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     

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     

Fluorescence polarization immunoassays for pesticides

Fluorescence polarization immunoassay methods for the detection of pesticides and their metabolites or degradation products are reviewed. Advantages and limitations for application to pesticide detection in environmental and food samples are discussed. The influence of the structure of fluorescent-labeled tracers and the affinity and specificity of antibodies on analytical performance is examined. The methods are simple, readily automated, and rapid (total time for assay of a water sample is about 1 min) with sensitivity of 1 - 10 ng/ml pesticide in 0.01 - 0.1 ml sample.     

Composition and structure of zirconium complexes in tributyl phosphate extracts of Zr from concentrated nitric acid solutions

Using quantitative difference IR spectroscopy we have found that the tibutyl phosphate & acts of zirconium from 12–15 M HN03 contain ionic associates [(TBP)₂H⁺]Zr(NO₃)₅ ^– (I) and [TBP· H₃0⁺ (H₂0)_n]Zr(N0₃)₅ ^– (II), where n = 1, 2, as well as the Zr(N0₃)₄(TBP)₂ complex at a lower concentration than (I) and (I.). The equilibrium I II is shifted toward II at higher C_{HNo 3} ⁰ and lower c_Zr ⁰. The structure of associates I and II is discussed.Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, D. I. Mendeleev Moscow Chemical Technological Institute. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 80–89, September–October, 1993.Translated by L. Smolina     

New Derivatives of 5-Substituted Uracils: Potential Agents with a Wide Spectrum of Biological Activity

Pyrimidine nucleoside analogues are widely used to treat infections caused by the human immunodeficiency virus (HIV) and DNA viruses from the herpes family. It has been shown that 5-substituted uracil derivatives can inhibit HIV-1, herpes family viruses, mycobacteria and other pathogens through various mechanisms. Among the 5-substituted pyrimidine nucleosides, there are not only the classical nucleoside inhibitors of the herpes family viruses, 2′-deoxy-5-iodocytidine and 5-bromovinyl-2′-deoxyuridine, but also derivatives of 1-(benzyl)-5-(phenylamino)uracil, which proved to be non-nucleoside inhibitors of HIV-1 and EBV. It made this modification of nucleoside analogues very promising in connection with the emergence of new viruses and the crisis of drug resistance when the task of creating effective antiviral agents of new types that act on other targets or exhibit activity by other mechanisms is very urgent. In this paper, we present the design, synthesis and primary screening of the biological activity of new nucleoside analogues, namely, 5′-norcarbocyclic derivatives of substituted 5-arylamino- and 5-aryloxyuracils, against RNA viruses.     

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).     

Spectra of certain types of polynomials and tiling of integers with translates of finite sets

We investigate Fuglede's spectral set conjecture in the special case when the set in question is a union of finitely many unit intervals in dimension 1. In this case, the conjecture can be reformulated as a statement about multiplicative properties of roots of associated with the set polynomials with (0,1) coefficients. Let be an N-term polynomial. We say that {θ₁,θ₂,…,θ_N−1} is an N-spectrum for A(x) if the θ_j are all distinct and

     

Self–regularization by projection for noisy pseudodifferential equations of negative order

It is well known, that pseudodifferential equations of negative order considered in Sobolev spaces with small smoothness indices are ill–posed. On the other hand, it is known that efficient discretization schemes with properly chosen discretization parameters allow to obtain a regularization effect for such equations. The main accomplishment of the present paper is the principle for the adaptive choice of the discretization parameters directly from noisy discrete data. We argue that the combination of this principle with wavelet–based matrix compression techniques leads to algorithms which are order–optimal in the sense of complexity.     

Determination of hyperfine tensor components from nuclear frequencies at canonical orientations of the g-tensor

The analytical procedure for the determination of all components of the symmetric hyperfine tensor of the I=1/2 nucleus in the g-tensor coordinate system is described, assuming that nuclear frequencies corresponding to the principal directions of the g-tensor and exact values of the external magnetic field (or nuclear Zeeman frequencies) are experimentally available.     

Entropy Bounds in R×S Geometries

Exact calculations are given for the Casimir energy for various fields in R×S³ geometry. The Green's function method naturally gives a result in a form convenient in the high-temperature limit, while the statistical-mechanical approach gives a form convenient for low temperatures. The equivalence of these two representations is demonstrated. Some discrepancies with previous work are noted. In no case, even for N=4 SUSY, is the ratio of entropy to energy found to be bounded. This deviation, however, occurs for low temperature, where the equilibrium approach may not be relevant. The same methods are used to calculate the energy and free energy for the transverse electric modes in a half-Einstein universe bounded by a perfectly conducting 2-sphere.