Ferrocenyl-substituted allenylidene complexes of chromium, molybdenum and tungsten: Synthesis, structure and reactivity

Bis(ferrocenyl)-substituted allenylidene complexes, [(CO)₅MCCCFc₂] (1a-c, Fc = (C₅H₄)Fe(C₅H₅), M = Cr (a), Mo (b), W (c)) were obtained by sequential reaction of Fc₂CO with Me₃Si-CCH, KF/MeOH, n-BuLi, and [(CO)₅M(THF)]. For the synthesis of related mono(ferrocenyl)allenylidene chromium complexes, [(CO)₅CrCCC(Fc)R] (R = Ph, NMe₂), three different routes were developed: (a) reaction of the deprotonated propargylic alcohol HCCC(Fc)(Ph)OH with [(CO)₅Cr(THF)] followed by desoxygenation with Cl₂CO, (b) Lewis acid induced alcohol elimination from alkenyl(alkoxy)carbene complexes, [(CO)₅CrC(OR)CHC(NMe₂)Fc], and (c) replacement of OMe in [(CO)₅CrCCC(OMe)NMe₂] by Fc. Complex 1a was also formed when the mono(ferrocenyl)allenylidene complex [(CO)₅CrCCC(Fc)NMe₂] was treated first with Li[Fc] and the resulting adduct then with SiO₂. The replacement route (c) was also applied to the synthesis of an allenylidene complex (7a) with a CC spacer in between the ferrocenyl unit and C_γ of the allenylidene ligand, [(CO)₅CrCCC(NMe₂)-CCFc]. The related complex containing a CHCH spacer (9a) was prepared by condensation of [(CO)₅CrCCC(Me)NMe₂] with formylferrocene in the presence of NEt₃. The bis(ferrocenyl)-substituted allenylidene complexes 1a-c added HNMe₂ across the C_α-C_β bond to give alkenyl(dimethylamino)carbene complexes and reacted with diethylaminopropyne by regioselective insertion of the CC bond into the C_β-C_γ bond to afford alkenyl(diethylamino)allenylidene complexes, [(CO)₅MCCC(NEt₂)CMeCFc₂]. The structures of 5a, 7a, and 9a were established by X-ray diffraction studies.     

The evolution of floral scent: the influence of olfactory learning by insect pollinators on the honest signalling of floral rewards

1.  The evolution of flowering plants has undoubtedly been influenced by a pollinator's ability to learn to associate floral signals with food. Here, we address the question of 'why' flowers produce scent by examining the ways in which olfactory learning by insect pollinators could influence how floral scent emission evolves in plant populations.
2.  Being provided with a floral scent signal allows pollinators to learn to be specific in their foraging habits, which could, in turn, produce a selective advantage for plants if sexual reproduction is limited by the income of compatible gametes. Learning studies with honeybees predict that pollinator-mediated selection for floral scent production should favour signals which are distinctive and exhibit low variation within species because these signals are learned faster. Social bees quickly learn to associate scent with the presence of nectar, and their ability to do this is generally faster and more reliable than their ability to learn visual cues.
3.  Pollinators rely on floral scent as a means of distinguishing honestly signalling flowers from deceptive ones. Furthermore, a pollinator's sensitivity to differences in nectar rewards can bias the way that it responds to floral scent. This mechanism may select for flowers that provide olfactory signals as an honest indicator of the presence of nectar or which select against the production of a detectable scent signal when no nectar is present.
4.  We expect that an important yet commonly overlooked function of floral scent is an improvement in short-term pollinator specificity which provides an advantage to both pollinator and plant over the use of a visual signal alone. This, in turn, impacts the evolution of plant mating systems via its influence on the species-specific patterns of floral visitation by pollinators.     

Hyperoxia-induced neurodegeneration as a tool to identify neuroprotective genes in Drosophila melanogaster

Oxidative stress has been reported to be a common underlying mechanism in the pathogenesis of many neurodegenerative disorders such as Alzheimer, Huntington, Creutzfeld–Jakob, and Parkinson disease. Despite the increasing number of articles showing a correlation between oxidative damage and neurodegeneration little is known about the genetic elements that confer protection against the deleterious effects of an oxidative imbalance in neurons. We show that oxygen-induced damage is a direct cause of brain degeneration in Drosophila and establish an experimental setup measuring dopaminergic neuron survival to model oxidative stress-induced neurodegeneration in flies. The overexpression of superoxide dismutase but not catalase was able to protect dopaminergic neurons against oxidative imbalance under hyperoxia treatment. In an effort to identify new genes involved in the process of oxidative stress-induced neurodegeneration, we have carried out a genome-wide expression analysis to identify genes whose expression is upregulated in fly heads under hyperoxia. Among them, a number of mitochondrial and cytoplasmic chaperones could be identified and were shown to protect dopaminergic neurons when overexpressed, thus validating our approach to identifying new genes involved in the neuronal defense mechanism against oxidative stress.     

The Arabidopsis thaliana Sucrose Transporter Gene AtSUC4 is Expressed in Meloidogyne incognita-induced Root Galls

The plant parasitic nematode Meloidogyne incognita is as an obligate parasite entirely dependent on the plants solute supply. Therefore, the nematodes induce the formation of several giant cells which are embedded into root galls. At present only little information is available about the solute transfer mechanisms of the plants to supply the induced galls and giant cells and consequently the nematodes. In the present work we could show by phloem-loading experiments that giant cells in the roots of Arabidopsis thaliana are not symplasmically connected to the phloem elements, thus differing considerably form the comparable plant–nematode interaction of Arabidopsis and Heterodera schachtii . Consequently the gene expression of the sucrose transporter AtSUC4 ( AtSUT4 ) was studied during nematode development, and its functionality was shown using RNAi gene silencing lines.     

Attitudes towards forest,biomass and certification – A case study approach to integrate public opinion in Japan

The purpose of this study was to contribute to filling the knowledge gap in public opinion and knowledge about forest and its certification in Japan, as well as to identify key elements and the possible role of public opinion within integrated bottom-up policies, bridging the sectors of forest, environment and energy. For the study 1930 questionnaires were disseminated in a small town in early 2007. Results from the statistical analysis indicated that forest was perceived as an ecosystem with a protective function against e.g. soil erosion or flooding, rather than a place that might serve for wood production and providing jobs. Forest certification and bioenergy from forest were identified as key elements for future integrated bottom-up policies that need to concentrate on facilitating the linkage between forestry and renewable energy as well as on promoting environmentally sound management and forest certification.     

Experimental evidence for male biased flight-to-light behavior in two moth species

Many studies report a greater abundance of male than female moths in light trap catches. The finding was interpreted as evidence for male-biased attraction to light, but alternatives could not be ruled out. For example, it is not known, how much the sex ratio in the catches deviates from the natural sex ratio. To overcome these limitations, we experimentally tested the flight-to-light behavior of two moth species, Yponomeuta cagnagella (Hübner) (Lepidoptera: Yponomeutidae) and Ligdia adustata (Denis and Schiffermüller) (Lepidoptera: Geometridae), under standardized conditions in an enclosed environment. In our test, we controlled the sex ratio, age, and population size. We recorded the moths caught in the trap and those that remained outside. Depending on the species, between 27 and 72% of all moths were caught in the light trap. We found that male moths were significantly and about 1.6 times more frequently attracted to the light than female moths. Our results were consistent for both species and hold good on the level of populations. We experimentally supported the general observation of a sexual dimorphism in the flight-to-light behavior of moths. Possible functional explanations include different flight activities of males and females or differences in the perception of light between males and females. Our experimental demonstration of a sexual dimorphism in the flight-to-light behavior of moths together with the common observation of an overrepresentation of males in light traps and other artificial light sources has implications for population and conservation biology.     

PIKfyve-dependent regulation of the Cl− channel ClC-2

The widely expressed chloride channel ClC-2 is stimulated by the serum and glucocorticoid inducible kinase SGK1. The SGK1-dependent regulation of several carriers involves the mammalian phosphatidylinositol-3-phosphate-5-kinase PIKfyve (PIP5K3). The present experiments explored whether SGK1-dependent regulation of ClC-2 similarly involves PIKfyve. The conductance of Xenopus oocytes is increased more than eightfold by ClC-2 expression. In ClC-2-expressing oocytes, but not in water-injected oocytes, the current was further enhanced by coexpression of either, PIKfyve or constitutively active ^S422DSGK1. Coexpression of the inactive SGK1 mutant ^K127NSGK1 did not significantly alter the current in ClC-2-expressing oocytes and abrogated the stimulation of the current by PIKfyve-coexpression. The stimulating effect of PIKfyve was abolished by replacement of the serine with alanine in the SGK1 consensus sequence (^S318APIKfyve). Coexpression of ^S318APIKfyve significantly blunted the stimulating effect of ^S422DSGK1 on ClC-2-activity. In conclusion, PIKfyve is a potent stimulator of ClC-2-activity and contributes to SGK1-dependent regulation of ClC-2.     

Biological activity and structural aspects of PGLa interaction with membrane mimetic systems

Peptidyl-glycine-leucine-carboxyamide (PGLa), isolated from granular skin glands of Xenopus laevis, is practically devoid of secondary structure in aqueous solution and in the presence of zwitterionic phospholipids, when added exogenously, but adopts an α-helix in the presence of anionic lipids. The peptide was shown to exhibit antifungal activity and to have antimicrobial activity towards both Gram-negative and Gram-positive bacteria. As a broad variety of peptides is found in the secretions of amphibian skin combinatorial treatment of PGLa and magainin 2 was studied showing enhanced activity by a heterodimer formation. Thus production of mutually recognizing peptides seems to be an effective way in nature to increase selective membrane activity. Biophysical studies on membrane mimics demonstrated that PGLa can discriminate between different lipid species, preferentially interacting with negatively charged lipids, which are major components of bacterial but not mammalian cell membranes. This emphasizes the role of electrostatic interactions as a major determinant to trigger the affinity of antimicrobial peptides towards bacterial membranes. PGLa induced the formation of a quasi-interdigitated phase in phosphatidylglycerol bilayers below their chain melting transition, which is due to the creation of voids below the peptide being aligned parallel to the membrane surface. In the fluid phase of phosphatidylglycerol the peptide inserts perpendicularly into the bilayer above a threshold concentration, which results in a hydrophobic mismatch of the peptide length and bilayer core for lipids ≤ C16. This mismatch is compensated by stretching of the acyl chains and in turn thickening of the bilayer demonstrating that membrane thinning cannot be taken generally as the hallmark of pore formation by antimicrobial peptides. Furthermore, PGLa was shown to affect membrane curvature strain of phosphatidylethanolamine, another main lipid component of bacterial membranes, where a cubic phase coexists with the fluid bilayer phase. Investigations on living Escherichia coli showed distinct changes in cell envelope morphology, when treated with the peptide. In a first stage loss of surface stiffness and consequently of topographic features was observed, followed in a second stage by permeabilization of the outer membrane and rupture of the inner (cytoplasmic) membrane supposedly by the mechanism(s) derived from model studies.     

Stair climbing results in more challenging patellofemoral contact mechanics and kinematics than walking at early knee flexion under physiological-like quadriceps loading

The mechanical environment during stair climbing has been associated with patellofemoral pain, but the contribution of loading to this condition is not clearly understood. It was hypothesized that the loading conditions during stair climbing induce higher patellofemoral pressures, a more lateral force distribution on the trochlea and a more lateral shift and tilt of the patella compared to walking at early knee flexion. Optical markers for kinematic measurements were attached to eight cadaveric knees, which were loaded with muscle forces at instances of walking and stair climbing cycles at 12° and 30° knee flexion. Contact mechanics were determined using a pressure sensitive film. At 12° knee flexion, stair climbing loads resulted in higher peak pressure (p=0.012) than walking, more lateral force distribution (p=0.012) and more lateral tilt (p=0.012), whilst mean pressure (p=0.069) and contact area (p=0.123) were not significantly different. At 30° knee flexion, although stair climbing compared to walking loads resulted in significantly higher patellofemoral mean (p=0.012) and peak pressures (p=0.012), contact area (p=0.025), as well as tilt (p=0.017), the medial–lateral force distribution (p=0.674) was not significantly different. No significant differences were observed in patellar shift between walking and stair climbing at either 12° (p=0.093) or 30° (p=0.575) knee flexion. Stair climbing thus leads to more challenging patellofemoral contact mechanics and kinematics than level walking at early knee flexion. The increase in patellofemoral pressure, lateral force distribution and lateral tilt during stair climbing provides a possible biomechanical explanation for the patellofemoral pain frequently experienced during this activity.