The large scale topology and algebraic K-theory of arithmetic groups

New compactifications of symmetric spaces of noncompact type X are constructed using the asymptotic geometry of the Borel–Serre enlargement. The controlled K-theory associated to these compactifications is used to prove the integral Novikov conjecture for arithmetic groups.     

The synthesis and thermal curing parameters of a novel quinoxaline monomer with terminal ethynyl thermoset and phenylethynyl intramolecular cycloaddition postcure capability

The Synthesis of 3,3′-bis(4-[3-ethynylphenoxy]phenyl)-7,7′-bis(phenylethynyl)-2,2′-diphenyl-6,6′-biquinoxaline (I) was accomplished by the reaction of 2,2′-bis(phenylethynyl)-5,5′-diaminobenzidine (II) and 4-(3-ethynylphenoxy)benzil. Thermal analysis of I indicated a softening temperature of 107°C, followed by an exotherm above 150°C that corresponded to a independent crosslinking reaction of the terminal acetylene groups and an intramolecular cycloaddition (IMC) reaction of the 2,2′-bis(phenylethynyl)biphenyl moieties. In the synthetic work substantial improvements were made in the synthesis of II. The sample of I was cured at 200°C and the maximum partially cured transition temperature attained was 280°C. A sample of 3,3′-bis(4,[3-ethynylphenoxy]phenyl)-2,2′-diphenyl-6,6′-biquinoxaline (IV) was similarly tested as a model without IMC capability and its corresponding value was 250°C. The difference between these two values is discussed briefly.     

Modification of the Orientation of Substitution Reactions on Thiophene and Furan Derivatives

Under normal conditions, thiophene and furan derivatives are substituted in the α position, and no convenient alternative methods for the preparation of β-substitution products have been available until now. The present article describes a method that permits the synthesis of many β-substituted thiophenes and furans. In this method, the carbonyl group in α-aldehydes or ketones of the thiophene and furan series is blocked by complex formation with an excess of aluminum chloride, so that electrophilic substitution takes place in position 4. In another useful method, the carbonyl group is blocked by acetalization. The acetals can be metalated in the ring by organolithium compounds.     

Distance measurements between paramagnetic centers and a planar object by matrix Mims electron nuclear double resonance

Frequency-domain electron nuclear double resonance (ENDOR), two time-domain electron nuclear double resonance techniques, and electron spin echo envelope modulation spectroscopy are compared with respect to their merit in measurements of small hyperfine couplings to nuclei with intermediate gyromagnetic ratio such as 31P. The frequency-domain Mims ENDOR experiment is found to provide the most faithful line shapes. In the limit of long electron-nuclear distances of more than 0.5 nm, sensitivity of this experiment is optimized by matching the first interpulse delay to the transverse relaxation time of the electron spins. In the same limit, Mims ENDOR efficiency scales inversely with the sixth power of distance. Hyperfine splittings as small as 33 kHz can be detected, corresponding to an electron-31P distance of 1 nm. In systems, where a certain kind of nuclei is distributed in a plane, measurements of intermolecular hyperfine couplings can be analyzed in terms of a distance of closest approach of a paramagnetic center to that plane. By applying this technique to spin-labeled lipids in a fully hydrated lipid bilayer it is found that for a fraction of lipids, chain tilt angles can be 25 degrees larger than the mean tilt angle of the lipid chains. This model of all-trans hydrocarbon chains with a broad distribution of tilt angles is also consistent with orientation selection effects in high-field ENDOR spectra.     

Orientation selective ESEEM studies on the blue oxidases laccase and ascorbate oxidase

The blue oxidases, laccase and ascorbate oxidase, contain three spectroscopically distinct copper binding sites, two of which are EPR detectable in the oxidized Cu(II) state, called type 1 (T1) and type 2 (T2). The three dimensional structure of ascorbate oxidase has recently been determined (Messerschmidt A.et al.: J. Mol. Biol.206, 513 (1989)) while that of laccase has not. We have therefore carried out comparative electron spin echo envelope modulation (ESEEM) measurements on ascorbate oxidase, laccase and laccase in which T1 Cu(II) was substituted with Hg(II) in order to obtain structural information about the copper sites in laccase. The ESEEM results clearly show that there are as many histidines in laccase as in ascorbate oxidase, i.e., at least two at each site. Orientation selective ESEEM experiments showed that in the T1 site in both enzymes the two remote (uncoordinated) nitrogens are magnetically inequivalent and have different hyperfine interactions. Furthermore, the isotropic hyperfine constants of both remote nitrogens in laccase T1 are larger than those in ascorbate oxidase T1. In laccase T2 two remote nitrogens show similar hyperfine couplings and the modulation depth is significantly deeper than in ascorbate oxidase. Finally, it is suggested that the difference between the NQR frequencies of the remote nitrogens in T1 and T2 in both oxidases can be attributed to the alkyl group of the side chain being adjacent to the bound imidazole in T1 and to the remote nitrogen in T2. This is in accordance with the known X-ray structure of ascorbate oxidase.     

Diazoalkanes in the Reactions with Dialkyl (Thio)-Phosphites

Abstract

The photochemical, thermo-catalytical and thermal reactions of diazoalkanes with dialkyl (thio)phosphites were studied.

Thus, the photolysis of dimethyldiazomalonate and methyl-diazoacetate with dialkyl(thio)phosphites gives P-H insertion products only upon triplet-sensitized conditions (i), whereas diphenyldiazomethane gives P-H insertion products upon direct photolysis as well (ii). The investigation of 31 the reaction mechanism is based on CIDNP ³¹P method. The catalytical reactions (iii) are a convenient method of preparing (thio)phosphonates.     

Review of Sublimation Thermodynamics of Polycyclic Aromatic Compounds and Heterocycles

This review details sublimation vapor pressure and thermodynamic data on 85 polycyclic aromatic compounds and heterocycles from the early 1900s through 2012. These data were collected using a variety of vapor pressure measurement techniques, from effusion to gas saturation to inclined‐piston manometry. A brief overview of each measurement technique is given; these methods yield reproducible sublimation vapor pressure data for low volatility organic compounds such as polycyclic aromatic compounds and heterocycles. Several conclusions can be drawn from this literature survey, specifically that there remains a dearth of data on the sublimation thermodynamics (and fusion thermodynamics) of heteroatomic high molecular weight aromatic compounds, inhibiting a holistic understanding of the effect of specific heteroatoms and substituent position on the thermodynamics of these compounds. However, we can clearly see from the data that there are a variety of potential intermolecular interactions at work that generally tend to increase the enthalpy of sublimation and decrease the vapor pressure of a substituted polycyclic aromatic compound/polycyclic heterocycles versus its parent compound.