969 resultados para Reversible Addition Fragmentation Chain Transfer (raft)


Relevância:

30.00% 30.00%

Publicador:

Resumo:

Sustainable forest restoration and management practices require a thorough understanding of the influence that habitat fragmentation has on the processes shaping genetic variation and its distribution in tree populations. We quantified genetic variation at isozyme markers and chloroplast DNA (cpDNA), analysed by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) in severely fragmented populations of Sorbus aucuparia (Rosaceae) in a single catchment (Moffat) in southern Scotland. Remnants maintain surprisingly high levels of gene diversity (H-E) for isozymes (H-E = 0.195) and cpDNA markers (H-E = 0.490). Estimates are very similar to those from non-fragmented populations in continental Europe, even though the latter were sampled over a much larger spatial scale. Overall, no genetic bottleneck or departures from random mating were detected in the Moffat fragments. However, genetic differentiation among remnants was detected for both types of marker (isozymes Theta(n) = 0.043, cpDNA Theta(c) = 0.131; G-test, P-value < 0.001). In this self-incompatible, insect-pollinated, bird-dispersed tree species, the estimated ratio of pollen flow to seed flow between fragments is close to 1 (r = 1.36). Reduced pollen-mediated gene flow is a likely consequence of habitat fragmentation, but effective seed dispersal by birds is probably helping to maintain high levels of genetic diversity within remnants and reduce genetic differentiation between them.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

The effect of addition of maltodextrin on drying kinetics of drops containing fructose, glucose, sucrose and citric acid individually and in mixtures was studied experimentally using single drop drying experiments and numerically by solving appropriate mass and heat transfer equations. The numerical predictions agreed with the experimental moisture and temperature histories within 5-6% average relative (absolute) errors and average differences of +/- 1degreesC, respectively. The stickiness of these drops was determined using the glass transition temperature (T-g) of the drops' surface layer as an indicator. The experimental stickiness histories followed the model predictions with reasonable accuracy. A safe drying (non-sticky) regime in a spray drying environment has been proposed, and used to estimate the optimum amount of addition of maltodextrin for successful spray drying of 120 micron diameter droplets of fruit juices. (C) 2003 Elsevier Ltd. All rights reserved.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

Purpose - In many scientific and engineering fields, large-scale heat transfer problems with temperature-dependent pore-fluid densities are commonly encountered. For example, heat transfer from the mantle into the upper crust of the Earth is a typical problem of them. The main purpose of this paper is to develop and present a new combined methodology to solve large-scale heat transfer problems with temperature-dependent pore-fluid densities in the lithosphere and crust scales. Design/methodology/approach - The theoretical approach is used to determine the thickness and the related thermal boundary conditions of the continental crust on the lithospheric scale, so that some important information can be provided accurately for establishing a numerical model of the crustal scale. The numerical approach is then used to simulate the detailed structures and complicated geometries of the continental crust on the crustal scale. The main advantage in using the proposed combination method of the theoretical and numerical approaches is that if the thermal distribution in the crust is of the primary interest, the use of a reasonable numerical model on the crustal scale can result in a significant reduction in computer efforts. Findings - From the ore body formation and mineralization points of view, the present analytical and numerical solutions have demonstrated that the conductive-and-advective lithosphere with variable pore-fluid density is the most favorite lithosphere because it may result in the thinnest lithosphere so that the temperature at the near surface of the crust can be hot enough to generate the shallow ore deposits there. The upward throughflow (i.e. mantle mass flux) can have a significant effect on the thermal structure within the lithosphere. In addition, the emplacement of hot materials from the mantle may further reduce the thickness of the lithosphere. Originality/value - The present analytical solutions can be used to: validate numerical methods for solving large-scale heat transfer problems; provide correct thermal boundary conditions for numerically solving ore body formation and mineralization problems on the crustal scale; and investigate the fundamental issues related to thermal distributions within the lithosphere. The proposed finite element analysis can be effectively used to consider the geometrical and material complexities of large-scale heat transfer problems with temperature-dependent fluid densities.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

Deep-frying, which consists of immersing a wet material in a large volume of hot oil, presents a process easily adaptable to dry rather than cook materials. A suitable material for drying is sewage sludge, which may be dried using recycled cooking oils (RCO) as frying oil. One advantage is that this prepares both materials for convenient disposal by incineration. This study examines fry-drying of municipal sewage sludge using recycled cooking oil. The transport processes occurring during fry-drying were monitored through sample weight, temperature, and image analysis. Due to the thicker and wetter samples than the common fried foods, high residual moisture is observed in the sludge when the boiling front has reached the geometric center of the sample, suggesting that the operation is heat transfer controlled only during the first half of the process followed by the addition of other mechanisms that allow complete drying of the sample. A series of mechanisms comprising four stages (i.e., initial heating accompanied by a surface boiling onset, film vapor regime, transitional nucleate boiling, and bound water removal) is proposed. In order to study the effect of the operating conditions on the fry-drying kinetics, different oil temperatures (from 120 to 180 degrees C), diameter (D = 15 to 25 mm), and initial moisture content of the sample (4.8 and 5.6 kg water(.)kg(-1) total dry solids) were investigated.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

Designer peptides have recently been developed as building blocks for novel self-assembled materials with stimuli-responsive properties. To date, such materials have been based on self-assembly in bulk aqueous solution or at solid-fluid interfaces. We have designed a 21-residue peptide, AM1, as a stimuli-responsive surfactant that switches molecular architectures at a fluid-fluid interface in response to changes in bulk aqueous solution composition. In the presence of divalent zinc at neutral pH, the peptide forms a mechanically strong 'film state'. In the absence of metal ions or at acid pH, the peptide adsorbs to form a mobile 'detergent state'. The two interfacial states can be actively and reversibly switched. Switching between the two states by a change in pH or the addition of a chelating agent leads to rapid emulsion coalescence or foam collapse. This work introduces a new class of surfactants that offer an environmentally friendly approach to control the stability of interfaces in foams, emulsions and fluid-fluid interfaces more generally.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

Markov chain Monte Carlo (MCMC) is a methodology that is gaining widespread use in the phylogenetics community and is central to phylogenetic software packages such as MrBayes. An important issue for users of MCMC methods is how to select appropriate values for adjustable parameters such as the length of the Markov chain or chains, the sampling density, the proposal mechanism, and, if Metropolis-coupled MCMC is being used, the number of heated chains and their temperatures. Although some parameter settings have been examined in detail in the literature, others are frequently chosen with more regard to computational time or personal experience with other data sets. Such choices may lead to inadequate sampling of tree space or an inefficient use of computational resources. We performed a detailed study of convergence and mixing for 70 randomly selected, putatively orthologous protein sets with different sizes and taxonomic compositions. Replicated runs from multiple random starting points permit a more rigorous assessment of convergence, and we developed two novel statistics, delta and epsilon, for this purpose. Although likelihood values invariably stabilized quickly, adequate sampling of the posterior distribution of tree topologies took considerably longer. Our results suggest that multimodality is common for data sets with 30 or more taxa and that this results in slow convergence and mixing. However, we also found that the pragmatic approach of combining data from several short, replicated runs into a metachain to estimate bipartition posterior probabilities provided good approximations, and that such estimates were no worse in approximating a reference posterior distribution than those obtained using a single long run of the same length as the metachain. Precision appears to be best when heated Markov chains have low temperatures, whereas chains with high temperatures appear to sample trees with high posterior probabilities only rarely. [Bayesian phylogenetic inference; heating parameter; Markov chain Monte Carlo; replicated chains.]

Relevância:

30.00% 30.00%

Publicador:

Resumo:

This study examined the effect of transfer to increased environmental salinity on the circulating levels of angiotensin II (ANG II), C-type natriuretic peptide (CNP), and arginine vasotocin (AVT) in the euryhaline elasmobranch, Carcharhinus letteas. Plasma levels of ANG 11 and CNP were significantly increased in C. leucas chronically acclimated to seawater (SW) in comparison to freshwater (FW) acclimated fish. There was no difference in plasma AVT levels. Acute transfer of FW fish to 75% SW induced an increase in plasma ANG II levels within 12 h, and subsequent transfer from 75 to 100% SW further increased plasma ANG 11 levels at both 24 and 72 h. No change in plasma CNP was observed during acute transfer to increased salinity. However, a significant increase in plasma AVT levels was observed following 96 h in 75% SW and 24 h in 100% SW. In chronically SW acclimated C leucas plasma osmolality, sodium, chloride, and Urea were all significantly higher than FW acclimated fish but there was no difference in haematocrit. Acute transfer of C letteas to 75% SW induced a significant increase in plasma osmolality, sodium and urea concentrations within 96 h of transfer. Subsequent transfer from 75 to 100% SW induced a further increase in these variables within 24 h in addition to a significant increase in plasma chloride above control levels. Haematocrit did not differ between the experimental and control groups throughout the acute study. Circulating levels of ANG 11 were significantly correlated to plasma, sodium, chloride, and urea concentrations during acclimation to SW. Conversely, circulating levels of CNP and AVT did not correlate to plasma osmolytes, however, CNP was significantly correlated to haematocrit during acclimation to seawater. (c) 2005 Elsevier Inc. All rights reserved.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

We propose that the Baxter's Q-operator for the quantum XYZ spin chain with open boundary conditions is given by the j -> infinity limit of the corresponding transfer matrix with spin-j (i.e., (2j + I)-dimensional) auxiliary space. The associated T-Q relation is derived from the fusion hierarchy of the model. We use this relation to determine the Bethe Ansatz solution of the eigenvalues of the fundamental transfer matrix. The solution yields the complete spectrum of the Hamiltonian. (c) 2006 Elsevier B.V. All rights reserved.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

Local mass transfer coefficients were determined by using the electrochemical technique. A simple model of a heat exchanger with segmental nickel tube joined to p.v.c. rods replaced the exchanger tubes. Measurements were made for both no-Ieakage, semi-leakage and total leakage configurations. Baffle-spacings of 47.6 mm, 66.6 mm, 97 mm and 149.2 mm wer studied. Also studied were the overall exchanger pressure drops for each configuration. The comparison of the heat transfer data with this work showed good agreement at high flow rates for the no-leakage case, but the agreement became poor for lower flow rates and leakage configurations. This disagreement was explained by non-analogous driving forces existing in the two systems. The no-leakage data showed length-wise variation of transfer coefficients along the exchanger length. The end compartments showing transfer coefficients inferior by up to 26% compared to tbe internal compartments, depending on Reynolds number. With the introduction of leakage streams this variation however became smaller than the experimental accuracy. A model is outlined to show the characteristic behaviour of individual electrode segments within the compartment. This was able to discriminate between cross and window zones for the no- leakage case, but no such distinction could be made for the leakage case. A flow area was found which, when incorporated in the Reynolds number, enabled the correlation of baffle-cut and baffle-spacing parameters for the no-leakage case . This area is the free flow area determined at the baffle edge. Addition of the leakage area to this flow area resulted in correlation of all commercial leakage geometrical parameters. The procedures used to correlate the pressure drop data from a total of eighteen different configurations on a single curve are also outlined.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

This paper investigates competition between chain-stores and independents in the UK opticians' industry, using the relationship between the number of outlets present in a local market and the market size. Chain-stores are shown to have a significant effect on local market competition. In addition, the empirical approach is extended to allow inferences on the nature and extent of product differentiation. The results are broadly consistent with a model of vertical product differentiation in which chain-stores adopt national pricing strategies. The evidence suggests that the nature of competition between independent retailers depends on whether a chain-store is present.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

The increasing demand for high capacity data storage requires decreasing the head-to-tape gap and reducing the track width. A problem very often encountered is the development of adhesive debris on the heads at low humidity and high temperatures that can lead to an increase of space between the head and media, and thus a decrease in the playback signal. The influence of stains on the playback signal of reading heads is studied using RAW (Read After Write) tests and their influence on the wear of the heads by using indentation technique. The playback signal has been found to vary and the errors to increase as stains form a patchy pattern and grow in size to form a continuous layer. The indentation technique shows that stains reduce the wear rate of the heads. In addition, the wear tends to be more pronounced at the leading edge of the head compared to the trailing one. Chemical analysis of the stains using ferrite samples in conjunction with MP (metal particulate) tapes shows that stains contain iron particles and polymeric binder transferred from the MP tape. The chemical anchors in the binder used to grip the iron particles now react with the ferrite surface to create strong chemical bonds. At high humidity, a thin layer of iron oxyhydroxide forms on the surface of the ferrite. This soft material increases the wear rate and so reduces the amount of stain present on the heads. The stability of the binder under high humidity and under high temperature as well as the chemical reactions that might occur on the ferrite poles of the heads influences the dynamic behaviour of stains. A model of stain formation taking into account the channels of binder degradation and evolution upon different environmental conditions is proposed.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

A specially-designed vertical wind tunnel was used to freely suspend individual liquid drops of 5 mm initial diameter to investigate drop dynamics, terminal velocity and heat and mass transfer rates. Droplets of distilled, de-ionised water, n-propanol, iso-butanol, monoethanolamine and heptane were studied over a temperature range of 50oC to 82oC. The effects of substances that may provide drop surface rigidity (e.g. surface active agents, binders and polymers) on mass transfer rates were investigated by doping distilled de-ionised water drops with sodium di-octyl sulfo-succinate surfactant. Mass transfer rates decreased with reduced drop oscillation as a result of surfactant addition, confirming the importance of droplet surface instability. Rigid naphthalene spheres and drops which formed a skin were also studied; the results confirmed the reduced transfer rates in the absence of drop fluidity. Following consideration of fundamental drop dynamics in air and experimental results from this study, a novel dimensionless group, the Oteng-Attakora, (OT), number was included in the mass transfer equation to account for droplet surface behaviour and for prediction of heat and mass transfer rates from single drops which exhibit surface instability at Re>=500. The OT number and the modified mass transfer equation are respectively: OT=(ava2/d).de1.5(d/) Sh = 2 + 0.02OT0.15Re0.88Sc0.33 Under all conditions drop terminal velocity increased linearly with the square root of drop diameter and the drag coefficient was 1. The data were correlated with a modified equation by Finlay as follows: CD=0.237.((Re/P0.13)1.55(1/We.P0.13) The relevance of the new model to practical evaporative spray processes is discussed.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

A study of clay chemistry has been approached with three aims: - to modify the conducting properties by intercalation of tetrathiafulvalene, - to study the electrochemistry of redox-active coordination compounds immobilised on clay coated electrodes, and - to study the role of clays as reagents in inorganic glass forming reactions using mainly solid-state magic-angle-spinning NMR. TTF was intercalated by smectites containing different interlayer and lattice cations. Evidence from ESR and 57Fe Mossbauer indicated charge-transfer from TTF to structural iron in natural montmorillonite, and to interlayer Cu2+ in Cu2+ exchanged laponite. No charge transfer was observed for laponite (Na+ form) itself. Ion exchange of TTF3(BF4)2 with laponite was found to proceed quantitatively. The intercalated species were believed to be (TTF)2+ dimers. Conductivity data showed an order of magnitude increase for the intercalated clays. The mechanism is thought to be ionic rather than CT as Na+ laponite showed a similar enhancement in conductivity. Mechanically robust colloidal clay films were prepared on platinum electrodes. After immersion in solutions containing redox active complexes [Co(bpy)3]3+ and [Cr(bpy)3]3+, the films became electroactive when a potential was applied. Cyclic voltammograms obtained for both complexes were found to be of the diffusion controlled type. For [Co(bpy)3]3+ immobilised on clay coated electrodes, a one-step oxidation and four-step reduction wave was observed corresponding to a one electron stepwise reversible reduction of Co(III), through Co(II), Co(I), Co(O) to Co(I) oxidation state. For [Cr(bpy)3]3+ the electrochemistry was complicated by the presence of additional waves corresponding to the dissociation of [Cr(bpy)3]3+ into the diaquo complex. ESR and diffuse reflectance data supported such a mechanism. 29Si, 27Al and 23Na MAS NMR spectroscopy, supported by powder XRD and FTIR, was used to probe the role of clays as reagents in glass forming reactions. 29Si MAS NMR was found to be a very sensitive technique for identifying the presence and relative abundance of crystalline and non-crystalline phases. In thermal reactions of laponite formation of new mineral phases such as forsterite, akermanite, sillimanite and diopside were detected. The relative abundance of each phase was dependent on thermal history, chemical nature and concentration of the modifier oxide present. In continuing work, the effect of selected oxides on the glass forming reactions of a model feldspar composition was investigated using solid state NMR alone. Addition of network modifying oxides generally produced less negative 29Si chemical shifts and larger linewidths corresponding to a wider distribution of Si-O-Si bond angles and lengths, and a dominant aluminosilicate phase with a less polymerised structure than the starting material. 29Si linewidths and 27Al chemical shifts were respectively correlated with cationic potential and Lewis acidity of the oxide cations. Anomalous Al(4) chemical shifts were thought to be due to precipitation of aluminate phases rather than a breakdown in Lowenstein's aluminium avoidance principle.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

The cationic polymerisation of various monomers, including cyclic ethers bearing energetic nitrate ester (-ON02) groups, substituted styrenes and isobutylene has been investigated. The main reaction studied has been the ring-opening polymerisation of 3- (nitratomethyl)-3-methyl oxetane (NIMMO) using the alcohol/BF3.0Et2 binary initiator system. A series of di-, tri- and tetrafunctional telechelic polymers has been synthesised. In order to optimise the system, achieve controlled molecular weight polymers and understand the mechanism of polymerisation the effects of certain parameters on the molecular weight distribution, as determined by Size Exclusion Chromatography, have been examined. This shows the molecular weight achieved depends on a combination of factors including -OH concentration, addition rate of monomer and, most importantly, temperature. A lower temperature and OH concentration tends to produce higher molecular weight, whereas, slower addition rates of monomer, either have no significant effect or produce a lower molecular weight polymer. These factors were used to increase the formation of a cyclic oligomer, by a side reaction, and suggest, that the polymerisation of NIMMO is complicated with endbiting and back biting reactions, along with other transfer/termination processes. These observations appear to fit the model of an active-chain end mechanism. Another cyclic monomer, glycidyl nitrate (GLYN), has been polymerised by the activated monomer mechanism. Various other monomers have been used to end-cap the polymer chains to produce hydroxy ends which are expected to form more stable urethane links, than the glycidyl nitrate ends, when cured with isocyanates. A novel monomer, butadiene oxide dinitrate (BODN), has been prepared and its homopolymerisation and copolymerisation with GL YN studied. In concurrent work the carbocationic polymerisations of isobutylene or substituted styrenes have been studied. Materials with narrow molecular weight distributions have been prepared using the diphenyl phosphate/BCl3 initiator. These systems and monomers are expected to be used in the synthesis of thermoplastic elastomers.

Relevância:

30.00% 30.00%

Publicador:

Resumo:

The methylation of cytosinc residues in DNA is thought to play an important role in the regulation of gene expression, with active genes generally being hypomethylated. With this in mind peptides were synthcsised to mimic the cytosine-5 methylation activity carried out by DNA mcthylase, which however, showed no ability to carry out this function. The imidazotetrazinoncs are a novel group of antitumour agents which have demonstrated good activity against a range of murinc tumours and human tumour xenografts, and hypomethylation of DNA has been implicated in the mechanism of action. Studies have been conducted on the mechanism by which such agents cause hypomethylation, using DNA methylase partially purified from murine L1210 leukaemia cells. Unmodified calf thymus DNA does not inhibit the transfer of methyl groups from SAM to M.lysodeikticus DNA by partially purified DNA methylase. However, if the calf thymus DNA is modified by alkylating agents such as imida-zotetrazinones or nitrosoureas, the treated DNA becomes an inhibitor of the methylation reaction. This has been correlated with the induction of DNA damage, such as single strand breaks, since X-ray treated DNA and deoxyribonuclease treatment produces a similar effect. The mechanism of inhibition by the drug treated or damaged DNA is thought to occur by binding of the enzyme to an increased concentration of non-substrate DNA, presumably by the occurrence of single strand breaks, since neither sonication nor treatment with the restriction enzyme Mspl caused an inhibition. Attempts were made to elucidate the strict structure activity relationship for antitumour activity observed amongst the imidazotctrazinones. The transfection of a murine colon adcnocarcinoma cell line (MAC 13) with DNA extracted from GM892 or Raji cells previously treated with either the methyl (temozolomide) or ethyl (ethazolastone) imidazotetrazinone was performed. X-irradiated DNA did not cause any suppression of cell growth, suggesting that it was not due to physical damage. Transfection of MAC 13 cells with DNA extracted from GM892 cells, was more effective at inhibiting growth than DNA from Raji cells. Temozolomide treated cellular DNA was a more potent growth inhibitor than that from ethazolastone treated cells. For both agents the growth inhibitory effect was most marked with DNA extracted 6h after drug addition, and after 24h no growth suppression was observed. This suggested that the growth inhibitory effect is due to a repairable lesion. .The methylation of M.lysodeikticus DNA by DNA methylase is inhibited potently and specifically by both hereto and homoribo and dcoxyri-bopolynucleotides containing guanine residues. The inhibitory effect is unaffected by chain length or sugar residue, but is abolished when the O-6 residue of guanine is substituted as in poly d(OGG)2o. Potent inhibition is also shown by polyinosinic and polyxanthylic acids but not by polyadenylic acid or by heteropolymers containing adcnine and thymine. These results suggest that the 6 position of the purine nucleus is important in binding of the DNA methylase to particular regions of the DNA and that the hydrogen bonding properties of this group are important in enzyme recognition. This was confirmed using synthetic oligonucleotides as substrates for DNA methylase. Enzymatic methylation of cytosine is completely suppressed, when O6 methylguanine replaces guanine in CG sites.