Ion solvation by channel carbonyls characterized by 17O solid-state NMR at 21 T

Recently available ultrahigh magnetic fields offer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of second-order quadrupole interactions. Here, we present a new approach for understanding the function and energetics of ion solvation in channels using solid-state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A. The chemical shift and quadrupole coupling parameters obtained in powder samples of lyophilized material are similar to those shown in the literature for carbonyl oxygens. In lipid bilayers, it is found that the carbonyl 17O anisotropic chemical shift of Leu10, one of the three carbonyl oxygens contributing to the ion binding site in gramicidin A, is altered by 40 ppm when K+ ion binds to the channel, demonstrating a high sensitivity to such interactions. Moreover, considering the large breadth of the carbonyl 17O chemical shift (>500 ppm), the recording of anisotropic 17O chemical shifts in bilayers aligned with respect to magnetic field B0 offers high-quality structural restraints similar to 15N and 13C anisotropic chemical shifts.     

The effect of chain structure on the annealing and deformation behaviour of polymers

Summary In a tensile test ductile thermoplastics may give either uniform deformation or necking. Recently it has been found that those giving uniform deformation either, are known to have extended chain configurations in solution, or have chemical formulae with linear structures and relatively few flexible bonds. The observed differences in behaviour can be predicted from a viscosity retarded rubber elasticity model in which a constant related to chain flexibility is introduced, which quantifies the strain hardening of the material. It is argued that the early development of strain hardening generally interferes with the localization of plastic strain in shear bands or crazes (as well as in a neck) and correlates with the stress cracking performance of high density polythenes.There is now also some evidence that polymers with extended chain configurations have small values ofcp (the change in specific heat atTg) and that this figure has an apparent correlation with draw ratio for different polymers.In the case of P.V.C. however it is possible to cause a changeover from the normal necking behaviour to uniform deformation by quenching the hot material in ice water. This process is believed to eliminate a structure which develops slowly in P.V.C. and most other thermoplastics when they are annealed at temperatures near toTg. The elimination of this structure during yielding causes strain softening and also promotes plastic strain localisation.This physical ageing or annealing process is still not well understood. It almost certainly includes free volume effects but recent studies have shown that a redistribution of rotational isomers also occurs. These observation, if correct, have fundamental implications for the physics of glassy polymers.

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Zusammenfassung Beim Zug-Test erfolgt bei dehnbaren Thermoplasten entweder eine gleichmäßige Deformation oder eine Einschnürung. Erstere tritt auf bei Vorliegen ausgestreckter Kettenkonfigurationen in Lösung oder bei Makromolekülen linearer Struktur und relativ unbiegsamer Bindungen. Die beobachteten Unterschiede wurden anhand eines ViskositätsModells mit verminderter Gummi-Elastizität unter Zugrundelegung von Literaturdaten diskutiert. Die Kettensteifheit wird rechnerisch durch Einfügung einer Konstanten berücksichtigt; sie steht in Konkurrenz mit der Lokalisierung der plastischen Dehnung und korreliert mit dem Auftreten einer Spannungsriß-Bildung im Polyäthylen hoher Dichte. Es wird darauf hingewiesen, daß sich die spezifische Wärme von Polymeren mit ausgedehnter Kettenkonfiguration beiTg nur wenig ändert; dieser Effekt steht mit dem Dehnungsverhältnis verschiedener Polymerer in Einklang.Bei PVC kann jedoch durch Abschrecken des heißen Materials in Eiswasser ein Übergang vom normalen Einschnürungsverhalten zu einer gleichmäßigen Deformation erzielt werden; dieser Effekt ist durch die Unterdrückung einer speziellen Struktur bedingt und kann auch bei der Temperung anderer thermoplastischer Polymerer nahe beiTg auftreten.Die sich bei der physikalischen Alterung und bei der Temperung abspielenden Vorgänge lassen sich noch nicht erklären. Sie umfassen sicherlich Effekte des freien Volumens und die Rückverteilung von Rotations-Isomeren. Beobachtungen dieser Art sind von grundsätzlicher Bedeutung für die Physik glasartiger Polymerer.

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Dedicated to Prof. Dr. Rehage on the occasion of his 60th birthday.

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With 22 figures and 2 tables     

Oxazoline chemistry. Part 12: A metal-mediated synthesis of DMU-212; X-ray diffraction studies of an important anti-cancer agent

An improved synthesis of the anti-cancer agent DMU-212 (trans-3,4,5,4′-tetramethoxystilbene) is described. The methodology involves the use of a Pd-oxazoline catalyst as a mediator of a regio-selective (Heck) C-C bond formation reaction. A simple isolation step is then used to obtain the title material. The compound has been further characterised in the solid-state by X-ray diffraction methods.     

The grapefruit diet

According to major research studies, 50 percent of all distributed data processing is really distributed document delivery. Up to 70 percent of all telephone calls do not reach the intended party, resulting in what has been aptly called, "telephone tag." Electronic mail is a rapidly emerging technology using computers and telecommunications networks to transmit notes, messages and documents instantaneously. Online information systems for document management, distribution and retrieval is an area of electronic mail far more powerful. Computer teleconferencing, as it is often called, allows for ongoing meetings online with persons from remote locations without regard to time zone limitations. This article will focus on the definitions of computer teleconferencing and other new "online" technologies, and how they will impact document development, management and distribution. It is based on the author's presentation at the 1983 NMA Annual Conference & Exposition in Philadelphia.     

Cellulose

Ohne Zusammenfassung     

Crystal and molecular structure, and P N.M.R. characteristics of di-μ-chlorodi(propionyl)bis(dimethylphenylphosphine)diplatinum(III). Trans-influence of ligands in binuclear complexes

The known complex, $\text{trans}$-(η-C₅H₅)₂Rh₂(CO)₂(CF₃C₂CF₃) is formed in high yield from (η-C₅H₅)Rh(CO)₂ and CF₃FCCF₃ at 100°. The less stable $\text{cis}$-isomer of the complex is obtained in low yield from the same reaction. The infrared, ¹H, ¹⁹F and ¹³C NMR spectra of the two isomers are compared. The $\text{trans}$-isomer undergoes CO scrambling in solution at room temperature, and the variable temperature ¹³C NMR spectra are consistent with a pairwise bridge opening and closing mechanism. The mechanism is extended to account for the isomerization of $\text{cis}$ to $\text{trans}$ isomer, whihc has a half-life of 12 h at room temperature. The ¹³C spectrum indicates that the $\text{cis}$-isomer is static in solution at room temperature. The $\text{trans}$-isomer is reversibly protonated by protonic acids, and BF₄^? and PF₆^? salts of the protonated species can be isolated. The spectroscopic properties of these salts are consistent with protonation at one of the alkynyl-carbons, but it is not possible to distinguish between two alternative structures for the complex cation.Treatment of (η-C₅H₅)₂Rh₂(CO)₂(CF₃C₂CF₃) with (η-C₅H₅)Rh(CO)₂ gives the trinuclear complex (η-C₅H₅)₃Rh₃(CO)(CF₃C₂CF₃) in 80% yield. The analogoug but-2-yne complex is formed from (η-C₅H₅)₃Rh₃(CO)₃ and MeCCMe. The infrared, ¹H, ¹⁹F and ¹³C NMR spectra indicate that the hexafluorobut-2-yne complex exists in two different structural arrangements in solution. One has an edge bridging, and the other a face bridging carbonyl. The proportion of the isomers is affected by the solvent polarity. The spectra of the but-2-yne complex indicate it is fluxional at room temperature, and has a face bridging structure in solution regardless of the polarity of the solvent. Reversible protonation of the hexafluorobut-2-yne complex occurs in protonic acids, and the salt [(η-C₅H₅)₃Rh₃(CO)(CF₃C₂CF₃)H]⁺[BF₄]^?,H₂O can be isolated. The spectroscopic properties of this complex are consistent with a structure incorporating an edge-bridging carbonyl, and probably, an edge-bridging hydride ligand.     

Untersuchung von Textilien und Textilrohstoffen

Ohne Zusammenfassung