Potentiality of partial least-squares multivariate calibration in the spectrophotometric analysis of binary mixtures of purine bases

Abstract  

A partial least-squares (PLS) modeling was developed for the simultaneous spectrophotometric determination of adenine (AD) and guanine (GU). The determination of these analytes is pharmacologically necessary. Multivariate calibration is used because of spectral overlapping. The calibration set contained AD and GU in the concentration range of 1.4–20.3 and 1.5–25.7 μg cm⁻³, respectively. The absorption spectra were recorded from 200 to 300 nm. The predicted residual error sum-of-squares for AD and GU was 0.0500 and 0.4000 for number of principal components 3 and 2, respectively. The root mean square error of prediction for AD and GU was 0.0913 and 0.2582, respectively. The limits of detection were 0.02 and 0.03 μg cm⁻³ for AD and GU, respectively. The proposed method allows the simultaneous determination of AD and GU in spiked real matrixes of human urine, serum, and plasma.     

Separation and quantitation of oxprenolol in urine and pharmaceutical formulations by HPLC using a Chiralpak IC and UV detection

Abstract  

A stereoselective HPLC method has been developed for the simultaneous determination of oxprenolol enantiomers in urine and pharmaceutical products. Enantiomeric resolution of oxprenolol was achieved on cellulose tris(3,5-dichlorophenylcarbamate) immobilized onto a 5 μm spherical porous silica chiral stationary phase (CSP) known as Chiralpak IC with UV detection at 273 nm. The mobile phase consisted of n-hexane:isopropanol:triethylamine 70:30:0.1 (v/v/v) at a flow rate of 1.0 cm³/min. The method was validated for its linearity, accuracy, precision, and robustness. The calibration curves were linear over the range of 0.5–75 μg/cm³, with a detection limit of 0.1 μg/cm³ for each enantiomer. An average recovery of 99.0% and a mean relative standard deviation of 2.6% at 40.0 μg/cm³ for S-(−)- and R-(+)-enantiomers were obtained. The overall recoveries of oxprenolol enantiomers from pharmaceutical formulations were in the range 97.5–99.0%, with RSDs ranging from 0.6 to 0.8%. The mean extraction efficiency of oxprenolol from urine was in the range of 86.0–93.0% at 0.5–5 μg/cm³ for each enantiomer. The assay method proved to be suitable as a chiral quality control for oxprenolol formulations using HPLC and for therapeutic drug monitoring.     

Chemiluminescence determination of surfactant Triton X-100 in environmental water with luminol-hydrogen peroxide system

Background  

The rapid, simple determination of surfactants in environmental samples is essential because of the extensive use and its potential as contaminants. We describe a simple, rapid chemiluminescence method for the direct determination of the non-ionic surfactant Triton X-100 (polyethylene glycol tert-octylphenyl ether) in environmental water samples. The optimized experimental conditions were selected, and the mechanism of the Luminol-H₂O₂-Triton X-100 chemiluminesence system was also studied.     

Selective masking and demasking for the stepwise complexometric determination of aluminium,lead and zinc from the same solution

Background  

A complexometric method based on selective masking and de-masking has been developed for the rapid determination of aluminium, lead and zinc from the same solution in glass and glass frit samples. The determination is carried out using potassium cyanide to mask zinc, and excess disodium salt of EDTA to mask lead and aluminium. The excess EDTA was titrated with standard Mn(II)SO₄ solution using Erichrome Black-T as the indicator. Subsequently selective de-masking agents – triethanolamine, 2,3-dimercaptopropanol and a formaldehyde/acetone mixture – were used to determine quantities of aluminium, lead and zinc in a stepwise and selective manner.     

High‐precision determination of lithium and magnesium isotopes utilising single column separation and multi‐collector inductively coupled plasma mass spectrometry

Rationale

Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single‐step cation‐exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices.

Methods

The column method utilises the macro‐porous AGMP‐50 resin and a high‐aspect ratio column, allowing quantitative separation of Li and Mg from natural waters, sediments, rocks and carbonate matrices following the same elution protocol. High‐precision isotope determination was conducted by multi‐collector inductively coupled plasma mass spectrometry (MC‐ICPMS) on the Thermo Scientific™ NEPTUNE Plus™ fitted with 10¹³ Ω amplifiers which allow accurate and precise measurements at ion beams ≤0.51 V.

Results

Sub‐nanogram Li samples (0.3–0.5 ng) were regularly separated (yielding Mg masses of 1–70 μg) using the presented column method. The total sample consumption during isotopic analysis is <0.5 ng Li and <115 ng Mg with long‐term external 2σ precisions of ±0.39‰ for δ⁷Li and ±0.07‰ for δ²⁶Mg. The results for geological reference standards and seawater analysed by our method are in excellent agreement with published values despite the order of magnitude lower sample consumption.

Conclusions

The possibility of eluting small sample masses and the low analytical sample consumption make this method ideal for samples of limited mass or low Li concentration, such as foraminifera, mineral separates or dilute river waters.

     

(E)-2-Benzylidenebenzocyclanones, part VIII: spectrophotometric determination of pKa values of some natural and synthetic chalcones and their cyclic analogues

Abstract  

UV–Vis spectrophotometry was used to determine acid dissociation constant (pK _a) values of the natural flavonoids phloretin, phlorizin, naringenin, and naringin, as well as 4′-hydroxychalcone, 4′-(dimethylamino)chalcone, and their cyclic analogues. Comparison of the results with those previously reported for the natural flavonoids showed the applied method is a relatively straightforward and easy-to-perform technique for the determination of pK _a values of compounds with relatively low solubility. Comparative analysis of the pK _a values of the synthetic chalcones showed a strong correlation between the degree of conjugation and the acid strength of the respective compounds with different geometry. Our results provide further evidence that modification of the three-dimensional structure of open-chain bioactive compounds is the method of choice to modify not only their stereochemistry but also their physicochemical properties.     

An optode membrane for determination of gold using a simple light-emitting diode-based device

Abstract  

A selective optode based on immobilization of 5-(p-dimethylaminobenzylidene)rhodanine on a triacetylcellulose membrane was developed for quantitative determination of Au(III). The determination procedure was performed using a simple light-emitting diode (LED)-based device as a new effort to overcome low reproducibility and repeatability problems which usually accompany optode-based determinations. The results obtained were compared with those of conventional spectrophotometric methods. The response characteristics of the sensor including dynamic range, reproducibility, response time, and lifetime are discussed in detail. This sensor was used for the determination of Au(III) in ore and electroplating liquid effluent samples with satisfactory results in comparison with flame atomic absorption spectroscopy as standard method. Under the optimum conditions, the calibration plot was linear in the concentration range of 0.3–6.0 μg cm⁻³. The relative standard deviations for five replicate determinations of 1.0 μg cm⁻³ Au(III) and the corresponding limits of detection were 1.76% and 0.12 μg cm⁻³, respectively.     

Granulated copper oxide nanocatalyst: a mild and efficient reusable catalyst for the one-pot synthesis of 4-amino-5-pyrimidinecarbonitriles under aqueous conditions

Abstract  

An efficient method for the synthesis of 4-amino-5-pyrimidinecarbonitriles by the three-component reaction of malononitrile, aldehydes, and N-unsubstituted amidines under aqueous conditions using CuO microspheres as catalyst is reported. The catalyst exhibited remarkable reusable activity.     

Spectrophotometric study of some Mn(II) ternary complexes and their analytical applications

Abstract  

New ternary complexes of Mn(II) with py, bipy, and terpy as primary ligand (L₁) and 2′,4′,5′,7′-tetraiodofluorescein (I₄FlCOOH) as secondary ligand (L₂) were prepared. The stoichiometry for these complexes was found to be Mn(II):L₁:L₂ = 1:2:1, and the complex formula proposed is [Mn(L₁)₂(I₄FlCOO)]⁺. The effect of substituent groups of L₂ and the nitrogen atoms of L₁ on complex formation with Mn(II) was studied. Moreover, the interference of some cations and anions in the determination of Mn(II) by this method was investigated and the interferences of Cu(II) and Fe(III) with Mn(II) in their corresponding alloys were considered. A simple, rapid, and sensitive spectrophotometric method for determination of Mn(II) in its salts and Mn in its alloys is suggested.     

A novel chemiluminescence assay of organophosphorous pesticide quinalphos residue in vegetable with luminol detection

Background  

Organophosphorous pesticides are the most popular pesticides used in agriculture. As acetylcholinesterase inhibitors, organophosphorous pesticides are toxic organic chemicals. The control and detection of organophosphorous pesticide residue in food, water, and environment therefore plays a very important role in maintaining physical health. A sensitive, rapid, simple chemiluminescence(CL) method has been developed for the determination of quinalphos based on the reaction of quinalphos with luminol-H₂O₂ in an alkaline medium. The method has been applied to detection of quinalphos in vegetable samples with satisfactory results.     

A novel synthetic approach towards pyrazole-4-carboxamides using N-(3-(dimethylamino)-2-formylacryloyl)formamide

Abstract  

A novel synthesis of pyrazole-4-carboxamides is reported. The reaction of N-(3-(dimethylamino)-2-formylacryloyl)formamide, an intermediate obtained by Vilsmeier–Haack formylation of acetonitrile, with hydrazine hydrate or monosubstituted hydrazines provides such compounds in good yields. This method has advantages over other methods for construction of such ring systems previously described in the literature.     

Enzymatic determination of vitamin A in pharmaceutical formulations with spectrophotometric detection

An enzymatic method for the determination vitamin A (retinol) is reported using soluble and immobilized alcohol dehydrogenase, isolated from rabbit liver. The reaction is based on the oxidation of retinol and simultaneous reduction of NAD⁺ to NADH followed by spectrophotometric detection at 340 nm. The calibration graph was linear over the range of 2.0–10 μM with correlation coefficients of 0.9967 and 0.9992 (n = 5) for soluble and immobilized alcohol dehydrogenase respectively, with relative standard deviations (n = 3) in the range of 0.5–1.2%. The limit of detection was lower than 1.0 μM. The proposed method was applied to determine vitamin A in pharmaceuticals, and the results obtained were in reasonable agreement with the amount labeled. The results were compared using spectrophotometric reference method, and no significant difference was found between the results of the both methods.     

Anodic voltammetric methods for determination of the antiparasitic drug nitazoxanide in bulk form, pharmaceutical formulation, and its metabolite tizoxanide in human serum

Abstract  

The oxidative behavior of nitazoxanide was studied on a carbon paste electrode in phosphate buffer solutions using cyclic and differential-pulse voltammetry. The oxidation process was shown to be irreversible over the pH range 3.4–11.0 and was adsorption-controlled process. An analytical method was developed for the determination of nitazoxanide in phosphate buffer solution at pH 5.6 as the supporting electrolyte. The anodic peak current varied linearly with nitazoxanide concentration in the range 4.0 × 10⁻⁷ to 1.0 × 10⁻⁵ M with a limit of detection of 7.5 × 10⁻⁸ M. Validation parameters such as sensitivity, accuracy, precision, and recovery were evaluated. The proposed method was applied to the determination of nitazoxanide in the pharmaceutical formulation. The results were compared with those obtained by a spectrophotometric method. No difference was found statistically. Based on the adsorption behavior of the metabolite tizoxanide onto the carbon paste electrode surface, a simple and sensitive differential-pulse adsorptive anodic stripping voltammetric method was developed for the determination of tizoxanide in spiked human serum without the need for extraction.     

Studies on the synthesis, characterization, binding with DNA and activities of two cis-planaramineplatinum(II) complexes of the form: cis-PtL(NH3)Cl2 where L = 3-hydroxypyridine and 2,3-diaminopyridine

Background  

Cis-planaramineplatinum(II) complexes like their trans isomers are often found to be active against cancer cell lines. The present study deals with the synthesis, characterization and determination of activity of new cis-planaramineplatinum(II) complexes.     

Simultaneous determination of cobalt(III)-copper(II) and cobalt(III)-nickel(II) mixtures by differential kinetic methods

A procedure is reported for the simultaneous determination of binary mixtures of cobalt(III)-copper(II) and cobalt(III)-nickel(II) by differential kinetic methods based on complex formation reactions with 3-(1H-1,2,4-triazolyl-3-azo)-2,6-diaminotoluene. The single-point method is used in both cases. The simultaneous determination of Co-Cu and Co-Ni is possible in the concentration range from 10/1 to 1/1. The interference caused by various ions is also studied. The method has been used to determine cobalt-copper and cobalt-nickel mixtures in synthetic samples, hydrofining catalysts and low alloy steels.     

Determination of phenylephrine hydrochloride and chlorpheniramine maleate in binary mixture using chemometric-assisted spectrophotometric and high-performance liquid chromatographic-UV methods

Four methods have been developed for the simultaneous determination of phenylephrine hydrochloride and chlorpheniramine maleate without previous separation. In the first method both drugs are determined using first derivative UV spectrophotometry, with zero-crossing measurement. The second method depends on first derivative of the ratios spectra. The third method describes the use of multivariate spectrophotometric calibration for the simultaneous determination of the analyzed binary mixture where the resolution is accomplished by using partial least squares (PLS) regression analysis. In the fourth method (HPLC), a reversed-phase column and a mobile phase of methanol:water:acetonitrile (80:12:8 v/v/v/) at 0.9 ml/min flow rate have been used to separate both drugs with a UV detection at 270 nm. All the proposed methods are extensively validated. They have the advantage to be economic and time saving. All the described methods can be readily utilized for analysis of pharmaceutical formulations. The results obtained using the proposed methods are statistically analyzed and compared with some reported methods.     

Ecofriendly and efficient procedure for hetero-Michael addition reactions with an acidic ionic liquid as catalyst and reaction medium

Abstract  

1-Methylimidazolium trifluoroacetate ([Hmim]TFA) is reported as a cost-effective catalyst for a simple and environmentally benign hetero-Michael reaction. [Hmim]TFA works both as reaction medium and catalyst. The reaction is applicable to various aromatic sulfur and nitrogen nucleophiles. This method has advantages such as high yields, short reaction time, and simple workup. The catalyst could be recycled several times without any loss of activity.     

A novel sensor for simultaneous determination of dopamine and uric acid using a new MFI-type zeolite prepared by microwave-assisted synthesis

Abstract  

This paper describes microwave-assisted synthesis of a new MFI-type zeolite, Zeolite Secony Mobile (ZSM-5), its characterization by X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM), and its application for fabrication of a modified carbon paste electrode. This novel electrode was employed for sensitive and simultaneous determination of dopamine and uric acid at biological pH (pH 7.0). The results show that this zeolite-modified carbon paste electrode significantly improves the electron transfer rate and reduces the overpotential of dopamine and uric acid oxidation without any fouling effect due to deposition of their oxidized products. The linear analytical curves were obtained in the ranges of 9.0 × 10⁻⁶–4.9 × 10⁻⁴ and 8.0 × 10⁻⁶–9.0 × 10⁻⁴ M for dopamine and uric acid, respectively, by using differential pulse voltammetry based on oxidation of these biomolecules. The detection limits (2σ) were determined for dopamine and uric acid as 7.9 × 10⁻⁶ and 7.1 × 10⁻⁶ M, respectively. This method has been successfully employed for quantification of dopamine and uric acid in real samples.     

Freezing point osmometry of milk to determine the additional water content – an issue in general quality control and German food regulation

Background  

The determination of the osmolality of aqueous samples using a freezing point osmometer is a well-established, routine laboratory method. In addition to their use in clinical and pharmaceutical laboratories, freezing point osmometers are also employed in food testing laboratories. One application is the determination of the osmolality of milk. Although cow's milk is a natural product whose water content is approximately 87%, the osmolality of milk is a significant value when the milk is collected from a larger population of animals. This value is used in milk processing to control the water content, based on the German Food Control Regulations for Milk.     

Simultaneous Spectrophotometric Determination of Silicate and Phosphate by Flow Injection Analysis

Abstract

A method is reported for the simultaneous determination of phosphate and silicate by flow injection analysis based on the different rate of formation of the heteromolybdic acids of the two anions. Measurements are based on the colour of the ion-pairs formed between the said molybdic acids and Rhodamine B. The method allows the determination of the two anions at a rate of 20 samples/h over the ranges 0.05–2.5 ppm (phosphate) and 0.8–15 ppm (silicate), which allows application to a variety of waters.