Krylov-Bogolyubov averaging of asymptotically autonomous differential equations

We apply the Krylov and Bogolyubov asymptotic integration procedure to asymptotically autonomous systems. First, we consider linear systems with quasi-periodic coefficient matrix multiplied by a scalar factor vanishing at infinity. Next, we study the asymptotically autonomous Van-der-Pol oscillator.

     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 2004     

H MAS NMR monitoring of the C-labeled carbon scrambling for propane in zeolite H-ZSM-5

It has been demonstrated that ¹H MAS NMR spectroscopy can be used as a tool for in situ monitoring the reaction kinetics of ¹³C-labeled carbon scrambling in alkane molecules adsorbed on zeolite catalysts at the reaction temperature of 540–570 K. The accuracy of the results and the time resolution are improved compared to ¹³C MAS NMR spectroscopy.     

Computing homotopic shortest paths in the plane

We address the problem of computing homotopic shortest paths in the presence of obstacles in the plane. Problems on homotopy of paths received attention very recently [Cabello et al., in: Proc. 18th Annu. ACM Sympos. Comput. Geom., 2002, pp. 160–169; Efrat et al., in: Proc. 10th Annu. European Sympos. Algorithms, 2002, pp. 411–423]. We present two output-sensitive algorithms, for simple paths and non-simple paths. The algorithm for simple paths improves the previous algorithm [Efrat et al., in: Proc. 10th Annu. European Sympos. Algorithms, 2002, pp. 411–423]. The algorithm for non-simple paths achieves O(log²n) time per output vertex which is an improvement by a factor of O(n/log²n) of the previous algorithm [Hershberger, Snoeyink, Comput. Geom. Theory Appl. 4 (1994) 63–98], where n is the number of obstacles. The running time has an overhead O(n²⁺) for any positive constant . In the case k<n²⁺, where k is the total size of the input and output, we improve the running to O((n+k+(nk)^2/3)log^O(1)n).     

Integrable Structure of Conformal Field Theory II. Q-operator and DDV equation

This paper is a direct continuation of [1] where we began the study of the integrable structures in Conformal Field Theory. We show here how to construct the operators ${\bf Q}_{\pm}(\lambda)$ which act in the highest weight Virasoro module and commute for different values of the parameter λ. These operators appear to be the CFT analogs of the Q - matrix of Baxter [2], in particular they satisfy Baxter's famous T- Q equation. We also show that under natural assumptions about analytic properties of the operators as the functions of λ the Baxter's relation allows one to derive the nonlinear integral equations of Destri-de Vega (DDV) [3] for the eigenvalues of the Q-operators. We then use the DDV equation to obtain the asymptotic expansions of the Q - operators at large λ; it is remarkable that unlike the expansions of the T operators of [1], the asymptotic series for Q(λ) contains the “dual” nonlocal Integrals of Motion along with the local ones. We also discuss an intriguing relation between the vacuum eigenvalues of the Q - operators and the stationary transport properties in the boundary sine-Gordon model. On this basis we propose a number of new exact results about finite voltage charge transport through the point contact in the quantum Hall system. Received: 2 December 1996 / Accepted: 11 March 1997     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006     

Application of Horner–Emmons Olefination to the Crown-Ether Derivatives

An effective synthetic approach to the preparation of a new crown-ether vinylogs involving the Horner–Emmons olefination of carbonyl precursors with the use of C₂- and C₅-phosphonates was proposed. The effects of the conjugation chain length and the nature of the terminal polar functions in the phosphonate reagent on the yield and process stereoselectivity were discussed.     

Luminescent Zn and Pd tetranaphthaloporphyrins

Zn and Pd complexes of meso-tetraphenyltetranaphthaloporphyrins (Ph(4)TNP) exhibit strong infrared absorption bands and luminesce in solutions at room temperature. S1 --> S0 fluorescence (lambda(max) = 732 nm, phi = 5.3%) is the predominant emission in the case of ZnPh(4)TNP (1). This emission is in part due to the delayed fluorescence (phi = 1.1%). Phosphorescence (T1 --> S0) of 1 (lambda(max) = 973 nm) is very weak (phi = 0.04%) and occurs with lifetime of about 440 micros in deoxygenated DMF. In the case of PdPh(4)TNP (2), almost no S1 --> S0 fluorescence could be observed, while the main emission detected was T1 --> S0 phosphorescence (lambda(max) = 938 nm). The phosphorescence of 2 occurs with lifetime of about 65 micros and (phi=6.5%) in deoxygenated DMF solution. Metalloporphyrins 1 and 2 are promising near infrared dyes biomedical applications.     

Kinetics and mechanism of the Co(II)-assisted oxidation of thioureas by dioxygen

Catalytic oxidation of N,N'-dimethylthiourea and thiourea by dioxygen in water using a new cobalt(II) complex of octasulfophenyltetrapyrazinoporphyrazine was performed under mild conditions. The reaction is shown to include the formation of an intermediate anionic five-coordinate complex followed by an unusual two-electron oxidation to produce the corresponding urea and elemental sulfur (S8). Kinetic and thermodynamic parameters for the different reaction steps of the process were determined. Drastic differences in catalytic activity of cobalt and iron octasulfophenyltetrapyrazinoporphyrazines were observed.