Anion analysis in uranium ore concentrates by ion chromatography

In the present exploratory study, the applicability of anionic impurities for attributing nuclear material to a certain chemical process or origin has been investigated. Anions (e.g., nitrate, sulphate, fluoride, chloride) originate from acids or salt solutions that are used for processing of solutions containing uranium or plutonium. The study focuses on uranium ore concentrates (“yellow cakes”) originating from different mines. Uranium is mined from different types of ore body and depending on the type of rock, different chemical processes for leaching, dissolving and precipitating the uranium need to be applied. Consequently, the anionic patterns observed in the products of these processes (the “ore concentrates”) are different. The concentrations of different anionic species were measured by ion chromatography using conductivity detection. The results show clear differences of anion concentrations and patterns between samples from different uranium mines. Besides this, differences between sampling campaigns in a same mine were also observed indicating that the uranium ore is not homogeneous in a mine. These within-mine variations, however, were smaller than the between-mine variations.     

Chromatographic method for the isolation of active 40S and 60S subunits from rat liver polyribosomes

A rapid and simple procedure for isolation of 40S and 60S ribosomal subunits by ion-exchange column chromatography is described. The dissociated ribosomes can be separated and non-ribosomal proteins and low-molecular-weight substances removed. An assessment by physicochemical and functional criteria showed that the ribosomal subunits obtained are active and sufficiently homogeneous.     

THE EFFECT OF DIFFERENTIATION ON PHOTOSENSITIZER UPTAKE BY HL60 CELLS

The capability of human promyelocytic leukemia cells HL60 to be induced to differentiate to various stages along the monocytic or myelocytic pathway was exploited for investigation of the uptake of selected photo-sensitizers by diverse types of cells of the same origin. The results showed that there was no substantial difference in photofrin uptake between noninduced HL60 cells, immature monocytes, immature neutrophils and cells differentiated along the eosinophilic pathway. In contrast, HL60 cells differentiated into macrophages (HL609) exhibited markedly increased photofrin uptake, which was further enhanced by their pretreatment with bacterial lipopolysaccharide. Similar results were obtained with other photosensitizers tested: di-and tetrasulfonated aluminum phthalocyanines (AIPcS₂ and AIPcS₄), tetrasulfonated zinc phthalocyanine (ZnPcS₄), tetraphenylporphine tetrasulfonate (TPPS₄) and benzoporphyrin derivative monoacid (BPD). Despite marked differences in the state of self-aggregation and other chemical properties of these compounds, the degree of their preferential uptake by HL60 PH cells showed very little variation. In a typical experiment, the uptake of these photosensitizers by HL60 PH cells was four to five times higher than the uptake by noninduced HL60 cells. In addition to the fluorometric assay employed in most of the experiments, cellular concentration of AlPcS₄ was determined by measurement of elementary aluminum using atomic absorption spectroscopy.     

Complex formation between dodecylpyridinium chloride and multicharged anionic planar substances

The complex formation between dodecylpyridinium chloride (DPC) and multicharged anionic planar substances, 14 azo dyes and 3 benzene- or naphthalenesulfonates, has been studied by the potentiometric titration using a surfactant selective electrode. The agreement between the observed maximum binding number and the number of anionic charges (n) on dye molecules showed n:1 complex formation. The binding isotherms were found to be composed of two types of binding; one is the noncooperative binding observed at low surfactant concentrations and the other is the cooperative binding at the higher concentrations. The microscopic binding constant for the noncooperative binding was found to take the values in the range of 50-200 mol(-)(1) dm(3) for many of the substances, but, takes more large values up to 2500 mol(-)(1) dm(3) for the substances which have a large hydrophobic part or the structure of separate hydrophobic and hydrophilic regions. A multiple regression analysis showed that the data of the corresponding standard free energy change of binding were well interpreted by the equation (in unit of kJ mol(-)(1)) DeltaG degrees = - 5.85 log P(S) - 1.68 log P(D) - 2.12z + 28.4, where P(S) and P(D) are the partition coefficients of the surfactants and planar substances in the 1-octanol/water system and z is the number of anionic charges on the planar molecules. At the beginning of the cooperative binding, precipitate formation was observed for almost all of the present systems. Among these, some of the dyes having the structure of separate hydrophobic and hydrophilic regions formed a needlelike crystal, which was accompanied by a hysteresis phenomenon in the binding isotherm. The stable complex formation by both the hydrophobic and electrostatic interactions between the surfactant and the planar substances was found to be important for the crystal formation. Depending on the manner of arrangement of the charged groups on the planar substances, the origin of the binding cooperativity was ascribed to the interactions between surfactants bound to one planar-substance molecule or to the association of the complexes. It was also found that the present small binding systems are useful as the model of ligand binding to protein local structures.     

Measurement of Phenols in Automobile Exhaust

Abstract

Methods were investigated to measure exhaust emission rates of individual low-molecular-weight phenols from gasoline and diesel vehicles driven on a chassis dynamometer using the FTP driving cycle. An extraction procedure to isolate the phenols from exhaust scrubs was evaluated. Separation of individual phenols was done by gas chromatography, with detection by a flame ionization detector. Phenol identifications were confirmed by mass spectroscopy. Results of a limited survey of gasoline and diesel vehicles are reported.     

Catalysis of slow charge transfer reactions at polypyrrole-coated glassy carbon electrodes

Oxidation of ascorbic acid, dihydroxyphenylacetic acid and dopamine are compared at polypyrrole-coated glassy carbon and naked glassy carbon electrodes. These currents are mass-transport limited and not limited by permeation into or through the polypyrrole film. Ascorbic acid oxidation occurs at potentials 300 mV more negative at polypyrrole-coated electrodes and the rising slope of rotated disk voltammograms changes by over 100 mV. A similar enhancement in electrochemical reversibility is observed for dihydroxyphenylacetic acid, whereas dopamine is oxidized at slightly more positive potentials at polypyrrole-coated electrodes. Comparing the electrochemistry of dopamine and dihydroxyphenyl-acetic acid, it appears that the electrochemical reversibility differences for these substances are to some degree result of electrostatic interactions between the anionic solutes, or anionic reaction intermediates, and anionic functional groups on carbon or cationic fixed sites in oxidized polypyrrole.     

Reactions of 2-(arylazo) aniline with RhCl3: synthesis and structure of new cyclometalated complexes of Rh(III) and recognition of RhCl3 assisted azo (-N=N-) cleavage

The reactions of 2-(arylazo) anilines, HL (1) [where HL is 2-(ArN=N)C6H4NH2; Ar is C6H5 (for HL1, 1a) and p-MeC6H4 (for HL2, 1b); H of HL represents the proton of Ar which gets dissociated upon orthometalation] with RhCl3 in methanol afforded new orthometalated complexes of composition (L)(HL)Rh(III)Cl2 (2) and (L)(ArNH2)Rh(III)Cl2 (3). The anionic L- binds the metal in tridentate (C, N, N) manner in both the complexes, while HL and ArNH2 bind the metal of 2 and 3 in monodentate fashion through the amino nitrogen. The ArNH2 of 3 was formed in situ due to cleavage of azo (-N=N-) function of monodentate HL of 2. The scission of N=N has been authenticated.     

Synthesis and Physicochemical Properties of Some Transition Metal Complexes with 3-Hydroxypyridine

The complexes ML₂ · 2H₂O and CrL₃ · 8H₂O were synthesized by the reaction of Cu(II), Ni(II), Co(II), Cd(II), and Cr(III) nitrates with 3-hydroxypyridine (HL) and identified. The spectroscopic characteristics of neutral, anionic, and cationic forms of the ligand were determined. It was shown that 3-hydroxypyridine enters the complex as an anion to give polymeric chains due to the ligand coordination through the N and O atoms. Complexation of copper, cobalt, and chromium nitrates with 3-hydroxypyridine in ethanol solutions was studied, and the formation constant of the copper complex was calculated. It was found that Cu(II) and Cr(III) complexes are formed in the solid state and in solutions (M : L = 1 : 2 and 1 : 3, respectively; in the case of Cu(II), the M : L ratio is 1 : 3).     

Stability of anionic liposome-cationic polymer complexes in water-salt media

Laser microelectrophoresis, dynamic light scattering, and fluorescence and UV spectroscopy are employed to study poly-N-ethyl-4-vinylpyridinium bromide adsorption on the surface of bilayer lipid vesicles (liposomes) formed from mixtures of anionic phosphatidyl serine and electroneutral phosphatidylcholine. It is established that polycation adsorption is accompanied by the neutralization of charges on liposomes and their aggregation. The subsequent addition of a low-molecular-weight salt (NaCl) solution to suspensions of complexes causes them to dissociate into their initial components, while the stability of the complexes with respect to the salt action increases with the fraction of the anionic lipid in the liposome membranes. The data obtained are interpreted from the position of the formation-disintegration of a molecular capacitor, the charge of which is generated by spatially separated anionic lipids located in the bilayer membrane and cationic units of the adsorbed polyamine.     

Complexes of 2,3-Dihydroxypyridine with Bivalent Metals. Crystal Structure of 2,3-Dihydroxypyridine

Crystal structure of 2,3-dihydroxypyridine (H₂L) is determined. Mn(HL)Cl · H₂O, Co(HL)Cl · 2H₂O, Cu(HL)Cl, Ni(HL)OH · H₂O, and Zn(HL)OH · H₂O complexes are synthesized by reacting Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) chlorides with H₂L in ethanol solutions and identified. In these complexes, 2,3-dihydroxypyridine is involved in coordination as a monoanion. Spectral parameters of neutral and anionic forms of a ligand are determined and the acidity and complex formation constants are calculated. The compositions of complexes are established.     

Dissolution of kaolinite induced by citric, oxalic, and malic acids

Kaolinite is a dominant clay mineral in the soils in tropical and subtropical regions, and its dissolution has an influence on a variety of soil properties. In this work, kaolinite dissolution induced by three kinds of low-molecular-weight organic acid, i.e., citric, oxalic, and malic acids, was evaluated under far-from-equilibrium conditions. The rates of kaolinite dissolution depended on the kind and concentration of organic acids, with the sequence R(oxalate)>R(citrate)>R(malate). Chemical calculation showed the change in concentration of organic ligand relative to change in concentration of organic acid in suspensions of kaolinite and organic acid. The effect of organic acid on kaolinite dissolution was modeled by species of organic anionic ligand. For oxalic acid, L(2-)(oxalic) and HL(-)(oxalic) jointly enhanced the dissolution of kaolinite, but for malic and citric acids, HL(-)(malic) and H2L-(citric) made a higher contribution to the total dissolution rate of kaolinite than L(2-)(malic) and L(3-)(citric), respectively. For oxalic acid, the proposed model was R(Si)=1.89x10(-12)x[(25x)/(1+25x)]+1.93x10(-12)x[(1990x1)/(1+1990x1)] (R2=0.9763), where x and x1 denote the concentrations of HL(oxalic) and L(oxalic), respectively, and x1=10(-3.81)xx/[H+]. For malic acid, the model was R(Si)=4.79x10(-12)x[(328x)/(1+328x)]+1.67x10(-13)x[(1149x1)/(1+1149x1)] (R2=0.9452), where x and x1 denote the concentrations of HL(malic) and L(malic), respectively, and x1=10(-5.11)xx/[H+], and for citric acid, the model was R(Si)=4.73x10(-12)x[(845x)/(1+845x)]+4.68x10(-12)x[(2855x1)/(1+2855x1)] (R2=0.9682), where x and x1 denote the concentrations of H2L(citric) and L(citric), respectively, and [Formula: see text] .     

Perylene Nanoparticles Prepared by Reprecipitation Method

Perylene nanoparticles with different sizes were prepared by reprecipitation method.It is found that the nanoparticles show size-dependent optical property.Electron diffraction patterns indicate that all the nanoparticles of different sizes are in crystalline state.The rapid growth of the nanoparticles during the aging process could be slowed down effectively by the addition of cationic or anionic surfactants.     

Flocculation of anionic surfactant micelles in the presence of hydrocarbons

Adsorptive micellar flocculation (AMF) is a surfactant-based separation process based on the flocculation of micelles of suitable anionic surfactants by Al³⁺. The micelles form large amorphous flocs which can be removed by filtration, which is attractive because soluble pollutants are captured by the floc, thus providing a simple separation method. As the primary aim of AMF is the removal of anionic pollutants from aqueous streams, it is important to investigate the influence of the various substances which may affect it. This article discusses the influence of the presence of insoluble hydrocarbons on the flocculation of micelles of the anionic surfactant dodecyl sulfate by Al³⁺. The ratio between surfactant remaining in solution and total surfactant and the ratio between Al³⁺ and surfactant in the flocculate are determined in systems composed of an aqueous solution containing a constant dodecyl sulfate concentration of 0.05 M and a variable Al³⁺ concentration and an organic phase (decane) with phase volume ratios of decane/water ranging from 0 (no decane) to 0.15. The flocculation is only slightly affected by the presence of decane for decane/solution ratios below 0.05, while the effect (lower flocculated fraction) is more marked above this ratio. Received: 25 October 1999/Accepted: 7 February 2000     

A computational strategy for metabolic network construction based on the overlapping ratio: Study of patients’ metabolic responses to different dialysis patterns

BackgroundUremia is a worldwide epidemic disease and poses a serious threat to human health. Both maintenance hemodialysis (HD) and maintenance high flux hemodialysis (HFD) are common treatments for uremia and are generally used in clinical applications. In-depth exploration of patients’ metabolic responses to different dialysis patterns can facilitate the understanding of pathological alterations associated with uremia and the effects of different dialysis methods on uremia, which may be used for future personalized therapy. However, due to variations of multiple factors (i.e., genetic, epigenetic and environment) in the process of disease treatments, identification of the similarities and differences in plasma metabolite changes in uremic patients in response to HD and HFD remains challenging.MethodsIn this study, a computational strategy for metabolic network construction based on the overlapping ratio (MNC-OR) was proposed for disease treatment effect research. In MNC-OR, the overlapping ratio was introduced to measure metabolic reactions and to construct metabolic networks for analysis of different treatment options. Then, MNC-OR was employed to analyze HD-pattern-dependent changes in plasma metabolites to explore the pathological alterations associated with uremia and the effectiveness of different dialysis patterns (i.e., HD and HFD) on uremia. Based on the networks constructed by MNC-OR, two network analysis techniques, namely, similarity analysis and difference analysis of network topology, were used to find the similarity and differences in metabolic signals in patients under treatment with either HD or HFD, which can facilitate the understanding of pathological alterations associated with uremia and provide the guidance for personalized dialysis therapy.ResultsSimilarity analysis of network topology suggested that abnormal energy metabolism, gut metabolism and pyrimidine metabolism might occur in uremic patients, and maintenance of both HFD and HD therapies have beneficial effects on uremia. Then, difference analysis of network topology was employed to extract the crucial information related to HD-pattern-dependent changes in plasma metabolites. Experimental results indicated that the amino acid metabolism was closer to the normal status in HFD-treated patients; however, in HD-treated patients, the ability of antioxidation showed greater reduction, and the protein O-GlcNAcylation level was higher. Our findings demonstrate the potential of MNC-OR for explaining the metabolic similarities and differences of patients in response to different dialysis methods, thereby contributing to the guidance of personalized dialysis therapy.     

Synthesis and crystal structure of Cu(I) and Ni(II) complexes of 1,1-diethyl-3-(4-fluorobenzoyl)-thiourea

The reaction of 1,1-diethyl-3-(4-fluorobenzoyl)-thiourea (HL) with CuCl₂ ·?2H₂O and NiCl₂ ·?6H₂O give two complexes, Cu(HL)₃Cl (1) and NiL₂ (2). The crystal structures of these products were determined by single crystal X-ray diffraction. In 1, three HL molecules are unidentate, coordinating through the sulfur, and the copper is tetrahedral with three S and one Cl. In 2, two HL molecules are O and S donor bidentate and coordinate as anionic species with loss of the proton from the acyl-substituted nitrogen; the nickel is square-planar.     

Separation methods in the chemistry of humic substances

Separation methods are widely used to isolate humic substances (HSs), to fractionate them before further investigation, and to obtain information about their structure and properties. Among the chromatographic methods, techniques based on a size-exclusion effect appear to be most useful, as they allow us to relate elution data to the molecular mass distribution of HSs. The limitations of this approach are discussed in this review. Gas chromatography with mass spectrometric detection is typically used to identify the products of pyrolysis or thermochemolysis of HSs; this technique is considered most important in the structural investigation of HSs. Electrophoretic methods (especially capillary zone electrophoresis) provide detailed characterization of HSs, but it is very difficult to relate the electrophoretic data to any specific subfraction, structure or properties of HSs. The electrophoretic patterns are often called "fingerprints" and can potentially be used for the identification and classification of HSs. This is limited, however, by the great diversity of the procedures employed and by the low degree of harmonization--no data on reproducibility and between-laboratory comparability are available. The same holds true, to a certain degree, for most methods utilized for the characterization of HSs. Separation methods play an important role in the examination of the interactions of HSs with heavy metals and other chemical pollutants. They allow us to determine binding constants and other data necessary to predict the mobility of chemical pollutants in the environment.     

Reduction of a Tetrafluoroterephthalonitrile‐β‐Cyclodextrin Polymer to Remove Anionic Micropollutants and Perfluorinated Alkyl Substances from Water

Organic micropollutants (MPs) are anthropogenic substances that contaminate water resources at trace concentrations. Many MPs, including per‐ and polyfluorinated alkyl substances (PFASs), have come under increased scrutiny because of their environmental persistence and association with various health problems. A β‐cyclodextrin polymer linked with tetrafluoroterephthalonitrile (TFN‐CDP) has high affinity for cationic and many neutral MPs from contaminated water because of anionic groups incorporated during the polymerization. But TFN‐CDP does not bind many anionic MPs strongly, including anionic PFASs. To address this shortcoming, we reduced the nitrile groups in TFN‐CDP to primary amines, which reverses its affinity towards charged MPs. TFN‐CDP exhibits adsorption distribution coefficients (log K_D values) of 2–3 for cationic MPs and ?0.5–1.5 for anionic MPs, whereas the reduced TFN‐CDP exhibits log K_D values of ?0.5–1.5 for cationic MPs and 2–4 for anionic MPs, with especially high affinity towards anionic PFASs. Kinetic studies of the removal of 10 anionic PFASs at environmentally relevant concentrations showed 80–98 % removal of all contaminants after 30 min and was superior to commercial granular activated carbon. These findings demonstrate the scope and tunability of CD‐based adsorbents derived from a single polymerization and the promise of novel adsorbents constructed from molecular receptors.     

The effect of froth stability and wettability on the flotation of a xerographic toner

The Separation of ink and pulp fibers in recycled paper is primarily achieved by flotation methods. Xerographic toners from photocopiers and laser printers are known to cause problems in flotation deinking. Wettability and froth stability are two important factors which determine the floatability of xerographic toners. The floatability is investigated for a selected toner using a cationic, a nonionic, and an anionic surfactant. At low surfactant concentrations the froth is too unstable to support flotation, whereas at high surfactant concentrations the toner is rendered hydrophilic by adsorbed surfactant molecules and does not stick to air bubbles. Consequently, a maximum in flotation response is found at an intermediate surfactant concentration near the critical micelle concentration. Cationic, nonionic, and anionic surfactants all adsorb with their hydrocarbon tails on the toner surface. By choosing appropriate froth-stabilizing additives it is possible to enhance the flotation performance.     

Atomic sublattices: Problems of indexing powder patterns, structural model determination

The second basic theorem of lattice crystallography (by N. V. Belov) underlies the theory of atomic sublattices characteristic of the overwhelming majority of crystal structures we have studied. By the example of structures of particular inorganic compounds (involving mercury chalcohalides) it is illustrated that a priory knowledge of cationic and anionic sublattices typical of a given class of compounds may provide useful information for analyzing powder diffraction patterns of substances with unknown crystal structures. It has been shown that complicated structures can be analyzed “in parts” by identifying their individual components discernable in powder diffraction patterns.     

Induction of apoptosis in human promyelocytic leukemia HL60 cells by panaxynol and panaxydol

Panaxynol and panaxydol are naturally occurring polyacetylenes, isolated from the lipophilic fractions of Panax notoginseng, that exert anti-proliferative effects against malignant cells. However, to the best of our knowledge, no study concerning the inhibitory effects of the two polyacetylenes on cell growth of human promyelocytic leukemia cells has been reported. In this paper, we examined the antiproliferation and proapoptotic effects of panaxynol and panaxydol on HL60 cells and investigated their mechanism of action. Cell growth inhibition of panaxynol and panaxydol were determined by trypan blue dye exclusion assays. Apoptosis of cells was revealed by morphological observation, analysis for nuclear DNA distribution and by annexin V-FITC/ PI staining using flow cytometry. It was found that panaxynol and panaxydol markedly inhibited proliferation of HL60 cells in a time- and dose-dependent manner via an apoptotic pathway. In concern with these ?ndings, Western blot analysis showed proteolytic activation of PKCδ, caspase-3 activation and cleavage of poly (ADP [adenosine diphosphate]-ribose) polymerase in HL60 cells treated by panaxynol and panaxydol. In conclusion, panaxynol and panaxydol have profound effects on growth and apoptosis of HL60 cells, suggesting those substances are worthy of further exploration as potential anti-cancer agents.