Miscible blends of modified poly(aryl ether ketones) with aromatic polyimides

The phase behavior of binary blends of poly(ether ether ketone) (PEEK), sulfonated PEEK, and sulfamidated PEEK with aromatic polyimides is reported. PEEK was determined to be immiscible with a poly(amide imide) (TORLON 4000T). Blends of sulfonated and sulfamidated PEEK with this poly(amide imide), however, are reported here to be miscible in all proportions. Blends of sulfonated PEEK and a poly(ether imide) (ULTEM 1000) are also reported to be miscible. Spectroscopic investigations of the intermolecular interactions suggest that formation of electron donoracceptor complexes between the sulfonated/sulfamidated phenylene rings of the PEEKs and the n-phenylene units of the polyimides are responsible for this miscibility. © 1993 John Wiley & Sons, Inc.     

Crystallization of Arthrobacter sp. strain 1C N-(1-D-carboxyethyl)-L-norvaline dehydrogenase and its complex with NAD+

The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres.     

On the formation of artefact peaks in linked scans of the magnet and electric sector fields in a mass spectrometer

The apperrance of peaks at non-integral masses in linked scans, where the ratio B/E is kept constant, is shown to be caused by fragmentations of metastable ions occuring in the region between the magnetic and electric sectors. A formula is given for calculating the mass of the parent metastable ion and that of its daughter ion.     

Reversible energy transfer

Analysis of the transient and steady-state kinetics of reversible energy transfer shows that while the interpretation of lifetime measurements is difficult unless the donor and acceptor lifetimes are appreciably different, quantum yield measurements are relatively easy to interpret.

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Zusammenfassung Die Analyse der Kinetik der Übergangszustände und der stationären Zustände der reversiblen Energieübertragung zeigt, daß im Gegensatz zu einer schwierigen Interpretation der Messungen der Lebensdauer — es sei denn die Lebensdauer von Donor und Acceptor sind wesentlich voneinander verschieden — die Messungen der Quantumausbeute verhältnismäßig einfach zu interpretieren sind.

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Résumé L'analyse de la cinétique de l'état transitoire et de l'état stationnaire du transfert réversible d'énergie montre que, si l'interprétation des mesures de durée de vie est difficile, à moins queles durées de vie du donneur et de l'accepteur soient très différentes, il est par contre relativement facile d'interpréter les mesures de rendement quantique.

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Dedicated to the memory of Professor K. H. Hansen.     

Lysine peroxycarbamates: free radical-promoted peptide cleavage

Strategies are reported that combine in one step a predictable chemical-based protein digestion with mass spectrometry. Lysine residue amino groups in peptides and proteins are modified by reaction with a peroxycarbonate derived from p-nitrophenol, and tert-butyl hydroperoxide. The peroxycarbonate reacts with lysine residues in peptides and proteins, and the resulting lysine peroxycarbamates undergo homolytic fragmentation under conditions of low-energy collision-induced dissociation (CID). Observed fragmentation of the peptides involves apparent free radical processes including Hofmann-L?ffler-type rearrangements that lead to peptide chain fragmentation. Strategies for directed cleavage of peptides by free radical promoted processes are feasible, and such strategies may well simplify schemes for protein analysis.     

Factors influencing the autoxidation of fatty acids: effect of olefin geometry of the nonconjugated diene

Autoxidations of cis,cis, cis,trans, and trans,trans nonconjugated octadecadienoates and pentadecadienes were carried out in the presence of alpha-tocopherol to investigate the effect of olefin geometry on this oxidation process and provide insight into the factors that influence the autoxidation of fatty acids. We have found that as the trans character of the diene increases, the amount of O(2) trapping at the central (bis-allylic) position of the pentadienyl radical also increases. In addition, the rate constant for beta-fragmentation (k(beta) approximately 10(6) s(-1)) of the bis-allylic peroxyl radical decreased on going from the cis,cis to the trans,trans diene. We have also found that for the cis,trans nonconjugated dienes, there is a preference for trapping of the pentadienyl radical by O(2) at the transoid end, generating the cis,trans conjugated hydroperoxide as the major product.     

Diastereoselective free radical halogenation,azidation, and rearrangement of beta-silyl Barton esters

[reaction: see text] Barton esters of beta-silylcarboxylic acids were decomposed by photolysis alone in organic solvents or in the presence of ethanesulfonyl azide or bromotrichloromethane. Products of the reaction, beta-silylthiopyridyl ethers, beta-silyl azides, or alkenes, were formed with significant control of stereochemistry.     

Green's functions associated with the edth operators

An integral representation for the inverses of the differential operators called edth is given in the two cases of particular interest. This operator plays a large role in the study ofH spaces and of self-dual solutions to the Yang-Mills field equations in the asymptotic domain.     

A numerical method for acoustic normal modes for shear flows

The normal modes and their propagation numbers for acoustic propagation in wave guides with flow are the eigenvectors and eigenvalues of a boundary value problem for a non-standard Sturm-Liouville problem. It is non-standard because it depends non-linearly on the eigenvalue parameter. (In the classical problem for ducts with no flow, the problem depends linearly on the eigenvalue parameter.) In this paper a method is presented for the fast numerical solution of this problem. It is a generalization of a method that was developed for the classical problem. A finite difference method is employed that combines well known numerical techniques and a generalization of the Sturm sequence method to solve the resulting algebraic eigenvalue problem. Then a modified Richardson extrapolation method is used that dramatically increases the accuracy of the computed eigenvalues. The method is then applied to two problems. They correspond to acoustic propagation in the ocean in the presence of a current, and to acoustic propagation in shear layers over flat plates.