An estimation of the surface ionization constant of oleic acid in aqueous sodium chloride solution

The zeta potential () measurements and the site binding theory were utilized for calculations of the parameters of the electrical double layer (edl), ionization, and complexation constants for oleic acid-aqueous sodium chloride solution interface. Assuming that is equal to the diffuse layer potential ( _d ) of the edl, the charge of the diffuse part of the edl was calculated from the Gouy-Chapman equation. The intrinsic ionizaiton constant was then determined by an extrapolation method to be . Subsequently, the surface potential ( ₀) was calculated, and it was found that ₀ changes by 50 mV per pH unit (50 mV/pH) or 42.5 mV/pH for 10^–3 and 10^–2 M NaCl, respectively. For further calculations, the integral capacity of the outer zone of the compact part of the edl was assumed to be for both ionic strengths. It was established that the intrinsic complexation constant for the binding of Na⁺ ions with the surface of oleic acid ispK _Na ^int = 2.9±0.5 if the integral capacity of the inner zone of the compact edl (K ₁) is 80 for 10^–3 M NaCl, but 280 for 10^–2 M NaCl. The use of the sameK ₁ value for both ionic strengths gives a differentpK _Na ^int for different NaCl concentrations, and also provides unrealistic surface charge ( _o ) values greaterfor 10^–3 M NaCl than for 10^–2 M NaCl, at the same pH of the solution.     

Effect of Surfactants on the Immobilization of 4-(2-Pyridylazo)resorcinol on Silochroms

The effect of cationic surfactants (cetyltrimethylammonium bromide, cetylpyridinium bromide, and tetrabutylammonium perchlorate) and a nonionic surfactant (OP-7) on the conditions of the immobilization of 4-(2-pyridylazo)resorcinol (PAR) on three types of silica gel (Silochrom S-120 (200–350 m), Silochrom S-120 (315–500 m), and Silochrom S-80 (200–350 m)) was studied. It was found that OP-7 does not affect the adsorption of surfactants. The effect of cationic surfactants increases in the order tetrabutylammonium perchlorate < cetyltrimethylammonium bromide < cetylpyridinium bromide. The adsorption activity of silica gels increases in the order Silochrom S-120 (315–500 m) < Silochrom S-80 (200–350 m) < Silochrom S-120 (200–350 m). Cetylpyridinium bromide provides full immobilization of PAR on silica gel Silochrom S-120 (200–350 m) in the pH range 2–9.     

Rapid analysis of pyrethroids in whole urine by high-performance liquid chromatography using a monolithic column and off-line preconcentration in a restricted access material cartridge

A rapid high-performance liquid chromatography (HPLC) method using a monolithic column with UV detection at 238 nm was developed for the determination of fenpropathrin, betacyfluthrin, deltamethrin, and permethrin (cis and trans isomers) in whole urine. The method is based on the use of a monolithic chromatographic column and a restricted access material (RAM) cartridge for sample preparation. The mobile phase was water/acetonitrile (42:58 v/v), the flow rate was 3 mL min^–1, and chromatographic separation was carried out in 10 min. The separation of cis and trans isomers of permethrin was also possible under the above-mentioned conditions. Detection limits in reconstituted whole urine samples were between 0.9 g L^–1 for betacyfluthrin and 4.4 g L^–1 for fenpropathrin and trans-permethrin. Recoveries for urine samples spiked with different amounts of pyrethroids (between 19 g L^–1 and 75 g L^–1) were in the 70±6 to 90±7% range.     

Extraction-spectrophotometric determination of nickel as Ni-(PAR)2-(CTAB)2 complex in polymetallic sea-bed nodules and steels

A red, water-soluble complex of nickel with PAR can be extracted into chloroform with CTAB at pH 7.0. The system obeys Beer's law upto 0.5 g/ml with a molar absorptivity of 45 200 L·mol^–1·cm^–1 at 540 nm. Job's method of continuous variations revealed that the composition of the extracting species is 1:2:2 for nickel:PAR:CTAB. Based on this extraction, a highly sensitive and selective spectrophotometric method for the determination of nickel in polymetallic sea-bed nodules and in steels, after prior separation of iron and manganese, was developed. The standard deviation was 0.04–0.127 g for 5–25 g of nickel.     

Kinetics of the thermal and photochemical decomposition of aquapentacyanoferrate(III) in aqueous solution

Summary The kinetics of the thermal and photochemical decomposition of aquapentacyanoferrate(III) ion in aqueous solution in the presence ofo-phenanthroline was studied spectrophotometrically. The first-order rate constant (k ) at 30° C [I=1 M(NaCl)] for the thermal reaction is (1.49±0.13)×10^–6 s^–1 with H =(158±7)kJ mol^–1 and S=(42±4) JK^–1 mol^–1. The initial quantum yield for the photochemical reaction at pH=7 is independent of the light intensity and is (1.49±0.33)×10^–2 mol einstein^–1.A communication on this subject was presented at the XVI Latinamerican Chemistry Congress held at Rio de Janeiro. Brasil, October 14–20, 1984.     

Determination of the Enantiomers of Tamsulosin Hydrochloride and its Synthetic Intermediates by Chiral Liquid Chromatography

A chiral liquid chromatographic method is described for the determination of the enantiomers of tamsulosin hydrochloride and its synthetic intermediates. Enantioseparation was achieved on a Chiralcel OD-R column (250 mm × 4.6 mm, 10 m) using a mobile phase consisting of a mixture of 0.5 mol L^–1 sodium perchlorate and acetonitrile (80:20, v/v, pH 4.0). The flow rate was 0.4 mL min^–1 and detection was at 223 nm. Excellent enantiomer separations were achieved for tamsulosin hydrochloride and its synthetic intermediates. No other methods are available for the separation of these enantiomers. The method developed in this study has been successfully applied for purity control.     

Solvent Extraction Separation of Th(IV) and U(VI) with PC-88A

Liquid-liquid extraction of Th(IV) and U(VI) has been investigated by commercial extractant PC-88A in toluene. The optimum conditions for extraction of these metals have been established by studying the various parameters like acid concentration/pH, reagent concentration, diluents and shaking time. The extraction of Th(IV) was found to be quantitative with 0.1–1.0M HNO₃ acid and in the pH range 1.0–4.0 while U(VI) was completely extracted in the pH range 1.0–3.5 with 2.5·10^–2M and 2.·10^–2M PC-88A in toluene, respectively. The probable extracted species have been ascertained by log D-log C plot as ThR₄·4HR and UO₂R₂·2HR, respectively. The method permits separation of Th(IV) and U(VI) from associated metals with a recovery of 99.0%.     

High-Performance Liquid Chromatographic Method for the Determination of Nimesulide in Pharmaceutical Preparations

A simple, rapid, and precise high-performance liquid chromatographic method for the determination of nimesulide in pharmaceutical preparations was proposed using Ibuprofen as an internal standard. The separation was performed on a CLC C₁₈ (5 m, 25 cm × 4.6 mm i.d.) column with a mobile phase consisting of an acetonitrile–0.05 M KH₂PO₄ buffer mixture of pH 7.00 (55 : 45, v/v). The detection was carried out at 230 nm and the linearity range was found to be 0.5–100 g/mL. The method has been applied successfully to the determination of nimesulide in pharmaceutical formulations. The recovery values were found to be in the range of 99.23–100.13% with RSD values of less than 0.97%.     

LC Method for the Determination of Multiple Components in a Compound Cold Formulation

An isocratic liquid chromatographic method for determination of acetaminophen (AMP), caffeine (CAF), chlorphenamine maleate (CPM) and guaiacol glyceryl ether (GGE) in a compound cold formulation is described. Separation and quantitation were achieved on a Diamonsil C18 column using a binary mixture of methanol and 1.5% aqueous acetic acid (55: 45, v/v, pH 3.6) as mobile phase delivered at 0.4 mL min^–1. Single wavelength detection was at 220 nm for all four drugs and the run time was < 10 min. The linearity, accuracy and precision of the method were found to be acceptable over the concentration ranges: 16.0–127.8 g mL^–1 for AMP, 6.0–48.2 g mL^–1 for CAF, 5.0–40.0 g mL^–1 for CPM and 10.1–80.6 g mL^–1 for GGE.     

Determination of Nisoldipine and Its Impurities in Pharmaceuticals

A method has been established for separation of nisoldipine and impurities, for example reactants, products of side-reactions, and photodegradation products, by HPTLC on LiChrospher Si 60 F_254s plates with detection at 280 nm. The mobile phase, cyclohexane–ethyl acetate–toluene, 7.5:7.5:10 (v/v), enables acceptable resolution of nisoldipine, in large excess, and possible impurities. Regression coefficients (r 0.997), recovery (98–108%), and determination limit (0.02–0.2%) were validated and found to be satisfactory. The method is convenient for quantitative analysis and purity control of nisoldipine in its raw material and dosage forms.     

Spectrophotometric Determination of Iron(III) After Separation by Adsorption of its 2-Thenoyltrifluoroacetone Complex on Microcrystalline Naphthalene

Summary A new spectrophotometric method for the determination of iron (III) after adsorption of its red TTA complex onto microcrystalline naphthalene has been developed. Iron(III) reacts with 2-thenoyltri-fluoroacetone in pH range 2.4–5.2 to form a water-insoluble 13 red complex which is easily adsorbed onto microcrystalline naphthalene from its acetone solution. The naphthalene mixture is separated, dried and dissolved in 10 ml dioxane. The red organic phase has a plateau around 480–500 nm while the reagent has no absorbance beyond 420 nm. The system obeys Beer's law over 20–120g iron(III) in 10 ml of dioxane solution or 0.4–2.4 ppm aqueous. The molar absorptivity of the complex species is 3.9×10³·l·mol^–1·cm^–1, while the sensitivity for Fe(III) extends to 1.43×10^–2 g cm^–2 for 0.001 absorbance. Samples containing 80g of iron gave a relative standard deviation of 1.23%. The effects of experimental variables such as pH, amount of reagents, shaking and digestion time, aqueous volume and diverse ions have been examined. The method has been applied to the determination of iron(III) in standard reference and environmental samples and results compared with other standard colorimetric procedures.

---

Spektrophotometrische Bestimmung von Eisen(III) nach Adsorption seines 2-Thenoyltrifluoraceton-Komplexes an mikrokristallines Naphthalin

Zusammenfassung Eine neue spektrophotometrische Methode zur Bestimmung von Eisen (III) nach Adsorption seines roten TTA-Komplexes an mikrokristallines Naphthalin wurde ausgearbeitet. Fe(III) reagiert mit 2-Thenoyltrifluoraceton bei pH 2,4-5,2 unter Bildung eines roten, wasser-unlöslichen 13-Komplexes, der sich aus seiner acetonischen Lösung leicht an mikrokristallines Naphthalin adsorbieren läßt. Das Naphthalin-Gemisch wird abgetrennt, getrocknet und in 10 ml Dioxan gelöst. Die rote organische Phase hat ein Adsorptions-Plateau bei 480–500 nm, während das Reagens jenseits 420 nm nicht adsorbiert. Das System entspricht dem Beerschen Gesetz von 20–120g Fe(III) in 10 ml Dioxan-Lösung bzw. 0,4–2,4 ppm in wäßriger Lösung. Die molare Extinktion der Komplexverbindung beträgt 3,9× 10³l·mol^–1·cm^–1. Die Empfindlichkeit für Fe(III) entspricht 1,43×10^–2 g cm^–2 für 0,001 Absorptionseinheiten. Proben mit 80g Fe(III) zeigen eine rel. Standardabweichung von 1,23%. Die Wirkung variabler Versuchsbedingungen pH, Reagensmenge, Zeit, Volumen und diverse Fremdionen wurden geprüft. Das Verfahren wurde an Standardsubstanzen geprüft und seine Ergebnisse mit denen anderer kolorimetrischer Verfahren verglichen.

     

Determination of methylviologen (Paraquat) by differential pulse polarography

Summary Determination of Methylviologen (Paraquat) by Differential Pulse Polarography The second reduction wave of methylviologen (Paraquat) has been studied at pH 2 by different polarographic techniques. The limiting current is diffusion-controlled. Evidence for dimerization of the radical formed in the first reduction step has been obtained. The n values for the reduction process have been calculated at concentration levels where the dimer and the monomer predominate. Paraquat can be determined by differential pulse polarography in the 6.0×10^–5–4.0×10^–7 M concentration range, the limit of determination being 1.7×10^–7 M. The method has been applied to paraquat determination in commercial herbicides.     

Improved high-performance liquid chromatographic method for the determination of domoic acid and analogues in shellfish: effect of pH

Domoic acid (DA) is a naturally-occurring amino acid that causes a form of human intoxication called amnesic shellfish poisoning (ASP) following the consumption of shellfish. A rapid and sensitive HPLC-UV method has been developed for analysis of DA and analogues in shellfish without the need for SPE clean-up. Isocratic chromatographic separation of DA and its isomers from shellfish matrix interferences and from the prevalent amino acid, tryptophan, was achieved by careful control of the mobile phase pH. The optimised pH was found to be 2.5 when using a Luna(2) C₁₈ column. Sample extraction was verified with control extracts from shellfish spiked at 5.0 and 10.0 g/g of DA and with certified reference material. The average extraction efficiency was 98.5%. The calibration, based on mussel tissue spiked with DA standard, was linear in the range 0.05–5.0 g/ml (r=0.9999) and the detection limit (signal:noise 3:1) was better than 25 ng/ml. The DA assay achieved good precision; %RSD=1.63 (intra-day, n=6) and %RSD=3.7 (inter-day, n=8). This method was successfully applied to a variety of shellfish species, allowing the rapid screening of a large number of samples per day (20–30), without the need for SPE clean-up. Quantitative data were obtained for shellfish samples containing domoic acid in the concentration range 0.25–330 g/g. Using the same chromatographic conditions, LC-MS³ was used to determine DA and its isomers, isodomoic acid D and epi-domoic acid, in scallop tissues.     

Separation of Structurally Related Anthocyanins by MEKC

Summary A method based on micellar electrokinetic chromatography has been developed for the simultaneous separation of six anthocyanins (malvidin-3,5-diglucoside, malvidin-3-glucoside, malvidin-3-galactoside, pelargonidin-3-glucoside, cyanidin-3,5-diglucoside, cyanidin-3-galactoside). Optimum selectivity was achieved in the buffer 30 mM phosphate + 400 mM borate-TRIS, pH=7.0 supported with 50 mM sodium dodecylsulphate. High content of borate was essential mainly for the separation of diastereomeric pair malvidin-3-glucoside-malvidin-3-galactoside. The calibration dependencies exhibit good linearity in the ranges of concentration 10–100 g mL^–1 for diglycosylated and 25–100 g mL^–1 for monoglycosylated derivatives (R² = 0.9711–0.9989). The optimized method was applied to a sample of wine grape skin extract. Malvidin-3-glucoside was identified as main anthocyanin colorant in this sample.     

Synthesis and Application of a Novel Poly(Acryl-p-Toluenesulfonamideamidine-p-Toluenesulfonylamide) Chelating Fiber for Preconcentration and Separation of Trace Noble Metal Ions from Solution Samples

A novel poly(acryl-p-toluenesulfonamideamidine-p-toluenesulfonylamide) chelating fiber containing S, N and O elements was synthesized from polyacrylonitrile fiber and p-toluenesulfonamide and used for the preconcentration and separation for traces of Ru(III), Rh(III), Au(III) and Pd(IV) ions from waste water and ore sample solution. The synthesis of this fiber was simple and rapid. The results indicate that 100ngmL^–1 of these ions can be quantitatively enriched by the chelating fiber at a flow rate of 6mLmin^–1 and a pH of 4 and desorbed quantitatively with 20mL of 6molL^–1 HCl and 5% CS(NH₂)₂ solution at 50°C (with recovery>95%). A 50 to 1000-fold excess of Ca²⁺, Mg²⁺, Mn²⁺, Co²⁺, Fe³⁺, Cu²⁺, Zn²⁺, and Al³⁺ ions caused little interference in the concentration and determination of the analyzed ions. When the fiber had been reused twenty times, the recoveries of the ions enriched by the fiber were still over 96%. The saturated adsorption capacities of the fiber were in the range of 22–96mgg^–1. The relative standard deviation (RSD) of the method was between 0.70% and 0.84%. Recoveries of a standard added to actual samples were in range of 95–101%. The results obtained for these ions in real solution samples were basically in agreement with the given values, the average errors being below 5.0%. FT-IR spectra show that the existence of –SO₂–Ar, HN=C–NH–, O=C–NH– and –NH–SO₂ functional groups are verified in the chelating fiber. The experiments show that the method is rapid, precise, simple and convenient.     

Kinetics and mechanism of formation and dissociation of copper(II) and nickel(II) complexes of the Schiff base bis(acetylacetone)ethylenediimine in aqueous-organic solvent media

Summary In NH₄NO₃+NH₄OH buffered 10% (v/v) dioxan-water media (pH 7.0–8.5), thePseudo-first-order rate constant for the formation of the title complexes M(baen),i.e. ML, conforms to the equation 1/k_obs=1/k+1/(kK_o.s · T_L), where T_L stands for the total ligand concentration in the solution, K_o.s is the equilibrium constant for the formation of an intermediate outer sphere complex and k is the rate constant for the formation of the complex ML from the intermediate. Under the experimental conditions the free ligand (pK_a>14) exists virtually exclusively in the undissociated form (baenH₂ or LH₂) which is present mostly as a keto-amine in the internally hydrogen-bonded state. Although the observed formation-rate ratio k^Cu/k^Ni is of the order of 10⁵, as expected for systems having normal behaviour, the individual rate constants are very low (at 25°C, k^Cu=50 s^–1 and k^Ni=4.7×10^–4s^–1) due to the highly negative S values (–84.2±3.3 JK^–1M^–1 for CuL and –105.8±4.1 JK^–1M^–1 for NiL); the much slower rate of formation of the nickel(II) complex is due to higher H value (41.2±1.0 kJM^–1 for CuL and 78.2±1.2 kJM^–1 for NiL) and more negative S value compared to that of CuL. The K_o.s values are much higher than expected for simple outer-sphere association between [M(H₂O)₆] and LH₂ and may be due to hydrogen bonding interaction.In acid media ([H⁺], 0.01–0.04 M) these complexes M(baen) dissociate very rapidly into the [M(H₂O)₆]²⁺ species and baenH₂, followed by a much slower hydrolytic cleavage of the ligand into its components,viz. acetylacetone and ethylenediamine (protonated). For the dissociation of the complexes k_obs=k₁[H⁺]+k₂[H⁺]². The reactions have been studied in 10% (v/v) dioxan-water media and also ethanolwater media of varying ethanol content (10–25% v/v) and the results are in conformity with a solvent-assisted dissociativeinterchange mechanism involving the protonated complexes.     

Determination of Eupatilin in Human Plasma by High-Performance Liquid Chromatography–Tandem Mass Spectrometry

A rapid, sensitive and selective liquid chromatography-tandem mass spectrometric method (LC-MS-MS) for the determination of eupatilin in human plasma has been developed. Eupatilin and an internal standard; (S)-N-(3-{3-fluoro-4-[6-(1-methyl-1H-tetrazol-5-yl)-pyridine-3-yl]-phenyl}-2-oxo-oxazolidin-5-ylmethyl)-acetamide (DA-7867) were extracted from human plasma by liquid-liquid extractionand analyzed on a phenyl-hexyl column using the mobile phase: acetonitrile-ammonium formate (10 mM, pH 3.0) (60:40, /). Analytes were detected using electrospray ionization-tandem mass spectrometry in multiple-reaction monitoring mode. The calibration curve was linear (r = 0.999) over the concentration range: 1.00–500 ng mL^–1 with a lower limit of quantification of 1.0 ng mL^–1 using a 100 L plasma sample. The precision (CV%) of this assay ranged: 2.4–7.0%, relative error: –7.0 to +2.0%. Recoveries of eupatilin ranged: 64.3–65.0%, with that of DA-7867 (internal standard) being 87.0 ± 5.3%.     

Direct and Derivative Spectrophotometric Determination of Thorium with 2,4-dihydroxybenzaldehyde Isonicotinoyl Hydrazone

A simple and sensitive spectrophotometric method is developed for the determination of throium in aqueous medium. The metal ion forms yellow coloured complex with 2,4-dihydroxybenzaldehyde isonicotinoyl hydrazone (2,4-DHBINH) in the pH range 2.0–8.0. The complex shows an absorption maximum at 390 nm. The absorbance of the complex is maximum at pH 5.5 Beer's law is obeyed in the range 0.30–7.00 g/ml of thorium(IV). The molar absorptivity and the Sandell's sensitivity of the method are 2.20· 10⁴ l·mol^–1·cm^–1 and 0.0106 g/cm^–2, respectively. The interference of various ions was studied. The composition of the complex is 1:1 {Th(IV) : 2,4-DHBINH}. The first derivative spectrum of the complex shows a zero cross at 391.2 nm and maximum amplitude at 415 nm. Thus a sensitive derivative spectrophotometric method for the determination of Th(IV) is proposed.     

The removal of endotoxins from protein solutions using column packings with aminated poly (γ-methyl L-glutamate) spheres

Summary A method is described for the selective removal of endotoxins from various protein solutions using columns packed with aminated poly (-methyl L-glutamate) (PMLG-NH₂) spheres. The PMLG-NH₂ adsorbents showed a high adsorbing activity for endotoxins which had an ionic strength of =0.05–1.0 and pH 5.0–9.0. The endotoxin-adsorbing capacity per millitre of the wet adsorbent increased from 0.40 to 1.35 mg (E. coli O111: B4 LPS) at =0.2 and pH 7.0 while the aminogroup content of the adsorbent increased from 0.8 to 3.5 meq g^–1. The PMLG-NH₂-3.5 has an amino-group content of 3.5 meq g^–1. This column packing selectively adsorbed endotoxins, without loss of the protein, from a -globulin or cytochromec solution which contained endotoxins at =0.05 and pH 7.0. On the other hand, when bovine serum albumin (BSA) was present in solution with endotoxins, both the endotoxins and the BSA were adsorbed by the column. The BSA-adsorbing activity increased with increasing amino-group content of the adsorbent. However, this undesirable adsorption was suppressed with increasing ionic strength of the buffer. As a result, when the packing which had an amino-group content of 1.5 meg g^–1 was used in conditions of =0.2 and pH 7.0, the endotoxins were removed from a BSA-containing solution without affecting the recovery of the BSA.     

Bimodal normal distribution model for binding of trivalent europium by soil fulvic acid

Complexation of trivalent europium by a well characterized soil fulvic acid was investigated by equilibrium dialysis titration method ([FA]=24 mg·dm^–3, [Eu] _t =9.0·10^–7–3.5·10^–6 mol·dm^–3, pH 6.0). The concentrations of the fulvate bound and free europium were measured radiometrically using¹⁵²Eu as a tracer. The experimental results were evaluated using a bimodal normal distribution model and a plot with two overlapping normal distributions was obtained which gave two means logK (µ_I=7.0, _I=1.1; µ_II=4.9, _II=0.5) values for binding of europium by two classes of sites in fulvic acid. A multiligand model was assumed for fulvic acid, based upon the Eu(III) luminescence studies (⁷F₀⁵D₀ excitation) on many organic acids as model ligands.