Analysis of the 19F and 1H NMR spectra of a number of polyfluoroindenes

¹⁹F and ¹H NMR spectra of the products of nucleophilic attack on octafluoroindene are analysed and structures assigned. The major product in the reaction of butyllithium with octafluoroindene is 3-methylheptafluoroindene, with sodium borohydride it is 2-hydroheptafluoroindene and with sodium methoxide it is 3-methoxyheptafluoroindene. Vacuum pyrolysis of undecafluorotricyclo[5.2.2.0^2,6]undeca- 2,5,8-triene, with elimination of C₂F₄, gives 6-hydroheptafluoroindene as the major product. The NMR assignments are based on the unambiguous synthesis via vacuum pyrolysis of 5,6-dihydrohexafluoroindene, 3-hydro- and 3-methyl-heptafluoroindene and the large long-range coupling of 15 Hz assigned to the F-2, F-6 interaction.     

Hermitian forms and the large and small sieves

The author observes that two Hermitian forms have the same largest eigenvalue. A large sieve result of Roth-Bombieri type and Selberg's upper bound sieve with a Montgomery type error term are derived.     

A limit on the lepton-family number violating process π → μe

A FNAL E799 Collaboration has carried out a search for the lepton-family number violating decay π⁰ → μ^±e using π⁰'s produced from K_L → π⁰π⁰π⁰ decays in flight. No events were observed. Assuming that lepton-family number violation is charge independent, the 90% confidence level upper limit on

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was determined to be 8.6 × 10⁻⁹.     

OH-stretch vibrational spectroscopy of hydroxymethyl hydroperoxide

We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH(2)OOH) and its partially deuterated analogue, HOCD(2)OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1nu(OH) and 2nu(OH) regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH(2)OOH initiated by excitation of the 4nu(OH) and 5nu(OH) overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4nu(OH) region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodissociation is not expected to significantly influence the atmospheric lifetime of hydroxymethyl hydroperoxide.     

A comparison of the dynamic mechanical relaxation behavior of linear low- and high-density polyethylenes

The mechanical relaxation behaviors of oriented samples of a linear low-density polyethylene (LLDPE) and a high-density polyethylene (HDPE) were studied using tensile dynamic mechanical measurements. The anisotropy and activation energies of the relaxations were determined for several different samples to investigate why the α-relaxation in HDPE has characteristics similar in some respects to both the α- and β-relaxations in LLDPE. It is concluded that the anisotropy of the α-relaxation in LLDPE is determined by c-shear, whereas in HDPE it relates to interlamellar shear. The activation energy measurements, however, show that the thermally activated process for the α-relaxation in both the LLDPE and HDPE is c-shear. It is proposed that, in HDPE, c-shear has to occur before there is enough mobility at the fold surface for interlamellar shear. It is concluded that the β-relaxation is not observed in HDPE because the interlamellar regions are too constrained to allow interlamellar shear without c-shear.     

Vibrational overtone initiated unimolecular dissociation of HOCH2OOH and HOCD2OOH: evidence for mode selective behavior

The vibrational overtone induced unimolecular dissociation of HMHP (HOCH(2)OOH) and HMHP-d(2) (HOCD(2)OOH) into OH and HOCH(2)O (HOCD(2)O) fragments is investigated in the region of the 4nu(OH) and 5nu(OH) bands. The unimolecular dissociation rates in the threshold region, corresponding to the 4nu(OH) band, exhibit measurable differences associated with excitation of the OH stretch of the alcohol versus the peroxide functional group, with the higher energy alcohol OH stretching state exhibiting a slower dissociation rate compared to the lower energy peroxide OH stretch in both HMHP and HMHP-d(2). Predictions using the Rice-Ramsperger-Kassel-Marcus theory give rates that are in reasonably good agreement with the measured dissociation rate for the alcohol OH stretch but considerably differ from the measured rates for the peroxide OH stretch in both isotopomers. The present results are interpreted as suggesting that the extent of intramolecular vibrational energy redistribution (IVR) is different for the two OH stretching states associated with the two functional groups in HMHP, with IVR being substantially less complete for the peroxide OH stretch. Analysis of the OH fragment product state distributions in conjunction with phase-space theory simulation gives a D(0) value of 38+/-0.7 kcal/mole for breaking the peroxide bond in HMHP.     

Toward beta-amino acid proteins: a cooperatively folded beta-peptide quaternary structure

Folded polymers in nature are assembled from simple monomers and adopt complex folded structures through networks of stabilizing noncovalent interactions. These interactions define secondary and tertiary structure and in most cases specify a unique three-dimensional architecture. Individual secondary or tertiary structures can also associate with one another to form multi-subunit quaternary structures. Nonnatural folded polymers have potential for similar structural versatility. Here we describe a pair of beta3-peptides whose sequences were designed to promote a 14-helix structure in water, favor hetero-oligomer formation, and disfavor nonspecific aggregation. These beta3-peptides assemble noncovalently into a well-defined hetero-oligomer characterized by a defined stoichiometry, a highly stabilized secondary structure, and a cooperative melting transition (TM > 55 degrees C). This work demonstrates that beta3-peptides can assemble into defined, cooperatively folded quaternary structures and constitutes an important step toward designing protein-like assemblies from nonnatural polymers.