Phenanthroline complexes bearing fused dipyrrolylquinoxaline anion recognition sites: efficient fluoride anion receptors

Novel anion recognition host molecules, tris-1,10-phenanthroline cobalt(III) and bis-2,2'-bipyridine mono-1,10-phenanthroline ruthenium(II) complexes bearing fused dipyrrolylquinoxaline moieties have been synthesized. As determined by UV-vis spectroscopic and electrochemical studies, these metal complexes bind fluoride with high affinity in polar media both in absolute terms and relative to the metal-free phenanthroline dipyrrolylquinozaline precursor from which they are derived (fluoride is bound to the tris-1,10-phenanthroline cobalt(III) dipyrrolylquinoxaline system with a 1:1 binding constant of 54 000 M-1 in DMSO). The large observed binding constants are ascribed to two factors, (i) the presence of a phenanthroline-coordinated cationic charge that decreases the electron density on the pyrrole NH protons and (ii) pure electrostatic effects.     

Polymer effect in graft polymerizations of acrolein onto imidazole-containing polymer

The graft polymerizations of acrolein (AL) onto an imidazole (Im)-containing polymer, such as a homopolymer of 4(5)-vinylimidazole (VIm) and several copolymers of VIm-4-vinylpyridine (VPy), VIm-1-vinyl-2-pyrrolidone (VPr), and VIm-styrene (St), have been studied in ethanol at 0°C. The degree of polymerization (P?_n) of the resulting polyacrolein graft depended on the number of Im units in the Im-containing polymer which produced a decrease in P?_n of grafted polyacrolein. The P?_n of the graft polyacrolein was determined to be in the range of 5-23. The rate of polymerization (R_p) was expressed by R_p = k(PVIm) (AL)². The graft polymerizability of the AL was influenced by the comonomer in the parent polymer, and was found to be in the order of VIm homopolymer > VIm-VPr copolymer > VIm-VPy copolymer > VIm-St copolymer. R_p was affected by the functional group around the Im group in the Im-containing polymer. These results were discussed by assuming the conformation of the parent polymer in ethanol.     

The birth of the X-ray refractive lens

In the X-ray region, no optics based on the principle of refraction existed since the discovery of the X-rays by Röentgen in November 1985, although mirrors and zone-plates that use the principle of reflection and diffraction have been employed. The idea of a practical X-ray refractive lens was first disclosed in February 1994, i.e., just one year before the centenary of the discovery of X-rays. The present paper reviews why the X-ray lens did not appear for so many years, and how the design was born. The paper also discusses technologies to be developed for high performance X-ray lenses, and advantages of refractive X-ray lenses over other X-ray optics.     

Additive Effect of p-Substituted Phenols on the Anionic Polymerization of Acrolein Induced by Imidazole

Anionic polymerization of acrolein (AL) by imidazole in the presence of several p-substituted phenols such as phenol, p-methyl-phenol, and p-nitrophenol were kinetically carried out in tetra-hydrofuran at 0°C. The initial polymerization rate R_p was estimated from the rate of monomer consumption by means of gas chromatography. A linear correlation was obtained from Hammett's equation, log R_pX/R_p H = 0.22. Meanwhile, the polymerizabilities were found to be in the following order: p-methylphenol > phenol > p-nitrophenol. The additive effect of phenols was kinetically discussed on the basis of these results.     

New polyethyleneglycol-functionalized texaphyrins: synthesis and in vitro biological studies

The synthesis of four new analogues of motexafin gadolinium (MGd), a gadolinium(III) texaphyrin complex in clinical trials for its anticancer properties, is described. These new derivatives contain either 1,2-diaminobenzene or 2,3-diaminonaphthalene subunits as the source of the imine nitrogens and bear multiple 2-[2-(2-methoxyethoxy)ethoxy]ethoxy (PEG) groups, on either meso aryl or beta-pyrrolic substituents, to increase their water solubility. All four analogues were found to be more active in vitro than the parent system MGd as judged from cell proliferation assays using the PC3 and A549 cell lines.     

Exact asymptotic formulae of the stationary distribution of a discrete-time two-dimensional QBD process

We propose an analytically tractable approach for studying the transient behavior of multi-server queueing systems and feed-forward networks. We model the queueing primitives via polyhedral uncertainty sets inspired by the limit laws of probability. These uncertainty sets are characterized by variability parameters that control the degree of conservatism of the model. Assuming the inter-arrival and service times belong to such uncertainty sets, we obtain closed-form expressions for the worst case transient system time in multi-server queues and feed-forward networks with deterministic routing. These analytic formulas offer rich qualitative insights on the dependence of the system times as a function of the variability parameters and the fundamental quantities in the queueing system. To approximate the average behavior, we treat the variability parameters as random variables and infer their density by using ideas from queues in heavy traffic under reflected Brownian motion. We then average the worst case values obtained with respect to the variability parameters. Our averaging approach yields approximations that match the diffusion approximations for a single queue with light-tailed primitives and allows us to extend the framework to heavy-tailed feed-forward networks. Our methodology achieves significant computational tractability and provides accurate approximations for the expected system time relative to simulated values.