Sławomir Oszwałdowski

Reversed-phase liquid chromatographic simultaneous determination of iron(III) and iron(II) as complexes with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol: Determination of iron(III) and iron(II) in water samples and ultrasound field effect on distribution of iron(III) and iron(II) in micellar solution

The formation of Fe(III) and Fe(II) chelates with pyridylazo and thiazolylazo reagents was examined. Optimum conditions for the formation of Fe(III) and Fe(II) chelates with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) were in detail evaluated. The LC method for simultaneous separation of Fe(III) and Fe(II) ions as 5-Br-PADAP chelates was evaluated using the PEEK column with C18 e.c. stationary phase and acetonitrile+water (90:10, v/v) eluent containing the 1x10(-3) mol l(-1) C(12)H(25)SO(3)Na, the ion-pairing reagent, pH 3.4-3.6. The simultaneous determination of 20-500 mug l(-1) Fe(II) ions (detection at 555 nm) and 20-500 mug l(-1) Fe(III) ions (detection at 585 nm) as 5-Br-PADAP chelates (for both ions, detection limit, 18 mug l(-1) for 20 mul loop) was established. The chromatographic method was applied to the water analysis. Although the present method is able to determine both Fe(III) and Fe(II) ions, the Fe(III) ion was not detected in all water samples. The Fe(II) was detected only in fresh gathered oligocene water at the level of 135 mug l(-1). The present method was used to the investigation of the distribution of Fe(III)/Fe(II) ions in aqueous and micellar solutions after action of external, ultrasonic field.

Simultaneous determination of zirconium and hafnium as ternary complexes with 5-Br-PADAP and fluoride using solid-phase extraction and reversed-phase liquid chromatography.

Solid-phase extraction (SPE) along with reversed-phase liquid chromatography (RP-LC) was used for the simultaneous determination of Zr(IV) and Hf(IV) by means of their ternary chelates with fluoride and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP). The conditions of SPE sorption were examined in detail: type of SPE column, volume of the sample, volume of the eluent, concentrations of metal ions, fluoride salt, chromogenic reagent, organic phase, and pH. It was established that the sorption of Zr(IV) and Hf(IV), as their ternary chelates, on SPE Zorbax SPE C18 (EC) cartridge was the most efficient, when the sample containing metal ion (Zr(IV), Hf(IV), both, up to 2 mug), 5-Br-PADAP 1.5x10(-4), NaF 7.5x10(-5) mol l(-1), methanol 40%, pH 4.5+/-1 was applied for the SPE sorption. The chelates were discarded from SPE cartridge using acetonitrile/water (99.75+0.25, v/v) eluent containing 3.8x10(-4) mol l(-1) sodium fluoride and subsequently separated by RP-LC method. The RP-LC separation of both chelates was optimized and Zorbax SB-C18 analytical LC column along with acetonitrile/water (65+35, v/v) eluent containing the 1.5x10(-4) mol l(-1) sodium fluoride was used. The established SPE/LC conditions allow Zr(IV) 0.08-2.0 mug and Hf(IV) 0.04-2.0 mug determination in a sample volume up to 150 ml. The detection limits, 0.03 mug Hf(IV) and 0.05 mug Zr(IV), were obtained. Recoveries, (94+/-2)% for Hf(IV) chelate and (106+/-2)% for Zr(IV) chelate were obtained, when 1 mug of Zr(IV) and Hf(IV) ions were determined by the present SPE/LC method from the sample volume of 100 ml. The established, pre-concentration SPE conditions, along with the LC separation and determination allow the assay of Zr(IV) and Hf(IV) in complicated matrix materials. The present SPE/LC method was applied to the determination of Zr(IV) and Hf(IV) in tap water and reference geological material (rock, NCS DC 73303; certified content: Zr, 27.7x10(-3)% (w/w) and Hf, 6.5x10(-4)% (w/w)).

Sensitive reversed-phase liquid chromatographic determination of fluoride based on its ternary systems with zirconium(IV) or hafnium(IV) and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol.

Optimum conditions for the direct reversed-phase LC determination of fluoride based on the ternary M-(F-)-(5-Br-PADAP) complexes [M = ZrIV or HfIV and 5-Br-PADAP = 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol] were evaluated. Chromatographic separation was performed with C18 end-capped column with an eluent consisting of acetonitrile-water (85 + 15 v/v) mixture of pH 4.0 +/- 0.3 (flow rate 1 ml min-1), and the eluate was monitored spectrophotometrically at lambda max = 585 nm. The calibration curves were linear over a wide range of fluoride concentrations: from 1 to 110 and 150 ng ml-1 for the ZrIV-(F-)-(5-Br-PADAP) and HfIV-(F-)-(5-Br-PADAP) systems, respectively (using a 20 microliters loop). Under such conditions the detection limits were 0.8 and 0.7 ng ml-1, respectively, and the quantification limit is 1.0 ng ml-1 for both methods. When a 100 microliters loop was used, the limits of both detection and quantification in the method based on the zirconium system were 0.2 ng ml-1. Using the proposed method, fluoride was determined directly in tap water, saliva and an anti-cancer agent for prostatic cancer (Leuprolid).

Capillary electrophoretic separation and characterizations of CdSe quantum dots

AbstractWe have developed a capillary electrophoresis method to characterize the QD surface ligand interactions with various surfactant systems. The method was demonstrated with 2–5 nm CdSe nanoparticles surface-passivated with trioctylphosphine oxide (TOPO). Water solubility was accomplished by surfactant-assisted phase transfer via an oil-in-water microemulsion using either cationic, anionic, or non-ionic surfactants. Interaction between the QD surface ligand (TOPO) and the alkyl chain of the surfactant molecule produces a complex and dynamic surface coating that can be characterized through manipulation of CE separation buffer composition and capillary surface modification. Additional characterization of the QD surface ligand interactions with surfactants was accomplished by UV-VIS spectroscopy, photoluminescence, and TEM. It is anticipated that studies such as these will elucidate the dynamics of QD surface ligand modifications for use in sensors.

An advanced application of the quantitative structure-activity relationship concept in electrokinetic chromatography of metal complexes.

The relevance of the quantitative structure–activity relationship (QSAR) principle in MEKC and microemulsion EKC (MEEKC) of metal–ligand complexes was evaluated for a better understanding of analyte migration mechanism. A series of gallium chelates were applied as test solutes with available experimental migration data in order to reveal the molecular properties that govern the separation. The QSAR models operating with n‐octanol–water partition coefficients or van der Waals volumes were found to be valid for estimation of the retention factors (log k′) of neutral compounds when using only an aqueous MEEKC electrolyte. On the other hand, consistent approximations of log k′ for both uncharged and charged complexes in either EKC mode (and also with hydro‐organic BGEs) were achievable with two‐parametric QSARs in which the dipole moment is additionally incorporated as a structural descriptor, reflecting the electrostatic solute–pseudostationary phase interaction. The theoretical analysis of significant molecular parameters in MEKC systems, in which the micellar BGE is modified with an organic solvent, confirmed that concomitant consideration of hydrophobic, electrostatic, and solvation factors is essential for explaining the migration behavior of neutral metal complexes.

Determination of fluoride impurities in Leuprolide. Comparison of analytical methods

Abstract Fluoride impurities were determined in technical samples of Leuprolide (anti-cancer drug for prosthetic cancer) using reverse-phase liquid chromatography and derivative spectrophotometry. The chromatographic method was based on the ternary fluoride complex with zirconium(IV) and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP). The analysis was performed on a Nucleosil C 18 column with LiChrosphere RP-100 end-capped phase, using as eluent acetonitrile (85%v/v) water mixture at pH 4.1±0.2. Fluoride content was determined with use of the method of standard additions (MOSA) as 2.34 mg g −1 and 0.29 mg g −1 in two different samples. A spectrophotometric determination has been carried out by La(III)-F − -ALC [ternary complex La(III)-F − -alizarin complexone] method with using third derivative spectrophotometry. By this method fluoride content was determined as 1.99 mg g −1 and 0.34 mg g −1 in the samples previously analyzed chromatographically. A validation for both (i.e. chromatographic and spectrophotometric) methods was performed. Statistical analysis showed that spectrophotometric methods could not be used for quantitative determination of fluoride in samples containing them in concentration less than 0.5 mg g −1 .

RP-HPLC study of redox equilibria in vanadium-PAR binary and ternary systems: Direct determination of vanadium in steel

The reversed-phase high-performance liquid Chromatographic (RP-HPLC) behaviour of the binary chelates of V(V) and V(IV) with 4-(2-pyridylazo) resorcinol (PAR) and ternary chelates of vanadium with PAR and auxiliary ligands: hydrogen peroxide, hydroxylamine, tartrate and citrate were studied using a C18 column. The complex double-peak chromatograms of V(IV)/V(V)-PAR systems were studied and the origin of each peak was proved. Vanadium in ternary systems with PAR and hydrogen peroxide was found exclusively in V(V)-H2O2-PAR complex (single peak on the chromatogram) despite its initial oxidation state. The double role of hydroxylamine (complex agent and reductor) in vanadium systems with PAR was confirmed: in the V(V) system three species were identified (V(V)-PAR, V(V)-NH2OH-PAR and V(IV)-PAR), but in the V(IV) system only two: V(IV)-PAR and V(V)-NH2OH-PAR. Citrate and tartrate giving single peak were found as auxiliary ligands in ternary V(V) systems of analytical importance. Due to its masking potential towards iron (III) ions, citrate was chosen as the most suitable third component of a ternary vanadium system with PAR, to form the basis of an RP-HPLC method for direct determination of V in steel.

Characterization of CdSe quantum dots with bidentate ligands by capillary electrophoresis

AbstractThe CdSe quantum dots (QDs) with bidentate ligands: a-diimine (NN) and dihydrolipoic acid (DHLA) were synthesized and characterized by UV-Vis, particle size and capillary electrophoretic techniques. Two systems were analyzed: CdSe with one ligand (CdSe/ligand) and CdSe with two different ligands (CdSe//ligand1/ligand2), where ligand = α-diimine or DHLA. Hydrodynamic features of functionalized QDs were characterized by zone capillary electrophoretic (CZE), and particle size techniques and these methods were consistent. It was established that CZE, micellar (MEKC) and microemulsion (MEEKC) modes were suitable for separating charged CdSe QDs and that no peaks were obtained for QDs passivated with electrically neutral ligands. For CdSe QDs with neutral (NN) ligands, a preconcentration method with the use of a micellar plug was introduced for visualizing these QDs. A sharp peak representing neutral QDs was obtained within the zone of micellar plug of a non-ionic surfactant, Here, a ligand character used for CdSe modification and the type of the electrophoretic method applied were the determining factors for the QDs peak visualization. Moreover, examples of visualization of charged and neutral QDs on the same run were presented, and for this purpose, dual mechanism (separation/preconcentration) was proposed.

Characterization of CdSe nanocrystals coated with amphiphiles. A capillary electrophoresis study.

AbstractWe have synthesized CdSe nanocrystals (NCs) possessing a trioctylphosphine surface passivation layer and modified with amphiphilic molecules to form a surface bilayer. The NCs covered with single amphiphiles are not stable in aqueous solution, but a mixed amphiphilic system is shown to provide stability in solution over several months. The solutions of the modified NCs were characterized by UV-Vis absorbance, photoluminescence, and transmission electron microscopy. An electrophoretic study revealed two operational modes. The first relies on the enrichment of NCs using a micellar plug as a tool. The accumulation of NCs at the plug-electrolyte buffer interface results in a sharp peak. By controlling the electrophoretic conditions, nanocrystals were forced to exit a micellar plug into an electrolyte buffer. We conclude that a system consisting of modified nanocrystals and a micellar plug can act as a mixed pseudomicellar system, where modified nanocrystals play the role of pseudomicelles. FigureElectrophoretic focusing of amphiphile coated CdSe nanocrystals using a micellar plug.

Capillary zone electrophoresis of quantum dots dispersed in mixed micelles: New evidence of the concentration effect

CZE was applied to characterizing a nanoparticle/micellar system, in which CdSe nanoparticles dispersed in a mixture of non-ionic and ionic surfactants are introduced into a capillary to form the sample zone that migrates being sandwiched by the background electrolyte (BGE). Parameters that affect the migration of the surface-modified CdSe nanoparticles and conditions under which they are focused within the micellar zone (or released from it into bulk BGE) were explored, including the sample composition, sample plug length, and applied voltage. The observed migration behavior was analyzed within the framework of a concept of formation of a mixed pseudomicellar system, according to which a nanoparticle coated with an ionic surfactant is treated as a micelle-like entity. It was found out that the nanoparticles are subject to transformation that results in building-up a mixed pseudomicellar system (with regular micelles), with a consequence of exhibiting distinctive migration phenomena. Particularly observed and brought into focus is the event of focusing of the nanoparticles.