974 resultados para Chain-end


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The statistical properties of fractional Brownian walks are used to construct a path integral representation of the conformations of polymers with different degrees of bond correlation. We specifically derive an expression for the distribution function of the chains’ end‐to‐end distance, and evaluate it by several independent methods, including direct evaluation of the discrete limit of the path integral, decomposition into normal modes, and solution of a partial differential equation. The distribution function is found to be Gaussian in the spatial coordinates of the monomer positions, as in the random walk description of the chain, but the contour variables, which specify the location of the monomer along the chain backbone, now depend on an index h, the degree of correlation of the fractional Brownian walk. The special case of h=1/2 corresponds to the random walk. In constructing the normal mode picture of the chain, we conjecture the existence of a theorem regarding the zeros of the Bessel function.

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The purpose of this study was to find out whether food-related lifestyle guides and explains product evaluations, specifically, consumer perceptions and choice evaluations of five different food product categories: lettuce, mincemeat, savoury sauce, goat cheese, and pudding. The opinions of consumers who shop in neighbourhood stores were considered most valuable. This study applies means-end chain (MEC) theory, according to which products are seen as means by which consumers attain meaningful goals. The food-related lifestyle (FRL) instrument was created to study lifestyles that reflect these goals. Further, this research has adopted the view that the FRL functions as a script which guides consumer behaviour. Two research methods were used in this study. The first was the laddering interview, the primary aim of which was to gather information for formulating the questionnaire of the main study. The survey consisted of two separate questionnaires. The first was the FRL questionnaire modified for this study. The aim of the other questionnaire was to determine the choice criteria for buying five different categories of food products. Before these analyses could be made, several data modifications were made following MEC analysis procedures. Beside forming FRL dimensions by counting sum-scores from the FRL statements, factor analysis was run in order to elicit latent factors underlying the dimensions. The lifestyle factors found were adventurous, conscientious, enthusiastic, snacking, moderate, and uninvolved lifestyles. The association analyses were done separately for each choice of product as well as for each attribute-consequence linkage with a non-parametric Mann-Whitney U test. The testing variables were FRL dimensions and the FRL lifestyle factors. In addition, the relation between the attribute-consequence linkages and the demographic variables were analysed. Results from this study showed that the choice of product is sequential, so that consumers first categorize products into groups based on specific criteria like health or convenience. It was attested that the food-related lifestyles function as a script in food choice and that the FRL instrument can be used to predict consumer buying behaviour. Certain lifestyles were associated with the choice of each product category. The actual product choice within a product category then appeared to be a different matter. In addition, this study proposes a modification to the FRL instrument. The positive towards advertising FRL dimension was modified to examine many kinds of information search including the internet, TV, magazines, and other people. This new dimension, which was designated as being open to additional information, proved to be very robust and reliable in finding differences in consumer choice behaviour. Active additional information search was linked to adventurous and snacking food-related lifestyles. The results of this study support the previous knowledge that consumers expect to get many benefits simultaneously when they buy food products. This study brought detailed information about the benefits sought, the combination of benefits differing between products and between respondents. Household economy, pleasure and quality were emphasized with the choice of lettuce. Quality was the most significant benefit in choosing mincemeat, but health related benefits were often evaluated as well. The dominant benefits linked to savoury sauce were household economic benefits, expected pleasurable experiences, and a lift in self-respect. The choice of goat cheese appeared not to be an economic decision, self-respect, pleasure, and quality being included in the choice criteria. In choosing pudding, the respondents considered the well-being of family members, and indulged their family members or themselves.

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Failure to repair DNA double-strand breaks (DSBs) can lead to cell death or cancer. Although nonhomologous end joining (NHEJ) has been studied extensively in mammals, little is known about it in primary tissues. Using oligomeric DNA mimicking endogenous DSBs, NHEJ in cell-free extracts of rat tissues were studied. Results show that efficiency of NHEJ is highest in lungs compared to other somatic tissues. DSBs with compatible and blunt ends joined without modifications, while noncompatible ends joined with minimal alterations in lungs and testes. Thymus exhibited elevated joining, followed by brain and spleen, which could be correlated with NHEJ gene expression. However, NHEJ efficiency was poor in terminally differentiated organs like heart, kidney and liver. Strikingly, NHEJ junctions from these tissues also showed extensive deletions and insertions. Hence, for the first time, we show that despite mode of joining being generally comparable, efficiency of NHEJ varies among primary tissues of mammals.

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We consider the Kramers problem for a long chain polymer trapped in a biased double-well potential. Initially the polymer is in the less stable well and it can escape from this well to the other well by the motion of its N beads across the barrier to attain the configuration having lower free energy. In one dimension we simulate the crossing and show that the results are in agreement with the kink mechanism suggested earlier. In three dimensions, it has not been possible to get an analytical `kink solution' for an arbitrary potential; however, one can assume the form of the solution of the nonlinear equation as a kink solution and then find a double-well potential in three dimensions. To verify the kink mechanism, simulations of the dynamics of a discrete Rouse polymer model in a double well in three dimensions are carried out. We find that the time of crossing is proportional to the chain length, which is in agreement with the results for the kink mechanism. The shape of the kink solution is also in agreement with the analytical solution in both one and three dimensions.

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An analysis of the base pair doublet geometries in available crystal structures indicates that the often reported intrinsic curvature of DNA containing oligo-(d(A).d(T)) tracts may also depend on the nature of the flanking sequences. The presence of CA/TG doublet in particular at the 5' end of these tracts is expected to enhance their intrinsic bending property. To test this proposition, three oligonucleotides, d(GAAAAACCCCCC), d(CCCCCCAAAAAG), d(GAAAAATTTTTC), and their complementary sequences were synthesized to study the effect of various flanking sequences, at the 5' and 3' ends of the A-tracts, on the curvature of DNA in solution. An analysis of the polyacrylamide gel electrophoretic mobilities of these sequences under different conditions of salts and temperatures (below their melting points) clearly showed that the oligomer with CA/TG sequence in the center was always more retarded than the oligomer with AC/GT sequence, as well as the oligomer with AT/AT sequence. Hydroxyl radical probing of the sequences with AC/GT and CA/TG doublet junctions gives a similar cutting pattern in the A-tracts, which is quite different from that in the C-tracts, indicating that the oligo(A)-tracts have similar structures in the two oligomers. KMnO4 probing shows that the oligomer with a CA/TG doublet junction forms a kink that is responsible for its inherent curvature and unusual electrophoretic mobility. UV melting shows a reduced thermal stability of the duplex with CA/TG doublet junction, and circular dichroism (CD) studies indicate that a premelting transition occurs in the oligomer with CA/TG doublet step before global melting but not in the oligomer with AC/GT doublet step, which may correspond to thermally induced unbending of the oligomer. These observations indicate that the CA/TG doublet junction at the 5' end of the oligo(A)-tract has a crucial role in modulating the overall curvature in DNA.

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Pseudomonas putida CSV86, a soil bacterium, grows on 1- and 2-methylnaphthalene as the sole source of carbon and energy. In order to deduce the pathways for the biodegradation of 1- and 2-methylnaphthalene, metabolites were isolated from the spent medium and purified by thin layer chromatography. Emphasis has been placed on the structural characterisation of isolated intermediates by CC-MS, demonstration of enzyme activities in the cell free extracts and measurement of oxygen uptake by whole cells in the presence of various probable metabolic intermediates. The data obtained from such a study suggest the possibility of occurrence of multiple pathways in the degradation of 1- and 2-methylnaphthalene. We propose that, in one of the pathways, the aromatic ring adjacent to the one bearing the methyl moiety is oxidized leading to the formation of methylsalicylates and methylcatechols. In another pathway the methyl side chain is hydroxylated to -CH2-OH which is further converted to -CHO and -COOH resulting in the formation of naphthoic acid as the end product. In addition to this, 2-hydroxymethylnaphthalene formed by the hydroxylation of the methyl group of 2-methylnaphthalene undergoes aromatic ring hydroxylation. The resultant dihydrodiol is further oxidised by a series of enzyme catalysed reactions to form 4-hydroxymethyl catechol as the end product of the pathway.

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Higher level of inversion is achieved with a less number of switches in the proposed scheme. The scheme proposes a five-level inverter for an open-end winding induction motor which uses only two DC-link rectifiers of voltage rating of Vdc/4, a neutral-point clamped (NPC) three-level inverter and a two-level inverter. Even though the two-level inverter is connected to the high-voltage side, it is always in square-wave operation. Since the two-level inverter is not switching in a pulse width modulated fashion and the magnitude of switching transient is only half compared to the convention three-level NPC inverter, the switching losses and electromagnetic interference is not so high. The scheme is experimentally verified on a 2.5 kW induction machine.

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Two bile acid derived molecules containing basic amino groups are reported to be efficient and unusual gelators of organic and aqueous solvents.

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Design and operational details for a self-supported polymer electrolyte fuel cell (PEFC) system with anodic dead-end fuel supply and internally humidified cathodic oxidant flow are described. During the PEFC operation, nitrogen and water back diffuse across the Nafion membrane from the cathode to the anode and accumulate in the anode flow channels affecting stack performance. The accumulated inert species are flushed from the stack by purging the fuel cell stack with a timer-activated purge valve to address the aforesaid problem. To minimize the system complexity, stack is designed in such a way that all the inert species accumulate in only one cell called the purge cell. A pulsed purge sequence comprises opening the valve for purge duration followed by purge-valve closing for the hold period and repeating the sequence in cycles. Since self-humidification is inadequate to keep the membrane wet, the anodic dead-end-operated PEFC stack with composite membrane comprising perflourosulphonic acid (Nafion) and silica is employed for keeping the membrane humidified even while operating the stack with dry hydrogen and internally humidified air.

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The entry of the plant toxin ricin and its A- and B-subunits in model membranes in the presence as well as absence of monosialoganglioside (GM(1)) has been studied. Dioleoylphosphatidylcholine and 5-, 10-, and 12-doxyl- or 9,10-dibromophosphatidylcholines serve as quenchers of intrinsic tryptophan fluorescence of the proteins. The parallax method of Chattopadhyay and London [(1987) Biochemistry 26, 39-45] has been employed to measure the average membrane penetration depth of tryptophans of ricin and its B-chain and the actual depth of the sole Trp 211 in the A-chain. The results indicate that both of the chains as well as intact ricin penetrate the membrane deeply and the C-terminal end of the A-chain is well inside the bilayer, especially at pH 4.5. An extrinsic probe N-(iodoacetyl)-N'-(5-sulfo-1-naphthyl) ethylenediamine (I-AEDANS) has been attached to Cys 259 of the A-chain, and the kinetics of penetration has been followed by monitoring the increase in AEDANS fluorescence at 480 nm. The insertion follows first-order kinetics, and the rate constant is higher at a lower pH. The energy transfer distance analysis between Trp 211 and AEDANS points out that the conformation of the A-chain changes as it inserts into the membrane. CD studies indicate that the helicity of the proteins increases after penetration, which implies that some of the unordered structure in the native protein is converted to the ordered form during this process. Hydrophobic forces seem to be responsible for stabilizing a particular protein conformation inside the membrane.

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A novel (main chain)-(side chain) vinyl polyperoxide, poly(alpha-(tert-butylperoxymethyl)styrene peroxide) (MCSCPP), an alternating copolymer of alpha-(tert-butylperoxymethyl)styrene (TPMS) and oxygen, has been synthesized by the oxidative polymerization of TPMS. The MCSCPP was characterized by H-1 NMR, C-13 NMR, IR, DSC, EI-MS, and GC-MS studies. The overall activation energy (E(a)) for the degradation of MCSCPP was found to be 27 kcal/mol. Formaldehyde and alpha-(tert-butylperoxy)acetophenone (TPAP) were identified as the primary degradation products of MCSCPP; TPAP was found to undergo further degradation. The side chain peroxy groups were found to be thermally more stable than those in the main chain. Polymerization of styrene in the presence of MCSCPP as initiator, at 80 degrees C, follows classical kinetics. The presence of peroxy segments in the polystyrene chain was confirmed by both H-1 NMR and thermal decomposition studies. Interestingly, unlike other vinyl polyperoxides, the MCSCPP initiator shows an increase in molecular weight with conversion.

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The dynamics of poly(isobutyl methacrylate) in toluene solution has been examined by C-13 spin-lattice relaxation time and NOE measurements as a function of temperature. The experiments were performed at 50.3 and 100.6 MHz. The backbone carbon relaxation data have been analyzed using the Dejean-Laupretre-Monnerie (DLM) model, which describes the dynamical processes in the backbone in terms of conformational transitions and bond librations. The relaxation data of the side chain nuclei have been analyzed by assuming different motional models, namely, unrestricted rotational diffusion, three site jumps, and restricted rotational diffusion. The different models have been compared for their ability to reproduce the experimental spin-lattice relaxation times and also to predict the behavior of NOE as a function of temperature. Conformational energy calculations have been carried out on a model compound by using the semiempirical quantum chemical method, AM1, and the results confirm the validity of the motional models used to describe the side-chain motion.