Synthèse du mèthyl-1 diformyl-2,3 pyrrole,de la méthyl-1 pyrrolo[2,3-d] pyridazine et de la méthyl-1 oxo-6 (6h)cycloheptatrieno[b] pyrrole

This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine.     

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.     

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.     

Branching Fraction Measurements of the SM Higgs with a Mass of 160 GeV at Future Linear e + e − Colliders

Assuming an integrated luminosity of 500 fb^–1 and a center-of-mass energy of 350 GeV, we examine the prospects for measuring branching fractions of a Standard Model-like Higgs boson with a mass of 160 GeV at the future linear e⁺e^–collider TESLA when the Higgs boson is produced via the Higgsstrahlung mechanism, e⁺e^– HZ. The Higgs boson mass chosen close to the W pair threshold covers a mass regime with complicated background structures. We study in detail including some detector responds the precisions achievable for the branching fractions of the Higgs boson into WW^(*), ZZ^* and , whereas the measurement of BF(H ) remains a great challenge. Expectations for the total Higgs width are discussed using either the BF(Z ZZ^*) measurement of this study and the expected error for the inclusive Higgsstrahlung cross section or in addition the precise cross section expected for the weak boson fusion process, e⁺e^– v H, or W,Z-universality.