A highly selective and sensitive thorium(IV) PVC membrane electrode based on a dithio-tetraaza macrocyclic compound.

A poly(vinyl chloride)-based membrane composed of dithio-tetraaza macrocyclic compound as a neutral carrier with sodium tetraphenylborate (NaTPB) as an anion excluder and nitrobenzene (NB) as plasticizer was prepared and investigated as a Th(IV)-selective electrode. The electrode exhibits a Nernstian slope of 14.2 +/- 0.3 mV per decade over a wide concentration range (1.0 x 10(-6) to 1.0 x 10(-1) M) with a detection limit of 8.0 x 10(-7) M between pH 3.5 and 9.5. The response time of the sensor is about 10 s and it can be used over a period of 5 months without any divergence in potential. The proposed membrane sensor revealed a good selectivity for Th(IV) over a wide variety of other metal ions and proved to be a better electrode in many respects than those reported in the literature. It was successfully applied as an electrode indicator as well as in the direct determination of thorium ions in standard and real samples.     

Counterion and solvent effects on the dilute solution viscosity of polystyrene ionomers

We present an analysis of data on the intrinsic viscosity [η] of sulfo-polystyrene ionomers in several solvents for a variety of sulfonation levels and counterions. For solvents of low dielectric constant, 2 < ε < 18, [η] decreases from the base polymer value [η]₀ with increasing substitution level. This behavior was attributed to intramolecular association of ionic dipoles. The ratio [η]/[η]₀ was found to depend on a single reduced variable α_Aα_Sx, where x is the fractional substitution, α_A depends only on the counterion, and α_S ∝ ε^?1 depends only on the solvent. For solvents of high dielectric constant, 36 < ε < 47, [η] increases approximately as x³, and counterion effects are small. This behavior was attributed to ionic dissociation, giving rise to a polyelectrolyte effect. Implications of the low ε results are discussed in relation to association-induced gelation behavior and possible generalizations of the reduced variables approach.     

A proposal for Ramsey interferences when spontaneous emission can occur between two interaction zones

The possibility of observing Ramsey fringes in situations where the time separation between two interaction zones is larger than the lifetime is discussed. The spectral characteristics of emission exhibit interferences which are shown to be due to the fact that the spontaneous emission event can occur in two different zones and thus erasing any Welcher-Weg information.It is indeed a great honor for me to contribute an article on the occasion of H. Walther's 60th birthday     

The overlay of lower envelopes and its applications

Let and be two collections of a total ofn (possibly partially defined) bivariate, algebraic functions of constant maximum degree. The minimization diagrams of are the planar maps obtained by the xy-projections of the lower envelopes of , respectively. We show that the combinatiorial complexity of the overlay of the minimization diagrams of and of is O(n^2+ɛ), for any ɛ>0. This result has several applications: (i) a near-quadratic upper bound on the complexity of the region in 3-space enclosed between the lower envelope of one such collection of functions and the upper envelope of another collection; (ii) an efficient and simple divide-and-conquer algorithm for constructing lower envelopes in three dimensions; and (iii) a near-quadratic upper bound on the complexity of the space of all plane transversals of a collection of simply shaped convex sets in three dimensions. Work on this paper by the first author was supported by National Science Foundation Grant CCR-93-01259 and an NYI award. Work on this paper by the second author was supported by the Netherlands’ Organization for Scientific Research (NWO) and partially supported by ESPRIT Basic Research Action No. 6546 (project PROMotion). His current address is Department of Computer Science, Postech, San 31, Hyoja-Dong, Pohang, Kyungbuk 790–784, South Korea. Email: otfried@vision.postech.ac.kr. Work on this paper by the third author was supported by NSF Grant CCR-91-22103, by a Max-Planck Research Award, and by grants from the U.S.-Israeli Binational Science Foundation the Fund for Basic Research administered by the Israeli Academy of Sciences, and the G.I.F., the German-Israeli Foundation for Scientific Research and Development.     

N,N-bis[2-oxo-3-oxazolidinyl]phosphorodiamidic chloride: a novel coupling reagent in the synthesis of oligodeoxyribonucleotides

Use of a novel coupling reagent, N,N-bis[2-oxo-3-oxazolidinyl]phosphorodiamidic chloride (BOPDC) in the synthesis of oligodeoxyribonucleotides is described. This reagent allows the synthesis of phosphotriesters in high yields (70–80%) without detectable side reactions. Synthesis of a hexanucleotide, d(A-A-C-C-C-G) is presented as an example.     

Toluene oxidation on LaCoO3, LaFeO3 and LaCrO3 perovskite catalysts. A comparative study

Vapor phase catalytic oxidation of toluene over perovskites viz., LaCoO₃, LaCrO₃ and LaFeO₃ has been studied. The maximum activity was observed at 450°C. The oxidation is first order. The order of catalytic reactivity is LaCoO₃>LaFeO₃>LaCrO₃. The activation energy (E_a) values for LaCoO₃, LaFeO₃ and LaCrO₃ are 13.4, 23.93 and 25.31 kJ/mol, respectively.     

A study of equilibrium between cadmium cyanide and alkali halides and thiocyanate by solubility measurements

Summary A study of the Cd(CN)₂ +x X^– [Cd(CN)₂X _x ] ^x– equilibrium (where X = Cl, Br or CNS) has been carried out at 18° and 38° by measuring the solubility of cadmium cyanide in potassium chloride, bromide and thiocyanate at various concentrations, and at a high ionic strength (6 M) maintained with sodium perchlorate to minimise the effect of activity coefficients. Equilibrium constants forx = 1 and 2 have been calculated and clearly favour the situation wherex = 1. H values for the dissociation of [Cd(CN)₂X]^– have also been calculated.