Osmotic coefficients of vinylic polyelectrolyte solutions without added salt

 The osmotic pressures of –polyelectrolyte solutions without added salt was measured in the concentration ranges 0.001–0.02 and 0.2–1.9 mol kg^-1. Our results show that the osmotic coefficients φ_p were strongly dependent on the chemical structures of polyelectrolyte through the polyion radius and the interaction between the ionic moiety and counterions. The osmotic pressures in polyelectrolyte solutions without added salt, calculated on the basis of the counterion contribution, are in agreement with the experimental results. We conclude that the counterion contribution is dominant in the osmotic pressures and thus, the polymer contribution is negligible in the examined concentration range 0.2–1.9 mol kg^-1. The P–B approach gave a fair prediction of the absolute values of the osmotic pressures with λ=4.5, where λ is the charge density parameter, except for NaPA. In other words, the concentration dependence of the φ_p values can be explained in terms of the counterion contribution. Received: 11 June 1997 Accepted: 19 August 1997     

Dynamic coordination polymers with 4,4'-oxybis(benzoate): reversible transformations of nano- and nonporous coordination frameworks responding to present solvents

Reversible construction of a nanoporous framework from a nonporous framework has been found in the zinc(II) coordination polymer with 4,4'-oxybis(benzoate) (oba). [Zn(2)(oba)(2)(dmf)(2)].2DMF (1), which has 1 nm scale channels, transforms to the nonporous coordination polymer [Zn(oba)(H(2)O)] (2) with the loss of the open framework. Compound 2 on treatment with DMF reversibly yields nanoporous compound 1.     

A first photochemical bis-germylation of C60 with digermirane

[reaction: see text]In the photochemical bis-germylation of C60 with 1,1,2,2-tetrakis(2,6-diethylphenyl)-1,2-digermirane (1), a cycloadduct (2) is obtained in high yield for the first time. Spectroscopic analysis and theoretical investigation confirm that 2 (which has C1 symmetry) results from 1,4-cycloaddition. Control experiments and laser flash photolysis experiments suggest that an exciplex intermediate is responsible for the formation of 2. The redox properties of 2 were examined by differential pulse voltammetry.     

Resazurin as an electron acceptor in glucose oxidase-catalyzed oxidation of glucose

The behavior of resazurin (1) as an electron acceptor in glucose oxidase (GOD)-catalyzed oxidation of glucose under anaerobic conditions is described. When a mixture of 1, glucose, and GOD in phosphate buffer (pH 7.4, 0.1 M) was incubated at 25 degrees C, the resulting solution turned purple to fluorescent pink due to the deoxygenated product, resorufin (2). On incubation of 1 with GOD alone or with H2O2 under essentially the same conditions, no color change was seen, indicating that generation of 2 in the enzymatic reaction is brought about through reduction of 1 by the reduced form (GODred) of GOD, which was also supported by the voltammetric behavior of 1. However, it was found that the enzymatic transformation of 1 to 2 is of no practical use as an indicator reaction for glucose determination using only GOD due to a slow reaction of 1 with GODred. Based on a ping-pong type mechanism with a steady-state approximation, KM and kcat for 1 as an electron acceptor from GODred were estimated to be 15+/-1.3 microM and (5.0+/-0.5) x 10(-2) s(-1), respectively.     

Y-931, a novel atypical antipsychotic drug,is less sensitive to oxidative phenomena

The oxidation behavior of Y-931, a potent atypical antipsychotic drug, was compared with that of clozapine and olanzapine. In two enzymatic systems (horseradish peroxidase (HRP)/glutathione (GSH) and HRP/H(2)O(2)/GSH) which generate thiyl radicals, clozapine markedly strengthened the electron paramagnetic resonance (EPR) signal for the radical. Olanzapine, Y-931 and the major metabolites (compounds 1-3) had no or minimal effect on the intensity of this signal. In addition, the redox potential values for the three derivatives were in accord with the EPR spin trapping results. In toxicological experiments in human leukocytes, a concentration-dependent toxicity was observed when neutrophils were incubated with clozapine (1-10 micromol/l) and H(2)O(2) (1 mmol/l). However, Y-931 and olanzapine did not show remarkable toxicity under the conditions.     

Quinoxaline-oligopyrroles: improved pyrrole-based anion receptors

Novel quinoxaline derivatives bearing dipyrromethane or tripyrromethane substituents act as improved anion receptors as compared to the unsubstituted dipyrrolylquinoxaline core from which they are derived.     

Penning ionization electron spectroscopy of C6H6 by collision with He*(2 3 S) metastable atoms and classical trajectory calculations: optimization of ab initio model potentials

The potential energy surface of benzene (C(6)H(6)) with a He*(2(3)S) atom was obtained by comparison of experimental data in collision-energy-resolved two-dimensional Penning ionization electron spectroscopy with classical trajectory calculations. The ab initio model interaction potentials for C(6)H(6)+He*(2(3)S) were successfully optimized by the overlap expansion method; the model potentials were effectively modified by correction terms proportional to the overlap integrals between orbitals of the interacting system, C(6)H(6) and He*(2(3)S). Classical trajectory calculations with optimized potentials gave excellent agreement with the observed collision-energy dependence of partial ionization cross sections. Important contributions to corrections were found to be due to interactions between unoccupied molecular orbitals and the He*2s orbital. A C(6)H(6) molecule attracts a He*(2(3)S) atom widely at the region where pi electrons distribute, and the interaction of -80 meV (ca. -1.8 kcal/mol) just cover the carbon hexagon. The binding energy of a C(6)H(6) molecule and a He* atom was 107 meV at a distance of 2.40 A on the sixfold axis from the center of a C(6)H(6) molecule, which is similar to that of C(6)H(6)+Li and is much larger than those of the C(6)H(6)+[He,Ne,Ar] systems.     

An anthracene-based Cd fluorescent chemosensor with a 4,7-bis(2-hydroxyethyl)-9-hydroxy-1,4,7-triazanonyl group as a highly selective chelator to Cd over Zn

We have developed a Cd²⁺ fluorescent chemosensor with high selectivity as well as sensitivity by tethering a 4,7-bis(2-hydroxyethyl)-9-hydroxy-1,4,7-triazanonyl chelator to anthracene. This sensor features the ability to discriminate Cd²⁺ from Zn²⁺ to a high degree (K_dZn/K_dCd = 560) in a pH 7.2 buffer.     

Phase behaviour of thermotropic banana-shaped compounds under pressure

The phase behaviour of two achiral bent core banana-shaped compounds, the hexyloxy (compound I) and decyloxy (compound II) members of the 1,3-phenylene bis[N-(2-hydroxy-4-n-alkoxybenzylidene)-4′-aminobenzoate] series was investigated under hydrostatic pressures up to 300?MPa using high pressure differential thermal analysis and light transmission methods. The reversible transition sequence crystal (Cr₁)–B₁ phase–isotropic liquid (I), observed at room pressure for compound I, remains in the pressure region up to c 70?MPa. At higher pressures a pressure-induced crystalline phase (Cr_i) appears between the Cr₁ and B₁ phases, its temperature region becoming wider with increasing pressure. The temperature vs. pressure phase diagram shows a triple point of 72.9?MPa and 160.3°C for the Cr₁, Cr_i and B₁ phases, indicating the lower limit of pressure for the Cr_i phase. In compound II the reversible transition sequence crystal (Cr₁)–B₂ phase–I is seen over the whole pressure region, and the temperature range of the B₂ phase remains unaltered. It is concluded that both the B₁ and B₂ banana phases are stable over the whole pressure region studied.