Cinnamate ester containing liquid crystalline side chain polymers

The synthesis of methacrylate esters of 4-cyanophenyl-(4-(ω-hydroxyalkyloxy)) cinnamates, with spacer lengths of 2 and 6 methylene units and the synthesis of the corresponding acrylate ester with a spacer of 2 methylene units are described. The methacrylate monomers were polymerized by free radical polymerization, both as homopolymers and as copolymers with the analogous benzoate monomer of spacer length 6. The acrylate ester could not be polymerized successfully under the same reaction conditions. Polymers were characterized by NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermo-optic observations. Of the monomers prepared, only the cinnamate with a hexamethylene spacer shows a mesophase, seen on supercooling of the melt. All of the polymers prepared were liquid crystalline, with smectic behavior predominating in the polymethacrylates with the longer spacer group. A narrow nematic region is seen just below the clearing temperature with a range of 3–9°C, nematic character is increased in the copolymer series with the degree of incorporation of the cinnamate monomer with the spacer group of length 2.

Enhancing the catalytic repertoire of nucleic acids: a systematic study of linker length and rigidity

The incorporation of potentially catalytic groups in DNA is of interest for the in vitro selection of novel deoxyribozymes, A series of 10 C5-modified analogues of 2'-deoxyuridine triphosphate have been synthesised that possess side chains of differing flexibility and bearing a primary amino or imidazole functionality, For each series of nucleotide analogues differing degrees of flexibility of the C5 side chain was achieved through the use of alkynyl, alkenyl and alkyl moieties, The imidazole function was conjugated to these CS-amino-modified nucleotides using either imidazole 4-acetic acid or imidazole 4-acrylic acid (urocanic acid), The substrate properties of the nucleotides (fully replacing dTTP) with Taq polymerase during PCR have been investigated in order to evaluate their potential applications for in vitro selection experiments, 5-(3-Aminopropynyl)dUTP and 5-(E-3-aminopropenyl)dUTP and their imidazole 4-acetic acid- and urocanic acid-modified conjugates were found to be substrates, In contrast, C5-amino-modified dUTPs with alkane or Z-alkene linkers and their corresponding conjugates were not substrates, The incorporation of these analogues during PCR has been confirmed by inhibition of restriction enzyme digestion using XbaI and by mass spectrometry of the PCR products.

The role of phase separation and feed cycle length in leach beds coupled to methanogenic reactors for digestion of a solid substrate (Part 2): Hydrolysis, acidification and methanogenesis in a two-phase system

The effect of phase separation and batch duration on the trophic stages of anaerobic digestion was assessed for the first time in leach beds coupled to methanogenic reactors digesting maize (Zea mays). The system was operated for consecutive batches of 7, 14 and 28 days for ~120 days. Hydrolysis rate was higher the shorter the batch, reaching 8.5 gTSdestroyed d-1 in the 7-day system. Phase separation did not affect acidification but methanogenesis was enhanced in the short feed cycle leach beds. Phase separation was inefficient on the 7-day system, where ~89% of methane was produced in the leach bed. Methane production rate increased with shortening the feed cycle, reaching 3.523 l d-1 average in the 7-day system. Low strength leachate from the leach beds decreased methanogenic activity of methanogenic reactors’ sludges. Enumeration of cellulolytic and methanogenic microorganisms indicated a constant inoculation of leach beds and methanogenic reactors through leachate recirculation.

Oppositely charged polyelectrolytes: complex formation and effects of chain asymmetry

The formation of complexes in solutions of oppositely charged polyions has been studied by Monte Carlo simulations. The amount as well as the length, and thus, the absolute charge of one of the polyions have been varied. There is an increasing tendency to form large clusters as the excess of one kind of polyion decreases. When all polyions have the same length, this tendency reaches a maximum near, but off, equivalent amounts of the two types of polyions. When one kind of polyion is made shorter, the propensity to form large clusters decreases and the fluctuations in cluster charge increases. Simple free-energy expressions have been formulated on the basis of a set of simple rules that help rationalize the observations. By calculating cluster distributions in both grand canonical and canonical ensembles, it has been possible to show the extent of finite-size effects in the simulations.

Effect of inclusion of lactulose and Lactobacillus plantarum on the intestinal environment and performance of piglets at weaning

The prebiotic lactulose, a probiotic strain of Lactobacillus plantarum (L. plantarum) and a synbiotic combination of these two agents were evaluated as growth promoters in 25–39-day old commercial weaning pigs. Ninety-six weaning pigs were allocated into 32 pens, taking initial weight into account, and distributed into four groups as follows: a control diet (CTR), the same diet supplemented daily with L. plantarum (109 CFU/mL sprayed on top; 20 mL/pig) (LPN); 10 g/kg lactulose (LAC) or a combination of both treatments (SYN). At day 14, eight piglets from each group were euthanized and proximal colon digesta was sampled for luminal pH, short-chain fatty acids (SCFA) and lactic acid concentrations. Deoxyribonucleic acid was extracted from colonic digesta and the microbial community was profiled by terminal restriction fragment length polymorphism analysis (T-RFLP) and qPCR. Blood urea nitrogen (BUN) and acute-phase proteins (Pig-MAP) were measured. Lactulose treatment (LAC) improved feed intake (P<0.05), average daily gain (P<0.01), feed:gain ratio (P<0.05) and reduced BUN (P<0.01). Both, LAC and LPN treatment, decreased the Enterobacteriaceae:Lactobacillus spp. ratio in the colonic luminal contents (P<0.05). Moreover LPN treatment promoted a decrease in the percentage of branched fatty acids (P<0.01) suggesting a reduction in proteolytic microbial activity. Microbial profiling of colonic luminal contents by T-RFLP revealed changes in some microbial species. Terminal restriction fragments (TRFs) compatible with Bifidobacterium thermoacidophilum were more frequently detected in experimental diets compared to CTR (P<0.05). Pigs receiving SYN diet demonstrated the combined positive effects of individual LAC and LPN treatment although we were not able to show a specific increase in the probiotic strain with the inclusion of lactulose. Collectively, these data suggest the combination of lactulose and L. plantarum acts as a complementary synbiotic, but not as a synergistic combination.

Identification and lineage genotyping of South American trypanosomes using fluorescent fragment length barcoding

Trypanosoma cruzi and Trypanosoma rangeli are human-infective blood parasites, largely restricted to Central and South America. They also infect a wide range of wild and domestic mammals and are transmitted by a numerous species of triatomine bugs. There are significant overlaps in the host and geographical ranges of both species. The two species consist of a number of distinct phylogenetic lineages. A range of PCR-based techniques have been developed to differentiate between these species and to assign their isolates into lineages. However, the existence of at least six and five lineages within T. cruzi and T. rangeli, respectively, makes identification of the full range of isolates difficult and time consuming. Here we have applied fluorescent fragment length barcoding (FFLB) to the problem of identifying and genotyping T. cruzi, T. rangeli and other South American trypanosomes. This technique discriminates species on the basis of length polymorphism of regions of the rDNA locus. FFLB was able to differentiate many trypanosome species known from South American mammals: T. cruzi cruzi. T. cruzi marinkellei, T. dionisii-like, T. evansi, T. lewisi, T. rangeli, T. theileri and T. vivax. Furthermore, all five T. rangeli lineages and many T. cruzi lineages could be identified, except the hybrid lineages TcV and TcVI that could not be distinguished from lineages III and II respectively. This method also allowed identification of mixed infections of T. cruzi and T. rangeli lineages in naturally infected triatomine bugs. The ability of FFLB to genotype multiple lineages of T. cruzi and T. rangeli together with other trypanosome species, using the same primer sets is an advantage over other currently available techniques. Overall, these results demonstrate that FFLB is a useful method for species diagnosis, genotyping and understanding the epidemiology of American trypanosomes. (C) 2010 Elsevier B.V. All rights reserved.

Thermal Phase Behavior of DMPG Bilayers in Aqueous Dispersions as Revealed by (2)H- and (31)P-NMR

The synthetic lipid 1,2-dimyristoyl-sn-3-phosphoglycerol (DMPG), when dispersed in water/NaCl exhibits a complex phase behavior caused by its almost unlimited swelling in excess water. Using deuterium ((2)H)- and phosphorus ((31)P)-NMR we have studied the molecular properties of DMPG/water/NaCl dispersions as a function of lipid and NaCl concentration. We have measured the order profile of the hydrophobic part of the lipid bilayer with deuterated DMPG while the orientation of the phosphoglycerol headgroup was deduced from the (31)P NMR chemical shielding anisotropy. At temperatures > 30 degrees C we observe well-resolved (2)H- and (31)P NMR spectra not much different from other liquid crystalline bilayers. From the order profiles it is possible to deduce the average length of the flexible fatty acyl chain. Unusual spectra are obtained in the temperature interval of 20-25 degrees C, indicating one or several phase transitions. The most dramatic changes are seen at low lipid concentration and low ionic strength. Under these conditions and at 25 degrees C, the phosphoglycerol headgroup rotates into the hydrocarbon layer and the hydrocarbon chains show larger flexing motions than at higher temperatures. The orientation of the phosphoglycerol headgroup depends on the bilayer surface charge and correlates with the degree of dissociation of DMPG-Na(+). The larger the negative surface charge, the more the headgroup rotates toward the nonpolar region.

Isosorbide Polyesters from Enzymatic Catalysis

The synthesis of isosorbide aliphatic polyesters is demonstrated by the use of Novozym 435, a catalyst consisting of Candida antarctica lipase B immobilized on a macroporous support Several experimental procedures were tested and azeotropic distillation was most effective in removing low mass byproduct Furthermore, the use of diethyl ester derivatives of diacid comonomers gave isosorbide copolyesters with highest Isolated yield and molecular weights The length of the diacid aliphatic chain was less restrictive, but with a clear preference for longer aliphatic chains The molecular mass values of the obtained products were equivalent or higher than those obtained by nonenzymatic polymerizations, a clear illustration of the potential of enzymatic over conventional catalysis The ability of Novozym 435 to catalyze the synthesis of isosorbide polyester with weight-average molecular weights in excess of 40000 Da was unexpected given that isosorbide has two chemically distinct secondary hydroxyl groups This is the first example in which isosorbide polyesters were synthesized by enzyme catalysis, opening a large array of possibilities for this important class of biomass-derived building blocks Because these polymers are potential biomaterials the total absence of conventional Lewis acid catalyst residues represents a major Improvement in the toxicity of the material

Evaluation of an average numerator relationship matrix model and a Bayesian hierarchical model for growth traits in Nellore cattle with uncertain paternity

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Controle on-line por atributos para o número de não-conformidades no item inspecionado com base em uma sequência de inspeção

This paper proposes a procedure to control on-line processes for attributes, using an Shewhart control chart with two control limits (warning limit and control limit) and will be based on a sequence of inspection (h). The inspection procedure is based on Taguchi et al. (1989), in which to inspect the item, if the number of non-conformities is higher than an upper control limit, the process needs to be stopped and some adjustment is required; and, if the last inspection h, from all items inspected present a number of non-conformities between the control limit and warning limit. The items inspected will suffer destructive inspection, being discarded after inspection. Properties of an ergodic Markov chain are used to get the expression of average cost per item and the aim was the determination of four optimized parameters: the sampling interval of the inspections (m); the constant W to draw the warning limit (W); the constant C to draw the control limit (C), where W £ C, and the length of sequence of inspections (h). Numerical examples illustrate the proposed procedure

Evaluation of Philips and Ziegler-Natta high-density polyethylene degradation during processing in an internal mixer using the chain scission and branching distribution function analysis

The oxidative and thermo-mechanical degradation of HDPE was studied during processing in an internal mixer under two conditions: totally and partially filled chambers, which provides lower and higher concentrations of oxygen, respectively. Two types of HDPEs, Phillips and Ziegler-Natta, having different levels of terminal vinyl unsaturations were analyzed. Materials were processed at 160, 200, and 240 degrees C. Standard rheograrns using a partially filled chamber showed that the torque is much more unstable in comparison to a totally filled chamber which provides an environment depleted of oxygen. Carbonyl and transvinylene group concentrations increased, whereas vinyl group concentration decreased with temperature and oxygen availability. Average number of chain scission and branching (n(s)) was calculated from MWD curves and its plotting versus functional groups' concentration showed that chain scission or branching takes place depending upon oxygen content and vinyl groups' consumption. Chain scission and branching distribution function (CSBDF) values showed that longer chains undergo chain scission easier than shorter ones due to their higher probability of entanglements. This yields macroradicals that react with the vinyl terminal unsaturations of other chains producing chain branching. Shorter chains are more mobile, not suffering scission but instead are used for grafting the macroradicals, increasing the molecular weight. Increase in the oxygen concentration, temperature, and vinyl end groups' content facilitates the thermo-mechanical degradation reducing the amount of both, longer chains via chain scission and shorter chains via chain branching, narrowing the polydispersity. Phillips HDPE produces a higher level of chain branching than the Ziegler-Natta's type at the same processing condition. (c) 2006 Elsevier Ltd. All rights reserved.

Economic design of two-stage (X)over-bar charts: the Markov chain approach

When the (X) over bar chart is in use, samples are regularly taken from the process, and their means are plotted on the chart. In some cases, it is too expensive to obtain the X values, but not the values of a correlated variable Y. This paper presents a model for the economic design of a two-stage control chart, that is. a control chart based on both performance (X) and surrogate (Y) variables. The process is monitored by the surrogate variable until it signals an out-of-control behavior, and then a switch is made to the (X) over bar chart. The (X) over bar chart is built with central, warning. and action regions. If an X sample mean falls in the central region, the process surveillance returns to the (Y) over bar chart. Otherwise. The process remains under the (X) over bar chart's surveillance until an (X) over bar sample mean falls outside the control limits. The search for an assignable cause is undertaken when the performance variable signals an out-of-control behavior. In this way, the two variables, are used in an alternating fashion. The assumption of an exponential distribution to describe the length of time the process remains in control allows the application of the Markov chain approach for developing the cost function. A study is performed to examine the economic advantages of using performance and surrogate variables. (C) 2003 Elsevier B.V. All rights reserved.

Economic design of (X)over-bar charts with variable parameters: the Markov chain approach

This paper presents an economic design of (X) over bar control charts with variable sample sizes, variable sampling intervals, and variable control limits. The sample size n, the sampling interval h, and the control limit coefficient k vary between minimum and maximum values, tightening or relaxing the control. The control is relaxed when an (X) over bar value falls close to the target and is tightened when an (X) over bar value falls far from the target. A cost model is constructed that involves the cost of false alarms, the cost of finding and eliminating the assignable cause, the cost associated with production in an out-of-control state, and the cost of sampling and testing. The assumption of an exponential distribution to describe the length of time the process remains in control allows the application of the Markov chain approach for developing the cost function. A comprehensive study is performed to examine the economic advantages of varying the (X) over bar chart parameters.

A atividade antimicrobiana de agentes desinfetantes incorporados ao gesso tipo IV

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estimativas de parâmetros genéticos para a produção de leite e idade ao primeiro parto em vacas da raça pardo-suiça utilizando amostrador de Gibbs

Registros de 2.981 lactações de vacas da raça Pardo-Suiça, distribuídas em 62 rebanhos, com parições nos anos de 1980 a 2002, foram utilizados para verificar a influência de fatores genéticos e não genéticos, sobre a produção de leite e idade ao primeiro parto. O modelo empregado incluiu os efeitos fixos de rebanho, ano e estação de parto, além dos efeitos aleatórios de animal e ambiente temporário. Para a produção de leite, além dos efeitos fixos descritos anteriormente, incluíram-se também os efeitos linear da duração da lactação e linear e quadrático da idade da vaca ao parto, como co-variáveis. Na estimação dos componentes de (co) variâncias foi utilizada a inferência Bayesiana por meio de amostrador de Gibbs, com tamanho de cadeia de 1.500.000 rounds e período de queima 500.000 rounds. A frequência de amostragem foi de 500 rounds. As médias estimadas para produção de leite e idade ao primeiro parto foram iguais a 5347,47 1849,13 kg e 29,65 4,51 meses, respectivamente. Os efeitos de rebanho, ano de parto e duração da lactação, influenciaram significativamente a produção de leite (P< 0,01). A idade ao primeiro parto foi influenciada pelos efeitos de rebanho, ano de parto (P<0,01), além do efeito de estação de parto (P<0,05). As estimativas de herdabilidade obtidas para a produção de leite e idade ao primeiro parto foram iguais a 0,23 e 0,18, respectivamente. A correlação genética entre as duas foi igual a -0,31. A tendência genética e fenotípica, em função do reprodutor, para produção de leite foi de 1,09 kg e 115,34 kg de leite, respectivamente, para cada ano de produção. Para idade ao primeiro parto, os valores genéticos dos reprodutores tornaram-se negativos a partir de 1988, com redução aproximada de 0,05 meses a cada ano e fenotipicamente verificou-se uma redução de 32 para 28 meses de idade ao primeiro. Filhas de touros com alto valor genético para produção de leite tendem a apresentar crescimento mais acelerado ou maturidade fisiológica a uma idade mais precoce, diminuindo a idade ao primeiro parto.