and sensitivity of detection of beads to the toxicants were tested, the stability of repeated use and storage were evaluated as well. The results showed that E. coli could be immobilized using alginate with response value was correlated with toxic concentration. The developed biosensor was more stable when used repeatedly and could be stored in a long time. The immobilization of E. coli in calcium alginate bead was successfully performed as a biosensor system for monitoring acute toxicity in water.

Separation of selected imidazole enantiomers using dual cyclodextrin system in micellar electrokinetic chromatography.

Cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) method was developed for simultaneous enantioseparation of three imidazole drugs namely tioconazole, isoconazole and fenticonazole. Three easily available and inexpensive cyclodextrins namely 2-hydroxypropyl-ß-cyclodextrin (HP-ß-CD), 2-hydroxypropyl-γ-cyclodextrin (HP-γ-CD) and heptakis(2,6-di-O-methyl)-ß-cyclodextrin (DM-ß-CD) were evaluated to discriminate the six stereoisomers of the drugs. However, none of the three CDs gave a complete enantioseparation of the drugs. Effective enantioseparation of tioconazole, isoconazole and fenticonazole was achieved using a combination of 35 mM HP-γ-CD and 10 mM DM-ß-CD as chiral selectors. The best separation using both HP-γ-CD and DM-ß-CD (35 mM:10 mM) as chiral selectors were accomplished in background electrolyte (BGE) containing 35 mM phosphate buffer (pH 7.0), 50 mM sodium dodecyl sulfate (SDS) and 15% (v/v) acetonitrile at 27 kV and 30 °C with all peaks resolved in less than 15 min with resolutions, Rs 1.90-27.22 and peak efficiencies, N > 180 000. The developed method was linear over the concentration range of 25-200 mg l(-1) (r(2) > 0.998) and the detection limits (S/N = 3) of the three imidazole drugs were found to be 2.7-7.7 mg l(-1). The CD-MEKC method was successfully applied to the determination of the three imidazole drugs in spiked human urine sample and commercial cream formulation of tioconazole and isoconazole with good recovery (93.6-106.2%) and good RSDs ranging from 2.30-6.8%.

Cyclodextrin-modified micellar electrokinetic chromatography for enantioseparations.

The separation of enantiomers is one of the important fields of modern analytical chemistry, especially for agrochemical and pharmaceutical products because the stereochemistry has a significant influence on the biological activities of compounds. Cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) has become an important capillary electrophoresis mode for enantioseparations. Here, we describe an example of a CD-MEKC method using hydroxypropyl-γ-cyclodextrin as chiral selector and sodium dodecyl sulfate as micellar solution for enantioseparation of triazole fungicides and the drug econazole.

Chiral separation of vinpocetine using cyclodextrin-modified micellar electrokinetic chromatography.

A cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) technique has been developed for enantioseparation of vinpocetine using an inexpensive 2-hydroxypropyl-ß-CD (HP-ß-CD) as the chiral selector (CS). The best chiral separation was achieved using 40 mM HP-ß-CD as the CS in 50 mM phosphate buffer (pH 7.0) consisting of 40 mM sodium dodecyl sulfate (SDS) at a separation temperature and separation voltage of 25°C and 25 kV, respectively. To the author's best knowledge, this is the first CD-MEKC study able to successfully separate the four stereoisomer of vinpocetine in separation time of 9.5 min and resolution of 1.04-3.87.

A practical approach for linearity assessment of calibration curves under the International Union of Pure and Applied Chemistry (IUPAC) guidelines for an in-house validation of method of analysis.

Linearity assessment as required in method validation has always been subject to different interpretations and definitions by various guidelines and protocols. However, there are very limited applicable implementation procedures that can be followed by a laboratory chemist in assessing linearity. Thus, this work proposes a simple method for linearity assessment in method validation by a regression analysis that covers experimental design, estimation of the parameters, outlier treatment, and evaluation of the assumptions according to the International Union of Pure and Applied Chemistry guidelines. The suitability of this procedure was demonstrated by its application to an in-house validation for the determination of plasticizers in plastic food packaging by GC.

Chiral separation of econazole using micellar electrokinetic chromatography with hydroxypropyl-gamma-cyclodextrin.

A cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) method with hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD) as chiral selector for the enantiomeric separation of econazole is reported. Enantioseparation of econazole was successfully achieved by the optimized CD-MEKC system containing 40mM HP-gamma-CD, 50mM SDS and 20mM phosphate buffer (pH 8) solution with an analysis time of less than 9min. Calibration curves were linear for the two stereoisomers of econazole (r(2)>0.998). Good repeatabilities in the migration time, peak area and peak height were obtained in terms of RSD% ranging from 0.30 to 7.67%. Combination of solid-phase extraction (SPE) procedure using diol column and the CD-MEKC method was successfully applied to the determination of econazole in a formulated cream sample.

Determination of partition coefficient and analysis of nitrophenols by three-phase liquid-phase microextraction coupled with capillary electrophoresis.

A three-phase hollow fiber liquid-phase microextraction method coupled with CE was developed and used for the determination of partition coefficients and analysis of selected nitrophenols in water samples. The selected nitrophenols were extracted from 14 mL of aqueous solution (donor solution) with the pH adjusted to pH 3 into an organic phase (1-octanol) immobilized in the pores of the hollow fiber and finally backextracted into 40.0 microL of the acceptor phase (NaOH) at pH 12.0 located inside the lumen of the hollow fiber. The extractions were carried out under the following optimum conditions: donor solution, 0.05 M H(3)PO(4), pH 3.0; organic solvent, 1-octanol; acceptor solution, 40 microL of 0.1 M NaOH, pH 12.0; agitation rate, 1050 rpm; extraction time, 15 min. Under optimized conditions, the calibration curves for the analytes were linear in the range of 0.05-0.30 mg/L with r(2)>0.9900 and LODs were in the range of 0.01-0.04 mg/L with RSDs of 1.25-2.32%. Excellent enrichment factors of up to 398-folds were obtained. It was found that the partition coefficient (K(a/d)) values were high for 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol and 2,6-dinitrophenol and that the individual partition coefficients (K(org/d) and K(a/org)) promoted efficient simultaneous extraction from the donor through the organic phase and further into the acceptor phase. The developed method was successfully applied for the analysis of water samples.

Simultaneous enantioseparation of cyproconazole, bromuconazole, and diniconazole enantiomers by CD-modified MEKC.

An efficient method for the simultaneous enantioseparation of cyproconazole, bromuconazole, and diniconazole enantiomers was developed by CD-modified MEKC using a dual mixture of neutral CDs as chiral selector. Three neutral CDs namely hydroxypropyl-beta-CD, hydroxypropyl-gamma-CD, and gamma-CD were tested as chiral selectors at different concentrations ranging from 10, 20, 30 and 40 mM, but enantiomers of the studied fungicides were not completely separated. The best dual chiral recognition mode for the simultaneous separation of cyproconazole, bromuconazole, and diniconazole enantiomers was achieved with a mixture of 27 mM hydroxypropyl-beta-CD and 3 mM hydroxypropyl-gamma-CD in 25 mM phosphate buffer (pH 3.0) containing 40 mM SDS to which methanol-acetonitrile (10%:5% v/v) was added as organic modifiers. The best separation was based on the appearance of 10 peaks simultaneously, with good resolution (R(s) 1.1-15.9), and peak efficiency (N>200,000). Good repeatabilities in the migration time, peak area, and peak height were obtained in terms of RSD ranging from (0.72 to 1.06)%, (0.39 to 3.49)%, and (1.90 to 4.84)%, respectively.

Cyclodextrin-modified MEKC for enantioseparation of hexaconazole, penconazole, and myclobutanil.

A CD-modified micellar EKC (CD-MEKC) method with 2-hydroxypropyl-gamma-CD (HP-gamma-CD) as chiral selector for the enantioseparation of three chiral triazole fungicides, namely hexaconazole, penconazole, and myclobutanil, is reported for the first time. Simultaneous enantioseparation of the three triazole fungicides was successfully achieved using a CD-MEKC system containing 40 mM HP-gamma-CD and 50 mM SDS in 25 mM phosphate buffer (pH 3.0) solution with resolutions (R(s)) greater than 1.60, peak efficiencies (N) greater than 200,000 for all enantiomers and an analysis time within 15 min compared to 36 min as previously reported using sulfated-beta-CD.

Comparison of signal-to-noise, blank determination, and linear regression methods for the estimation of detection and quantification limits for volatile organic compounds by gas chromatography.

LOD and LOQ are two important performance characteristics in method validation. This work compares three methods based on the International Conference on Harmonization and EURACHEM guidelines, namely, signal-to-noise, blank determination, and linear regression, to estimate the LOD and LOQ for volatile organic compounds (VOCs) by experimental methodology using GC. Five VOCs, toluene, ethylbenzene, isopropylbenzene, n-propylbenzene, and styrene, were chosen for the experimental study. The results indicated that the estimated LODs and LOQs were not equivalent and could vary by a factor of 5 to 6 for the different methods. It is, therefore, essential to have a clearly described procedure for estimating the LOD and LOQ during method validation to allow interlaboratory comparisons.

On-line preconcentration and chiral separation of propiconazole by cyclodextrin-modified micellar electrokinetic chromatography.

A method for the chiral separation of propiconazole using cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) with hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD) as chiral selector is reported. The use of a mixture of 30 mM HP-gamma-CD, 50mM SDS, methanol-acetonitrile 10%:5% (v/v) in 25 mM phosphate buffer solution was able to separate two enantiomeric pairs of propiconazole. Stacking- and sweeping-CD-MEKC under neutral pH (pH 7) and under acidic condition (pH 3.0) were used as two on-line preconcentration methods to increase detection sensitivity of propiconazole. Good repeatabilities in the migration time, peak area and peak height were obtained in terms of relative standard deviation (RSD). A sensitivity enhancement factor of 100-fold was achieved using sweeping-CD-MEKC at acidic pH. This is the first report on the separation of two pairs of propiconazole enantiomers and all the enantiomers of fenbuconazole and tebuconazole using sweeping-CD-MEKC. The limit of detection (S/N=3) for the three triazole fungicides ranged from 0.09 to 0.1 microg/mL, which is well below the maximum residue limits (MRL) set by Codex Alimentarius Commission (CAC). Combination of solid-phase extraction (SPE) pretreatment and sweeping-CD-MEKC procedure was applied to the determination of selected triazole fungicides in grapes samples spiked at concentration 10-40 times lower than the MRL established by the CAC. The average recoveries of the selected fungicides in spiked grapes samples were good, ranging from 73% to 109% with RSD of 9-12% (n=3).