The investigation of P- and As diffusion in liquid Gallium

The results on the As- and P-diffusion in gallium melt are discussed. The definition method of P- and As-diffusion coefficients in liquid gallium was stated. This method was based on the analysis of concentration profile formed during the diffusion annealing with following tempering. The diffusion coefficients were measured on temperature region 1113 to 1383 K. The expression for temperature dependence of diffusion coefficients was obtained.     

Ferrocene‐modified thiopyrimidines: synthesis,enantiomeric resolution,antitumor activity

Ferrocenylalkyl thiopyrimidines ( 6a–d to 9a–d ) were prepared via the reaction of the α‐(hydroxy)alkyl ferrocenes, FcCHR(OH) ( 1a–d ; Fc = ferrocenyl; R = H, Me, Et, Ph), with 2‐thiopyrimidines ( 2 – 5 ) in acetone at room temperature in the presence of TFA, yielding 50–95%. The resulting enantiomers were resolved using HPLC on modified cellulose as chiral selector. The antitumor activities of S‐ferrocenylethyl 2‐thiopyrimidine ( 6b ) against two murine solid tumor models, carcinoma 755 (Ca755) and Lewis lung carcinoma (LLC) were evaluated in vivo. The strong antitumor effect of compound 6b on Ca755 and LLC was demonstrated. The index of tumor growth inhibition on Ca755 equaled 95% in comparison with control. Copyright © 2010 John Wiley & Sons, Ltd.     

Unusual rheological effects observed in polyacrylonitrile solutions

Unusual rheological effects have been revealed during the deformation of polyacrylonitrile (PAN) solutions in DMSO. The effects are observed during the study of rheological properties in a wide range of PAN concentrations and are explained by the structuring occurring at low polymer concentrations. At concentrations of at most 0.1%, the solutions exhibit the behavior of soft gels, which are characterized by yield stresses and frequency-independent storage moduli. As concentration is increased, both effects gradually vanish and the solutions are almost transformed into Newtonian liquids. The results have been explained by the formation of a supramolecular spatial structure at low polymer concentrations. As concentration is increased, the role of structuring is suppressed by the formation of a network of intermacromolecular entanglements. The ability of dilute PAN solutions to exist in two states, i.e., with destroyed structuring and in the form of a physical polymer gel, leads to stress self-oscillations and thixotropic effects. The addition of a precipitant (water) to the PAN-DMSO solutions leads to the formation of a gel throughout the concentration range.     

Phase equilibrium and rheology of poly(1-trimethylsilyl-1-propyne) solutions

The phase equilibrium and rheological properties of poly(1-trimethylsilyl-1-propyne) solutions obtained with tantalum catalysts are studied. For three polymers with different molecular masses, phase diagrams are determined in a number of solvents. From these diagrams, the Hansen solubility parameters of poly(1-trimethylsilyl-1-propyne) are calculated by the method proposed in this work. Dilute solutions of poly(1-trimethylsilyl-1-propyne) behave as Newtonian liquids, whereas the viscosity of viscoelastic concentrated systems decreases as the shear rate grows. The molecular and rheological characteristics of studied poly(1-trimethylsilyl-1-propyne) samples are compared with the samples prepared with NbCl₅ catalysts. Poly(1-trimethylsilyl-1-propyne) obtained with a catalytic system involving tantalum pentachloride is characterized by high intrinsic viscosity and solution viscosity compared to poly(1-trimethylsilyl-1-propyne) prepared with niobium catalyst. The difference in properties is due to the dissimilar ratios of cis and trans units in the samples.     

Effect of coagulating agent viscosity on the kinetics of formation,morphology, and transport properties of cellulose nanofiltration membranes

Low-viscous coagulating agents are tradionally used to precipitate polymers from their solutions and obtain films and fibers from them; they represent, as a rule, the combinations of solvent and nonsolvent of the polymer used. At the same time, since the structure of the precipitated polymer is formed under non-equilibrium conditions, the influence of the coagulant viscosity can be quite substantial. The influence of the viscosity of the medium on the formation of structure, morphology, and transport characteristics of the precipitated polymer is studied by example of forming of the cellulose membranes from solution in N-methyl-morpholine N-oxide using some proton-donor coagulants. In this regard, the interdiffusion processes proceeding at the contact of cellulose solutions and coagulating agents (water, propylene glycol, glycerin) are explored using the laser interferometry method. Varying the precipitator viscosity allows one to change the rate of formation and correspondingly the morphology of the cellulose films. In turn, the membrane structure determines its transport characteristics, which were assessed by the filtration of aprotic media with anionic dyes—Orange II and Remazol Brilliant Blue R. The application of the low-viscous precipitator provides the formation of a uniform film structure in the bulk, but leads to development of defects close to the surface, while a viscous medium promotes the formation of a relatively thin dense shell on the films.     

On the regularization mechanism for the periodic Korteweg–de Vries equation

In this paper we develop and use successive averaging methods for explaining the regularization mechanism in the the periodic Korteweg–de Vries (KdV) equation in the homogeneous Sobolev spaces Ḣ^s for s ≥ 0. Specifically, we prove the global existence, uniqueness, and Lipschitz‐continuous dependence on the initial data of the solutions of the periodic KdV. For the case where the initial data is in L₂ we also show the Lipschitz‐continuous dependence of these solutions with respect to the initial data as maps from Ḣ^s to Ḣ^s for s ∈(−1,0]. © 2010 Wiley Periodicals, Inc.     

Synthesis and properties of optically active ferrocenylethylindazoles

The stereochemistry of two processes, viz., -ferrocenylalkylation of indazole with optically active S-(+)-1-ferrocenylethanol and the thermal rearrangement of S-(+)-2-N-(ferrocenylethyl)indazole into S-(+)-1-N-(ferrocenylethyl)indazole, was studied. Both reactions proceed stereoselectively.     

Hypercrosslinked polystyrene as a novel type of high-performance liquid chromatography column packing material. Mechanisms of retention

An experimental material, Chromalite 5HGN (Purolite, UK), that represents hypercrosslinked polystyrene as a new type of neutral stationary phase for HPLC was examined. The material contains no functional groups, but is compatible with any kind of nonpolar and highly polar mobile phase, and even with water. It is chemically resistant and thermally stable. When using aqueous organic mobile phases, Chromalite 5HGN works similar to standard C18 reversed-phase packings, but is characterized by much greater hydrophobicity and, sometimes, unusual selectivity. When using nonpolar mobile phases, i.e. under "quasi normal-phase" conditions, the retention is mostly governed by the interactions between pi-electronic systems of the adsorbent and adsorbate. Adding highly polar, even hydrophilic solvents into the mobile phase, leads to a shift of retention times toward the "reversed-phase" kind of chromatography, which gives an additional possibility in fine tuning the column selectivity.     

Gene expression analysis for high throughput screening applications

To meet growing needs for high throughput gene expression profiling, we established a new automated high throughput TaqMan RT-PCR method for quantitative mRNA expression analysis. In this method, the Allegro( trade mark ) (Zymark) system conducts all sample tracking and liquid handling steps, and ABI PRISM 7900 HT (Applied Biosystems) is used to conduct real-time determination of the C(t) value when amplification of PCR products is first detected and accumulation of inhibitory PCR products is unlikely to occur. The ABI PRISM 7900 HT Sequence Detection System features a real-time PCR instrument with 384-well-plate compatibility and robotic loading, and continuous wavelength detection, which enables the use of multiple fluorophores in a single reaction. The Allegro System offers an assembly line approach with a modular design that allows reconfiguration of the components to accommodate variations in the assay flow. In the present study, we have established and validated a new automated High Throughput (HT) TaqMan RT-PCR- based method for quantitative mRNA expression analysis. The data demonstrate that HT-Taqman PCR is a powerful tool that can be used for measuring low concentrations of mRNA, and is highly accurate, reproducible, and amenable to high throughput analysis. Results suggest that HT-TaqMan is a reliable method for the quantification of low-expression genes and a powerful tool with HT capability for target identification/validation, structure-activity relationship (SAR) study, compound selection for efficacy studies, and biomarker identification in drug discovery and development.