Unsteady axisymmetric stagnation flow on a circular cylinder

Unsteady, axisymmetric stagnation flow about a circular cylinderis examined when the far-field flow is a periodic function oftime with a fixed time average and an oscillatory part of prescribedamplitude and frequency. Solutions are computed for arbitraryvalues of the Reynolds number, quantifying the effects of surfacecurvature, and a frequency parameter based on the period ofthe far-field flow. It is found that solutions remain regularand periodic provided that the far-field amplitude lies belowa critical value. Above this value, solutions terminate in afinite-time singularity. The blow-up time is delayed by increasingthe curvature of the surface. These results are corroboratedby asymptotic predictions valid in the limits of small and largeamplitude and frequency. For large Reynolds number, the problemreduces to the two-dimensional stagnation-point flow againsta plane wall studied by previous authors.     

Novel radial oligothienyl silanes

A series of thiophene-based homologues with a silicon core surrounded by mono-, bi-, terthiophene, and their derivatives with alkylsilyl linkages has been prepared using hydrosilylation and Stille coupling methods.     

Synthesis and psychotropic properties of furyl- and thienyl-germatranes

Trihalogermyl-furans and -thiophenes were prepared by inserting germanium dibromide (GeBr₂) generated from the dibromogermane(II) dioxanate complex into the carbon-halogen bond of halo-furans and -thiophenes. Their ethanolysis and transesterification by triethanolamine yielded the germatranes which were subjected to psychotropic activity assays. The psychotropic properties of germatranes were found to depend on the type of the heterocycle and on the position of the germatrane moiety.     

Novel Stereoselective Phase Transfer Catalytic Synthesis and Some Applications of ( E )-2-Chlorovinylthioarenes and Hetarenes

A novel two-step method for the preparation of ( E )-2-chlorovinylthioarenes (or hetarenes) from thiols and 1,1,2-trichloroethane in the phase transfer catalytic systems solid K 2 CO 3 /solid KI/18-crown-6/xylene and solid KOH/18-crown-6/toluene has been developed. ( E )-2-chlorovinylthioarenes were isolated in yields up to 98%. Utilization of ( E )-2-chlorovinylthioarenes in the Heck and Stille reactions has been shown.     

Validation of an analytical method to quantify the permeation and penetration of flurbiprofen into human pharynx tissue

The aim of this investigation was to develop receiver and extraction fluids, and subsequently validate an analytical method to quantify the permeation and penetration of flurbiprofen into human pharynx tissue using a Franz diffusion cell. The solubility and stability of flurbiprofen in a suitable receiver fluid, and a suitable extraction method and fluid to recover and quantitate flurbiprofen from human pharynx tissue, were investigated using high‐performance liquid chromatography (HPLC). The potential interference of human pharynx tissue in the receiver fluid was also investigated. The HPLC analytical method was successfully validated according to current guidelines. The final receiver fluid demonstrated sufficient solubility and stability, and the extraction method and fluid resulted in >95% recovery of flurbiprofen following exposure to human pharynx tissue. The lower limit of quantitation of flurbiprofen was 0.045 μg/mL in both the receiver and extraction fluids. There was no interference of the human pharynx tissue with the HPLC method. This investigation validated an analytical method for quantitating flurbiprofen, and determined a suitable receiver fluid and extraction method and fluid, which can be used to investigate the permeation and penetration of flurbiprofen through human pharynx tissue using the Franz diffusion cell method.     

Novel trialkylsilyl(germyl)-substituted thienyl- and furylbenzimidazoles and their N-substituted derivatives – synthesis,structure and cytotoxic activity

The reaction of 1,2-phenylenediamine with a variety of silicon- or germanium-containing 2-furaldehydes or 2-thienylcarbaldehydes in DMFA gave the corresponding benzimidazole derivatives in moderate yields (36–49%) in the presence of sodium hydrogen sulfite. As a result, a new series of silyl, germyl substituted hetarylbenzimidazoles were synthesized and their in vitro cytotoxicity was studied. The quaternisation of N-substituted benzimidazoles by heating with various alkyl, allyl and propargyl chlorides and bromides leads to the formation of benzimidazolinium salts. Potential cytotoxic activity of synthesized new benzimidazoles and benzimidazolinium salts was tested in vitro on two monolayer tumour cell lines: MG-22A (mouse hepatoma), HT-1080 (human fibrosarcoma) and normal mouse fibroblasts (NIH 3T3) and compared with corresponding benzimidazoles.     

Study on the Regioselectivity of Rhodium-Catalyzed Ring Opening Reactions of C1-Substituted 7-Oxabenzonorbornadienes with Boronic Acids

An optimized condition for the rhodium-catalyzed ring-opening reaction of C₁-substituted oxabicyclic alkenes with aryl boronic acids was developed and the effect of aryl boronic acid as well as the effect of C₁ substitution on the oxabicyclic alkenes was studied. Aryl boronic acids carrying electron-donating substituents provided the ring-opened products in excellent yields regardless of the position, while electron-withdrawing substituents were more susceptible to steric interactions. Although two different regioisomers are possible, all the rhodium-catalyzed ring-opening reactions of C₁ substituted oxabicyclic alkenes studied with aryl boronic acids were found to be highly regioselective, giving single regioisomers in all cases.     

Synthesis and characterization of nanoparticles with an iron oxide magnetic core and a biologically active trialkylsilylated aliphatic alkanolamine shell

Water-soluble double-coated magnetic nanoparticles (NPs) containing cytotoxic decyldimethyl(β$\beta$-dimethylaminoethoxy)silane methiodide (AA) molecule sorbed at biocompatible magnetic particles, which consist of magnetite pre-coated with oleic acid (OA), have been prepared. X-ray line profile broadening analysis was used for crystallite size determination. The method of magnetogranulometry has been used for determination of diameter of iron oxide magnetic core and magnetic properties of NPs prepared. In vitro cytotoxicity on monolayer tumor cell lines HT-1080 (human fibrosarcoma), MG-22A (mouse hepatoma) and normal mouse fibroblasts (NIH 3T3) has been studied. It was revealed that all the water-based colloidal solutions obtained are non-toxic and possess high NO-induction ability.     

Polyethylene glycol matrix reduces the rates of photochemical and thermal release of nitric oxide from S-nitroso-N-acetylcysteine

S -nitrosothiols have many biological activities and may act as nitric oxide (NO) carriers and donors, prolonging NO half-life in vivo. In spite of their great potential as therapeutic agents, most S -nitrosothiols are too unstable to isolate. We have shown that the S -nitroso adduct of N -acetylcysteine (SNAC) can be synthesized directly in aqueous and polyethylene glycol (PEG) 400 matrix by using a reactive gaseous (NO/O₂) mixture. Spectral monitoring of the S–N bond cleavage showed that SNAC, synthesized by this method, is relatively stable in nonbuf-fered aqueous solution at 25°C in the dark and that its stability is greatly increased in PEG matrix, resulting in a 28-fold decrease in its initial rate of thermal decomposition. Irradiation with UV light (λ= 333 nm) accelerated the rate of decomposition of SNAC to NO in both matrices, indicating that SNAC may find use for the photogeneration of NO. The quantum yield for SNAC decomposition decreased from 0.65 ± 0.15 in aqueous solution to 0.047 ± 0.005 in PEG 400 matrix. This increased stability in PEG matrix was assigned to a cage effect promoted by the PEG microenvironment that increases the rate of geminated radical pair recombination in the homolytic S–N bond cleavage process. This effect allowed for the storage of SNAC in PEG at −20°C in the dark for more than 10 weeks with negligible decomposition. Such stabilization may represent a viable option for the synthesis, storage and handling of S -nitrosothiol solutions for biomedical applications.