Theory of aging in structural glasses

The random first-order transition theory of the dynamics of supercooled liquids is extended to treat aging phenomena in nonequilibrium structural glasses. A reformulation of the idea of "entropic droplets" in terms of libraries of local energy landscapes is introduced which treats in a uniform way the supercooled liquid (reproducing earlier results) and glassy regimes. The resulting microscopic theory of aging makes contact with the Nayaranaswamy-Moynihan-Tool nonlinear relaxation formalism and the Hodge-Scherer extrapolation of the Adam-Gibbs formula, but deviations from both approaches are predicted and shown to be consistent with experiment. The nonlinearity of glassy relaxation is shown to quantitatively correlate with liquid fragility. The residual non-Arrhenius temperature dependence of relaxation observed in quenched glasses is explained. The broadening of relaxation spectra in the nonequilibrium glass with decreasing temperature is quantitatively predicted. The theory leads to the prediction of spatially fluctuating fictive temperatures in the long-aged glassy state, which have non-Gaussian statistics. This can give rise to "ultraslow" relaxations in systems after deep quenches.     

Rhodopsin exhibits a preference for solvation by polyunsaturated docosohexaenoic acid

An all-atom molecular dynamics simulation of rhodopsin in a membrane environment has been carried out with lipid composition similar to that of the retinal membrane. The initial conformation of the protein was taken from the X-ray crystallographic structure (1F88), while those of the lipids came from a previous molecular dynamics simulation. During the course of the 12.5 ns simulation, the initially randomly placed lipids adopt an anisotropic solvation structure around the protein. The lipids, having one saturated stearic acid chain and one polyunsaturated docosohexaenoic acid chain with a zwitterionic phosphatidylcholine headgroup, arrange themselves to maximize contact between the polyunsaturated chain and the protein surface. This organization is driven by energetically favorable interactions between the transmembrance helices and the docosohexaenoyl chains that are largely of the van der Waals type. These observations are consistent with various experimental studies on rhodopsin and other G-protein coupled receptors and with the picture of extreme flexibility in polyunsaturated fatty acid chains that has arisen from recent NMR and computational work.     

Photon-induced dissociation with a four-sector tandem mass spectrometer

The feasibility of using photodissociation of protonated peptide molecules to sequence specific fragment ions with a 193-nm pulsed laser beam in a magnetic deflection tandem mass spectrometer of EBEB configuration was demonstrated. Although the short pulse (15 ns) and low repetition rate (100 Hz) of the excimer laser permitted the irradiation of only ～ 0.02% of the (M + H)⁺ ions exiting MS-1, a photon-induced decomposition spectrum of the heptapeptide angiotensio III (M _r 930.5) was produced that was practically the same (but with better signal-to-noise ratio) as that generated by collision-activated dissociation at the same low duty cycle. Because of the low and pulsed fragment ion currents, an array detector was used to record the spectra. A dependence between laser power and abundance of fragment ions was observed (increased power increases the relative abundance of ions of low mass). Laser power was varied from 6 to 80 mJ. Formation of fragment ions from a large peptide (melittin, M, 2844.75) was also observed. The results permit the design of modifications that may increase the fragment ion yield to 10% or higher, which would make photon-induced decomposition a useful method for magnetic deflection mass spectrometers.     

Oxydation von Allylalkoholen mit Blei(IV)-acetat

Lead tetraacetate (LTA) oxidation of the allylic alcohols 1, 10, 14 and 19 leads to the formation of the epoxides 2, 11, 15 and 20 , products of a novel internal addition reaction of the electron deficient alcohol oxygen to the allylic double bond. In some cases ( 10, 14 ) the formation of a new type of acetoxylated enolethers ( 12, 16 ) is observed. The LTA oxidation of the allylic dienols 21 and 29 gives rise to the formation of the epoxyacetates 25 and 33 , products of a similar internal addition reaction. Furthermore, a variety of cyclization products ( 22, 23, 24, 26, 30, 31, 32 and 34 ) has been isolated whose formation requires an isomerisation of the allylic trans double bond to a cis one.     

Beiträge zur Chemie der Pyrrolpigmente, 38. Mitt.: Zur Assoziation von Gallenpigmenten

The long standing problem of solvent dependent absorption spectra of certain bile pigments such as bilirubindimethylester has been solved by measurement of molecular masses by means of vapour pressure osmometry. Using this method and the investigation of the concentration and temperature dependence of the absorption spectra on several model compounds an association equilibrium for pigments of the rubinoid structural type could be confirmed. Moreover the optical properties of the coexisting species and the corresponding equilibrium constants could be deduced by spectroscopic techniques. Verdinoid pigments lacking free carboxylic functions on the other hand tend to be monomeric in solution. A heteroassociated species involving equimolar amounts of a verdinoid and a rubinoid pigment could be verified existing on adsorbents like silicagel.

37. Mitt.:Falk, H., Thirring, K., Tetrahedron, im Druck.     

Notiz zur quantitativen Bestimmung von Si-H- und Si-Si-Gruppen

Zusammenfassung Eine einfache und genaue Methode zur Bestimmung von Si-H- und Si-Si-Gruppen wird vorgeschlagen, die auf alkalischer Hydrolyse der Substanz in einem verschlossenen und evakuierten Kolben und AuswÄgen des dem entwickelten Wasserstoff entsprechenden Wasservolumens beruht. Bei H-Gehalten von 1–2% betrÄgt die Genauigkeit ± 0,03% (abs.).

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Note on the quantitative determination of Si-H- and Si-Si-groups

A simple, robust and surprisingly exact method for the quantitative determination of Si-H- or Si-Si-groups is based on alkaline hydrolysis of the Si-H- or Si-Si-containing substances in a sealed and evacuated vessel and weighing of the volume of water equivalent to the developed volume of hydrogen. The accuracy is ± 0.03% (abs.) with H contents of 1–2%.

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Herrn Prof. Dr. E. Asmus zum 60. Geburtstag gewidmet.     

Halogenated 3-pyridylketones

The oxidation of 2,6-dichloro-3-benzylpyridines and bis(2,6-dichloro-3-pyridyl)methanes, respectively, was accomplished using chromic trioxide in a highly acidic medium. The synthesis of several phenyl-3-(2,6-dichloropyridyl)ketones and of bis(2,6-dichloro-3-pyridyl)ketone are reported.     

Perturbed sites and host—guest—host exciton cascade in the biphenyl isotopic mixed crystal phosphorescence

An interesting energy cascade is observed in the phosphorescence spectra of 1% biphenyl-h₁₀ in biphenyl-d₁₀ (2–15 K); strongly perturbed host sites, with energy levels below that of the protonated guest, quench the guest sites at higher temperatures (11–15 K). The identification of the perturbed sites is based on vibrational characteristics (both intensity and frequency), obtained with the help of phosphorescence spectra of biphenyl-h₁₀ and biphenyl-d₁₀ in an argon matrix, indicating an isotope dependent vibronic structure. A partial vibrational analysis is presented, resulting in confirmation of the first triplet state of biphenyl as orbitally ungerade. The dynamics of the triplet excitation are discussed, including several possible mechanisms explaining the non-Boltzmann nature of the low-temperature steady state.