The effect of mixed solvents pyridine–carbon tetrachloride on the radical polymerization of methyl methacrylate

A study was made of the methyl methacrylate (MMA) solution polymerization in CCl₄-pyridine mixtures as well as in net components at 30, 50, and 70°C. The results obtained show that there are no significant deviations from additivity in the overall chain transfer constants that fit the straight line between the values of Cs for CCl₄ and pyridine. It can be concluded that the EDA interaction between CCl₄ and pyridine does not change the sensitivity of each component for chain transfer from propagation PMMA free radical. The pyridine in the system increases the rate of MMA polymerization as a result of the higher rate of initiation.     

On permutations of central quadrics which preserve an inner distance

Letq be a regular quadratic form on a vector space (V, $\mathbb{F}$ ) and assume dimV ≥ 4 and ¦ $\mathbb{F}$ ¦ ≥ 4. We consider a permutation ? of the central affine quadric $\mathcal{F}$ := {x εV ¦q(x) = 1} such that $$(*)x \cdot y = \mu \Leftrightarrow x^\varphi \cdot y^\varphi = \mu \forall x,y\varepsilon \mathcal{F}$$ holds true, where μ is a fixed element of $\mathbb{F}$ and where “·” is the scalar product associated withq. We prove that ? is induced (in a certain sense) by a semi-linear bijection (σ,?): (V, $\mathbb{F}$ ) → (V, $\mathbb{F}$ ) such thatq o ?o q, provided $\mathcal{F}$ contains lines and the pair (μ, $\mathbb{F}$ ) has additional properties if there ar no planes in $\mathcal{F}$ . The cases μ,≠ 0 and μ = 0 require different techniques.     

Codings of graphs with binary edge labels

LetG(V,E) be a graph. A mappingf:E{0,1} ^m is called a (binary) coding ofG, if the induced mapping , assigns different vectors to the vertices. For the Boolean sum,f is called aB-code, and for the mod 2 sum anM-code. Letm _B (G) resp.m _M (G) be the smallest lengthm for whichB-codes resp.M-codes are possible. Trivially,m _B (G),m _M (G) log₂|V|. Improving results of Z. Tuza we showm _B (G)log₂|V| + 1,m _M (G)log₂|V|+4.     

Investigations into the Pd-catalysed cross-coupling of phenylacetylene with aryl chlorides: simple one-pot procedure and the effect of ZnCl2 co-catalysis

[PdCl(C6H3(OPPri2)2-2,6)] 1 catalyses the coupling of electron-rich, electron-neutral and electron-deficient aryl chlorides with phenylacetylene in the presence of ZnCl2 as cocatalyst to give the products in modest to excellent yields.     

Analysis of free and esterified sterols in vegetable oil methyl esters by capillary GC

The introduction of quality standards for vegetable oil methyl esters is gaining in importance due to their increased use as diesel fuel substitutes and as technical products. Free and esterified sterols, the main constituents of the unsaponifiable matter in vegetable oils, are recovered in vegetable oil methyl esters and may influence the technical properties of vegetable oil methyl ester products. A rapid gas chromatographic method for the qualitative and quantitative determination of free and esterified sterols in vegetable oil methyl esters has therefore been developed. The concentration of the free sterols as well as their qualitative and quantitative composition and the concentration of the sterol esters have been determined in rape seed oil methyl ester samples by GC–FID. Prior to analysis, the free sterols were silylated with N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane; betulinol was used as an internal standard. Calibration was performed by analysis of standard solutions containing β-sitosterol, cholesteryl stearate, and betulinol. The reproducibility of the quantitative results has been evaluated by repeated injections of the same test solution and by repeated complete analysis of the same sample.     

The rhodium complex of a tris(bipyridine) ligand—Its electrochemical behaviour and function as mediator for the regeneration of NADH from NAD+

The tris-bipyridine ligand3a and its stoichiometric Rh³⁺ complex have been prepared. Cyclovoltammograms of the complex at pH 7.4 using a glassy carbon disk electrode reveal a strong reduction peak at –620 mV and two weak reduction peaks at more negative voltage. The reduction potential of the new complex is shifted by 300 mV to more positive values as compared to [Rh(bipy)₃]³⁺. There is no reversible reoxidation peak of the Rh(I) complex formed due to the decomplexation of one of the three bipyridine units in the course of the transition Rh(III)Rh(I). The Rh(III) complex of3a was also studied with respect to its function as a possible redox mediator for the electrochemical regeneration of NADH from NAD⁺. The preparative electrolysis of the Rh³⁺ complex of3a in the presence of NAD⁺ yields a selective formation of NADH, whereas NAD dimers were not detected. On the other hand, a significant acceleration of this reaction compared to [Rh(bipy)₃]³⁺ was not observed.     

Inhibition of UV-induced immune suppression and interleukin-10 production by plant oligosaccharides and polysaccharides

Application of Aloe barbadensis poly/oligosaccharides to UV-irradiated skin prevents photosuppression of delayed-type hypersensitivity (DTH) responses in mice. We tested the hypothesis that these carbohydrates belong to a family of biologically active, plant-derived polysaccharides that can regulate responses to injury in animal tissues. C3H mice were exposed to 5 kJ/m2 UVB from unfiltered FS40 sunlamps and treated with between 1 pg and 10 micrograms tamarind xyloglucans or control polysaccharides methylcellulose or dextran in saline. The mice were sensitized 3 days later with Candida albicans. Tamarind xyloglucans and purified Aloe poly/oligosaccharides prevented suppression of DTH responses in vivo and reduced the amount of interleukin (IL)-10 observed in UV-irradiated murine epidermis. Tamarind xyloglucans were immunoprotective at low picogram doses. In contrast, the control polysaccharides methylcellulose and dextran had no effect on immune suppression or cutaneous IL-10 at any dose. Tamarind xyloglucans and Aloe poly/oligosaccharides also prevented suppression of immune responses to alloantigen in mice exposed to 30 kJ/m2 UVB radiation. To assess the effect of the carbohydrates on keratinocytes, murine Pam212 cells were exposed to 300 J/m2 UVB radiation and treated for 1 h with tamarind xyloglucans or Aloe poly/oligosaccharides. Treatment of keratinocytes with immunoprotective carbohydrates reduced IL-10 production by approximately 50% compared with the cells treated with UV radiation alone and completely blocked suppressive activity of the culture supernatants in vivo. The tamarind xyloglucans also blocked UV-activated phosphorylation of SAPK/JNK protein but had no effect on p38 phosphorylation. These results indicate that animals, like plants, may use carbohydrates to regulate responses to environmental stimuli.     

Photocatalyzed [2 + 2 + 2]-cycloaddition of nitriles with acetylene: an effective method for the synthesis of 2-pyridines under mild conditions

The photocatalyzed [2 + 2 + 2]-cycloaddition of nitriles with 2 equiv of acetylene to 2-pyridines can be carried out under mild conditions and represents a valuable extension to common synthetical methods. For the ideal wavelength range (350-500 nm), lamps as well as sunlight can be used. Working at room temperature and in organic solvents such as toluene or hexane as well as in water gives satisfying results in many cases. However, it is also possible to vary the solvent and the reaction temperature of the photocatalyzed synthesis and to choose, with respect to the specific substrate, specific requirements for this particular reaction and general requirements of the method. This simple and selective method derives its potential mainly from the large variety of applicable nitriles. Suitable substrates include (functionalized) aliphatic and aromatic nitriles as well as cyanamides derived from secondary amines.     

Electrokinetic investigations of charged porous membranes

Asymmetric ultrafiltration membranes were prepared from fully aromatic polyamides differing in the diamine monomers of the polymeric backbone and from polysulfone. Nanofiltration membranes were made from polysulfone and polyethersulfone. The polysulfone as well as the polyethersulfone were chemically modified to change the surface charges of the membranes that were made from these polymers. This means neutral, positively as well as negatively charged membranes could be employed for the measurements. The surface properties of the membranes as a function of pH were determined by measuring the streaming potential in a perpendicular and horizontal mode. Applying proteins the values of the streaming potential changed depending on the original charges of the membranes as well as on the pH of the solution. The values shifted to either higher or lower absolute values. Thus, characterization of unused and used membranes can be carried out by electrokinetic measurements. This was also demonstrated using a membrane fitted out with invertase. The zeta potential of nanofiltration membranes, however, was only evaluated from the results obtained with the horizontally run cell.