Heterologous Expression,Biosynthetic Studies,and Ecological Function of the Selective Gq‐Signaling Inhibitor FR900359

The cyclic depsipeptide FR900359 (FR), isolated from the tropical plant Ardisia crenata, is a strong and selective inhibitor of Gq proteins, making it an indispensable pharmacological tool to study Gq‐related processes, as well as a promising drug candidate. Gq inhibition is a novel mode of action for defense chemicals and crucial for the ecological function of FR, as shown by in vivo experiments in mice, its affinity to insect Gq proteins, and insect toxicity studies. The uncultured endosymbiont of A. crenata was sequenced, revealing the FR nonribosomal peptide synthetase (frs) gene cluster. We here provide a detailed model of FR biosynthesis, supported by in vitro enzymatic and bioinformatic studies, and the novel analogue AC‐1, which demonstrates the flexibility of the FR starter condensation domains. Finally, expression of the frs genes in E. coli led to heterologous FR production in a cultivable, bacterial host for the first time.     

Perspectives on bioenergy and biotechnology in Brazil

Brazil is one of the world’s largest producers of alcohol from biomass at low cost and is responsible for more than 1 million direct jobs. In 1973, the Brazilian Program of Alcohol (Proalcool) stimulated the creation of a bioethanol industry that has led to large economic, social, and scientific improvements. In the year 1984, 94.5% of Brazil’s cars used bioethanol as fuel. In 2003/2004, 350.3 million of sugarcane produced 24.2 million t of sugar and 14.4 billion L of ethanol for an average 4.3 million cars using ethanol. Since its inception, cumulative investment in Proalcool totals US$11 billion, and Brazil has saved US$27 billion in oil imports. The ethanol production industry from sugarcane generates 152 times more jobs than would have been the case if the same amount of fuel was produced from petroleum, and the use of ethanol as a fuel is advantageous for environmental reasons. In 2003, one of the biggest Brazilian ethanol industries started consuming 50% of the residual sugarcane bagasse to produce electrical energy (60 MW), a new alternative use of bioenergy for the Brazilian market. Other technologies for commercial uses of bagasse are in development, such as in the production of natural fibers, sweeteners (glucose and xylitol), single-cell proteins, lactic acid, microbial enzymes, and many other products based on fermentations (submerged and semisolid). Furthermore, studies aimed at the increase in the biosynthesis of sucrose and, consequently, ethanol productivity are being conducted to understand the genetics of sugarcane. Although, at present, there remain technical obstacles to the economic use of some ethanol industry residues, several research projects have been carried out and useful data generated. Efficient utilization of ethanol industry residues has created new opportunities for new value-added products, especially in Brazil, where they are produced in high quantities.     

Synthesis,characterization and crystal structures of two 2‐naphthyl substituted pyrazoles

The synthesis, characterization and X‐ray crystal structures of two 2‐naphthyl‐substituted pyrazoles ‐ 3‐(2‐naphthyl) pyrazole ( 1 ) and 5‐(2‐naphthyl)‐3‐trifluoromethyl‐pyrazole ( 3 ) ‐ are reported. In addition, the isolation and structural characterization of 5‐hydroxy‐3‐(2‐naphthyl)‐5‐trifluoromethyl‐4,5‐dihydropyrazole ( 2 ), an intermediate of the synthesis of 3 , is included. Two simple methods of dehydration of 2 are also presented.     

The influence of nanoparticle fillers on the morphology of a spin-cast thin film polymer blend

Polymer/nanoparticle composite films are receiving growing attention thanks to their potential for application in ultra-thin electronic and optical devices. Polymer blend demixing has been shown to be a suitable technique for the structuring of polymer thin films and the patterning of nanoparticles (NP) within them. In this work we show that the morphology of thin polymer films made by spin-casting a polymer blend solution containing NP fillers on a surface depends strongly on the concentration of NP fillers. More specifically, polystyrene/polymethylmethacrylate (PS/PMMA) films formed from a toluene solution, and which demix following a nucleation and growth mechanism, were studied. It was found that both the height and the surface density of PMMA domains increased as the concentration of CoPt:Cu NPs in the film was increased. We find that similar effects are induced in a NP-free PS/PMMA demixed film upon increasing the molecular weight of the PS molecules. This suggests that under certain conditions the NPs and the polymer molecules in the blend do not behave as separate species but form aggregates.     

Anomalous dissociative behavior of the major glycosylated component of the cellulosome of clostridium thermocellum

The cellulosome of Clostridium thermocellum is a highly cohesive multienzyme complex that is capable of completely solubilizing insoluble cellulose. One of the major cellulosomal components, the glycosylated S1 subunit, is believed to play an important structural role and normally migrates in sodium dodecyl sulfate-polyacrylamide gel electrophoresis with an Mr of 210,000. It is shown here that by simply altering the conditions (pH or ionic strength) of the environment prior to electrophoresis, a different migratory profile for S1 emerges, yielding a collection of bands, all of which migrate faster than the parent band. The original electrophoretic behavior of S1 can be reproduced on restoration of the original pH and ionic strength. These results may bear important significance for the physiological role of the S1 subunit in facilitating the observed synergistic action of the other (cellulolytic) components of the cellulosome.     

Compactness and the maximal Gibbs state for random Gibbs fields on a lattice

We prove for a general class of Gibbsian Random Field on that the set of tempered Gibbs states is compact. This class contains the Euclidean random fields. Moreover if the interaction is attractive, there is a unique minimal and maximal Gibbs state _– and ₊×_± are unique translation invariant ant and have the global Markov property. We also prove that uniqueness of the tempered Gibbs state is equivalent to the magnetizationsm _±=_±(q _x ) being equal which is true if the pressure is differentiable.     

Capillaranalyse

Zusammenfassung Die Art des Papiers kann den Ausfall der Capillaranalyse von Farbstoffgemischen usw. erheblich beeinflussen. Man kann aus den Bildern oft Schlüsse ziehen auf die Eigenschaften des Papiers. Einfluß auf den Ausfall der Capillaranalyse haben auch der Gehalt der aufsteigenden Flüssigkeiten an Alkohol, Schutzkolloiden, ihr p_H-Wert usw.Ein abgeändertes Verfabren besteht darin, einen Tropfen der Farbstofflösung auf Papier eintrocknen und dann reines Wasser oder andere Lösemittel hochsteigen zu lassen. Diese Begrenzung der Menge des capillar Aufsteigenden schafft eine ähnliche Wirkung wie die Entwicklung in der Chromatographie. Genügt das Auseinanderziehen der einzelnen Farbbänder noch nicht, so kann man nachträglich senkrecht dazu nochmals eine Flüssigkeit hochsteigen lassen.     

Isolation and properties of a thermostable endoglucanase from a thermophilic mutant strain ofTielavia terrestris

A heat-stable enzyme was isolated from the cellulase complex of a thermophilic strain of the micromyceteThielavia terrestris. The purified enzyme exhibited both endoglucanase and xylanase activities and had a mol mass of 69,000 Daltons and an isoelectric point of 6.4. When the cells were grown at 48°C, the initial activity of the purified enzyme using carboxymethylcellulose as a substrate was 150 nkat/mg and the Michaelis constant was 6.6 g/L. The heat stability of the enzyme was high, losing only 20% of the initial activity after a 6-h incubation at 65 °C. When cultures were grown on microcrystalline cellulose and xylose was added after 48 h of growth, endoglucanase and xylanase activities were more than doubled. Similar increases in these activities were observed by growing the cultures on straw.     

Lifetime of an emitting dipole near various types of interfaces including magnetic and negative refractive materials

A classical electromagnetic calculation of the lifetime of an emitting electric dipole near a material slab is presented. The lifetime is deduced from the imaginary part of the electric field Green's tensor associated with the stratified medium. The method is applied not only to the well known case of metallic reflectors, but also to magnetic reflectors and to negative refractive index slabs. The frequency dependence of the nonradiative decay rate at small distances is analyzed and interpreted in terms of the surface polariton modes of the slab.     

Pyrrolic and Dipyrrolic Chlorophyll Degradation Products in Plants and Herbivores

The degradation of chlorophyll, the omnipresent green pigment, has been investigated intensively over the last 30 years resulting in many elucidated tetrapyrrolic degradation products. With a comparison to the degradation of the structurally similar heme, we hereby propose a novel additional chlorophyll degradation mechanism to mono- and dipyrrolic products. This is the first proof of the occurrence of a family of mono- and dipyrrols in leaves that are previously only known as heme degradation products. This product family is also found in spit and feces of herbivores with specific metabolomic patterns reflecting the origin of the samples. Based on chromatographic and mass spectrometric evidence as well as on mechanistic considerations we also suggest several tentative new degradation products. One of them, dihydro BOX A, was fully confirmed as a novel natural product by synthesis and comparison of its spectroscopic data.