Probe electrode study of cathodically polarized PtIr-YSZ interfaces

Journal of Solid State Electrochemistry - Local cathodic polarizations of yttria-stabilized zirconia were carried out with a PtIr probe as the working electrode in a controlled atmosphere high...     

On the Relation between the Scalar Moment Problem and the Matrix Moment Problem on *-Semigroups

There is a countable cancellative commutative *-semigroup S withzero (in fact, a *-subsemigroup of G × N₀ for some abelian group G carrying the inverse involution) such that the answer to the question “if f is a function on S , with values in M_d(C) (the square matrices of order d) and such that $\sum^{n}_{j,k=1} \lbrak f(s^*_k s_j)\xi_j, \xi_k \rbrak \ge 0$ for all n in N, s₁, . . . , s_n in S , and $\xi_1$, . . . , $\xi_n$ in C^d, does it follow that $f(s) = \int_{S^*}\sigma (s) d\mu(\sigma) (s \memb S)$ for some measure $\mu$ (with values in M_d(C)₊ , the positive semidenite matrices) on the space S of hermitian multiplicative functions on S?” is “yes” if d = 1 but “no” if d = 2 (hence also for d > 2).     

Diels-Alder-Reaktionen von Vinylindolen mit Arin und 1,4-Benzochinonen: Neue potentielle DNA-Interkalatoren

Summary Diels-Alder reactions of 2- and 3-vinylindoles with aryne, 1,4-benzo- and 1,4-naphtho-quinone lead to new six-ring annellated carbazoles. Molecular modeling studies predict that the compounds with coplanar framework are able to intercalate with the B-DNA.

     

Correlation between molecular orbitals and doping dependence of the electrical conductivity in electron-doped metal-phthalocyanine compounds

We have performed a comparative study of the electronic properties of six different electron-doped metal-phthalocyanine (MPc) compounds (ZnPc, CuPc, NiPc, CoPc, FePc, and MnPc), in which the electron density is controlled by means of potassium intercalation. Despite the complexity of these systems, we find that the nature of the underlying molecular orbitals produces observable effects in the doping dependence of the electrical conductivity of the materials. For all the MPc's in which the added electrons are expected to occupy orbitals centered on the ligands (ZnPc, CuPc, and NiPc), the doping dependence of the conductivity has an essentially identical shape. This shape is different from that observed in MPc materials in which electrons are also added to orbitals centered on the metal atom (CoPc, FePc, and MnPc). The observed relation between the macroscopic electronic properties of the MPc compounds and the properties of the molecular orbitals of the constituent molecules clearly indicates the richness of the alkali-doped metal-phthalocyanines as a model class of compounds for the investigation of the electronic properties of molecular systems.     

On the mechanism of the copper-catalyzed cyclopropanation reaction

The selectivity-determining step in enantioselective copper-catalyzed cyclopropanation with diazo compounds has been studied by experimental and computational methods. The addition of the very reactive metallacarbene intermediate in an early transition state to the substrate alkene is concerted but strongly asynchronous, with substantial cationic character on one alkene carbon in the neighborhood of the transition state. Evidence from isotope effects and Hammett studies supports the nature of the transition state. Formation of a metallacyclobutane intermediate by a [2+2] addition is kinetically disfavored. Ligand-substrate interactions influencing the enantio- and diastereoselectivity have been identified, and the preferred orientation of the alkene substrate during the addition is suggested.     

Direct determination of rate constants for coupling between aromatic radical anions and alkyl and benzyl radicals by laser-flash photolysis

Coupling rates between the radicals methyl, n-, sec-, tert-butyl and benzyl (R.) and the aromatic radical anions of 1,4-dicyanonaphthalene, 9,10-dicyanoanthracene and fluorenone (A-.) have been obtained using a new laser-flash photolysis method. The radicals R. and the radical anions A-. were generated by a photoinduced electron transfer reaction between the aromatic compound A and the alkyl or benzyl triphenylborate anion RB(Ph)3-. For the first time the rate constants of the coupling reaction between methyl and benzyl radicals with aromatic radical anions have been obtained. For all the measured coupling rate constants an average value of k1 = 1.9 x 10(9) M-1 s-1 was found with a relatively small variation in the coupling rates (0.8-2.9 x 10(9) M-1 s-1). The results demonstrate that the coupling rate k1 is insensitive to changes in the steric and electronic properties of the radicals and the structure and standard potentials of the aromatic radical anions.     

On three problems for sequences

If ξ∈ (0,1) and A=a_n, n?? is a sequence of real numbers define S_n(ξ,A)∶=Σ{a_k∶:k=[nξ]+1 to n}, n??, where [x] is the greatest integer less than or equal to x. In the theory of regularly varying sequences the problem arose to conclude from the convergence of the sequence S_n (ξ,A), n??, for all ξ in an appropriate set K of real numbers, that the sequence a_n, n??, converges to zero. It was shown that such a conclusion is possible if K={ξ,1?ξ} with ξ∈ (0,1) irrational. Then the following three questions were posed and will be answered in this paper:

1. does the convergence of S_n (ξ,A), n??, for a single irrational number ξ imply a_n→0.
2. does the convergence of S_n(ξ,A), n??, for finitely many rational numbers ξ∈ (0, 1) imply a_n→0.
3. does the convergence of S_n (ξ,A), n??, for all rational numbers ξ∈ (0,1) imply a_n→0?