ОСОБЕННОСТИ КОМПЛЕКСООБРАЗОВАНИЯ КСИЛЕНОЛОВОГО ОРАНЖЕВОГО С Bi(III) И ЕГО СПЕКТРОФОТОМЕТРИЧЕСКОЕ ОПРЕДЕЛЕНИЕ В ФАРМАЦЕВТИЧЕСКИХ ПРЕПАРАТАХ

The complexation features of Bi(III) with xylenol orange (XO) have been studied. It was found that three complexes of different stoichiometry have been formed in the studied system. The complex composition of Bi(III) : XO = 1 : 1 (λ = 540 nm, ε = 17000, log β = 10.5) has been formed at pH = 1.0 in reagent excess, and its dimerization with the formation of the complex stoichiometry 2 : 2 (λ = 560 nm, ε = 24000, log β = 17.8) has been observed in excess of Bi (III). The complex composition of Bi(III) : XO = 1 : 2 has been formed with weak light absorbing properties (λ = 500 nm, ε = 9000, log β = 9.9) at pH = 6.8. The complexation mechanism of Bi(III) with XO has been proposed based on the totality of the spectrophotometric data and its theoretical interpretations. In the acidic environment (pH = 1.0) the coordinating ion is Bi3+ and coordinated ligand is an ionized by sulfo-groups reagent form. At pH = 6.8, the ion chelator is BiOH2+, and XO reacts in ionized by sulfo and carboxyl groups form. The effect of extraneous ions on the absorbance value of the complex Bi (III) with a XO at pH = 1.0 was studied. The complex with molar ratio 1 : 1 is recommended as an analytical form. Beer’s law holds in the Bi(III) concentrations range 0.4-10.0 μg/cm3. The detection limit is 0.12 μg/cm3 and the limit of quantification is 0.37 μg/cm3. The simple method of spectrophotometric determination of Bi(III) with xylenol orange in pharmaceuticals has been developed.Keywords: spectrophotometric analysis, complexation, xylenol orange, bismuth (III), pharmaceuticals(Russian)DOI: http://dx.doi.org/10.15826/analitika.2016.20.3.007 A.N. Chebotarev, D.V. Snigur, V.P. Dubovyiy  Odessa I.I. Mechnikov National University ul. Dvorianskaya, 2, Odessa, Ukraine, 65082Изучены особенности комплексообразования Ві(ІІІ) с ксиленоловым оранжевым (КО) и установлено, что в исследуемой химической системе образуется три комплекса разной стехиометрии. При рН = 1.0 в избытке реагента образуется комплекс состава Ві(ІІІ) : КО = 1 : 1 (λ = 540 нм, ε = 17000, log β = 10.5), а в избытке Ві(ІІІ) наблюдается его димеризация с образованием комплекса состава 2 : 2 (λ = 560 нм, ε = 24000, log β = 17.8). При рН = 6.8 образуется комплекс состава 1 : 2 со слабыми светопоглощающими свойствами (λ = 500 нм, ε = 9000, log β = 9.9). На основании совокупности спектрофотометрических данных и их теоретической интерпретации предложен химизм комплексообразования Ві(ІІІ) с КО. В кислой среде (рН = 1.0) координирующим ионом является Bi3+, а координированным лигандом – ионизированная по сульфо-группе форма реагента. При рН = 6.8 комплексообразователем выступает ион BiОН2+, а КО вступает в реакцию в ионизированной по сульфо- и карбоксильным группам форме. Изучено влияние посторонних ионов на величину оптической плотности комплекса Ві(ІІІ) с КО при рН = 1.0. В качестве аналитической формы рекомендован комплекс состава 1 : 1, при использовании которого закон Бэра выполняется в диапазоне концентраций Ві(ІІІ) 0.4-10.0 мкг/см3. Нижний предел обнаружения – 0.12 мкг/см3, предел количественного определения – 0.37 мкг/см3. Предложена методика спектрофотометрического определения Ві(ІІІ) в фармацевтических препаратах с ксиленоловым оранжевым, характеризующаяся относительной погрешностью определения не превышающей 3.5 %.Ключевые слова: спектрофотометрический анализ, комплексообразование, ксиленоловый оранжевый, висмут(ІІІ), фармацевтические препараты DOI: http://dx.doi.org/10.15826/analitika.2016.20.3.00

The complexation features of xylenol orange with Bi(III) and its spectrophotometric determination in pharmaceuticals

The complexation features of Bi(III) with xylenol orange (XO) have been studied. It was found that three complexes of different stoichiometry have been formed in the studied system. The complex composition of Bi(III) : XO = 1 : 1 (λ = 540 nm, ε = 17000, log β = 10.5) has been formed at pH = 1.0 in reagent excess, and its dimerization with the formation of the complex stoichiometry 2 : 2 (λ = 560 nm, ε = 24000, log β = 17.8) has been observed in excess of Bi (III). The complex composition of Bi(III) : XO = 1 : 2 has been formed with weak light absorbing properties (λ = 500 nm, ε = 9000, log β = 9.9) at pH = 6.8. The complexation mechanism of Bi(III) with XO has been proposed based on the totality of the spectrophotometric data and its theoretical interpretations. In the acidic environment (pH = 1.0) the coordinating ion is Bi3+ and coordinated ligand is an ionized by sulfo-groups reagent form. At pH = 6.8, the ion chelator is BiOH2+, and XO reacts in ionized by sulfo and carboxyl groups form. The effect of extraneous ions on the absorbance value of the complex Bi (III) with a XO at pH = 1.0 was studied. The complex with molar ratio 1 : 1 is recommended as an analytical form. Beer’s law holds in the Bi(III) concentrations range 0.4-10.0 μg/cm3. The detection limit is 0.12 μg/cm3 and the limit of quantification is 0.37 μg/cm3. The simple method of spectrophotometric determination of Bi(III) with xylenol orange in pharmaceuticals has been developed.Изучены особенности комплексообразования Ві(ІІІ) с ксиленоловым оранжевым (КО) и уста- новлено, что в исследуемой химической системе образуется три комплекса разной стехиометрии. При рН = 1.0 в избытке реагента образуется комплекс состава Ві(ІІІ) : КО = 1 : 1 (λ = 540 нм, ε = 17000, log β = 10.5), а в избытке Ві(ІІІ) наблюдается его димеризация с образованием комплекса состава 2 : 2 (λ = 560 нм, ε = 24000, log β = 17.8). При рН = 6.8 образуется комплекс состава 1 : 2 со слабы- ми светопоглощающими свойствами (λ = 500 нм, ε = 9000, log β = 9.9). На основании совокупности спектрофотометрических данных и их теоретической интерпретации предложен химизм комплексо- образования Ві(ІІІ) с КО. В кислой среде (рН = 1.0) координирующим ионом является Bi3+, а коорди- нированным лигандом – ионизированная по сульфо-группе форма реагента. При рН = 6.8 комплек- сообразователем выступает ион BiОН2+, а КО вступает в реакцию в ионизированной по сульфо- и карбоксильным группам форме. Изучено влияние посторонних ионов на величину оптической плот- ности комплекса Ві(ІІІ) с КО при рН = 1.0. В качестве аналитической формы рекомендован комплекс состава 1 : 1, при использовании которого закон Бэра выполняется в диапазоне концентраций Ві(ІІІ) 0.4-10.0 мкг/см3 . Нижний предел обнаружения – 0.12 мкг/см3 , предел количественного определения – 0.37 мкг/см3 . Предложена методика спектрофотометрического определения Ві(ІІІ) в фармацевти- ческих препаратах с ксиленоловым оранжевым, характеризующаяся относительной погрешностью определения не превышающей 3.5 %

MORPHOGENESIS OF KNEE HYALINE CARTILAGE DURING INTRAARTICULAR INJECTION OF PLATELET-RICH AUTOLOGOUS PLASMA AND/OR HYALURONIC ACID PREPARATION IN RATS WITH EXPERIMENTAL OSTEOARTHRITIS

According to current concepts, the influence of autologous platelet-rich plasma (PRP) and high molecular hyaluronates (HA) on the repair of hyaline cartilage during its inflammatory and degenerative changes has been insufficiently studied yet. The objective of the work was to evaluate the morphological changes in the structure of hyaline cartilage in experimental osteoarthritis after intra-articular injection of PRP and/or HA. Material and methods. The authors used 50 adult rats of Wistar line, weighing 250±2,2 g., distributed into five groups of 10 animals (two control and three experimental groups). An experimental gonarthosis was simulated on four groups of animals. Animals of the first experimental group received intra-articular injection of PRP, the second group – HA, the third – both PRP and HA. Results. No morphological signs of degenerative and inflammatory changes in the first control group were identified. Following osteoarthritis simulation the articular cartilage thinned to 121±20,4 microns (p<0,05) and the volume fraction of chondrocyte decreased to 1,2±0,6% (p<0,05). The authors observed an uneven coloration of collagen fibers with severe tinctorial properties disorder of the articular cartilage matrix. After the RPR introduction the authors observed tickening of the articular cartilage up to 275±18,9 micron (p<0,05) and the volume fraction of chondrocytes up to 18,4±2,0% (p<0,05). The contour of the cartilage surface became smoother with the formation of a cell-free zone. Collagen fibers demonstrated a uniform distribution, tinctorial properties of cartilage matrix in all areas were preserved, no signs of inflammation were noted. After HA introduction the authors observed thickening of the cartilage plate up to 264±21,3 microns (p<0,05) and the volume fraction of chondrocytes up to 11,6±1,2% (p<0,05). The surface of the cartilage featured uneven contours due to multiple areas of pulping. Uneven tinctorial properties of cartilage matrix, thickness and orientation of collagen fibres were retained. No signes of inflammation were observed. After the combined consecutive application of PRP and HA cartilage thickness increased up to 268±15,3 microns (p<0,05) and the volume fraction of chondrocytes increased up to 12,7±0,9% (p<0,05). Individual portions of pulping on the cartilage surface were observed. Tinctorial properties of the cartilage matrix were preserved; the focal uneven staining of collagen fibers in the basal zone was observed. No signs of inflammation were noted. Conclusion. During osteoarthritis simulation in knee joints of experimental Wistar line rats the authors observed severe structural changes in articular hyaline cartilage including complete destruction accompanied by vascular proliferation and granulomatous inflammation. Intraarticular injections of PRP, HA as well as PRP in combination with HA during the simulation of osteoarthrosis were accompanied by a decrease in the severity of degenerative and dystrophic processes and improval of tinctorial properties of articular cartilage matrix. Sole application of PRP or consecutive application of PRP followed by HA were observed as having the more significant reparative effect on articular cartilage as compared to HA

MODIFICATION OF THE ORGANO-POLYMERIC ANIONITES SURFACE WITH XYLENOL ORANGE BY SORPTION

In this paper, the peculiarities of xylenol orange sorption removal with the help of organopolymeric anion exchangers AB-17-8 and Granion AWA-G1 in the static mode are studied. The state of the matrix and the surface of the organopolymeric anion exchanger granion AWA-G1 was characterized by the IR and Raman spectroscopy. It was established that at pH 5 and 9 the maximum sorption removal (90-95%) of xylenol orange by organopolymeric anion exchanger Granion AWA-G1 lasts for 60 minutes. On the basis of the obtained sorption isotherms and the calculated thermodynamic characteristics, it was concluded that the formation of the adsorption layer occurs spontaneously by a mixed mechanism. The initial process of adsorption layer formation due to chemisorption mechanism. Below, at high concentration of xylenol orange the sorption mechanism changes to the physical nature. It was shown that with changes in temperature and pH, the type of isotherms changes from L3 to H4, which indicates a high affinity of the adsorbate to the adsorbent surface. The obtained sorption isotherms are satisfactorily described by the Langmuir adsorption model. It was shown that the increase in temperature is accompanied by an increase in the amount of sorbed xylenol orange, which is due to the acceleration of the process of reorientation of sorbate molecules to the vertical. In the study of xylenol orange desorption from the Granion AWA-G1 anionite surface, it was found that distilled water and 1M solutions of sulphuric acid slightly desorb xylenol orange (Sdes ≤ 25%), in contrast, the desorption of xylenol orange with 1 M sodium hydroxide solutions reaches Sdes ~ 65%. Thus, the organopolymeric anion exchanger granion AWA-G1 modified with xylenol orange is resistant to water and acid desorption and can subsequently be used as a solid-phase reagent

MODIFICATION OF THE ORGANO-POLYMERIC ANIONITES SURFACE WITH XYLENOL ORANGE BY SORPTION

In this paper, the peculiarities of xylenol orange sorption removal with the help of organopolymeric anion exchangers AB-17-8 and Granion AWA-G1 in the static mode are studied. The state of the matrix and the surface of the organopolymeric anion exchanger granion AWA-G1 was characterized by the IR and Raman spectroscopy. It was established that at pH 5 and 9 the maximum sorption removal (90-95%) of xylenol orange by organopolymeric anion exchanger Granion AWA-G1 lasts for 60 minutes. On the basis of the obtained sorption isotherms and the calculated thermodynamic characteristics, it was concluded that the formation of the adsorption layer occurs spontaneously by a mixed mechanism. The initial process of adsorption layer formation due to chemisorption mechanism. Below, at high concentration of xylenol orange the sorption mechanism changes to the physical nature. It was shown that with changes in temperature and pH, the type of isotherms changes from L3 to H4, which indicates a high affinity of the adsorbate to the adsorbent surface. The obtained sorption isotherms are satisfactorily described by the Langmuir adsorption model. It was shown that the increase in temperature is accompanied by an increase in the amount of sorbed xylenol orange, which is due to the acceleration of the process of reorientation of sorbate molecules to the vertical. In the study of xylenol orange desorption from the Granion AWA-G1 anionite surface, it was found that distilled water and 1M solutions of sulphuric acid slightly desorb xylenol orange (Sdes ≤ 25%), in contrast, the desorption of xylenol orange with 1 M sodium hydroxide solutions reaches Sdes ~ 65%. Thus, the organopolymeric anion exchanger granion AWA-G1 modified with xylenol orange is resistant to water and acid desorption and can subsequently be used as a solid-phase reagent

THE YELLOWNESS INDEX USE FOR THE ACID-BASE EQUILIBRIUM STUDY IN XYLENOL ORANGE AQUEOUS SOLUTIONS

The possibility of the yellowness index use for the acid-base equilibrium study and ionization constants determination in dyes solutions is studied. It is shown that the yellowness index is suitable for the set task. Its use enables a more reasonable mathematical apparatus algorithmization, automation, simplification and in comparison with the existing approaches of the chemical chromaticity method and classical physico-chemical methods

ЕЛЕКТРОНОДОНОРНІ ВЛАСТИВОСТІ НІТРОГЕНВМІСНИХ ОРГАНІЧНИХ ОСНОВ У ВОДНО-ЕТАНОЛЬНИХ І ВОДНО-АЦЕТОНОВИХ РОЗЧИНАХ

In this paper, the dissociation constants (pKa) of some nitrogen-containing organic bases (aniline, pyridine and octylamine) in water-ethanol and water-acetone media at various concentrations of organic solvent in the system has been determined by the potentiometric titration method. It was established that the value of pKa of nitrogen-containing organic bases in aqueous-organic media naturally decreases with increasing content of organic solvent in the system. It was shown that their nature (aliphatic, aromatic, heterocyclic) and the physicochemical properties of the medium are significantly influenced by the nature and degree of change in the electron donor ability of the nitrogen-containing organic bases studied. It was noted that for aniline in water-ethanol solutions in the transition from water to an organic solvent, the value of pKa does not change much (ΔpKa = 0,9), while for pyridine and octylamine these changes are significant, and the values of ΔpKa are 2,9 and 1,7, respectively, which can be explained by the specific solvation of the aniline amino group with ethanol. In the case of water-acetone solutions, the behavior of the nitrogen-containing organic bases was studied generally similar, and the values of ΔpKa are within the range of 1,7-2,6. It was established that the dependence of the values of pKa of nitrogen-containing organic bases on the inverse of the dielectric constant of water-ethanol and water-acetone solutions tends to be linear, consistent with Izmailov’s theory. Thus, we can conclude that the change in the ratio of the mixed solvent components and, as a result, in general, dielectric permeability of the medium does not lead to a significant change in the solvation characteristics of the nitrogencontaining organic bases studied.У даній роботі методом потенціометричного титрування визначено константи дисоціації (pKa)ряду нітрогеновмісних органічних основ різної природи(аніліну, піридину і октиламіну) в водно-етанольних і водно-ацетонових середовищах при різних концентраціях (0-100 об. %) органічного розчинника в хімічній системі. Встановлено, що значення pKaнітрогеновмісних органічних основ у водно-органічних середовищах закономірно зменшуються при збільшенні вмісту органічного розчинника (етанолу або ацетону) в системі.Показано, що на характер і ступінь зміни електронодонорної здатності досліджуваних нітрогеновмісних органічних основ істотно впливає їх природа (аліфатичні, ароматичні, гетероциклічні) і фізико-хімічні властивості середовища. Відзначено, що для аніліну в водно-етанольних розчинах при переході від води до органічного розчинника величина pKa мало змінюється (ΔpKa = 0,9), при цьому для піридину і октиламіну такі зміни досить істотні, а значення ΔpKa становлять 2,9 і 1, 7 відповідно, що ймовірно можна пояснити специфічною сольватацією аміногрупи аніліну етанолом. У разі водно-ацетонових розчинів поведінка досліджуваних нітрогеновмісних органічних основ в цілому подібна, а відповідні значення ΔpKa знаходяться в межах 1,7-2,6.Встановлено, що залежність величин pKaнітрогеновмісних органічних основ від оберненої величини діелектричної проникностіводно-етанольних і водно-ацетонових розчинів прагне до лінійної, що узгоджується з теорією Ізмайлова. Таким чином можна зробити висновок, що зміна співвідношення компонентів змішаного водно-етанольного (водно-ацетонового) розчинника і, як наслідок, в цілому діелектричної проникності хімічної системи не призводить до істотної зміни сольватаційних характеристик водно-органічного середовища щодо досліджуваних нітрогеновмісних органічних основ

THE ELECTRON DONATING PROPERTIES OF NITROGENCONTAINING ORGANIC BASES IN WATER-ETHANOL AND WATER-ACETONE SOLUTIONS

In this paper, the dissociation constants (pKa) of some nitrogen-containing organic bases (aniline, pyridine and octylamine) in water-ethanol and water-acetone media at various concentrations of organic solvent in the system has been determined by the potentiometric titration method. It was established that the value of pKa of nitrogen-containing organic bases in aqueous-organic media naturally decreases with increasing content of organic solvent in the system. It was shown that their nature (aliphatic, aromatic, heterocyclic) and the physicochemical properties of the medium are significantly influenced by the nature and degree of change in the electron donor ability of the nitrogen-containing organic bases studied. It was noted that for aniline in water-ethanol solutions in the transition from water to an organic solvent, the value of pKa does not change much (ΔpKa = 0,9), while for pyridine and octylamine these changes are significant, and the values of ΔpKa are 2,9 and 1,7, respectively, which can be explained by the specific solvation of the aniline amino group with ethanol. In the case of water-acetone solutions, the behavior of the nitrogen-containing organic bases was studied generally similar, and the values of ΔpKa are within the range of 1,7-2,6. It was established that the dependence of the values of pKa of nitrogen-containing organic bases on the inverse of the dielectric constant of water-ethanol and water-acetone solutions tends to be linear, consistent with Izmailov’s theory. Thus, we can conclude that the change in the ratio of the mixed solvent components and, as a result, in general, dielectric permeability of the medium does not lead to a significant change in the solvation characteristics of the nitrogencontaining organic bases studied

THE PECULIARITIES OF THE COMPLEXATION OF Co(II) WITH 4-SULFO-2 (4'-SULFONAFTALIN-1'-AZO)-NAPHTHOL-1 IN SOLUTIONS

In this paper, the features of the complexation of the “Cobalt(II) -carmoazine-H2O2” system were studied spectrophotometrically. It is shown that the complexation of carmoazine (CAN) with Co(II) is possible only after its oxidation in the presence of hydrogen peroxide. In contrast to the previously investigated ions of variable valency metals that interact with carmoazine according to the mechanism of mutual oxidationreduction, in this case, carmoazine acts as a typical organic ligand. The optimal conditions of interaction in the investigated chemical system (pH 8, 10 vol% H2O2) were established. The complex composition (Co(III):KAN = 1:3) was determined by classical spectrophotometric methods (molar ratios and equilibrium shift). Using the Komar method molar absorbtivity of the complex was calculated (ε600 = 5300). The complex stability constant which is 2.4 ∙ 109, was calculated. The presence of Co(III) ions in the newly formed as a result of the oxidation-reduction reaction to the chemical system was proved by using the intake of “interception” of trivalent cobalt ions by the competing ligand – EDTA. The charge (-6) of the product of interaction in the system “Cobalt(II) -carmoazine-H2O2” was determined by the extraction spectrophotometric method. Given the stoichiometry of the complex and the presence in the molecule of carmoazine of two negatively charged outer-sphere sulfo groups, as well as the positive charge of cation of cetylpyridinium (CP+Сl-), the composition of the ion pair extracted with chloroform [Co(III) · 3CAN2- · 6CP+] was determined. An assumption was made about the mechanism of interaction of Co (II) with carmoazine, which is preceded by the oxidation stage of Co(II) in Co(III) to form the transition peroxide complex and its subsequent complexation with carmoazine by the acid-base mechanism

THE ELECTRON DONATING PROPERTIES OF NITROGEN-CONTAINING ORGANIC BASES IN MIXED MEDIA

The thermodynamic ionization constants of aniline, pyridine and octylamine in waterdimethylformamide and water-dioxane media were determined by potentiometric titration method. Mathematical models that adequately describe the change of the nitrogencontaining organic bases рК were constructed by varying characteristics of chemical systems