Extraction of medicinal compounds of the benzodiazepines class from aqueous solutions and their following gas chromatographic determination

In extraction systems hexane–water, hexane–aqueous solutions of inorganic salts (sodium chloride, dipotassium phosphate and potassium carbonate), chloroform–water using the method of gas chromatography–mass spectrometry, the distribution constants of psychotropic substances, limited to movement through the customs border of the Republic of Belarus – alprazolam, lorazepam, temazepam, and as well as clozapine, a medicinal product permitted for movement, were determined. The greatest dynamics of the growth of the distribution constant versus salt concentration was observed in alprazolam. It was found that replacing hexane with chloroform leads to increasing the distribution constants and the quantitative extraction of all substances. However, for the selective extraction of substances from various objects and the simultaneous removal of matrix components, it is necessary to use the systems as hexane–aqueous solutions of salts or hexane–water. Based on the obtained values of the distribution constants of substances, extraction-chromatographic technique for the determination of organic non­electrolytes (benzodiazepines) in various objects is proposed. Metrological characteristics of the techniques are: relative standard deviation does not exceed 2 %, the range of determined concentrations in solutions is 0,05– 1,00 g/dm3.

On the possibility of evaluative prediction of the extraction of organic substances of complex structure using the method of group increments

The distribution of pesticides of different classes (amides, anilinopyrimidines, benzene derivatives, benzoylphenylureas, benzenesulfonates, hydrazides, dinitroanilines, carbamates, pyretroids, pyrimidines, tetrazines, triazoles, pheny lureas, organophosphorus compounds, esters of carboxylic acids) was studied at 20 ± 1 °C in the extraction systems of hexane–water, hexane–acetonitrile, hexane– acetonitrile and water mixture that are most often used in analytical chemistry of pesticides. The distribution constants P of pesticides and the increments of logarithms of the distribution constants If of their functional groups between the hydrocarbon and polar phases are calculated. Two main methods for evaluative prediction of lg P of pesticides are proposed and approved – substitutive method based on the calculation of lg P by replacing the substituents in the base molecule and the method of absolute addition of increments. The possibilities of the both methods are illustrated. The reasons for the deviations of the experimental values from the calculated ones are discussed. The influence of the nature and composition of the polar phase on the magnitudes of the observed deviations is estimated. In particular, they decrease dramatically with an increase in the acetonitrile content in the polar phase. Averaged values of correction to the calculated values of lg P are introduced. In most cases, they allow predicting lg P of pesticides with a deviation of not more than 0.5–1.0 from the calculated one.

Determination of the bifenazate insecticide in apples and cucumbers by high performance liquid chromatography

Based on the distribution constants of biphenazate, obtained experimentally and also calculated from literature data on the solubility of biphenazate in water and organic solvents, as well as experimental data on the extraction of biphenazate from plant matrices by various extractants, we selected the optimal conditions for extracting biphenazate from apples and cucumbers. The conditions for the purification of the extracts were also selected. Acetonitrile in the presence of ammonium sulfate and hexane was used for extraction of the pesticide. Purification of extracts of plant materials was carried out by partitioning between hexane and water-acetonitrile mixture. The samples obtained after this treatment were pure enough to determine the residual amounts of biphenazate in them at the maximum residue level determined in Belarus and the countries of the European Union, or lower using widespread liquid chromatography with diode-array (ultraviolet) detection.

Pb(II) Extraction with Benzo-18-Crown-6 Ether into Benzene under the Co-Presence of Cd(II) Nitrate in Water

Extraction of Pb(II) with picrate ion [Pic−] and 0, 0.58, 15, 48, or 97 mmol dm−3 Cd(NO3)2 by benzo-18-crown-6 ether (B18C6; L as its symbol) into benzene (Bz) was studied. Three kinds of extraction constants, Kex, Kex±, and KPb/PbL (or Kex2±), were determined at 298 K: these constants were defined as [PbLPic2]Bz/P, [PbLPic+]Bz[Pic−]Bz/P, and [PbL2+]Bz/[Pb2+][L]Bz (or [PbL2+]Bz([Pic−]Bz)2/P), respectively. The symbol P shows [Pb2+][L]Bz[Pic−]2 and the subscript “Bz” denotes the Bz phase, Bz saturated with water. Simultaneously, conditional distribution constants, KD,Pic (=[Pic−]Bz/[Pic−]), of Pic− with distribution equilibrium-potential differences (dep) were determined. Then, based on the above four constants and others, the component equilibrium constants of K1,Bz (=[PbLPic+]Bz/[PbL2+]Bz[Pic−]Bz), K2,Bz (=[PbLPic2]Bz/[PbLPic+]Bz[Pic−]Bz), and KD,PbL (=[PbL2+]Bz/[PbL2+]) were obtained. Using these constants, the Pb(II) extraction with B18C6 under the co-presence of Cd(II) in the water phase was characterized. In such a characterization, I and IBz dependences on the constants were mainly discussed, where their symbols denote the ionic strength of the water phase and that of the Bz one, respectively.

The development of methods for the determination of residues of the herbicide halauxifen-methyl in barley and rape

Optimal conditions for the extraction of halauxifen-methyl from grain, straw and green mass of barley; seeds, oil and green mass of rape, as well as the conditions for the purification of extracts were selected on the basis of the distribution constants (P) and distribution coefficients (D) experimentally determined at a temperature of (20 ± 1) °C. At the first stage, acetonitrile, or acidified acetonitrile, or a mixture of water and acetonitrile were used to extract the pesticide. Halauxi fen-methyl was found to be a weakly hydrophobic substance and it exhibits the properties of a weak base in aqueous solutions. For the purification of plant material extracts hexane – 1 mol/L aqueous solution of hydrochloric acid and hexane – 10 % K2HPO4 aqueous solution were successfully used (to neutralize the acid and increase the extraction constant due to the salting out effect). The samples obtained after purification are sufficiently pure. So, the residual amounts of halauxifen-methyl can be determined by widespread liquid chromatography with diode array (ultraviolet) detection at the level, which is equal or lower to the maximum allowable content of herbicide in barley and rape.

Determination of Distribution Equilibrium-Potential Differences Based on Extraction with Several Crown Ethers by Nitrobenzene, 1,2-Dichloroethane and Dichloromethane

Extraction constants (Kex± & Kex) were determined at 298 K for the extraction of sodium picrate (NaPic) by nitrobenzene (NB), 1,2-dichloroethane (DCE) and dichloromethane using 3m-crown-m ethers and their benzo-derivatives (m = 5, 6; abbreviated as L) together with the determination of conditional distribution constants (KD,Pic) of picrate ion, Pic-, into these diluents. The K1,org (= [NaLPic]org/[NaL+]org[Pic-]org) values at the organic (org) phases, such as NB & DCE, were calculated from the relation Kex/Kex± = K1,org. Distribution equilibrium-potential differences (Dfeq) at extraction equilibria were evaluated from the equation Dfeq = -0.05916´(log KD,Pic - constant) at 298 K. Correlations of the above equilibrium constants, particularly Kex±, with Dfeq were examined. Furthermore, the standard formal potentials for Na+ transfers across the interfaces were briefly evaluated from calculated Dfeq, [Na+] and [Pic-]org. The above extraction systems were characterized by K1,org and the complex formation constants of Na+ with L in the org phases.

MONOATOMIC ALCOHOLS IN A SYSTEM ”FORMATION WATER–n-DODECANE”

The paper presents the experimental research of distribution of nine С1–С5 aliphatic monoatomic alcohols of normal and isomeric structure in a two-phased heterogenous system ”formation water–n-dodecane” using gas-chromatography method for the purpose of a choice of the most effective tracers for the characterization of filtrational streams and oil saturation when waterflooding. There were defined distribution constants K_с in interval of temperatures 25–75С on which basis appeared the conclusion that alcohols С1–С3 can be used as water (non-partitioning) tracers whereas alcohols С4–С5 approach for a role of partitioning tracers.