The separation of molybdenum valencies by paper chromatography part II1

The preparation of Mo^VI oxinate and a purported Mo^V oxine complex is described. The latter was analysed, and a number of its properties, including separation from the Mo^VI compound by paper chromatography, were studied.The preparation of a solution containing trivalent molybdenum and the separation of this valency from the pentavalent state by chromatography upon cellulose is also described.Suggestions as to the stability of thiocyanate and oxine compounds of Mo^III were made from the results of some extraction experiments performed upon trivalXnt molybdenum solutions.     

On the volatility of ruthenium

When annealing the evaporation residue formed by evaporating a solution containing ruthenium, phosphates and nitrates, ruthenium volatilizes. The amount of volatilized ruthenium (both¹⁰⁶Ru traces and milligram amuonts of Ru) depends on the solution composition before evaporation and on the temperature and time of annealing. Volatility occurs at a temperature as low as 300°C. We suppose that the volatility is due to thermal decomposition of the ruthenium compounds with phosphates. The released atoms of ruthenium are oxidized by the decomposition products of the nitrate. The formation of complex compounds of ruthenium with phosphates during the evaporation of the solution follows from the data of elemental and spectral analysis and ion exchange chromatography.     

Study of the state of95Zr+95Nb in aqueous solutions

The adsorption on paraffine and polyethylene and the paper chromatography in aqueous solutions in the pH range of 2–12 were used for the study of the behaviour of⁹⁵Zr and⁹⁵Nb. The effect of complexing ions (SO ₄ ^2? and CO ₃ ^2? ) was studied in the same pH range. The constants of hydrolysis and the composition of hydrolytic species of⁹⁵Zr in the solution containing sulphate ions were determined in the pH range of 1–2. The paper chromatography was used for the control of the purity of⁹⁵Zr after an extractive separation from⁹⁵Nb with α-benzoinoxime. The possibility of studying the extraction processes of Zr (without its previous separation from Nb) by reversed phase chromatography is shown. Conditions for the formation of polynuclear compounds of Zr and Nb and their influence on the extraction separation in nitrate media were studied.     

Speciation of butyltins in fish and sediment by means of gas chromatography with flame photometric detection

A modified method for the determination of tributyl-, dibutyl-, and monobutyl-tin in fish and sediment samples is proposed. The samples are digested with hydrochloric acid and the butyltin compounds are extracted into a tropolone solution in pentane and pentylated by a Grignard reaction. The products are cleaned up by washing with a sodium hyrdoxide solution, dried over sodium sulphate, concentrated by evaporation and analysed by gas chromatography with flame photometric detection, using an interence filter at 610 nm. Problems peculiar to the fish and sediment samples are overcome by this improved clean-up procedure. The limit of detection for tributyltin in fish is 0.04 m?g g^?1 and the reproducibility at 0.06 μg g^?1, expressed as the relative standard deviation, is 6.8%. Contaminated sediment samples were found to contain the mixed methylbutyl-tin compounds Me₂BuSn⁺ and MeBu₂Sn⁺.     

Comparison of Micellar and Reversed-Phase Liquid Chromatography for Determination of Sulfamethoxazole and Trimethoprim

A simple, sensitive, and precise micellar liquid chromatographic method for simultaneous analysis of sulfamethoxazole and trimethoprim, with ultraviolet detection at 245 nm, has been developed, validated, and used for determination of the compounds in commercial pharmaceutical products. The compounds were well separated on a Hypersil ODS reversed-phase column at 35°C by use of a mobile phase consisting of 0.1M sodium dodecyl sulfate in a 2:98 (V/V) mixture of 1-butanol and pH 3.0 phosphate buffer solution at a flow rate of 1.0 mL min^?1. A comparative study of the performance of reversed-phase liquid chromatography with aqueous-organic or micellar-organic mobile phases for separation of sulfamethoxazole and trimethoprim is reported. The study showed that micellar liquid chromatography (MLC) and reversed-phase liquid chromatography (RP HPLC) are of similar efficiency, sensitivity, and selectivity for determination of sulfamethoxazole and trimethoprim.     

Poly(1-allylimidazole)-grafted silica,a new specific stationary phase for reversed-phase and anion-exchange liquid chromatography

A new specific stationary phase based on poly(1-allylimidazole)-grafted silica has been synthesized and characterized, by infrared spectra, elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. The results of test showed that poly(1-allylimidazole) can effectively mask the residual silanol groups and reduce the adverse effect of residual silanol. Using this stationary phase, phenol compounds, aniline compounds, and polycyclic aromatic hydrocarbons were successfully separated with symmetric peak shapes in the reversed-phase chromatography. Inorganic anions (IO₃⁻, BrO₃⁻, Br⁻, NO₃⁻, I⁻, SCN⁻) were also separated completely in the anion-exchange chromatography using sodium chloride solution as the mobile phase. The effects of pH and the concentration of eluent on the separation of inorganic anions were studied. The separation mechanism appears to involve the mixed interactions of hydrogen bonding, hydrophobic, π–π, electrostatic, and anion-exchange interactions.     

Radiation stability of methionine-35S and selenomethionine-75Se

The radiation stability of methionine-³⁵S and selenomethionine⁷⁵Se was investigated using the methods of thin-layer chromatography, gas chromatography and ESR. Radiation decomposition of methionine-³⁵S mainly consists in an oxidation process and in the release of volatile products. The ESR-spectra of irradiated DL-methionine indicated a strong localization of the unpaired electrons on sulfur atoms. Radiation damage to selenomethionine-⁷⁵Se as a function of radiation dose proved an increased stability of this compound, and its radiation decomposition consists in the formation of oxidized products and by direct rupture of the selenium bonds accompanied by the formation of volatile compounds like CH₃SeH and SeH₂. The self-radiolysis of the aqueous solution of selenomethionine-⁷⁵Se during its storage in air leads, however, to a lower decomposition rate which consists in the release of inorganic selenium and in an oxidation process.     

A simplified procedure for the determination of butyltin species in water

A method is described for the analysis of solutions containing inorganic tin and butyltin compounds. It can be used to determine total tin at a concentration of 20 ng dm^?3 using a 5 dm³ sample. The method is based on solvent extraction with dichloromethane containing tropolone and determination of the tin as inorganic tin by atomic absorption spectroscopy using electrothermal atomization. The extracted butyltin compounds can be separated by paper chromatography and the tin content of the individual spot determined as above. Observations on the stability of butyltin compounds in water at the ～2 mg dm^?3 (Sn) are included.     

Buffered Silicagel Systems - An Alternative Method for the Separation of Polar Compounds

Abstract

The adsorption chromatography of polar compounds on normal silicagel gives very often strongly tailing peaks and, therefore, poor resolution. By coating the surface of the silicagel with a buffer salt, the tailing disappears and all the advantages of adsorption chromatography can be used. On buffered silicagel, nonionic compounds behave in the same way as on the untreated adsorbent. In this paper we describe the influence of type, pH and concentration of the buffer solution used to modify the silicagel on the performance of the separation system. The changes in separation selectivity and various applications are shown.     

Preconcentration and separation of some organic water pollutants with polyurethane foam and activated carbon

Summary Although pesticides and phenols, cause reproductive failure in many areas of the world, there is a no effective means of treating waste water containing these compounds. This work deals with the adsorption of insecticides and phenols from aqueous solution by untreated porous polyurethane foam and activated carbon. Static experiments showed that in comparison with activated carbon a reasonable percentage of the compounds was adsorbed by the foam. Attempts were therefore made to extract these species from aqueous solution by foam column chromatography.The results showed that the adsorption of the compounds was brought about by a mechanism similar to that of solvent extraction. The effect of various experimental conditions such as temperature, extracting medium, pH, contact time, volume of sample flow rate, compound concentration, and eluting solvents on the retention and separation of the compounds has been determined. The height equivalent to a theoretical plate (HETP) was calculated from breakthrough capacity curves and from chromatograms obtained from polyurethane foam columns for the insecticide Dyfonate; values were in the range 2.1–2.3 mm at 10–15 ml min^–1. Extraction of the compounds from natural water, and subsequent recovery, were both found to be complete. The high capacity of polyurethane provides advantages over activated carbon; in particular, large sample volumes can be analyzed at high flow rates.     

Modeling of chromatographic retention of the selected antiarrhythmics and structurally related compounds in the hydrophilic interactions under the TLC and HPLC conditions

Abstract

High-performance liquid chromatography (HPLC) plays an important role in testing the pharmaceutically active compounds. In despite of the advantages of HPLC, thin-layer chromatography (TLC) retains its applicability to the different experimental tasks. The experimental conditions which allow hydrophilic interactions in the chromatographic system were tested in the HPLC and TLC systems for ivabradine, its related compounds, diltiazem and verapamil. Under the TLC conditions, retention behavior of the investigated compounds was tested on silica gel modified with cyanopropyl ligands as stationary phase and acetonitrile?+?methanol containing 25% v/v formic acid. Under the HPLC conditions, we used silica gel modified with cyanopropyl ligands as a column packing and the acetonitrile + 0.25% aqueous solution of formic acid as mobile phase. Retention behavior of the investigated analytes depending on the changing volume fractions of the mobile phase modifier was characterized both for TLC and HPLC data sets by the Soczewiński–Wachtmeister equation. Linear relationships were established between the retention coefficients characterizing the retention mechanism (R_M⁰/m, logk₀/m) and molecular properties of the investigated compounds. The Quantitative Structure Retention Relationship (QSRR) modeling was performed with the use of the stepwise multiple linear regression, in order to select molecular properties which influence retention.     

Chemical and enzymatic stability of the oleanoyl oxime ibuprofenate

The stress tests as well as photostability analysis in solutions and the solid phase of the oleanoyl oxime ibuprofenate (Ibu-OxOA) were determined according the International Conference on Harmonization guidelines. For observation of the degradation of tested compounds, the reversed phase high-performance liquid chromatography (RP-HPLC) method was used. The study included the effect of temperature, water, H⁺ and OH⁻ ions, hydrogen peroxide, and light (6.0 × 10⁶, 1.2 × 10⁶ lux·h) on the stability of the tested hybrid. Studies have shown that these compounds are not stable in a neutral, acidic, or oxidizing medium; very unstable in an alkaline medium; and photostable in a solution and photostable in the solid phase. Studies on the enzymatic stability of the tested hybrid showed that it is not susceptible to degradation in the presence of plasma enzymes as well as in the presence of esterase (37°C, 80% human plasma). The degradation of this compound was observed in the presence of lipase (from Candida antarctica), and the linear dependence of the determined kinetic parameters of the reaction on the enzyme activity was demonstrated.     

Preparation of99mTc complexes with compounds structurally related to (4r)-1,3-thiazolidine-4-carboxylic acid

The preparation of^99mTc-Sn-complexes with derivatives of (4R)-1,3-thiazolidine-4-carboxylic acid is described. The labeling efficiency of all labeled compounds was checked by paper chromatography, thin layer chromatography and paper electrophoresis. Preliminary results of the biodistribution studies performed in mice are given. The proposed structure of the^99mTc-labled monocomplexes is also discussed.     

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.     

Fluorimetric determination of α-keto acids with 4,5-dimethoxy-1,2-diaminobenzene and its application to high-performance liquid chromatography

A highly sensitive fluorimetric method for the determination of α-keto acids of biological importance is described. The α-keto acids react in dilute hydrochloric acid with 4,5-dimethoxy-1,2-diaminobenzene to give a compound which fluoresces in neutral solution. The method is selective for α-keto acids and the limits of detection are 30–750 pmol ml^?1 of test solution. The fluorescent compounds in a reaction mixture of ten α-keto acids are separated within 18 min by high-performance liquid chromatography on a reversed-phase column with isocratic elution. The limits of detection for the acids are in the range 9–780 fmol in a 10-μl injection volume.     

Combination of H nuclear magnetic resonance spectroscopy and mass spectrometry as tools for investigation of the thermolytic and solvolytic effects: Case of carbamates analysis

The carbamate pesticides are a well known thermo-sensible compound class. Under unfavourable conditions, these compounds are highly prone to degradation via fragmentation and/or rearrangement mechanisms. Their transformation processes are observed in consequence of two factors: structure with fragile bonds on the one hand and a stressing environment on the other hand leading to a difficult direct gas chromatography (GC) analysis, i.e. without derivatisation. In this paper, we investigated an original methodology based on the complementarity of analysis by proton nuclear magnetic resonance spectroscopy (¹H NMR) and those provided by GC hyphenated with ion-trap mass selective detection (GC–ITMS) to investigate combined effects of temperature and solvent nature affecting the behaviour of 16 carbamates. Among tested solvents, toluene and acetonitrile with 0.1% acetic acid were considered as the best solvents for storage and GC analysis respectively. Carbaryl, chlorpropham, carbofuran and N-sulfenylated compounds began to be thermodegraded with a loss equal to 1–5% even at 50 °C. An on-column injection validated as providing no degradation was used to analyse the identical solution that in ¹H NMR and it was emphasised that results of the measured degradation rates were identical at ±2%. It was highlighted that this methodology was extensible to study mechanisms and parameters with other (bio)molecules.     

气体组分的离子色谱分析检测技术

传统的离子色谱主要应用于水溶液中的阴、阳离子和极性化合物。随着离子色谱应用范围的扩大,通过合适的样品制备,将非水溶液的样品转化为水溶液,包括有机溶剂、固体样品和气态样品,特别是随着我们对大气环境、气体纯度以及呼出气体中气态样品的组成等方面的重视,越来越多的气体和气态样品,特别是离子态和极性化合物,可通过合适的样品制备、采集转化为水溶液,通过离子色谱技术进行分析。综述了气体组分的离子色谱检测技术,总结了气体样品、气溶胶以及液态样品中气体物质的制备和采集方法,运用离子色谱技术对上述样品进行测定,并对该技术运用过程中存在的问题及发展前景进行了展望。     

Fast liquid chromatography/multiple‐stage mass spectrometry of coccidiostats

Drugs that are used as medicines and also as growth promoters in veterinary care are considered as emerging environmental contaminants and in recent years concern about their potential risk to ecosystems and human health has risen. In this paper we used a method based on liquid chromatography/electrospray tandem mass spectrometry to analyze eight coccidiostatic compounds: diclazuril, dinitrocarbanilide (the main metabolite of nicarbazin), robenidine, lasalocid, monensin, salinomycin, maduramicin and nasarin. Multiple‐stage mass spectrometry (MSⁿ) based on the precursor ions [M+Na]⁺ (polyether ionophores), [M+H]⁺ (robenidine) and [M–H]^? (diclazuril and dinitrocarbanilide) was used to study the fragmentation of these compounds. MSⁿ data and genealogical relationships were used to propose a tentative assignment of the different fragment ions. Loss of water, decarboxylations, ketone β‐cleavages and rearrangement of cyclic ethers and amide groups were some of the fragmentations observed for these compounds. Liquid chromatography with a sub‐2 µm particle size column was coupled to tandem mass spectrometry (LC/MS/MS) allowing the separation of these compounds in less than 7 min. Method detection limits ranging from 11 to 71 ng L^?1 and run‐to‐run values in terms of relative standard deviation (RSD) (up to 12%) were obtained. Copyright © 2009 John Wiley & Sons, Ltd.     

Development and validation of new methods for the determination of melatonin and its oxidative metabolites by high performance liquid chromatography and capillary electrophoresis,using multivariate optimization

Melatonin (N-acetyl-5-metoxytriptamine, MEL) has focused a lot of attention as consequence of its multiple functions. MEL is a potent endogenous antioxidant and a free radical scavenger that reacts with several sort of radicals generating various metabolites. Two of them are N1-acetyl-N2-formyl-5-methoxykynurenine (AFMK) and N1-acetyl-5-methoxykynurenine (AMK). These compounds are important because they have also antioxidant actions as well as other important biological properties. In the present work, we develop two methods to detect and quantify these compounds (MEL, AFMK and AMK) in the same sample. For this purpose we used an experimental design, and utilized high performance liquid chromatography (HPLC-DAD) and micellar electrokinetic chromatography (MEKC) techniques with diode array detector in both of them. The limit of detection/quantification for MEL, AFMK and AMK were respectively 44/94, 18/38 and 23/51 ng mL⁻¹ by using HPLC and 13/44, 37/124 and 47/156 ng mL⁻¹ by using MEKC. This is the first time that these compounds have been separated in the same chromatogram or electroferogram. The time of analysis was faster using MEKC. Furthermore, this technique showed better resolution but HPLC offered better limit of detection and quantification for metabolites. Both methods were validated and correlation coefficients were higher than 0.999 and the range of recovery of those methods were 99.6–103.7%. Precision was evaluated as repeatability and intermediate precision with relative standard derivation <5%. When a 5 μg mL⁻¹ solution of these compounds were analyzed with both methods we do not observed any statistically significance differences. Moreover, we analyzed 3COHM (cyclic-3-hydroximelatonin), another known metabolite of melatonin, by using the same methods. The employment of these methods will offer a useful tool to contribute to answer the role of MEL, AFMK and AMK in biological system and both methods can be used in routine analysis for these compounds.     

Radioanalytical quality control of11C,18F and123I-labelled compounds and radiopharmaceuticals

Radiochemical quality control using high performance high pressure liquid chromatography and, to some extent, gas chromatography is described for a variety of carrier-free¹¹C-,¹⁸F-and¹²³I-labelled compounds and radiopharmaceuticals. The particular problems associated with the handling of carrier-free compounds labelled with short-lived radionuclides are outlined, and chromatographic data are given for the separation and purification of such products.