Sample stacking in CZE using dynamic thermal junctions I. Analytes with low dpK(a)/dT crossing a single thermally induced pH junction in a BGE with high dpH/dT

The possibility to compress analyte bands at the beginning of CE runs has many advantages. Analytes at low concentration can be analyzed with high signal-to-noise ratios by using the so-called sample stacking methods. Moreover, sample injections with very narrow initial band widths (small initial standard deviations) are sometimes useful, especially if high resolutions among the bands are required in the shortest run time. In the present work, a method of sample stacking is proposed and demonstrated. It is based on BGEs with high thermal sensitive pHs (high dpH/dT) and analytes with low dpK(a)/dT. High thermal sensitivity means that the working pK(a) of the BGE has a high dpK(a)/dT in modulus. For instance, Tris and Ethanolamine have dpH/dT = -0.028/degrees C and -0.029/degrees C, respectively, whereas carboxylic acids have low dpK(a)/dT values, i.e. in the -0.002/degrees C to+0.002/degrees C range. The action of cooling and heating sections along the capillary during the runs affects also the local viscosity, conductivity, and electric field strength. The effect of these variables on electrophoretic velocity and band compression is theoretically calculated using a simple model. Finally, this stacking method was demonstrated for amino acids derivatized with naphthalene-2,3-dicarboxaldehyde and fluorescamine using a temperature difference of 70 degrees C between two neighbor sections and Tris as separation buffer. In this case, the BGE has a high pH thermal coefficient whereas the carboxylic groups of the analytes have low pK(a) thermal coefficients. The application of these dynamic thermal gradients increased peak height by a factor of two (and decreased the standard deviations of peaks by a factor of two) of aspartic acid and glutamic acid derivatized with naphthalene-2,3-dicarboxaldehyde and serine derivatized with fluorescamine. The effect of thermal compression of bands was not observed when runs were accomplished using phosphate buffer at pH 7 (negative control). Phosphate has a low dpH/dT in this pH range, similar to the dK(a)/dT of analytes. It is shown that vertical bar dK(a)/dT-dpH/dT vertical bar >> 0 is one determinant factor to have significant stacking produced by dynamic thermal junctions.

Sample stacking in CZE using dynamic thermal junctions II: Analytes with high dpK(a)/dT crossing a single thermal junction in a BGE with low dpH/dT

In a previous work [M. Mandaji, et al., this issue] a sample stacking method was theoretically modeled and experimentally demonstrated for analytes with low dpK(a)/dT (analytes carrying carboxylic groups) and BGEs with high dpH/dT (high pH-temperature-coefficients). In that work, buffer pH was modulated with temperature, inducing electrophoretic mobility changes in the analytes. In the present work, the opposite conditions are studied and tested, i.e. analytes with high dpK(a)/dT and BGEs that exhibit low dpH/dT. It is well known that organic bases such as amines, imidazoles, and benzimidazoles exhibit high dpK(a)/dT. Temperature variations induce instantaneous changes on the basicity of these and other basic groups. Therefore, the electrophoretic velocity of some analytes changes abruptly when temperature variations are applied along the capillary. This is true only if BGE pH remains constant or if it changes in the opposite direction of pK(a) of the analyte. The presence of hot and cold sections along the capillary also affects local viscosity, conductivity, and electric field strength. The effect of these variables on electrophoretic velocity and band stacking efficacy was also taken into account in the theoretical model presented. Finally, this stacking method is demonstrated for lysine partially derivatized with naphthalene-2,3-dicarboxaldehyde. In this case, the amino group of the lateral chain was left underivatized and only the alpha amino group was derivatized. Therefore, the basicity of the lateral amino group, and consequently the electrophoretic mobility, was modulated with temperature while the pH of the buffer used remained unchanged.

Influence of low and high levels of grain defects on maize wet milling

Yields and starch pasting characteristics obtained from wet milling of maize samples with low and high levels of defect grains were compared to those from sound samples. Defect grain groups ere established taking into account the defect degree. Thus the first group consisted of fermented, molded, heated and sprouted grains and the second of insect damaged. hollow, fermented (up to 1/4) grains and those injured by other causes. The grain groups, if present at low levels in the samples, 10% for first group and 17% for second group did not affect the chemical composition of starch and its pasting properties. obtained by the rapid visco analyser. Samples with high levels of grain groups (up to 100%). affected wet milling yields and starch viscosity. Samples with 100% of grains in the first group decreased starch, germ yield and peak viscosity and increased gluten yield. Samples with 100% of grains in the second group decreased germ and fiber yield but increased starch yield. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

High hydrostatic pressure processing on microstructure of probiotic low-fat yogurt

The effect of milk processing on the microstructure of probiotic low-fat yogurt was studied. Skim milk fortified with skim milk powder was subjected to three treatments prior to innoculation: thermal treatment at 85 degrees C for 30 min, high hydrostatic pressure at 676 MPa for 5 min, and combined treatments of high hydrostatic pressure (HHP) and heat. The processed milk was then fermented by using two different starter cultures containing Streptococcus thermophilus, Lactobacillus delbrueckii ssp. bulgaricus, Lactobacillus acidophilus, and Bifidobacterium longum. The microstructure of heat-treated milk yogurt had fewer interconnected chains of irregularly shaped casein micelles, forming a network that enclosed the void spaces. on the other hand, microstructure of HHP yogurt had more interconnected clusters of densely aggregated protein of reduced particle size, with an appearance more spherical in shape, exhibiting a smoother more regular surface and presenting more uniform size distribution. The combined HHP and heat milk treatments led to compact yogurt gels with increasingly larger casein micelle clusters interspaced by void spaces, and exhibited a high degree of cross-linking. The rounded micelles tended to fuse and form small irregular aggregates in association with clumps of dense amorphous material, which resulted in improved gel texture and viscosity. (C) 2007 Elsevier Ltd. All rights reserved.

Viscosity of fluoroindate glasses

The viscosity of two fluoroindate glasses was measured as a function of temperature in the range of 310 °C - 362 °C. In such interval, the viscosity values were found to be similar to those reported for fluorozirconate glasses. The log η - 1/T plots had an unexpected behavior: two viscosity regions that seem to obey Arrhenius equation were identified and the activation energy for viscous flow (EA) for the region near Tg is smaller than the value found above the transition range. This behavior is probably due to structural changes occurred around Tg. The low values of the activation energy for viscous flow obtained for the indium fluoride-based glasses studied, suggest a good resistance against the devitrification process, what can make them suitable for fiber preparation.

A Simple maxwell Based Model in Order to Represent the frequency-dependent viscosity measured by ultrasound

A previous work showed that viscosity values measured high frequency by ultrasound agreed with the values at low frequency by the rotational viscometer when conditions are met, such as relatively low frequency viscosity. However, these conditions strongly reduce the range of the measurement cell. In order to obtain a measurement range and sensitivity high frequency must used, but it causes a frequency-dependent decrease on the viscosity values. This work introduces a new simple in order to represent this frequency-dependent behavior.model is based on the Maxwell model for viscoelastic , but using a variable parameter. This parameter has physical meaning because it represents the linear behavior the apparent elasticity measured along with the viscosity by .Automotive oils SAE 90 and SAE 250 at 22.5±0.5oC viscosities at low frequency of 0.6 and 6.7 Pa.s, respectively,tested in the range of 1-5 MHz. The model was used in to fit the obtained data using an algorithm of non-linear in Matlab. By including the viscosity at low frequency an unknown fitting parameter, it is possible to extrapolate its . Relative deviations between the values measured by the and extrapolated using the model for the SAE 90 and SAE 250 oils were 5.0% and 15.7%, respectively.©2008 IEEE.

Shear viscosity of a pion gas resulting from rho pi pi and sigma pi pi interactions

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

Variations in Structure Explain the Viscometric Behavior of AOT Microemulsions at Low Water/AOT Molar Ratios

The viscosity of AOT/water/decane water-in-oil microemulsions exhibits a well-known maximum as a function of water/AOT molar ratio, which is usually attributed to increased attractions among nearly spherical droplets. The maximum can be removed by adding salt or by changing the oil to CCl4. Systematic small-angle X-ray scattering (SAXS) measurements have been used to monitor the structure of the microemulsion droplets in the composition regime where the maximum appears. On increasing the droplet concentration, the scattering intensity is found to scale with the inverse of the wavevector, a behavior which is consistent with cylindrical structures. The inverse wavevector scaling is not observed when the molar ratio is changed, moving the system away from the value corresponding to the viscosity maximum. It is also not present in the scattering from systems containing enough added salt to essentially eliminate the viscosity maximum. An asymptotic analysis of the SAXS data, complemented by some quantitative modeling, is consistent with cylindrical growth of droplets as their concentration is increased. Such elongated structures are familiar from related AOT systems in which the sodium counterion has been exchanged for a divalent one. However, the results of this study suggest that the formation of non-spherical aggregates at low molar ratios is an intrinsic property of AOT.

H-1 low- and high-field NMR study of the effects of plasma treatment on the oil and water fractions in crude heavy oil

The chemical and physical properties of a Brazilian heavy oil submitted to plasma treatment were investigated by H-1 low-and high-field nuclear magnetic resonance (NMR) combined to the characterization of rheological properties, thermogravimetry and measurement of basic sediments and water (BSW) content. The crude oil was treated in a dielectric barrier discharge plasma reactor, using natural gas, CO2 or H-2 as working gas. The results indicated a large drop in the water content of the plasma-treated samples as compared to the crude oil, giving rise to a reduction in the viscosity. No significant chemical change was produced in the oil portion itself, as observed by H-1 NMR. The water contents determined by H-1 low-field NMR analyses agreed well with those obtained by BSW, indicating the low-field NMR methods as a useful tool for following the effects of plasma treatments on heavy oils, allowing the separation of the effects caused on the water and oil fractions. (C) 2011 Elsevier Ltd. All rights reserved.

Aqueous dispersions of DMPG in low salt contain leaky vesicles

Aqueous dispersions of dimyristoyl phosphatidylglycerol (DMPG), at low ionic strength, display uncommon thermal behavior. Models for such behavior need to assign a form to the lipid aggregate. Although most studies accept the presence of lipid vesicles in the lipid gel and fluid phases, this is still controversial. With electron spin resonance (ESR) spectra of spin labels incorporated into DMPG aggregates, quantification of [C-14]sucrose entrapped by the aggregates, and viscosity measurements, we demonstrate the existence of leaky vesicles in dispersions of DMPG at low ionic strength, in both gel and fluid phases of the lipid. As a control system, the ubiquitous lipid dimyristoyl phosphatidylcholine (DMPC) was used. For DMPG in the gel phase, spin labeling only indicated the presence of lipid bilayers, strongly suggesting that DMPG molecules are organized as vesicles and not micelles or bilayer fragments (bicelles), as the latter has a non-bilayer structure at the edges. Quantification of [C-14]sucrose entrapping by DMPG aggregates revealed the presence of highly leaky vesicles. Due to the short hydrocarbon chains (C-14 atoms), DMPC vesicles were also found to be partially permeable to sucrose, but not as much as DMPG vesicles. Viscosity measurements, with the calculation of the intrinsic viscosiiy of the lipid aggregate, showed that DMPG vesicles are rather similar in the gel and fluid phases, and quite different from aggregates observed along the gel-fluid transition. Taken together, our data strongly supports that DMPG forms leaky vesicles at both gel and fluid phases. (C) 2011 Elsevier Ireland Ltd. All rights reserved.

Properties of an injectable low modulus PMMA bone cement for osteoporotic bone

The use of polymethylmethacrylate (PMMA) cement to reinforce fragile or broken vertebral bodies (vertebroplasty) leads to extensive bone stiffening. Fractures in the adjacent vertebrae may be the consequence of this procedure. PMMA with a reduced Young's modulus may be more suitable. The goal of this study was to produce and characterize stiffness adapted PMMA bone cements. Porous PMMA bone cements were produced by combining PMMA with various volume fractions of an aqueous sodium hyaluronate solution. Porosity, Young's modulus, yield strength, polymerization temperature, setting time, viscosity, injectability, and monomer release of those porous cements were investigated. Samples presented pores with diameters in the range of 25-260 microm and porosity up to 56%. Young's modulus and yield strength decreased from 930 to 50 MPa and from 39 to 1.3 MPa between 0 and 56% porosity, respectively. The polymerization temperature decreased from 68 degrees C (0%, regular cement) to 41 degrees C for cement having 30% aqueous fraction. Setting time decreased from 1020 s (0%, regular cement) to 720 s for the 30% composition. Viscosity of the 30% composition (145 Pa s) was higher than the ones received from regular cement and the 45% composition (100-125 Pa s). The monomer release was in the range of 4-10 mg/mL for all porosities; showing no higher release for the porous materials. The generation of pores using an aqueous gel seems to be a promising method to make the PMMA cement more compliant and lower its mechanical properties to values close to those of cancellous bone.

(Table 1) Viscosity coefficients at various temperatures of samples from ODP Hole 176-735B

Ocean Drilling Program (ODP) Hole 735B was drilled to a depth of 1.5 km in a tectonic window of gabbroic lower oceanic crust created at the Southwest Indian Ridge. The gabbros have a very stable natural remanent magnetization (NRM) of reversed polarity with most unblocking temperatures slightly below the Curie temperature of magnetite. The NRM includes a drilling-induced overprint but its intensity decays strongly towards the interior of the drill core. The demagnetization data yield no or only a very small secondary magnetization component acquired during the present Brunhes chron or an earlier normal chron, suggesting cooling through most of the blocking temperature range during chron C5r and a strong resistance against the acquisition of thermoviscous magnetization. A novel furnace has been designed to measure magnetizations and their time dependences at high temperatures (up to 580 deg C) inside a commercial SQUID magnetometer. Magnetic viscosity experiments have been conducted on the gabbros at temperatures up to 550 deg C to determine the time and temperature stability of remanent magnetization. Viscosities are generally small and increase little with temperature below the main blocking temperature, where the increase becomes almost an order of magnitude. Extrapolations to geological times infer viscous acquisitions that would be 5-25% of a thermoremanence in 100 kyr and at temperatures of 200-500 deg C. At ocean bottom temperature the predicted magnetization of one sample acquired in the present Brunhes chron should be 10% of the NRM. However, this is not recognized during NRM demagnetization and partial thermoremanent magnetization (pTRM) acquisitions at 250 deg C are also much smaller than predicted. It thus appears that the NRMs are generally magnetically harder than magnetizations acquired after heating to 570 deg C in the laboratory. Susceptibility changes during heating are small (<5%) indicating a seemingly stable magneto-mineralogy, but conspicuous minima occur after heating to 520 deg C. Also, quasi paleointensity experiments reveal characteristic patterns in the NRM/pTRM ratios and also large increases in pTRM capacity after heating to 570 deg C. Moreover, anhysteretic remanent magnetization acquisition in the low field range (<=10 mT) is strongly enhanced after heating by factors up to three. The alteration of the magneto-mineralogy is interpreted to result from the annealing of defects in magnetite that originate from tectonically induced strain. The oceanic gabbros of Hole 735B are thus ideal source layer material for marine magnetic anomalies, and secondary thermoviscous acquisition, as a possible cause for anomalous skewness, is essentially absent.

Changes in dynamic viscosity of sea water with depth in the Pacific Ocean at Stations DM9-613W and DM9-618W

To check on the assumption that metabolic products of planktonic organisms can affect the coefficient of dynamic viscosity of seawater, viscosity was measured in water samples taken from depths of 0 to 1843 m, west of the Hawaiian Islands. Obtained results showed that plankton has no effect on viscosity of water in regions of low productivity and that viscosity can be determined with high degree of accuracy from the appropriate tables.

Influence of acrylic adhesive viscosity and surface roughness on the properties of adhesive joint

In adhesion, the wetting process depends on three fundamental factors: the surface topography of the adherend, the viscosity of the adhesive, and the surface energy of both. The aim of this paper is to study the influence of viscosity and surface roughness on the wetting and their effect on the bond strength. For this purpose, an acrylic adhesive with different viscosities was synthesized and some properties, such as viscosity and surface tension, were studied before adhesive curing took place. Furthermore, the contact angle and the lap-shear strength were analyzed using aluminum adherends with two different roughnesses. Scanning electron microscopy was used to determine the effect of the viscosity and the roughness on the joint interface. The results showed that the adhesive exhibits an optimal value of viscosity. Below this value, at low viscosities, the low neoprene content produces poor bond strength due to the reduced toughness of the adhesive. Additionally, it also produces a high shrinkage during curing, which leads to the apparition of residual stresses that weakens the interfacial strength. However, once the optimum value, an increase in the viscosity produces a negative effect on the joint strength as a result of an important decrease in the wettability.

Root Growth and Oxygen Relations at Low Water Potentials. Impact of Oxygen Availability in Polyethylene Glycol Solutions1

Polyethylene glycol (PEG), which is often used to impose low water potentials (ψw) in solution culture, decreases O2 movement by increasing solution viscosity. We investigated whether this property causes O2 deficiency that affects the elongation or metabolism of maize (Zea mays L.) primary roots. Seedlings grown in vigorously aerated PEG solutions at ambient solution O2 partial pressure (pO2) had decreased steady-state root elongation rates, increased root-tip alanine concentrations, and decreased root-tip proline concentrations relative to seedlings grown in PEG solutions of above-ambient pO2 (alanine and proline accumulation are responses to hypoxia and low ψw, respectively). Measurements of root pO2 were made using an O2 microsensor to ensure that increased solution pO2 did not increase root pO2 above physiological levels. In oxygenated PEG solutions that gave maximal root elongation rates, root pO2 was similar to or less than (depending on depth in the tissue) pO2 of roots growing in vermiculite at the same ψw. Even without PEG, high solution pO2 was necessary to raise root pO2 to the levels found in vermiculite-grown roots. Vermiculite was used for comparison because it has large air spaces that allow free movement of O2 to the root surface. The results show that supplemental oxygenation is required to avoid hypoxia in PEG solutions. Also, the data suggest that the O2 demand of the root elongation zone may be greater at low relative to high ψw, compounding the effect of PEG on O2 supply. Under O2-sufficient conditions root elongation was substantially less sensitive to the low ψw imposed by PEG than that imposed by dry vermiculite.