Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. V. Multiblock and random copolymers of L‐lactide with trimethylene carbonate obtained in copolymerizations initiated with zirconium(IV) acetylacetonate

Using zirconium(IV) acetylacetonate as an initiator of lactide/trimethylene carbonate copolymerization allowed us to obtain high‐molecular‐weight copolymers with high efficiency. The reactivity ratios of the comonomers were 13.0 for lactide and 0.53 for trimethylene carbonate. Despite the large differences between the values of the reactivity ratios, copolymers with randomized chain structures were obtained. This phenomenon occurred as a result of an intensive intermolecular transesterification process proceeding along with the reaction of copolymer chain growth and modifying its final structure. Conducting the copolymerization at the relatively low temperature of about 110 °C, which minimized the influence of intermolecular transesterification, made it possible to obtain semicrystalline copolymers with multiblock structures. Increasing the temperature of copolymerization up to 180 °C was associated with strong intensification of the transesterification reactions. At this temperature, amorphous copolymers were obtained with identical compositions but highly randomized chain structures. An analysis of the chain microstructures of the obtained copolymers, determining the average length of the blocks, the intermolecular transesterification ratio, and the degree of chain randomization, was conducted by means of NMR spectroscopy. For this purpose, very specific signal assignment in the carbonyl and methylene carbon regions of the ¹³C NMR spectra to appropriate comonomer sequences of polymeric chains was performed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3184–3201, 2006     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. IV. Copolymerization of glycolide with trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate: Microstructure analysis of copolymer chains by high‐resolution nuclear magnetic resonance spectroscopy

The results of the copolymerization of glycolide with cyclic trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate are described. The copolymerization was conducted in the presence of low‐toxicity zirconium(IV) acetylacetonate as an initiator. With this kind of initiator, the composition of the comonomer units in the copolymer chains was assumed to be obtained with high efficiency. Despite significant differences in the comonomer reactivity, in copolymers containing comparable amounts of glycolidyl and carbonate sequences, highly randomized chain structures were observed. This effect resulted from strong intermolecular transesterification that proceeded during the studied copolymerization and caused glycolidyl microblock randomization. The assignment of the spectral NMR lines to appropriate comonomer sequences of polymeric chains was performed in the region of methylene protons of glycolidyl units in ¹H NMR spectra of the copolymers and in the carbonyl region of carbon spectra. The equations were formulated for a detailed characterization of the obtained copolymer chains, the average lengths of the blocks, and the transesterification and randomization coefficients. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 98–114, 2006     

The effect of fluorine-based plasma treatment on morphology and chemical surface composition of biocompatible silicone elastomer

X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) have been used to investigate the effect of reactive ion etching (RIE) on poly(methylhydrogensiloxane-co-dimethylsiloxane) surface in fluorine-based plasmas. Polysiloxane layers supported on the standard silicon wafers were etched using SF₆ + O₂ or CF₄ + O₂ plasmas. SEM studies show that the polysiloxane morphology depends on plasma chemical composition strongly. Presence of a columnar layer likely covered with a fluorine rich compound was found on the elastomer surface after the CF₄ + O₂ plasma exposure. After the SF₆ + O₂ or CF₄ + O₂ plasma treatment the polysiloxane surface enriches with fluorine or with fluorine and aluminum, respectively. Different morphologies and surface chemical compositions of the silicone elastomer etched in both plasmas indicate different etching mechanisms.     

Quasielastic nucleon and hyperon production by neutrinos and antineutrinos with energies below 30 GeV

The cross sections of neutrino and antineutrino quasielastic reactions \(vn \to \mu ^ - p,\bar vp \to \mu ^ + n,\bar vp \to \mu ^ + \Lambda\) were studied in the neutrino energy range between 3 and 30 GeV. In comparison withV-A theory axial mass parameters ofM _A =(1.06±0.05±0.14) GeV/c² from neutrino andM _A =(0.71±0.10±0.20) GeV/c² from antineutrino data were found. The total cross-section for the hyperon production process can be described byM _A =1.0 GeV/c².     

Primitive lattice points in rational ellipses and related arithmetic functions

Assuming the Riemann Hypothesis to be true, an asymptotic with a sharp error term is established for the number of primitive lattice points inside a rational ellipseau ²+buv+cv ²x (a, b, c integers,b ²–4ac<0). A generalization of the result is given applying (as an example) to counting functions of Pythagorean triangles.     

Unions and Intersections of Families of Lp-Spaces

Let L^Ψ and E^Ψ be the ORLICZ space and the space of finite elements respectively, on a measure space (Ω, Σ, μ), and let T ? (0, ∞). It is proved that if inf {p: p ? T} ? T or sup {p: p ? T} ? T and μ is an infinite atomless measure, then there is no ORLICZ function Ψ such that: \documentclass{article}\pagestyle{empty}\begin{document}$ L^\varphi = Lin\mathop { \cup L^p }\limits_{p\varepsilon T} $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ E^\varphi = Lin\mathop { \cup L^p }\limits_{p\varepsilon T} $\end{document} and moreover, there is no ORLICZ function Ψ such that: \documentclass{article}\pagestyle{empty}\begin{document}$ L^\varphi = Lin\mathop { \cap L^p }\limits_{p\varepsilon T} $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ E^\varphi = Lin\mathop { \cap L^p }\limits_{p\varepsilon T} $\end{document}.     

Final results on μe-pair production in neutrino interactions in the SKAT freon bubble chamber experiment

We present the final results from the search for μe pairs produced in neutrino interactions using the freon filled bubble chamber SKAT. The rate of μ^? e ⁺ pairs to charged current events above the charm threshold is \(R_{\mu ^ - e^ + } = (4.8 \pm 1.1)10^{ - 3} \) . Assuming charm particle production to be the origin of the positron we calculate \(R_{\Lambda _c^ + } = (6.2 \pm 3.1)10^{ - 2} \) andR _D =(2.8±0.9)10^?2. We observe no considerable μ^? e ^? pair production above the background. In the regionE _v >3 GeV,p _μ,e >1.0 GeV/c andp _μ>p _e we find with a 90% confidence level the limit \(R_{\mu ^ - e^ - }< 1.7 10^{ - 4} \) .     

Sensitised decomposition of microcystin-LR using UV radiation

UV radiation was applied to degrade cyanobacterial hepatotoxin, microcystin-LR in the presence of phycocyanin as a model natural sensitiser. The concentrations of both the toxin and the pigment used in the experiments were higher by several orders of magnitude than found in the environment. The photoreaction parameters were optimised. The process was found to be of limited use for water treatment due to its low efficacy. Additionally, pronounced UV-induced bleaching of the pigment significantly reducing the photoreaction rates of the toxin was observed for the highest UV radiation intensities applied.     

PHOTOCYTOTOXICITY OF CURCUMIN

Curcumin, bis (4-hydroxy-3-methoxyphenyl)-l,6-diene-3,5-dione, is a yellow-orange dye derived from the rhizome of the plant Curcuma longa. Curcumin has demonstrated phototoxicity to several species of bacteria under aerobic conditions (Dahl, T. A., et al. , 1989, Arch. Microbiol. 151 183), denoting photodynamic inactivation. We have now found that curcumin is also phototoxic to mammalian cells, using a rat basophilic leukemia cell model, and that this phototoxicity again requires the presence of oxygen. The spectral and photochemical properties of curcumin vary with environment, resulting in the potential for multiple or alternate pathways for the exertion of photodynamic effects. For example, curcumin photogenerates singlet oxygen and reduced forms of molecular oxygen under several conditions relevant to cellular environments. In addition, we detected carbon-centered radicals, which may lead to oxidation products (see accompanying paper). Such products may be important reactants in curcumin's phototoxicity since singlet oxygen and reduced oxygen species alone could not explain the biological results, such as the relatively long lifetime (t¹²= 27 s) of the toxicant responsible for decreased cell viability.