Positron Emission Tomography and Random Coefficients Regression

We further explore the relation between random coefficients regression (RCR) and computerized tomography. Recently, Beran et al. (1996, Ann. Statist., 24, 2569–2592) explored this connection to derive an estimation method for the non-parametric RCR problem which is closely related to image reconstruction methods in X-ray computerized tomography. In this paper we emphasize the close connection of the RCR problem with positron emission tomography (PET). Specifically, we show that the RCR problem can be viewed as an idealized (continuous) version of a PET experiment, by demonstrating that the nonparametric likelihood of the RCR problem is equivalent to that of a specific PET experiment. Consequently, methods independently developed for either of the two problems can be adapted from one problem to the other. To demonstrate the close relation between the two problems we use the estimation method of Beran, Feuerverger and Hall for image reconstruction in PET.     

On the mechanism of aromatic hydroxylation by O(3P) atoms

It is shown that O(³P) oxidation of aromatic compounds in the liquid phase leading to phenols may involve the intermediacy of triplet diradicals.     

Violatinctamine, a new heterocyclic compound from the marine tunicate Cystodytes cf. violatinctus

A new alkaloid designated violatinctamine and four known metabolites were isolated from the tunicate Cystodytes cf. violatinctus collected in Kenya. Violatinctamine has a unique heterocyclic skeleton, which combines a benzothiazole unit and a dihydroisoquinoline unit. The structure of violatinctamine was elucidated by interpretation of MS results as well as 1D and 2D NMR spectra of the alkaloid and of its O,O′-dimethyl derivative. Analysis of the spectral information also implies that violatinctamine exists as a mixture of two tautomers—the imino-phenol and the amino quinone-methide.     

Kitungolides A, B, and C, new diterpenes from a soft coral of a new genus

Three novel compounds, designated kitungolides A (1), B (2), and C (3), were isolated from a soft coral of a new genus collected at Kitungamwe, Kenya. The three new compounds are of a unique heterotricyclic skeleton. The structures and relative stereochemistry of the compounds were elucidated by interpretation of MS, COSY, HMQC, HMBC, and NOESY experiments. [structure: see text]     

A valence bond analysis of electronic degeneracies in Jahn-Teller systems: low-lying states of the cyclopentadienyl radical and cation

The lowest doublet electronic state of the cyclopentadienyl radical (CPDR) and the lowest singlet state of the cyclopentadienyl cation (CPDC) are distorted from the highly symmetric D(5h) structure due to the Jahn-Teller effect. A valence bond analysis based on the phase-change rule of Longuet-Higgins reveals that in both cases the distortion is due to the first-order Jahn-Teller effect. It is shown that, while for the radical an isolated Jahn-Teller degeneracy is expected, in the case of the cation the main Jahn-Teller degeneracy is accompanied by five satellite degeneracies. The method offers a chemically oriented way for identifying the distortive coordinates.     

Reactions in dry media: reactions of cholesterol and cholestanes on silica bound ferric chloride : Cholestane—diacholestene rearrangement

Reaction of cholesterol with silica bound FeCl₃ resulted in a mixture of 3β-cholesteryl chloride and dicholesteryl ether.5-Cholestene and hydroxy- and halogeno-substituted cholestane derivatives gave on heating at 100° with this reagent a 1:1 mixture of 20-epimeric diacholestenes. The 20(R)-isomer gave with meta-chloroperbenzoic acid 20(R)-α-epoxide, while the 20(S)-gave a mixture of 20(S)-α- and 20(S)-β-epoxides.5α,6β-Dihydrocholestane reacted with the FeCl₃/SiO₂ under milder conditions (50°) to give 6β-hydroxy-20(R)-diacholestene, which was converted to the 20(R)-diacholestene.     

Callynormine A, a new marine cyclic peptide of a novel class

[structure: see text] A novel cyclic peptide, callynormine A, was isolated from the Kenyan marine sponge Callyspongia abnormis and its structure elucidated by interpretation of its NMR data and X-ray diffraction analysis. Callynormine A represents a new class of heterodetic cyclic peptides (designated endiamino peptides) possessing an alpha-amido-beta-aminoacrylamide cyclization functionality.     

A linear dichroism study of pyrromethene-, pyrromethenone- and bilatriene-abc-derivatives

The linear dichroism of several pyrromethene, pyrromethenone and bilatriene-abc derivatives embedded in a polyethylene film and oriented by stretching is investigated. On dissolving these pigments in the polymer matrix no changes in their conformations are observed, as compared to solutions in apolar solvents. Polarisation of the absorption bands of the pigments is deduced from the polarisation spectra. To enhance the solubility and orientation in the polymer, a pyrromethenone and a bilatriene-abc bearing a C₁₈-alkyl chain were synthesised for the first time.

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Zum Lineardichroismus von Pyrromethen-, Pyrromethenon- und Bilatrien-abc-Derivaten

Zusammenfassung Der Lineardichroismus einiger Pyrromethen-, Pyrromethenon- und Bilatrienabc-Derivate, die in eine Polyethylenfolie eingebettet vorliegen, wird untersucht. Bei der Lösung dieser Pigmente in der polymeren Matrix wird keine Veränderung der Konformation im Vergleich mit Lösungen in apolaren Lösungsmitteln beobachtet. Aus den Polarisationsspektren wird die Polarisation der Absorptionsbanden dieser Chromophore abgeleitet. Ein Pyrromethenon und ein Bilatrien-abc mit C₁₈-Alkylseitenkette wurden zur Verbesserung der Löslichkeit und Orientierung in der Polymerfolie erstmals dargestellt.

     

Twentyfold increase in alkaline phosphatase activity by sequential reversible activation of the enzyme followed by coupling with a copolyme of ethylene and maleic anhydride

Alkaline phosphatase, APase, (EC 3.1.31) from calf intestine, after shifting the equilibrium by effector molecules towards the dimeric form of the enzyme, was coupled (ratio 1:2, protein: copolymer) to a copolymer of ethylene and maleic anhydride, EMA. The water-soluble APase-EMA was separated from APase and the unbound EMA by DEAE-cellulose ion exchange chromatography. The specific activity of the APase-EMA, compared to APase, increased 26-fold at pH 7.1 and 10-fold at pH 8.6. The pH optimum of APase-EMA was shifted down from pH 9.5 (native APase) to 8.6. This change could be interpreted in terms of polyelectrolyte theory. APase-EMA retained 50–70% of its optimum activity in the pH range 7–8, while APase retained only 5–15% of its optimum activity within the same pH range. Its isoelectric point, pI, was 4.2 (APase 6.0) and it migrated on polyacrylamide gel electrophoresis in a single band, anodic movement twice as fast as APase. Parallel with the kinetic measurements, the reactive-enzyme sedimentation method was used to measure S_20,w values. S_20,w values obtained for APase-EMA, activated APase, and APase dialyzed against wafer were 6.56S, 6.46S, and 5.17S, respectively. Molecular weights, M_r, were determined by equilibrium sedimentation: the values obtained were 180,000, 160,000, and 84,500. M_r values of APase-EMA and APase (native) estimated by Sepharose-4B gel filtrations were essentially the same. The above-mentioned values remained unchanged for APase-EMA after intensive dialysis against water, whereas for the activated APase, separation from the effector molecules caused the equilibrium to shift back to the monomeric, very slightly active enzyme with concomitant changes of S_20,w to 5.15 and M_r to 82,000.