Salting-out chromatography : Aldehydes and Ketones

Mixtures of aldehydes and/or ketones have been separated by salting-out chromatography. The effects of such variables as sample size, flow rate, concentration of the eluent, cross-linking, mesh size, and type of resin on the elution behavior of the compounds were studied. Salting-out parameters were determined for thirteen ketones and four aldehydes. The differential pH method of Roe and Mitchell is applicable to the determination of carbonyl compounds in aqueous salt solutions.     

Extraction of Nitric Acid and Np(IV) by some aliphatic ketones and alcohols

The extraction behaviour of HNO₃ and Np(IV) from aqueous nitrate solutions with some aliphatic alcohols and ketones using hexane, carbon tetrachloride, benzene and chloroform as diluents was studied. The acid concentration in the aqueous phase varied from 0.25 to 10 M and that of the extractant in the organic phase varied from 0.5 M to the undiluted fraction. In the alcohol systems, solutions of the same alcohol in the diluents CCl₄ and CHCl₃ showed similar capacity for acid extraction, and also in the same diluents, solutions of diisopropyl and diisobutyl alcohol showed similar capacity for extraction. Extraction of Np(IV) with the different ketones and alcohols used follow the same pattern as HNO₃.     

Studies on the extraction of chromium(VI) by ketones

A study of the extraction of chromium(VI) from aqueous media by ketones was made. Extraction of chromium was found to be most efficient from aqueous hydrochloric acid solutions. A mechanism for the extraction of chromium(VI) from aqueous hydrochloric acid solutions by methyl isobutyl ketone is proposed involving the formation of a receptor in the organic phase, the exchange of the chloride ion of the receptor for the anionic chromium(VI) species of the aqueous phase, and the solvation of the extracted chromium species. The differences in the abilities of various ketones to extract chromium(VI) from aqueous hydrochloric acid solutions, and the differences in the extraction of chromium (VI) from various aqueous acids by methyl isobutyl ketone are attributed to the differences in the formation of receptors.     

Separation of Dyes from Aqueous Solutions by Paper Adsorption

Separation of the dyes methyl violet, methylene blue, and congo red from aqueous solutions by paper capillary permeation adsorption method was studied using paper. Nearly 100% of the investigated dyes could be separated under the optimum conditions. The effect of pH on the separation efficiency was studied in particular. At pH 5–9, 1.3–11, and 7–11, the maximum separation was achieved for methyl violet, methylene blue and congo red, respectively. The effects of dye concentration and some foreign ions on the separatability were examined. Moreover, the selective separation of some dyes was attempted by elution with chemical reagents.     

Electrochemical Properties of Oxidized Carbon Nano‐Onions: DRIFTS‐FTIR and Raman Spectroscopic Analyses

The electrochemical reactions of carboxylic and lactone groups on carbon nano‐onions (CNOs) in aqueous solutions result in non‐Kolbe products: alcohols, ketones, ethers and epoxides. The anodic/cathodic conversion of ox‐CNOs was assessed by Boehm titrations and by Raman and DRIFTS‐FTIR (diffuse reflectance infrared Fourier transform spectroscopy). The electrochemical properties of oxidized carbon nano‐onions were investigated by cyclic voltammetry in aqueous solutions. The ox‐CNOs are electrochemically active as a result of the reduction of the oxygen‐containing groups.     

Use of 2,2-dimethoxypropane for the direct gas chromatographic-mass spectrometric determination of some organic compounds in water

The well known reaction between 2,2-dimethoxypropane and water allows for the conversion of an aqueous into an organic solution ready to be injected directly into a gas chromatographic-mass spectrometric (GC-MS) system. Only time, temperature and water/ketal ratio were the parameters studied among those which influence the equilibrium reaction. The reaction environment is not suitable for all compounds: acids, esters, alcohols, amines, ketones and phenols may react with methanol, acetone and ketal owing to Amberlyst being present as catalyst. This method is proposed for the GC-MS analysis of aqueous solutions containing hydrocarbons, halogenated hydrocarbons and ethers. The determination of some pesticides in water is reported.     

Influence of the pressure on the properties of chromatographic columns. I. Measurement of the compressibility of methanol-water mixtures on a mesoporous silica adsorbent

The compressibilities of aqueous solutions of methanol or acetonitrile containing 0, 20, 40, 60, 80 and 100% (v/v) organic solvent were measured with a dynamic chromatographic method. The elution volumes of thiourea samples (2 microL) in these solutions were measured at different average column pressures, adjusted by placing suitable capillary restrictors on-line, after the detector. The reproducibility of the measurements was better than 0.2%. In the range of average pressures studied (10-350 bar), the maximum change in elution volume of thiourea is 1.3% (in pure water) and 4.0% (in pure methanol). This difference is due to the different compressibilities of these pure solvents. For mixtures, the plots of the elution volume of thiourea versus the pressure are convex downward, which is inconsistent with the opposite curvature predicted by the classical Tait model of liquid compressibility. This difference is explained by the variation of the amount of thiourea adsorbed with the pressure. The deconvolution of the two effects, adsorption of thiourea and solvent compressibility, allows a fair and consistent determination of the compressibilities of the methanol-water mixtures. A column packed with non-porous silica particles was also used to determine the compressibility of methanol-water and acetonitrile-water mixtures. A negative deviation by respect to ideal behavior was observed.     

Oxidation of Benzyl Halides to Aldehydes and Ketones with Potassium Nitrate Catalyzed by Phase-Transfer Catalyst in Aqueous Media

The catalytic oxidation of benzyl halides to aldehydes and ketones in aqueous media was studied under relatively mild reaction conditions by using phase-transfer catalyst combined with potassium nitrate and 10% aqueous potassium hydroxide solution. As a result, a simple high-yield procedure has been developed.     

The interaction mechanisms between aqueous solutions of137Cs and134Ba radionuclides and local natural zeolites for an deactivation scenario

¹³⁷Cs and¹³⁴Ba were removed from synthetic aqueous solutions by means of natural zeolites of Slovakian origin. The equilibrium sorption behavior of Cs and Ba ions onto clinoptilolite and mordenite were studied under static as well as dynamic experimental conditions. Both Freundlich and Langmuir isotherms describe satisfactory by Cs and Ba adsorption on the zeolites studied. The elution of Cs and Ba ions from zeolite columns after the loading cycle was undertaken additionaly, in order to compare column operating runs of various exchanged zeolite forms.     

Sorption and preconcentration of some heavy metals by 2-mercaptobenzothiazole-clay

2-Mercaptobenzothiazole loaded on previously treated clay was prepared, characterized and used for sorption and preconcentration of Hg(II), Pb(II), Zn(II), Cd(II), Cu(II) and Mn(II) from an aqueous solution. The support used was a natural clay previously treated with sulphuric acid solution. Adsorption isotherms of metal ions from aqueous solutions as function of pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The chemically treated clay was very selective to Hg(II) in solution in which Zn(II), Cd(II), Pb(II), Cu(II) and Mn(II) were also present.     

Solubilization chromatography : Phenols and Alcohols

Mixtures of four phenols and of six aliphatic alcohols C⁵ to C⁹ have been separated by solubilization chromatography, a procedure in which the mixture is eluted from an ion-exchange resin with aqueous solutions of acetic acid. The effects of such variables as cross-linking, flow rate, and concentration of eluent on the elution behavior of the compounds were studied, and the results were compared with thosc obtained for the lower alcohols in salting-out chromatography.     

Direct trace determination of organic compounds in aqueous solutions by capillary gas chromatography

The possibility of the direct determination of methyl alkyl ketones with four to eight carbon atoms in the alkyl chain and heterocyclic compounds (2-acetylpyridine, 2,3-diethylpyrazine, and 2-acetylthiophene) in aqueous solutions at a level ofn × 10^-3 vol % by gas chromatography with the injection of samples into an open tubular column with carrier gas flow splitting is studied. A significant effect of the calibration plot relating the concentration and the relative area of a gas-chromatographic peak on the results of determination is demonstrated. Factors that make it possible to optimize the calibration process, increase the rapidness of analysis, and decrease the relative error in the determination of organic compounds in water to 3% are discussed. Model mixtures of compounds were analyzed on a open tubular column with the nonpolar OV-101/KF stationary phase, which is stable in work with aqueous solutions for three years     

Sorption of aliphatic ketones from aqueous solutions by starch cryotextures

Capillary gas chromatography was applied to study the sorption of aliphatic ketones (C₆—C₁₁), including metamers, from aqueous solutions by corn starch cryotextures. The amount of ketones sorbed by cryotextures depends linearly on their concentrations in the initial sol. Equations describing the concentration dependence of sorption were proposed. The shape of sorption isotherms reflects the strength of sorption. The binding constants and the number of binding sites were determined for weakly sorbed ketones. The length of alkyl substituent and the position of the functional group are the crucial factors governing the sorption of ketones under conditions of excess binding sites. It was found that the degree of sorption increases with an increase in the carbon chain length from 6 to 9 carbon atoms. The presence of cooperation of binding sites for ketone sorption by cryotextures was demonstrated. The major part of ketones is sorbed irreversibly. This fact points to the formation of supramolecular complexes. Ketones with lower molecular masses are better sorbed by cryotextures than by native starch grains.     

Tandem solid-phase extraction of atrazine ozonation products in water

The preconcentration of aqueous solutions containing atrazine degradation products was investigated using solid-phase extraction on octadecyl and cation-exchanger silica phases. The retention and elution steps were studied and evaluated separately in order to define and optimize the critical experimental parameters involved. A strategy which combines sequentially both phases is proposed to fractionate compounds into two groups of increasing polarities: firstly, the native pesticide, hydroxyatrazine and most chlorotriazines on octadecyl support, and secondly monodealkylated hydroxytriazines, ammeline and ammelide on cation-exchanger. This tandem procedure was successfully applied for analysing and quantifying atrazine ozonation products and its efficiency demonstrated using [U-ring 14C]-labelled atrazine experiments.     

Paper solubilization chromatography : Part III. Ketones

A series of 8 high-molecular-weight ketones was separated directly by development on ion-exchange paper with aqueous methanol. The effects of a number of variables on the results were studied and an attempt was made to elucidate a simple mechanism for paper solubilization chromatography.     

Synthesis of substituted pyridines by reaction of tetracyanoethylated ketones with hydrochloric and hydrobromic acids

Previously unknown derivatives of pyridine have been synthesized by reaction of tetracyanoethylated ketones with concentrated aqueous solutions of hydrochloric and hydrobromic acids. The unique course of the reaction of 4,4,5,5-tetracyano-2-pentanone with gaseous hydrogen chloride has been demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 653–656, May, 1987.     

Gradient chromatographic elution of sulphur anions

The distribution coefficient of sulphide, sulphite, sulphate and thiosulphate anions between different concentrations of aqueous alkali metal chloride solutions and the anion exchanger Dowex 1X8 is studied. The obtained distribution deportment of these anions is explained in the light of water-water, anion-cation and ion-ion interactions as well as the different tendencies of the alkali ions to hydration. Based on the separation factors encountered between adjacent anions, a chromatographic method is adopted for isolation of the sulphur anions by gradient elution. This method is further compared with the chromatographic procedures so far reported for separation of the investigated anions.     

Cetyltrimethylammonium Bromide as a Regulator in Paper Separation of Pentachlorophenol Herbicide and Methyl Orange Dye

An experimental investigation is presented for separation of pentachlorophenol (PCP) and methyl orange (MO) from an aqueous solution by use of cetyltrimethylammonium bromide (CTAB) as a regulator in the paper capillary permeation adsorption process (PCPA). The effects of pH, concentration of CTAB, and ionic strength on the separatability of the molecules were studied. The maximum separatability of nearly 100% PCP and MO was obtained in the optimum pH range 5–11 and 7–11, respectively. The ionic strength has an appreciable effect on separatability. The recovery of PCP and MO from paper by elution with acetone: isooctane solvent gradients was also studied. The selective separation of PCP and MO admixed in aqueous solution by a developed solvent elution technique was also reported. It was believed that PCP and MO were separated as their ion pairs with CTA cations by adsorption on the fiber surface.     

PHOTOCHEMICAL REACTIONS OF AROMATIC KETONES WITH NUCLEIC ACIDS AND THEIR COMPONENTS I—. PURINE AND PYRIMIDINE BASES AND NUCLEOSIDES*.

Abstract— The photochemical reactions of benzophenone and acetophenone with purine and pyrimidine derivatives in aqueous solutions have been investigated by flash photolysis and steady-state experiments. Upon excitation of these two ketones in aqueous solutions, two transient species are observed: molecules in their triplet state and ketyl radicals. The triplet state lifetimes are 65 μsec for benzophenone and 125 μsec for acetophenone. The ketyl radicals disappear by a second order reaction, controlled by diffusion. In the presence of pyrimidine derivatives, the triplet state is quenched and the ketyl radical concentration is decreased without any change in its kinetics of disappearance. Ketone molecules in their triplet state react with purine derivatives leading to an increase in the yield of ketyl radicals due to H-atom abstraction from the purines. Steady-state experiments show that benzophenone and acetophenone irradiated in aqueous solution at wavelengths longer than 290 nm undergo photochemical reactions. The rate of these photochemical reactions is increased in the presence of pyrimidine derivatives and even more in the presence of purine derivatives. Following energy transfer from the triplet state of benzophenone to diketopyrimidines, cyclobutane dimers are formed. The energy transfer rate decreases in the order orotic acid > thymine > uracil. Benzophenone molecules in their triplet state can also react chemically with pyrimidine derivatives to give addition photoproducts. All these results are discussed with respect to photosensitized reactions in nucleic acids involving ketones as sensitizers.     

Insect antifeedant potent 6-substituted ω-bromo-2-naphthones

A series of some 6-substituted ω-bromo-2-naphthyl ketones have been synthesized by a greener synthetic method using fly-ash: water catalyzed aqueous phase reaction. The purities of these ketones and esters checked by their physical constants and spectral data have been published earlier in the literature. The insect antifeedant activities of these ketones have been studied using 4th instar larvae Achoea janata L and castor semilooper.