Synthesis of Functionalized Spiro[cycloalkanono-2,3'-thiophenes] via Tandem Conjugate Addition-Cyclization of 3-Oxoacid Thioanilides to Nitroalkenes

A convenient method is described for the synthesis of functionalized spiro[cycloalkanono-2,3-thiophenes] by treatment of cyclic 3-oxoacid thioanilides with -nitrostyrenes. Reaction of the obtained products with acetic anhydride yielded the corresponding oxime acetates.     

Zur Synthese von Human-Big-Gastrin I

The synthesis of the tetratriacontapeptide amide corresponding to the revised primary structure of human big gastrin I is described. For this purpose the fragments were designed in view of the maximum use of those utilized in our previous synthesis of human big gastrin I according to the first sequence proposal. Consequently the key tripeptide-Pro-Pro-His- (sequence 7–9) was prepared in suitably protected form to be used as amino or carboxyl component for assembly of the segments 1–9 and 1–14, respectively. Final condensation of the latter nona- and tetradecapeptide derivatives with the C-terminal segments 10–34 and 15–34 via the azide and the dicyclohexylcarbodiimide/N-hydroxysuccinimide procedure, respectively, leads to crude fully protected human big gastrin I. Upon deprotection by exposure to trifluoroacetic acid in presence of ethanedithiol-(1,2) as scavanger, ion exchange chromatography and partition chromatography, the desired tetratriacontapeptide amide was isolated in satisfactory yield with a high degree of purity. The identical immunological behaviour of the synthetic material, if compared with that of natural human big gastrin I, represents ulterior strong evidence for the correctness of the newly proposed structure for this putative prohormonal form of the gastrins.

Kurzmitteilung:Wünsch E., Wendlberger G., Mladenova-Orlinova L., Göhring W., Jaeger E., Scharf R., Gregory R. A., Dockray G. J., Hoppe-Seyler's Z. Physiol. Chem.362, 179 (1981).     

Untersuchungen von Mischvorgängen bei der Herstellung technischer Kohleprodukte unter Anwendung der Methode der radioaktiven Markierung

Es werden die Ergebnisse von Mischverfahren für Kohlepulver, Pech und andere Komponenten mitgeteilt, die unter Markierungen mit ²⁴Na-Benzoat im Laboratorium (Mischvolumen etwa 1 Liter) und im Betrieb (Mischvolumen etwa 100 Liter) durchgführt wurden. Die Experimente dienten dem Vergleich der Vergleich der Wirksamkeit verschiedener Mischmaschinen, der Ermittlung optimaler Mischzeiten und der Bestimmung des Verhaltens einzelner Komponenten beim Mischprozeβ. Dis mittels Szintillationszählung gewonnenen Meβwerte werden dabei mit einem Ergebnisdrucker registriert und mit Hilfa einer Rechenanlage mathematisch ausfewertet.     

Convergence rates of a global optimization algorithm

Second order conditions for the (pseudo-) convexity of a function restricted to an affine subspace are obtained by extending those already known for functions on ⁿ . These results are then used to analyse the (pseudo-) convexity of potential functions of the type introduced by Karmarkar.This research was completed while the first author was on sabbatical leave at the Département d'Informatiques et de Recherche Opérationelle, Université de Montréal, and supported by NSERC (grant Q015807). This research was also supported by NSERC (grants A8312 and A5408) and la Coopération franco-québécoise (project 20-02-13).     

Maximal monotonicity, conjugation and the duality product

Recently, the authors studied the connection between each maximal monotone operator and a family of convex functions. Each member of this family characterizes the operator and satisfies two particular inequalities.

The aim of this paper is to establish the converse of the latter fact. Namely, that every convex function satisfying those two particular inequalities is associated to a unique maximal monotone operator.

     

Ultrastructural architecture of colonies of different morphologies produced by phenotypic switching of a clinical strain of Candida tropicalis and biofilm formation by variant phenotypes

Candida tropicalis has been identified as one of the most prevalent pathogenic yeast species of the Candida-non-albicans (CNA) group. Study of switching in C. tropicalis has not been the subject of extensive research. Therefore, we investigated switching event and characterized the ultrastructural architecture of different phenotypes and biofilm produced in a C. tropicalis clinical strain. Cells switched heritably, reversibly, and at a high frequency between four phenotypes readily distinguishable by the shape of colonies formed on agar at 25°C. SEM analysis was used to verify the architecture of whole Candida colonies at ultrastructural level. The smooth phenotype (parental phenotype) colony showed a hemispherical shape character, while the semi-smooth was characterized by the presence of shallow marginal depressions. The ring and rough phenotypes exhibited more complex architecture and were characterized by the presence of deep central and peripheral depressions areas. The biofilm-forming ability varied among the switch phenotypes. After 12h incubation, the smooth phenotype formed less biofilm compared to the other phenotypes (P<0.05). The electron microscopy analysis revealed that filamentation (pseudohyphae) was associated with ring and rough colonies. The ultrastructural analysis allowed the observation of the arrangement of individual cells within the colonies. At the deep central and peripheral depressions areas of the ring and rough colonies extracellular material was seen in different arrangements. The data presented here open new avenues to study a possible role for extracellular material in the formation and maintenance of the architecture of switch phenotypes in C. tropicalis. It is therefore essential that more strains be investigated to determine the biological significance of extracellular material in C. tropicalis phenotypic switching phenomenon.     

Diffusion equations and the time evolution of foreign exchange rates

We investigate which type of diffusion equation is most appropriate to describe the time evolution of foreign exchange rates. We modify the geometric diffusion model assuming a non-exponential time evolution and the stochastic term is the sum of a Wiener noise and a jump process. We find the resulting diffusion equation to obey the Kramers–Moyal equation. Analytical solutions are obtained using the characteristic function formalism and compared with empirical data. The analysis focus on the first four central moments considering the returns of foreign exchange rate. It is shown that the proposed model offers a good improvement over the classical geometric diffusion model.     

Study of Blood Porphyrin Spectral Profile for Diagnosis of Chronic Renal Failure

The progression to end-stage renal failure is independent of the initial pathogenic mechanism. Metabolic acidosis is a common consequence of chronic renal failure that results from inadequate ammonium excretion and decreased tubular bicarbonate reabsorption. Protoporphyrin IX (PpIX) is the immediate metabolic precursor of the heme molecule. The purpose of this study was to evaluate the levels of erythrocytes protoporphyrin IX at an animal model during progressive renal disease. A total of 36 eight-week-old male Wistar rats were divided into six groups: Normal, 4 and 8 weeks after 5/6 nephrectomy (NX). Renal function was evaluated by creatinine clearance and plasma creatinine levels. The autofluorescence of erythrocytes porphyrin of healthy and NX rats was analyzed using fluorescence spectroscopy. Emission spectra were obtained by exciting the samples at 405 nm. Significant differences between normal and NX rats autofluorescence shape occurred in the 600–700 nm spectral region. A correlation was observed between emission band intensity at 635 nm and progression of renal disease.     

Spectral Properties of Amphiflavins in Polymer Matrices

The parameters characterizing the absorption, fluorescence and phosphorescence of 10-dodecylisoalloxazine (DIA), 10-octadecylisoalloxazine (OIA) 3-methyl-10-dodecylisoalloxazine (MDIA) embedded into polymeric matrices (polystyrene – PS, polymethacrylate methyl – PMM and poly(vinyl alcohol) – PVA) were studied. It was found that both the polarity of microenvironment and its structure influenced the changes of the spectral properties of the examined amphiflavins.