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Shuttle
Kinds of Shuttle Terms modified by Shuttle Selected AbstractsA GLOBE THAT FILLS THE SKY: GEOGRAPHY FROM THE SPACE SHUTTLEGEOGRAPHICAL REVIEW, Issue 1-2 2001Article first published online: 21 APR 2010, THOMAS D. JONES First page of article [source] The role of oceanographic conditions and plankton availability in larval fish assemblages off the Catalan coast (NW Mediterranean)FISHERIES OCEANOGRAPHY, Issue 3 2010M. PILAR OLIVAR Abstract In the northwestern Mediterranean, most fish species reproduce in early summer and fewer in the autumn mixing period. This study analyses and compares larval fish assemblages (LFA) in both seasons, and is the first attempt to characterize LFA structure for the autumn period. We analyze horizontal and vertical distribution of fish larvae and the micro- and mesozooplankton biomass and abundance of the main zooplankton groups. The oceanographic situation was analyzed through the study of data from CTD, N,-Shuttle and ADCP surveys. LFA were determined by ordination analyses based on larval abundance, and the relationships between larval assemblages and environmental variables were investigated through canonical correspondence analysis. The importance of some hydrographic variables (temperature, salinity and stability of the water column), current fields (along-shelf and across-shelf transport) and the abundance of zooplankton are discussed as important factors shaping the structure of larval assemblages. In early summer, LFA were mainly structured by a combination of bathymetry and trophic components, although sea surface temperature also played a role in shaping the horizontal larval distributions. In autumn, trophic variables were the main factors influencing the shelf-dwelling species assemblage. Larvae of oceanic species, on the other hand, were not related to trophic variables but were more affected by current fields. [source] Distinct Nanostructures from a Molecular Shuttle: Effects of Shuttling Movement on Nanostructural MorphologiesADVANCED FUNCTIONAL MATERIALS, Issue 1 2009Weidong Zhou Abstract A solvent driven molecular shuttle that contains a TCBD chromophore and in which the macrocycle can be positioned close to or far from the TCBD unit with a change of solvent is prepared. Several distinct nanostructures are obtained by control of the shuttling movement of the macrocycle: i) in a mixed solvent of CHCl3/n -C6H14 (1/1, v/v), the macrocycle locates at the peptide station, and interlaced nanofibers form as a result of the extended intermolecular dipole,dipole interactions of the TCBD units; ii) in a solvent of dimethyl sulfoxide, the macrocycle moves along the long alkyl-chain, and worm-like nanoparticles form because the macrocycle obstructs the intermolecular dipole,dipole interactions of the TCBD units. This system confirms that the molecular aggregation behaviors can be controlled by the shuttling movement of the macrocycle. Exploitation of the molecular shuttle to control the molecular aggregation behaviors will provide greater understanding in the field of molecular shuttle applications. [source] 2-(2,4-Dinitrobenzyl)pyridine (DNBP): A Potential Light-Activated Proton ShuttleHELVETICA CHIMICA ACTA, Issue 10 2009Catrin Goeschen Abstract The well-known photochromic tautomerism of 2-(2,4-dinitrobenzyl)pyridine (1; CH; Scheme,1) was re-investigated by flash photolysis in aqueous solution in view of its potential application as a light-activated proton pump. Irradiation of 1 yields the enamine tautomer NH (,max=520,nm) that rapidly equilibrates with its conjugate base CNO, (,max=420,nm). The pH,rate profile for the first-order decay of NH and CNO, provides a direct determination of the acidity constant of NH, pK=5.94±0.12 (I=0.1M) and serves to clarify the mechanisms of proton transfer prevailing in aqueous solutions. The acidity constant of protonated 1 (CHNH+), pK=4.18±0.02, was determined by spectrophotometric titration. [source] Apocrustacyanin C1 crystals grown in space and on earth using vapour-diffusion geometry: protein structure refinements and electron-density map comparisonsACTA CRYSTALLOGRAPHICA SECTION D, Issue 7 2003Jarjis Habash Models of apocrustacyanin C1 were refined against X-ray data recorded on Bending Magnet 14 at the ESRF to resolutions of 1.85 and 2,Å from a space-grown and an earth-grown crystal, respectively, both using vapour-diffusion crystal-growth geometry. The space crystals were grown in the APCF on the NASA Space Shuttle. The microgravity crystal growth showed a cyclic nature attributed to Marangoni convection, thus reducing the benefits of the microgravity environment, as reported previously [Chayen et al. (1996), Q. Rev. Biophys.29, 227,278]. A subsequent mosaicity evaluation, also reported previously, showed only a partial improvement in the space-grown crystals over the earth-grown crystals [Snell et al. (1997), Acta Cryst. D53, 231,239], contrary to the case for lysozyme crystals grown in space with liquid,liquid diffusion, i.e. without any major motion during growth [Snell et al. (1995), Acta Cryst. D52, 1099,1102]. In this paper, apocrustacyanin C1 electron-density maps from the two refined models are now compared. It is concluded that the electron-density maps of the protein and the bound waters are found to be better overall for the structures of apocrustacyanin C1 studied from the space-grown crystal compared with those from the earth-grown crystal, even though both crystals were grown using vapour-diffusion crystal-growth geometry. The improved residues are on the surface of the protein, with two involved in or nearby crystal lattice-forming interactions, thus linking an improved crystal-growth mechanism to the molecular level. The structural comparison procedures developed should themselves be valuable for evaluating crystal-growth procedures in the future. [source] Electronic Tuning of Nickel-Based Bis(dicarbollide) Redox Shuttles in Dye-Sensitized Solar Cells,ANGEWANDTE CHEMIE, Issue 31 2010Alexander Redox nach Belieben: Die Synthese einer Reihe neuer borfunktionalisierter NiIII/NiIV -Bis(dicarbollid)-Cluster führt zu einer Familie von robusten und justierbaren Redox-Shuttles. Dies bietet eine Möglichkeit zur gezielten Steuerung der Redoxeigenschaften farbstoffsensibilisierter Solarzellen, was in außergewöhnlich hohen Leerlaufspannungen resultierte. [source] A New Polyphenol Oxidase Biosensor Mediated by Azure B in Laponite Clay MatrixELECTROANALYSIS, Issue 19 2003Dan Shan Abstract Amperometric biosensor based on the entrapment of polyphenol oxidase within a laponite clay coating and cross-linked by glutaraldehyde is described for catechol detection. Laponite provides a hydrophilic enzyme surrounding increasing the long term stability of the biosensor compared to the corresponding biosensors obtained by chemical cross-linking of PPO with glutaraldehyde. Azure B, a cationic dye exchanged within the clay matrix, is used as an electron shuttle allowing the mediated detection of phenol derivatives at ,0.05 V. The detection limits obtained with the optimized biosensor configuration for catechol, p -cresol and phenol are 1, 1 and 17,nM, respectively. [source] Characterization of carbonic anhydrase from Neisseria gonorrhoeaeFEBS JOURNAL, Issue 6 2001Björn Elleby We have investigated the steady state and equilibrium kinetic properties of carbonic anhydrase from Neisseria gonorrhoeae (NGCA). Qualitatively, the enzyme shows the same kinetic behaviour as the well studied human carbonic anhydrase II (HCA II). This is reflected in the similar pH dependencies of the kinetic parameters for CO2 hydration and the similar behaviour of the kinetics of 18O exchange between CO2 and water at chemical equilibrium. The pH profile of the turnover number, kcat, can be described as a titration curve with an exceptionally high maximal value of 1.7 × 106 s,1 at alkaline pH and a pKa of 7.2. At pH 9, kcat is buffer dependent in a saturable manner, suggesting a ping-pong mechanism with buffer as the second substrate. The ratio kcat/Km is dependent on two ionizations with pKa values of 6.4 and 8.2. However, an 18O-exchange assay identified only one ionizable group in the pH profile of kcat/Km with an apparent pKa of 6.5. The results of a kinetic analysis of a His66,Ala variant of the bacterial enzyme suggest that His66 in NGCA has the same function as a proton shuttle as His64 in HCA II. The kinetic defect in the mutant can partially be overcome by certain buffers, such as imidazole and 1,2-dimethylimidazole. The bacterial enzyme shows similar Ki values for the inhibitors NCO,, SCN, and N3, as HCA II, while CN, and the sulfonamide ethoxzolamide are considerably weaker inhibitors of the bacterial enzyme than of HCA II. The absorption spectra of the adducts of Co(II)-substituted NGCA with acetazolamide, NCO,, SCN,, CN, and N3, resemble the corresponding spectra obtained with human Co(II)-isozymes I and II. Measurements of guanidine hydrochloride (GdnHCl)-induced denaturation reveal a sensitivity of the CO2 hydration activity to the reducing agent tris(2-carboxyethyl)phosphine (TCEP). However, the A292/A260 ratio was not affected by the presence of TCEP, and a structural transition at 2.8,2.9 m GdnHCl was observed. [source] Photoinduced Shuttling Dynamics of Rotaxanes in Viscous Polymer SolutionsADVANCED FUNCTIONAL MATERIALS, Issue 21 2009Dhiredj C. Jagesar Abstract The effect of external friction, caused by medium viscosity, on the photoinduced translational motion in a rotaxane-based molecular shuttle 1 is investigated. The shuttle is successfully operated in solutions of poly(methacrylonitrile) (PMAN) of different molecular weights in MeCN and PrCN. The viscosity of the medium is tuned by changing the PMAN concentration. The rheological behavior of the polymer solution gives insight into the structure of the polymer solution on the microscopic scale. In PrCN, the entanglement regime is reached at lower concentration than in MeCN. This is also reflected by the effect on the shuttling: in the PrCN/PMAN system, a larger viscosity effect is observed compared to MeCN/PMAN. The shuttle is found to be slowed down in the polymer solutions but is still active at high viscosities. The observed retardation effect on the kinetics of shuttling in MeCN/PMAN and PrCN/PMAN can be correlated to the PMAN concentration through the hydrodynamic scaling model. The Stokes,Einstein relationship proves inadequate to correlate the shuttling rates to macroscopic viscosity, but the dependence of the shuttling rate on the bulk viscosity fits well to a commonly observed power-law relationship. The viscosity effect on the shuttling is found to be weak in all cases. [source] Distinct Nanostructures from a Molecular Shuttle: Effects of Shuttling Movement on Nanostructural MorphologiesADVANCED FUNCTIONAL MATERIALS, Issue 1 2009Weidong Zhou Abstract A solvent driven molecular shuttle that contains a TCBD chromophore and in which the macrocycle can be positioned close to or far from the TCBD unit with a change of solvent is prepared. Several distinct nanostructures are obtained by control of the shuttling movement of the macrocycle: i) in a mixed solvent of CHCl3/n -C6H14 (1/1, v/v), the macrocycle locates at the peptide station, and interlaced nanofibers form as a result of the extended intermolecular dipole,dipole interactions of the TCBD units; ii) in a solvent of dimethyl sulfoxide, the macrocycle moves along the long alkyl-chain, and worm-like nanoparticles form because the macrocycle obstructs the intermolecular dipole,dipole interactions of the TCBD units. This system confirms that the molecular aggregation behaviors can be controlled by the shuttling movement of the macrocycle. Exploitation of the molecular shuttle to control the molecular aggregation behaviors will provide greater understanding in the field of molecular shuttle applications. [source] A theoretical study on the catalytic mechanism of Mus musculus adenosine deaminaseJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2010Xian-Hui Wu Abstract The catalytic mechanism of Mus musculus adenosine deaminase (ADA) has been studied by quantum mechanics and two-layered ONIOM calculations. Our calculations show that the previously proposed mechanism, involving His238 as the general base to activate the Zn-bound water, has a high activation barrier of about 28 kcal/mol at the proposed rate-determining nucleophilic addition step, and the corresponding calculated kinetic isotope effects are significantly different from the recent experimental observations. We propose a revised mechanism based on calculations, in which Glu217 serves as the general base to abstract the proton of the Zn-bound water, and the protonated Glu217 then activates the substrate for the subsequent nucleophilic addition. The rate-determining step is the proton transfer from Zn-OH to 6-NH2 of the tetrahedral intermediate, in which His238 serves as a proton shuttle for the proton transfer. The calculated kinetic isotope effects agree well with the experimental data, and calculated activation energy is also consistent with the experimental reaction rate. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] The in vivo neuron-to-astrocyte lactate shuttle in human brain: evidence from modeling of measured lactate levels during visual stimulationJOURNAL OF NEUROCHEMISTRY, Issue 2009Silvia Mangia Abstract Functional magnetic resonance spectroscopy (fMRS) allows the non-invasive measurement of metabolite concentrations in the human brain, including changes induced by variations in neurotransmission activity. However, the limited spatial and temporal resolution of fMRS does not allow specific measurements of metabolites in different cell types. Thus, the analysis of fMRS data in the context of compartmentalized metabolism requires the formulation and application of mathematical models. In the present study we utilized the mathematical model introduced by Simpson et al. (2007) to gain insights into compartmentalized metabolism in vivo from the fMRS data obtained in humans at ultra high magnetic field by Mangia et al. (2007a). This model simulates brain glucose and lactate levels in a theoretical cortical slice. Using experimentally determined concentrations and catalytic activities for the respective transporter proteins, we calculate inflow and export of glucose and lactate in endothelium, astrocytes, and neurons. We then vary neuronal and astrocytic glucose and lactate utilization capacities until close correspondence is observed between in vivo and simulated glucose and lactate levels. The results of the simulations indicate that, when literature values of glucose transport capacity are utilized, the fMRS data are consistent with export of lactate by neurons and import of lactate by astrocytes, a mechanism that can be referred to as a neuron-to-astrocyte lactate shuttle. A shuttle of lactate from astrocytes to neurons could be simulated, but this required the astrocytic glucose transport capacity to be increased by 12-fold, and required that neurons not respond to activation with increased glycolysis, two conditions that are not supported by current literature. [source] Energy sources for glutamate neurotransmission in the retina: absence of the aspartate/glutamate carrier produces reliance on glycolysis in gliaJOURNAL OF NEUROCHEMISTRY, Issue 1 2007Y. Xu Abstract The mitochondrial transporter, the aspartate/glutamate carrier (AGC), is a necessary component of the malate/aspartate cycle, which promotes the transfer into mitochondria of reducing equivalents generated in the cytosol during glycolysis. Without transfer of cytosolic reducing equivalents into mitochondria, neither glucose nor lactate can be completely oxidized. In the present study, immunohistochemistry was used to demonstrate the absence of AGC from retinal glia (Müller cells), but its presence in neurons and photoreceptor cells. To determine the influence of the absence of AGC on sources of ATP for glutamate neurotransmission, neurotransmission was estimated in both light- and dark-adapted retinas by measuring flux through the glutamate/glutamine cycle and the effect of light on ATP-generating reactions. Neurotransmission was 80% faster in the dark as expected, because photoreceptors become depolarized in the dark and this depolarization induces release of excitatory glutamate neurotransmitter. Oxidation of [U- 14C]glucose, [1- 14C]lactate, and [1- 14C]pyruvate in light- and dark-adapted excised retinas was estimated by collecting 14CO2. Neither glucose nor lactate oxidation that require participation of the malate/aspartate shuttle increased in the dark, but pyruvate oxidation that does not require the malate/aspartate shuttle increased to 36% in the dark. Aerobic glycolysis was estimated by measuring the rate of lactate appearance. Glycolysis was 37% faster in the dark. It appears that in the retina, ATP consumed during glutamatergic neurotransmission is replenished by ATP generated glycolytically within the retinal Müller cells and that oxidation of glucose within the Müller cells does not occur or occurs only slowly. [source] The glutamate/GABA-glutamine cycle: aspects of transport, neurotransmitter homeostasis and ammonia transferJOURNAL OF NEUROCHEMISTRY, Issue 3 2006Lasse K. Bak Abstract Neurons are metabolically handicapped in the sense that they are not able to perform de novo synthesis of neurotransmitter glutamate and ,-aminobutyric acid (GABA) from glucose. A metabolite shuttle known as the glutamate/GABA-glutamine cycle describes the release of neurotransmitter glutamate or GABA from neurons and subsequent uptake into astrocytes. In return, astrocytes release glutamine to be taken up into neurons for use as neurotransmitter precursor. In this review, the basic properties of the glutamate/GABA-glutamine cycle will be discussed, including aspects of transport and metabolism. Discussions of stoichiometry, the relative role of glutamate vs. GABA and pathological conditions affecting the glutamate/GABA-glutamine cycling are presented. Furthermore, a section is devoted to the accompanying ammonia homeostasis of the glutamate/GABA-glutamine cycle, examining the possible means of intercellular transfer of ammonia produced in neurons (when glutamine is deamidated to glutamate) and utilized in astrocytes (for amidation of glutamate) when the glutamate/GABA-glutamine cycle is operating. A main objective of this review is to endorse the view that the glutamate/GABA-glutamine cycle must be seen as a bi-directional transfer of not only carbon units but also nitrogen units. [source] Neuronal uptake and metabolism of glycerol and the neuronal expression of mitochondrial glycerol-3-phosphate dehydrogenaseJOURNAL OF NEUROCHEMISTRY, Issue 4 2003Nga Huynh Tran Nguyen Abstract Glycerol is effective in the treatment of brain oedema but it is unclear if this is due solely to osmotic effects of glycerol or whether the brain may metabolize glycerol. We found that intracerebral injection of [14C]glycerol in rat gave a higher specific activity of glutamate than of glutamine, indicating neuronal metabolism of glycerol. Interestingly, the specific activity of GABA became higher than that of glutamate. NMR spectroscopy of brains of mice given 150 µmol [U- 13C]glycerol (0.5 m i.v.) confirmed this predominant labelling of GABA, indicating avid glycerol metabolism in GABAergic neurones. Uptake of [14C]glycerol into cultured cerebellar granule cells was inhibited by Hg2+, suggesting uptake through aquaporins, whereas Hg2+ stimulated glycerol uptake into cultured astrocytes. The neuronal metabolism of glycerol, which was confirmed in experiments with purified synaptosomes and cultured cerebellar granule cells, suggested neuronal expression of glycerol kinase and some isoform of glycerol-3-phosphate dehydrogenase. Histochemically, we demonstrated mitochondrial glycerol-3-phosphate dehydrogenase in neurones, whereas cytosolic glycerol-3-phosphate dehydrogenase was three to four times more active in white matter than in grey matter, reflecting its selective expression in oligodendroglia. The localization of mitochondrial and cytosolic glycerol-3-phosphate dehydrogenases in different cell types implies that the glycerol-3-phosphate shuttle is of little importance in the brain. [source] Mitochondrial transport proteins of the brainJOURNAL OF NEUROSCIENCE RESEARCH, Issue 15 2007D.A. Berkich Abstract In this study, cellular distribution and activity of glutamate and ,-aminobutyric acid (GABA) transport as well as oxoglutarate transport across brain mitochondrial membranes were investigated. A goal was to establish cell-type-specific expression of key transporters and enzymes involved in neurotransmitter metabolism in order to estimate neurotransmitter and metabolite traffic between neurons and astrocytes. Two methods were used to isolate brain mitochondria. One method excludes synaptosomes and the organelles may therefore be enriched in astrocytic mitochondria. The other method isolates mitochondria derived from all regions of the brain. Immunological and enzymatic methods were used to measure enzymes and carriers in the different preparations, in addition to studying transport kinetics. Immunohistochemistry was also employed using brain slices to confirm cell type specificity of enzymes and carriers. The data suggest that the aspartate/glutamate carriers (AGC) are expressed predominantly in neurons, not astrocytes, and that one of two glutamate/hydroxyl carriers is expressed predominantly in astrocytes. The GABA carrier and the oxoglutarate carrier appear to be equally distributed in astrocytes and neurons. As expected, pyruvate carboxylase and branched-chain aminotransferase were predominantly astrocytic. Insofar as the aspartate/glutamate exchange carriers are required for the malate/aspartate shuttle and for reoxidation of cytosolic NADH, the data suggest a compartmentation of glucose metabolism in which astrocytes catalyze glycolytic conversion of glucose to lactate, whereas neurons are capable of oxidizing both lactate and glucose to CO2 + H2O. © 2007 Wiley-Liss, Inc. [source] Activity of the lactate,alanine shuttle is independent of glutamate,glutamine cycle activity in cerebellar neuronal,astrocytic culturesJOURNAL OF NEUROSCIENCE RESEARCH, Issue 1-2 2005Lasse K. Bak Abstract The glutamate,glutamine cycle describes the neuronal release of glutamate into the synaptic cleft, astrocytic uptake, and conversion into glutamine, followed by release for use as a neuronal glutamate precursor. This only explains the fate of the carbon atoms, however, and not that of the ammonia. Recently, a role for alanine has been proposed in transfer of ammonia between glutamatergic neurons and astrocytes, denoted the lactate,alanine shuttle (Waagepetersen et al. [ 2000] J. Neurochem. 75:471,479). The role of alanine in this context has been studied further using cerebellar neuronal cultures and corresponding neuronal,astrocytic cocultures. A superfusion paradigm was used to induce repetitively vesicular glutamate release by N -methyl- D -aspartate (NMDA) in the neurons, allowing the relative activity dependency of the lactate,alanine shuttle to be assessed. [15N]Alanine (0.2 mM), [2- 15N]/[5- 15N]glutamine (0.25 mM), and [15N]ammonia (0.3 mM) were used as precursors and cell extracts were analyzed by mass spectrometry. Labeling from [15N]alanine in glutamine, aspartate, and glutamate in cerebellar cocultures was independent of depolarization of the neurons. Employing glutamine with the amino group labeled ([2- 15N]glutamine) as the precursor, an activity-dependent increase in the labeling of both glutamate and aspartate (but not alanine) was observed in the cerebellar neurons. When the amide group of glutamine was labeled ([5- 15N]glutamine), no labeling could be detected in the analyzed metabolites. Altogether, the results of this study support the existence of the lactate,alanine shuttle and the associated glutamate,glutamine cycle. No direct coupling of the two shuttles was observed, however, and only the glutamate,glutamine cycle seemed activity dependent. © 2004 Wiley-Liss, Inc. [source] Protein disulfide bond generation in Escherichia coli DsbB,DsbAJOURNAL OF SYNCHROTRON RADIATION, Issue 3 2008Kenji Inaba Protein disulfide bond formation is catalyzed by a series of Dsb enzymes present in the periplasm of Escherichia coli. The crystal structure of the DsbB,DsbA,ubiquinone ternary complex provided important insights into mechanisms of the de novo disulfide bond generation cooperated by DsbB and ubiquinone and of the disulfide bond shuttle from DsbB to DsbA. The structural basis for prevention of the crosstalk between the DsbA,DsbB oxidative and the DsbC,DsbD reductive pathways has also been proposed. [source] Overcoming the restriction barrier to plasmid transformation of Helicobacter pyloriMOLECULAR MICROBIOLOGY, Issue 5 2000John P. Donahue Helicobacter pylori strains demonstrate substantial variability in the efficiency of transformation by plasmids from Escherichia coli, and many strains are completely resistant to transformation. Among the barriers to transformation are numerous strain-specific restriction-modification systems in H. pylori. We have developed a method to protect plasmid DNA from restriction by in vitro site-specific methylation using cell-free extracts of H. pylori before transformation. In two cases, plasmid DNA treated with cell-free extracts in vitro acquired the restriction pattern characteristic of genomic DNA from the source strain. Among three strains examined in detail, the transformation frequency by treated plasmid shuttle and suicide vectors was significantly increased compared with mock-treated plasmid DNA. The results indicate that the restriction barrier in H. pylori can be largely overcome by specific DNA methylation in vitro. The approach described should significantly enhance the ability to manipulate gene function in H. pylori and other organisms that have substantial restriction barriers to transformation. [source] Analysis of fluid-structure interaction in low pressure MEMS by Integral EquationsPROCEEDINGS IN APPLIED MATHEMATICS & MECHANICS, Issue 1 2008Attilio FrangiArticle first published online: 25 FEB 200 The evaluation of gas dissipation occurring in inertial polysilicon MEMS is addressed focusing the attention on the free,molecule flow. In this regime, which is very often of interest for industrial applications, collisions between molecules can be neglected and the momentum transfer to the moving shuttle can be easily computed. Since the surfaces of silicon MEMS are generally very rough, a complete diffusion model is adopted to describe the wall,molecule interaction. A Boundary Integral Equation approach is proposed and it is shown that the introduction of the key assumption of small perturbations is crucial in the development of a robust and fast numerical tool. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] A glia,neuron alanine/ammonium shuttle is central to energy metabolism in bee retinaTHE JOURNAL OF PHYSIOLOGY, Issue 8 2008Jonathan A. Coles It has been proposed that glial cells may supply carbon fuel to neurons and also that there are fluxes of ammonium from neurons to glia. We have investigated both these proposals in Apis retinal slices, in which virtually all the mitochondria are in the photoreceptor neurons. Normally the superfusate contained no substrate of energy metabolism; addition of glucose or alanine did not increase oxygen consumption , confirming that the neurons received adequate substrate from glycogen in the glia. 1,4-Dideoxy-1,4-imino- d -arabinitol (DAB, 100 ,m), an inhibitor of glycogen phosphorylase, progressively decreased . This decrease was reversed by alanine but not glucose. Ammonium-sensitive microelectrodes did not detect significant extracellular [NH4+] ([NH4+]e) in slices superfused with normal superfusate. Removal of Cl,, necessary for cotransport of NH4+ into the glia, increased [NH4+]e so that at the end of 2 min photostimulation mean [NH4+]e was 0.442 mm (s.e.m.= 0.082 mm, n= 16). In 0 Cl,, [NH4+]e was reduced by 2-(methylamino)isobutyrate (MeAIB) an inhibitor of alanine transport. MeAIB also blocked oxidation of alanine in the presence of DAB, but did not decrease in normal superfusate. Lactate (l and d) and pyruvate (but not glucose) increased in DAB and decreased [NH4+]e in 0 Cl,. These results strengthen the evidence that in superfused retinal slices, glucose is metabolized exclusively in the glia, which supply alanine to the neurons, and that ammonium returns to the glia. They also show that another fuel (perhaps lactate) can be supplied by the glia to the neurons. [source] Regulation of lactate production at the onset of ischaemia is independent of mitochondrial NADH/NAD+: insights from in silico studiesTHE JOURNAL OF PHYSIOLOGY, Issue 3 2005Lufang Zhou Ischaemia decreases mitochondrial NADH oxidation, activates glycolysis, increases the NADH/NAD+ ratio, and causes lactate production. The mechanisms that regulate anaerobic glycolysis and the NADH/NAD+ ratio during ischaemia are unclear. Although continuous measurements of metabolic fluxes and NADH/NAD+ in cytosol and mitochondria are not possible in vivo with current experimental techniques, computational models can be used to predict these variables by simulations with in silico experiments. Such predictions were obtained using a mathematical model of cellular metabolism in perfused myocardium. This model, which distinguishes cytosolic and mitochondrial domains, incorporates key metabolic species and processes associated with energy transfer. Simulation of metabolic responses to mild, moderate and severe ischaemia in large animals showed that mitochondrial NADH/NAD+ was rapidly reset to higher values in proportion to the reduced O2 delivery and myocardial oxygen consumption . Cytosolic NADH/NAD+, however, showed a biphasic response, with a sharp initial increase that was due to activation of glycogen breakdown and glycolysis, and corresponded with lactate production. Whereas the rate of glycolysis and the malate,aspartate shuttle had a significant effect on the cytosolic NADH/NAD+, their effects on the mitochondrial NADH/NAD+ were minimal. In summary, model simulations of the metabolic response to ischaemia showed that mitochondrial NADH/NAD+ is primarily determined by O2 consumption, while cytosolic NADH/NAD+ is largely a function of glycolytic flux during the initial phase, and is determined by mitochondrial NADH/NAD+ and the malate,aspartate shuttle during the steady state. [source] Parking and Restarting a Molecular Shuttle In SituCHEMISTRY - A EUROPEAN JOURNAL, Issue 9 2008Nai-Chia Chen Abstract Herein we report an easy-to-synthesize [2]rotaxane, which incorporates two ionic monopyridinium stations and one 2,2,-bipyridine station as the shaft of the dumbbell-shaped component and a bis- p -xylyl[26]crown-6 (BPX26C6) unit as the macrocyclic component. In this molecular shuttle, the BPX26C6 unit can be docked selectively on either the central 2,2,-bipyridine station or one of the two terminal pyridinium stations, and subsequently, returned to its shuttling molecular motion through the in situ addition of simple reagents (acid/base or metal ion/metal-ion-complexing ligand pairs). [source] A [3]Rotaxane with Three Stable States That Responds to Multiple-Inputs and Displays Dual Fluorescence AddressesCHEMISTRY - A EUROPEAN JOURNAL, Issue 20 2005Da-Hui Qu Abstract A [3]rotaxane molecular shuttle containing two ,-cyclodextrin (,-CD) macrocycles, an azobenzene unit, a stilbene unit, and two different fluorescent naphthalimide units has been investigated. The azobenzene unit and the stilbene unit can be E/Z -photoisomerized separately by light excited at different wavelengths. Irradiation at 380 nm resulted in the photoisomerization of the azobenzene unit, leading to the formation of one stable state of the [3]rotaxane (Z1- NNAS-2CD); irradiation at 313 nm resulted in the photoisomerization of the stilbene unit, leading to the formation of another stable state of the [3]rotaxane (Z2- NNAS-2CD). The reversible conversion of the Z1 and Z2 isomers back to the E isomer by irradiation at 450 nm and 280 nm, respectively, is accompanied by recovery of the absorption and fluorescence spectra of the [3]rotaxane. The E isomer and the two Z isomers have been characterized by 1H NMR spectroscopy and by two-dimensional NMR spectroscopy. The light stimuli can induce shuttling motions of the two ,-CD macrocycles on the molecular thread; concomitantly, the absorption and fluorescence spectra of the [3]rotaxane change in a regular way. When the ,-CD macrocycle stays close to the fluorescent moiety, the fluorescence of the moiety become stronger due to the rigidity of the ,-CD ring. As the photoisomerization processes are fully reversible, the photo-induced shuttling motions of the ,-CD rings can be repeated, accompanied by dual reversible fluorescence signal outputs. The potential application of such light-induced mechanical motions at the molecular level could provide some insight into the workings of a molecular machine with entirely optical signals, and could provide a cheap, convenient interface for communication between micro- and macroworlds. [source] Theoretical Study on Proton-Transfer Reaction of Intracellular Second-messenger 3,,5,-Cyclic NucleotideCHINESE JOURNAL OF CHEMISTRY, Issue 8 2008Ai-Hua ZHANG Abstract The gas-phase proton-transfer reaction mechanism of intracellular second-messenger 3,,5,-cyclic nucleotide (cAMPm) has been theoretically investigated at the B3LYP/6-31G, , level. One or two H2O molecules have been used to simulate the catalyst. It is found that H shift reaction between conformation Bm and conformation Dm of cAMPm involves a cyclic transition state with one or two water molecules as a shuttle. Furthermore, H shift reaction proceeds easily with the participation of two water molecules. The results provide evidence in theory to study proton-transfer reaction mechanism of related phosphodiesters. Our present calculations have rationalized all the possible reaction channels. [source] Metagenome and mRNA expression analyses of anaerobic methanotrophic archaea of the ANME-1 groupENVIRONMENTAL MICROBIOLOGY, Issue 2 2010Anke Meyerdierks Summary Microbial consortia mediating the anaerobic oxidation of methane with sulfate are composed of methanotrophic Archaea (ANME) and Bacteria related to sulfate-reducing Deltaproteobacteria. Cultured representatives are not available for any of the three ANME clades. Therefore, a metagenomic approach was applied to assess the genetic potential of ANME-1 archaea. In total, 3.4 Mbp sequence information was generated based on metagenomic fosmid libraries constructed directly from a methanotrophic microbial mat in the Black Sea. These sequence data represent, in 30 contigs, about 82,90% of a composite ANME-1 genome. The dataset supports the hypothesis of a reversal of the methanogenesis pathway. Indications for an assimilatory, but not for a dissimilatory sulfate reduction pathway in ANME-1, were found. Draft genome and expression analyses are consistent with acetate and formate as putative electron shuttles. Moreover, the dataset points towards downstream electron-accepting redox components different from the ones known from methanogenic archaea. Whereas catalytic subunits of [NiFe]-hydrogenases are lacking in the dataset, genes for an [FeFe]-hydrogenase homologue were identified, not yet described to be present in methanogenic archaea. Clustered genes annotated as secreted multiheme c -type cytochromes were identified, which have not yet been correlated with methanogenesis-related steps. The genes were shown to be expressed, suggesting direct electron transfer as an additional possible mode to shuttle electrons from ANME-1 to the bacterial sulfate-reducing partner. [source] Metalloporphyrin solubility: A trigger for catalyzing reductive dechlorination of tetrachloroethyleneENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 2 2004Ishai Dror Abstract Metalloporphyrins are well known for their electron-transfer roles in many natural redox systems. In addition, several metalloporphyrins and related tetrapyrrole macrocycles complexed with various core metals have been shown to catalyze the reductive dechlorination of certain organic compounds, thus demonstrating the potential for using naturally occurring metalloporphyrins to attenuate toxic and persistent chlorinated organic pollutants in the environment. However, despite the great interest in reductive dechlorination reactions and the wide variety of natural and synthetic porphyrins currently available, only soluble porphyrins, which comprise a small fraction of this particular family of organic macrocycles, have been used as electron-transfer shuttles in these reactions. Results from the present study clearly demonstrate that metalloporphyrin solubility is a key factor in their ability to catalyze the reductive dechlorination of tetrachloroethylene and its daughter compounds. Additionally, we show that certain insoluble and nonreactive metalloporphyrins can be activated as catalysts merely by changing solution conditions to bring about their dissolution. Furthermore, once a metalloporphyrin is fully dissolved and activated, tetrachloroethylene transformation proceeds rapidly, giving nonchlorinated and less toxic alkenes as the major reaction products. Results from the present study suggest that if the right environmental conditions exist or can be created, specific metalloporphyrins may provide a solution for cleaning up sites that are contaminated with chlorinated organic pollutants. [source] Synthesis of Fullerene-Stoppered Rotaxanes Bearing Ferrocene Groups on the Macrocycle,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 7 2010Aurelio Mateo-Alonso Abstract The synthesis, characterisation and behaviour of a series of rotaxanes containing a fulleropyrrolidine stopper and two ferrocene moieties on the macrocycle is reported. Remarkably, the presence of large and bulky ferrocene groups does not interfere either in the synthesis or in the translocation of the macrocycle induced by ,,, interactions between the macrocycle and the fullerene. The synthetic routes developed can also be applied to the preparation of rotaxane scaffolds that can be complexed to [Ru(CO)TPP] by axial coordination. Overall, the synthetic routes presented herein provide an efficient way to prepare a variety of rotaxanes and molecular shuttles with potential applications in different fields. [source] A steady-state modeling approach to validate an in vivo mechanism of the GAL regulatory network in Saccharomyces cerevisiaeFEBS JOURNAL, Issue 20 2004Malkhey Verma Cellular regulation is a result of complex interactions arising from DNA,protein and protein,protein binding, autoregulation, and compartmentalization and shuttling of regulatory proteins. Experiments in molecular biology have identified these mechanisms recruited by a regulatory network. Mathematical models may be used to complement the knowledge-base provided by in vitro experimental methods. Interactions identified by in vitro experiments can lead to the hypothesis of multiple candidate models explaining the in vivo mechanism. The equilibrium dissociation constants for the various interactions and the total component concentration constitute constraints on the candidate models. In this work, we identify the most plausible in vivo network by comparing the output response to the experimental data. We demonstrate the methodology using the GAL system of Saccharomyces cerevisiae for which the steady-state analysis reveals that Gal3p neither dimerizes nor shuttles between the cytoplasm and the nucleus. [source] A kinetic perspective on extracellular electron transfer by anode-respiring bacteriaFEMS MICROBIOLOGY REVIEWS, Issue 1 2010César I. Torres Abstract In microbial fuel cells and electrolysis cells (MXCs), anode-respiring bacteria (ARB) oxidize organic substrates to produce electrical current. In order to develop an electrical current, ARB must transfer electrons to a solid anode through extracellular electron transfer (EET). ARB use various EET mechanisms to transfer electrons to the anode, including direct contact through outer-membrane proteins, diffusion of soluble electron shuttles, and electron transport through solid components of the extracellular biofilm matrix. In this review, we perform a novel kinetic analysis of each EET mechanism by analyzing the results available in the literature. Our goal is to evaluate how well each EET mechanism can produce a high current density (>10 A m,2) without a large anode potential loss (less than a few hundred millivolts), which are feasibility goals of MXCs. Direct contact of ARB to the anode cannot achieve high current densities due to the limited number of cells that can come in direct contact with the anode. Slow diffusive flux of electron shuttles at commonly observed concentrations limits current generation and results in high potential losses, as has been observed experimentally. Only electron transport through a solid conductive matrix can explain observations of high current densities and low anode potential losses. Thus, a study of the biological components that create a solid conductive matrix is of critical importance for understanding the function of ARB. [source] | |||||||||||||||||||||||||||||||