State and tendency of developing physical-chemical methods for making actinide microspherical particles

To obtain actinides oxides as microspheres, the internal gelation method is suggested. As a dispersive medium, we propose to use hydrocarbons containing fluorine and having a density of 2000 kg/m³. These substances are chemically inert, fire-proof, non-toxic and resistant to -radiolysis. Using a fluorohydrocarbon-containing liquid creates in the gelation column a vertical temperature gradient with minimal temperature in the zone of working solution dispersion and maximal one in the upper part of the column. This article treats the mechanism and model of a drop-forming process to control the process of microspheres formation, in which a working solution is dispersed in a dispersive medium.     

Determination of hydroperoxides in liposomes by the modified IDF and the modified tiron methods

Two new methods, the modified International Dairy Federation and the modified Tiron methods, were developed for the determination of hydroperoxides in liposomes. Interferences of alpha-tocoferol and egg-phosphatidylcholine (EPC) required a solid-phase extraction before the analysis to eliminate alpha-tocoferol and a fluid-fluid extraction based on the solvent triangle of Bligh and Dyer to separate EPC. The developed color, using thiocyanate and Tiron, respectively, as complex-formers for the generated ferri-ions, was measured spectrophotometrically. Both techniques showed good reproducibility and high sensitivity. Peroxide contents of 0.04 and 0.07% (g/g) in EPC samples were easily determined.     

Comparison of methods for characterizing microporous membranes for plasma separation

To design membranes suitable for therapeutic use, the relationship between membrane structure and permeability needs to be studied. In this work, the solute permeability of small tubular membranes for plasma separation was determined by using radioisotope-labeled solutes. Through analysis of data on solute and pure water permeability and on water content, by means of a tortuous pore model that we have proposed, we can obtain pore diameter, surface porosity and tortuosity. Membrane structure was also analyzed by mercury intrusion and scanning electron microscopy, and the results were compared with each other. The mercury intrusion method is unsuitable for the structural analysis of polymer membranes because of the damage and/or expansion resulting from highly elevated pressure. The tortuous pore model is recommended for the elucidation of membrane structure.     

Investigation of mechanochemically modified kaolinite surfaces by thermoanalytical and spectroscopic methods

The effect of mechanochemical activation (dry grinding), formamide intercalation, and thermal deintercalation on high- and low-defect kaolinite surfaces was studied by thermogravimetry and diffuse reflectance Fourier transform infrared spectroscopy. These investigations were completed with specific surface area and pore size distribution measurements. The surface acidity of the ground and the ground-and-intercalated kaolinites was probed with ammonia adsorption. The surface area and the pore volume as well as the amount of adsorbed ammonia increased with the rate of mechanochemical activation. At the same time the thermally deintercalated minerals showed increased surface area but decreased pore volume with the time of grinding. Adsorbed ammonia was detected as ammonium ion in the 1400-1500 cm(-1) spectral range.     

Obtaining ultradispersed dioxidine powder modified via cryochemical synthesis and determining its antibacterial activity

One way to increase bioavailability and efficiency of drug substances is to decrease their particles up to nanoscale level and to change their crystal structure. A new stable nanoscale form of a polymorphic antibacterial 2,3-bis-(hydroxymethyl)-quinoxaline-N,N′-dioxyde (dioxidine) modification characterized with a gas chromatography, NMR, XRF, TEM, and thermoanalytic methods (TG, DTG, DSC) was obtained via cryochemical synthesis. The new polymorphic dioxidine modification was proved to be more active in growth inhibition processes of gram-positive M. cyaneum 98 and gram-negative E. coli bacterial strains than officinal modification.     

Design and evaluation of modified simplex methods

The Modified Simplex method and the Controlled Weighted Centroid method, both with minor but essential alterations, are evaluated for four test functions. An attempt to design a combination of these two methods is discussed. The tests show that the altered Modified Simplex method outperforms both other methods.     

Design and optimization of modified simplex methods

Four test functions are used to evaluate different modifications of the modified simplex method and to optimize the contraction, reflection and expansion parameters. The evaluation shows that some of the modifications and the optimization of the parameters result in a simplex method that has gained in convergence ability, with some improvement in speed.     

Silica gel modified with lumogallion for aluminum determination by spectroscopic methods

Simple, easy to use and selective method of Al(III) sorption-spectroscopic (SS) determination was proposed. For this purpose, silica modified with tridecyloctadecylammonium chloride(SGII) using adsorption technique and glass slide modified with thin silica-poly(dimethyldiallyl-ammonium chloride) (SGI) composite film obtained by sol-gel technique were worked out. It was shown that lumogallion (LG) easily absorbs on SGI and SGII. Obtained sorbents SGIII and SGIV, respectively, were used for aluminum(III) determination by diffuse reflectance and spectrophotometric methods. The ranges of determination were (mg L⁻¹): (0.08-0.54), s_r ≤ 0.13, n = 4 for SGIII and (0.05-2.0), s_r ≤ 0.11, n = 4 for SGIV. The detection limits (blank + 3σ) for aluminum were 70 and 30 μg L⁻¹ using SGIII and SGIV, respectively, where σ is the standard deviation of blank estimation. The accuracy of the developed spectrophotometric method was examined by the determination of standard addition of aluminum in alcohol-free beverages. The relative error did not exceed 9%. SGIII can be regenerated by 0.05 M EDTANa₂H₂ solution and reused. SGIV was shown to be perspective for determination of aluminum in solution in the range of 0.01-0.13 mg L⁻¹ by solid phase luminescent technique.     

Growth of void-free 3C-SiC films by modified two-step carbonization methods

Highly preferred orientation 3C-SiC films were deposited on Si (111) substrates by a modified two-step carbonization method. The crystal quality of SiC films were examined by XRD. To evaluate the effect of the introducing of silane during carbonization, cross-sectional SEM was carried out. Results indicated that the introducing of silane during carbonization is effective to prevent the out-diffusion of silicon atoms from silicon substrates. And by adjusting the carbonization conditions, void-free 3C-SiC films were obtained. XPS results demonstrated that the prepared 3C-SiC films were corresponding with the stoichiometric ratio.     

Obtaining Kinetic Parameters by Modulated Thermogravimetry

A new technique, called modulated thermogravimetry, is introduced as a tool for obtaining continuous kinetic information for decomposition and volatilization reactions. The approach makes use of an oscillatory temperature program to obtain kinetic parameters during a mass loss. MTGA™ may be used under quasi-isothermal conditions to observe a single mass loss or may be combined with linear heating rate or Hi-Res™ controlled rate thermogravimetry to scan from one mass loss region to another. Results obtained are in agreement with those obtained by other kinetic methods. This revised version was published online in July 2006 with corrections to the Cover Date.     

Obtaining reaction coordinates by likelihood maximization

We present a new approach for calculating reaction coordinates in complex systems. The new method is based on transition path sampling and likelihood maximization. It requires fewer trajectories than a single iteration of existing procedures, and it applies to both low and high friction dynamics. The new method screens a set of candidate collective variables for a good reaction coordinate that depends on a few relevant variables. The Bayesian information criterion determines whether additional variables significantly improve the reaction coordinate. Additionally, we present an advantageous transition path sampling algorithm and an algorithm to generate the most likely transition path in the space of collective variables. The method is demonstrated on two systems: a bistable model potential energy surface and nucleation in the Ising model. For the Ising model of nucleation, we quantify for the first time the role of nuclei surface area in the nucleation reaction coordinate. Surprisingly, increased surface area increases the stability of nuclei in two dimensions but decreases nuclei stability in three dimensions.     

Determination of tannins in tea by potentiometry and atomic absorption spectrometry

Summary Different alternatives for the determination of tannins in tea with Cu ionspecific electrodes and atomic absorption spectrometry are discussed. The methods are based on the precipitation of tannins with copper acetate. A screening of methods is carried out in three successive steps: determination of (1) Cu in a simple aqueous solution, (2) tannic acid in aqueous solution and (3) tannins in tea. Two procedures are proposed as suitable tools for tannin determination in tea, i.e. direct potentiometry of excess Cu²⁺ and AAS, the first being the easiest and most rapid.

---

Bestimmung von Tanninen in Tee durch Potentiometrie und Atomabsorptions-Spektrometrie

Zusammenfassung Verschiedene Möglichkeiten zur Bestimmung von Tanninen in Tee mit Hilfe einer kupferionenselektiven Elektrode sowie der AAS werden diskutiert. Die Methoden beruhen auf der Tanninfällung mit Kupferacetat. Im einzelnen wurden folgende Stufen untersucht: Kupferbestimmung in wäßriger Lösung, Gerbsäurebestimmung in wäßriger Lösung, Tanninbestimmung in Tee. Sowohl die potentiometrische Bestimmung des Kupferüberschusses bei der Fällung als auch die AAS-Bestimmung haben sich als geeignet erwiesen, wobei erstere als das einfachste und schnellste Verfahren empfohlen wird.

     

The main and modified CUPRAC methods of antioxidant measurement

The antioxidant activity/capacity levels of biological fluids and foods are measured for the diagnosis and the treatment of oxidative stress-associated diseases in clinical biochemistry, and for meaningful comparison of the antioxidant content of foods. Currently, there is no “total antioxidant” as a nutritional index available for food labeling and biological fluids due to the lack of standardized quantitative methods.The CUPRAC (CUPric Reducing Antioxidant Capacity) method of antioxidant measurement, introduced by our research group, is based on the absorbance measurement of Cu(I)-neocuproine (Nc) chelate formed as a result of the redox reaction of chain-breaking antioxidants with the CUPRAC reagent, Cu(II)-Nc, where absorbance is recorded at the maximal light-absorption wavelength of 450 nm.We introduce the main CUPRAC method and describe modifications to it in the past six years.     

Doubly excited configurations in modified CNDO and INDO methods

The effect of different CI basis sets, including doubly excited configurations, on transition energies calculated by modified CNDO and INDO methods is examined for H₂O, NH₃, CH₄, and H₂CO.     

Detection methods and performance criteria for genetically modified organisms

Detection methods for genetically modified organisms (GMOs) are necessary for many applications, from seed purity assessment to compliance of food labeling in several countries. Numerous analytical methods are currently used or under development to support these needs. The currently used methods are bioassays and protein- and DNA-based detection protocols. To avoid discrepancy of results between such largely different methods and, for instance, the potential resulting legal actions, compatibility of the methods is urgently needed. Performance criteria of methods allow evaluation against a common standard. The more-common performance criteria for detection methods are precision, accuracy, sensitivity, and specificity, which together specifically address other terms used to describe the performance of a method, such as applicability, selectivity, calibration, trueness, precision, recovery, operating range, limit of quantitation, limit of detection, and ruggedness. Performance criteria should provide objective tools to accept or reject specific methods, to validate them, to ensure compatibility between validated methods, and be used on a routine basis to reject data outside an acceptable range of variability. When selecting a method of detection, it is also important to consider its applicability, its field of applications, and its limitations, by including factors such as its ability to detect the target analyte in a given matrix, the duration of the analyses, its cost effectiveness, and the necessary sample sizes for testing. Thus, the current GMO detection methods should be evaluated against a common set of performance criteria.     

Analysis of oak tannins by liquid chromatography-electrospray ionisation mass spectrometry

Extractable tannins were analysed by liquid chromatography-electrospray ionisation mass spectrometry in two oak species, North American white oak (Quercus alba) and European red oak (Quercus robur). They mainly included various glucose gallic and ellagic acid esters. The structures were partially determined, and they included grandinin/roburin E, castalagin/vescalagin, gallic acid, valoneic acid bilactone, monogalloyl glucose, digalloyl glucose, trigalloyl glucose, ellagic acid rhamnose, quercitrin and ellagic acid.     

Characterization of oxidized tannins: comparison of depolymerization methods,asymmetric flow field-flow fractionation and small-angle X-ray scattering

Condensed tannins are a major class of plant polyphenols. They play an important part in the colour and taste of foods and beverages. Due to their chemical reactivity, tannins are not stable once extracted from plants. A number of chemical reactions can take place, leading to structural changes of the native structures to give so-called derived tannins and pigments. This paper compares results obtained on native and oxidized tannins with different techniques: depolymerization followed by high-performance liquid chromatography analysis, small-angle X-ray scattering (SAXS) and asymmetric flow field-flow fractionation (AF4). Upon oxidation, new macromolecules were formed. Thioglycolysis experiments showed no evidence of molecular weight increase, but thioglycolysis yields drastically decreased. When oxidation was performed at high concentration (e.g., 10 g L⁻¹), the weight average degree of polymerization determined from SAXS increased, whereas it remained stable when oxidation was done at low concentration (0.1 g L⁻¹), indicating that the reaction was intramolecular, yet the conformations were different. Differences in terms of solubility were observed; ethanol being a better solvent than water. We also separated soluble and non-water-soluble species of a much oxidized fraction. Thioglycolysis showed no big differences between the two fractions, whereas SAXS and AF4 showed that insoluble macromolecules have a weight average molecular weight ten times higher than the soluble ones.     

Enzymatic sulfation of polyphenols related to tannins by arylsulfotransferase.

This report discusses a novel type of arylsulfotransferase (AST) which was derived from human intestinal bacterium sulfated polyphenolic compounds when p-nitrophenyl sulfate (PNS) was taken as a donor substrate. (+)-Catechin, (+/-)-catechin, (-)-epicatechin and (-)-epicatechin gallate were better substrates than tyramine. (-)-Epigallocatechin and (-)-epigallocatechin gallate were slightly worse substrates than tyramine. Although gallic acid was a bad substrate, alkyl gallate esters were better substrates than tyramine. The degree of acceptor specificity increased in proportion to the length of the alkyl group up to the carbon number of five. Pedunculagin, geraniin and corilagin were less effective than tyramine. Rosmarinic acid and penta-O-galloyl-beta-D-glucose were similarly well sulfated. Two products, 4'-monosulfate and 4',5-disulfate of (+)-catechin, were detected at a two-fold molar excess of PNS over (+)-catechin. When (+)-catechin-4'-monosulfate as an acceptor was enzymatically sulfated with PNS as a donor, only the 4',5-disulfate was produced. Thus, arylsulfotransferase was useful for the convenient preparation of sulfate esters of polyphenols at their specific hydroxyl groups.