Reconstitution of apomyoglobin with bile pigments

Summary Apomyoglobin was reconstituted with bile pigments of the verdinoid, 2,3-dihydroverdinoid, pterobilinoid, and violinoid type. Absorption and circular dichroism data as well as formation constants of the complexes were measured. From these results it was concluded that chromophore binding and induced chirality of these pigments are mainly governed by a lipophilic region opposite to the propionic side chain(s) and the asymmetric position of the hydrogen bonding acceptors of the propionic acid side chain(s) at the entrance of the protein pocket.Dedicated to Prof. Dr. A. Eschenmoser on occasion of his 65th birthday     

Active to sterile neutrino mixing limits from neutral-current interactions in MINOS

Results are reported from a search for active to sterile neutrino oscillations in the MINOS long-baseline experiment, based on the observation of neutral-current neutrino interactions, from an exposure to the NuMI neutrino beam of 7.07×10(20) protons on target. A total of 802 neutral-current event candidates is observed in the Far Detector, compared to an expected number of 754 ± 28(stat) ± 37(syst) for oscillations among three active flavors. The fraction f(s) of disappearing ν(μ) that may transition to ν(s) is found to be less than 22% at the 90% C.L.     

Measurement of the neutrino mass splitting and flavor mixing by MINOS

Measurements of neutrino oscillations using the disappearance of muon neutrinos from the Fermilab NuMI neutrino beam as observed by the two MINOS detectors are reported. New analysis methods have been applied to an enlarged data sample from an exposure of 7.25×10(20) protons on target. A fit to neutrino oscillations yields values of |Δm(2)|=(2.32(-0.08)(+0.12))×10(-3) eV(2) for the atmospheric mass splitting and sin(2)(2θ)>0.90 (90% C.L.) for the mixing angle. Pure neutrino decay and quantum decoherence hypotheses are excluded at 7 and 9 standard deviations, respectively.     

Glass physics: from fundamentals to applications

The European Physical Journal E -     

Elementare Eigenschaften lokaler–Polynom–Schätzer: ein Streifzug durch die lineare Algebra

Zusammenfassung. Der lokale–Polynom–Sch?tzer besteht darin, an eine Sequenz von aufeinanderfolgenden Datenpunkten lokal ein Polynom anzupassen und damit zuf?llige Schwankungen in den Daten wegzugl?tten. Dieser Ansatz gewinnt in der nichtparametrischen Kurvensch?tzung st?ndig an Bedeutung. Es wird gezeigt, wie die Herleitung einiger elementarer Eigenschaften dieses Handwerkszeuges des Datenanalytikers einen Streifzug durch die lineare Algebra erforderlich macht. Eingegangen am 27.03.1998 / Angenommen am 15.06.1998     

Testing for a $$delta $$ -neighborhood of a generalized Pareto copula

Annals of the Institute of Statistical Mathematics - A multivariate distribution function F is in the max-domain of attraction of an extreme value distribution if and only if this is true for the...     

Tuning of switching properties and excited-state dynamics of fulgides by structural modifications

The ultrafast photo-induced dynamics of the E-isomers of four selected photochromic fulgides with distinct structural motifs have been elucidated by femtosecond broadband transient absorption spectroscopy in n-hexane as solvent. E→C and E→Z isomerisations, respectively, with time constants of ～0.12 ± 0.02 ps and ～0.34 ± 0.03 ps taking place in parallel were found for derivatives with a methyl substituent at the central hexatriene (HT) unit. In contrast, fulgides with increased steric constraints by an iso-propyl substituent or by intramolecular bridging displayed virtually zero E→Z isomerisation, but instead a desired accelerated and more efficient ring closure in a reaction time of only ～50 ± 10 fs. Both photoisomerisations appear to follow excited-state pathways with distinctive conical intersections. For the ring closure, direct barrierless pathways with steep downhill gradients are likely. Furthermore, the results indicate conformer-specific reactions, with ring closure exclusively by the E(α) conformer and E→Z isomerisation predominantly by the E(β) conformer, because the E(α)→Z channel is unfavoured by the faster and kinetically more competitive E(α)→C reaction. DFT calculations of the equilibrium structures showed that the sterically demanding groups at the HT unit shift the conformer equilibria towards the E(α) conformers. At the same time, they appear to cause a favourable pre-orientation of the furyl unit that accelerates the conrotatory ring closure in the E(α)→C reaction. Benzo-annulation of the furyl unit has little effect on the observed dynamics. Overall, the results demonstrate how the excited-state dynamics and thereby the photoswitching properties of fulgides can be successfully tuned and improved by structural modifications at the chromophores.