The entropies of renewal systems

Renewal systems are symbolic dynamical systems originally introduced by Adler. IfW is a finite set of words over a finite alphabetA, then the renewal system generated byW is the subshiftX _W ⊂A ^Z formed by bi-infinite concatenations of words fromW. Motivated by Adler’s question of whether every irreducible shift of finite type is conjugate to a renewal system, we prove that for every shift of finite type there is a renewal system having the same entropy. We also show that every shift of finite type can be approximated from above by renewal systems, and that by placing finite-type constraints on possible concatenations, we obtain all sofic systems. The authors were supported in part by NFS grants DMS-8706284, DMS-8814159 and DMS-8820716.     

THE REACTIVITY OF SUPEROXIDE (O2-) and ITS ABILITY TO INDUCE CHEMILUMINESCENCE WITH LUMINOL

Abstract— The quantum yield and the kinetics of O -induced luminol chemiluminescence was investigated in a broad pH interval at varying luminol and concentrations. It is suggested that the weak chemiluminescence observed is mediated via a luminol-superoxide-adduct proposed to be an a-hydroxyperoxyl radical. At pH 7 the maximum quantum yield of chemiluminescence per initial percent was determined to be 4 times 10^-8. The degree of involvement in phagocytosis and related processes should be viewed against this maximum limit.     

Study on the retention behaviour of low-molar-mass polystyrenes and polyesters in reversed-phase liquid chromatography by evaluation of thermodynamic parameters

Polymers can be characterized under sorption conditions, to obtain information on molar mass and chemical composition. In order to get a better understanding of their retention behaviour under such conditions, the evaluation of thermodynamic parameters obtained from van't Hoff analyses on low-molar-mass polystyrenes (PS) and polyesters (PE) in various THF–water mixtures on a C₁₈ column is described in this study. Linear van't Hoff behaviour was observed in almost all cases. Negative values for both ΔH and ΔS were found for both PS and PE oligomers, which increase with increasing %THF. For ΔS this is explained from multi-site attachment effects. For PS, the non-linear relations between ΔH and ΔS, and degree of polymerization (p) could be properly described by the Stockmayer–Fixman equation. Although less clear, similar trends were found for PE. For PS, evidence for penetration effects of oligomer chains into the bonded chains was obtained. Martin plots for both PS and PE were shown to be non-linear in all investigated eluent compositions. The extent of non-linearity is suggested to depend on the conformation of a polymer in solution. No distinct enthalpy–entropy-compensation temperature (EECT) independent of p was found for PS, thus confirming the findings of an earlier study in which no exact molar mass independence was found under critical conditions. Further evaluation of EECT for PS oligomers revealed a retention mechanism independent of the binary eluent composition. This indicates that conclusions from this study can also be used for a qualitative understanding of sorption mechanisms in the gradient elution mode. Finally, for PS it was shown that ΔG equals zero under critical conditions, thus confirming theoretical predictions.     

The rate of homolysis of adducts of peroxynitrite to the C=O double bond.

Nucleophilic addition of the peroxynitrite anion, ONOO(-), to the two prototypical carbonyl compounds, acetaldehyde and acetone, was investigated in the pH interval 7.4-14. The process is initiated by fast equilibration between the reactants and the corresponding tetrahedral adduct anion, the equilibrium being strongly shifted to the reactant side. The adduct anion also undergoes fast protonation by water and added buffers. Consequently, the rate of the bimolecular reaction between ONOO(-) and the carbonyl is strongly dependent on the pH and on the concentration of the buffer. The pK(a) of the carbonyl-ONOO adduct was estimated to be approximately 11.8 and approximately 12.3 for acetone and acetaldehyde, respectively. It is shown that both the anionic and the neutral adducts suffer fast homolysis along the weak O-O bond to yield free alkoxyl and nitrogen dioxide radicals. The yield of free radicals was determined to be about 15% with both carbonyl compounds at low and high pH, while the remainder collapses to molecular products in the solvent cage. The rate constants for the homolysis of the adducts vary from ca. 3 x 10(5) to ca. 5 x 10(6) s(-1), suggesting that they cannot act as oxidants in biological systems. This small variation around a mean value of about 10(6) s(-1) suggests that the O-O bond in the adduct is rather insensitive to its protonation state and to the nature of its carbonyl precursor. An overall reaction scheme was proposed, and all the corresponding rate constants were evaluated. Finally, thermokinetic considerations were employed to argue that the formation of dioxirane as an intermediate in the reaction of ONOO(-) with acetone is an unlikely process.     

Cyclopentadienyl(iron)arene-bis-(p-N,N-dimethylaminobenzylidene)-cyclopentanone Photoinitiated Polymerization of Methyl Methacrylate and Styrene

Abstract

Polymerization of methyl methacrylate and styrene can be effectively photoinitiated by a binary photoinitiator system consisting of cyclopentadienyl(iron)arene hexafluorophosphonate salt and bis(p-N, N-dimethylaminobenzylidene)cyclopentanone in the spectral range of 400–500 nm. The amine-type radical formed from the exciplex of the binary photoinitiator system is probably responsible for the radical polymerization of vinyl monomers. A probable mechanism of initiation of polymerization is discussed.     

Design tables for a class of data-transmission filters

Some practical design tables are given for all-pole lowpass filters with minimal intersymbol interference. The tables include a selection chart, pole locations and passive-filter-element values. Having this information, the user can rapidly determine the applicability of these filters to his requirements.     

On Designing PAM Pulses Optimally Tolerant to Timing Jitter

This paper deals with the design of bandlimited baseband PAM pulses that are optimally tolerant to timing jitter in a maximally flat sense. In this design the bandwidth can be chosen arbitrarily. The resulting time responses are relatively insensitive to small amounts of timing jitter and so represent an optimal solution for this type of impairment. Analytic results are derived in the frequency domain after translating conditions on maximal flatness from the time domain into the frequency domain by means of the Poisson sum formula.     

Biodegradable and bioactive hybrid organic–inorganic PEG-siloxane fibers. Preparation and characterization

A mixture of triethoxysilanefunctionalized poly(ethylene glycol), f-PEG, and tetraethoxysilane, TEOS, was used as precursors in the preparation of continuous hybrid f-PEG-siloxane sol–gel derived fibers. The fibers were spun by extrusion through a spinneret. The thus prepared fibers had a diameter of 20–50 m. ²⁹Si-CPMAS NMR measurements confirmed that the functionalized PEG is incorporated into the siloxane network through covalent bonds. The hybrid fiber elasticity was much higher than that of fibers spun from sols with TEOS as the only source for silica. However, the f-PEG chain length plays a crucial role for the spinnability of the sol, since, as a result of bridging flocculation, macroscopic phase separation occurred readily with increasing chain length of the f-PEG. The fibers were shown to be effective substrates for the nucleation and growth of bone-like hydroxyapatite.     

Antimatter and matter production in heavy ion collisions at CERN (The NEWMASS experiment NA52)

Besides the dedicated search for strangelets NA52 measures light (anti)particle and (anti)nuclei production over a wide range of rapidity. Compared to previous runs the statistics has been increased in the 1998 run by more than one order of magnitude for negatively charged objects at different spectrometer rigidities. Together with previous data taking at a rigidity of ?20 GeV/c we obtained $10^6 \bar p, 10^3 \bar d$ and two $\overline {^3 He} $ without centrality requirements. We measured nuclei and antinuclei (p, d, $\bar p,\bar d$ ) near midrapidity covering an impact parameter range of b ～ 2–12 fm. Our results strongly indicate that nuclei and antinuclei are mainly produced via the coalescence mechanism. However, the centrality dependence of the antibaryon to baryon ratios shows that antibaryons are diminished due to annihilation and breakup reactions in the hadron dense environment. The volume of the particle source extracted from coalescence models agrees with results from pion interferometry for an expanding source. The chemical and thermal freeze-out of nuclei and antinuclei appear to coincide with each other and with the thermal freeze-out of hadrons.