14 resultados para INTRINSIC VISCOSITY
em Biblioteca Digital da Produção Intelectual da Universidade de São Paulo
Resumo:
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.
Resumo:
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.
Resumo:
Purpose: The claudin-low molecular subtype of breast cancer includes triple negative invasive carcinomas, with a high frequency of metaplastic and medullary features. The aim of this study was to evaluate the immunohistochemistry expression of claudins in a series of metaplastic breast carcinomas. We also assessed other claudin-low features, such as the cancer stem cell-like and epithelial-to-mesenchymal transition phenotypes. Results: The majority of the cases showed weak or negative staining for membrane claudins expression. We found 76.9% (10/13) low expressing cases for claudin-1, 84.6% (11/13) for claudin-3 and claudin-4, and 92.3% (12/13) for claudin-7. Regarding the cancer stem cell marker ALDH1, 30.8% (4/13) showed positive staining. We also showed that the majority of the cases presented a CD44(+)CD24(-/low) phenotype, positivity for vimentin and lack of E-cadherin expression. Interestingly, these claudin-low molecular features were specific of the mesenchymal component of metaplastic breast carcinomas, since its frequency was very low in other breast cancer molecular subtypes, as luminal, HER2-overexpressing and non-metaplastic triple negative tumors. Conclusions: The negative/low expression of claudins and E-cadherin, high levels of vimentin, and the breast cancer stem cell phenotype suggests that metaplastic breast carcinomas have similar features to the ones included in the claudin-low molecular subtype, specially their mesenchymal components. (C) 2012 Elsevier Ltd. All rights reserved.
Resumo:
Objective. To compare the dynamic viscosity (DV) of superficial layer of temporalis fascia (SLTF) with that of other biological tissues traditionally used for vocal fold implants to treat vocal fold rigidity. Study Design. Experimental. Method. Measurement of DV of samples of SLTF, deep layer of temporalis fascia (DLTF), and abdominal fat of 12 cadavers. Results. DV values of the different samples were presented in the following increasing order: SLTF, DLTF, and abdominal fat. There was statistical difference between the samples. Conclusion. DV of SLTF is lower than of other tissues tested.
Resumo:
Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most "confused" isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH3, allowing its prompt differentiation from the other isomers.
Resumo:
Ionic liquids based on 1-alkyl-3-methylimidazolium cations and the hydrogen sulfate (or bisulfate) anion, HSO4-, are much more viscous than ionic liquids with alkyl sulfates, RSO4-. The structural origin of the high viscosity of HSO4- ionic liquids is unraveled from detailed comparison of the anion Raman bands in 1-ethyl-3-methylimidazolium hydrogen sulfate and 1-butyl-3-methylimidazolium hydrogen sulfate with available data for simple HSO(4)(-) salts in crystalline phase, molten phase, and aqueous solution. Two Raman bands at 1046 and 1010 cm(-1) have been assigned as symmetric stretching modes nu(s)(S = O) of HSO4-, the latter being characteristic of chains of hydrogen-bonded anions. The intensity of this component increases in the supercooled liquid phase. For comparison purposes, Raman spectra of 1-ethyl-3-methylimidazolium ethyl sulfate and 1-butyl-3-methylimidazolium methyl sulfate have been also obtained. There is no indication of difference in the strength of hydrogen bond interactions of imidazolium cations with HSO4- or RSO4- anions. Raman spectra at high pressures, up to 2.6 GPa, are also discussed. Raman spectroscopy provides evidence that hydrogen-bonded anions resulting in anion-anion interaction is the reason for the high viscosity of imidazolium ionic liquids with HSO4-. If the ionic liquid is exposed to moisture, these structures are disrupted upon absorption of water from the atmosphere.
Resumo:
Be stars possess gaseous circumstellar decretion disks, which are well described using standard alpha-disk theory. The Be star 28 CMa recently underwent a long outburst followed by a long period of quiescence, during which the disk dissipated. Here we present the first time-dependent models of the dissipation of a viscous decretion disk. By modeling the rate of decline of the V-band excess, we determine that the viscosity parameter alpha = 1.0 +/- 0.2, corresponding to a mass injection rate (M) over dot = (3.5 +/- 1.3) x 10(-8) M-circle dot yr(-1). Such a large value of a suggests that the origin of the turbulent viscosity is an instability in the disk whose growth is limited by shock dissipation. The mass injection rate is more than an order of magnitude larger than the wind mass-loss rate inferred from UV observations, implying that the mass injection mechanism most likely is not the stellar wind, but some other mechanism.
Resumo:
Lattice calculations of the QCD trace anomaly at temperatures T < 160 MeV have been shown to match hadron resonance gas model calculations, which include an exponentially rising hadron mass spectrum. In this paper we perform a more detailed comparison of the model calculations to lattice data that confirms the need for an exponentially increasing density of hadronic states. Also, we find that the lattice data is compatible with a hadron density of states that goes as rho(m) similar to m(-a) exp(m/T-H) at large m with a > 5/2 (where T-H similar to 167 MeV). With this specific subleading contribution to the density of states, heavy resonances are most likely to undergo two-body decay (instead of multiparticle decay), which facilitates their inclusion into hadron transport codes. Moreover, estimates for the shear viscosity and the shear relaxation time coefficient of the hadron resonance model computed within the excluded volume approximation suggest that these transport coefficients are sensitive to the parameters that define the hadron mass spectrum.
Resumo:
Background: Several studies in Drosophila have shown excessive movement of retrogenes from the X chromosome to autosomes, and that these genes are frequently expressed in the testis. This phenomenon has led to several hypotheses invoking natural selection as the process driving male-biased genes to the autosomes. Metta and Schlotterer (BMC Evol Biol 2010, 10:114) analyzed a set of retrogenes where the parental gene has been subsequently lost. They assumed that this class of retrogenes replaced the ancestral functions of the parental gene, and reported that these retrogenes, although mostly originating from movement out of the X chromosome, showed female-biased or unbiased expression. These observations led the authors to suggest that selective forces (such as meiotic sex chromosome inactivation and sexual antagonism) were not responsible for the observed pattern of retrogene movement out of the X chromosome. Results: We reanalyzed the dataset published by Metta and Schlotterer and found several issues that led us to a different conclusion. In particular, Metta and Schlotterer used a dataset combined with expression data in which significant sex-biased expression is not detectable. First, the authors used a segmental dataset where the genes selected for analysis were less testis-biased in expression than those that were excluded from the study. Second, sex-biased expression was defined by comparing male and female whole-body data and not the expression of these genes in gonadal tissues. This approach significantly reduces the probability of detecting sex-biased expressed genes, which explains why the vast majority of the genes analyzed (parental and retrogenes) were equally expressed in both males and females. Third, the female-biased expression observed by Metta and Schltterer is mostly found for parental genes located on the X chromosome, which is known to be enriched with genes with female-biased expression. Fourth, using additional gonad expression data, we found that autosomal genes analyzed by Metta and Schlotterer are less up regulated in ovaries and have higher chance to be expressed in meiotic cells of spermatogenesis when compared to X-linked genes. Conclusions: The criteria used to select retrogenes and the sex-biased expression data based on whole adult flies generated a segmental dataset of female-biased and unbiased expressed genes that was unable to detect the higher propensity of autosomal retrogenes to be expressed in males. Thus, there is no support for the authors' view that the movement of new retrogenes, which originated from X-linked parental genes, was not driven by selection. Therefore, selection-based genetic models remain the most parsimonious explanations for the observed chromosomal distribution of retrogenes.
Resumo:
Nitrogen removal coupled with sulfide oxidation has potential for the treatment of effluents from anaerobic reactors because they contain sulfide, which can be used as an endogenous electron donor for denitrification. This work evaluated the intrinsic kinetics of sulfide-oxidizing autotrophic denitrification via nitrate and nitrite in systems containing attached cells. Differential reactors were fed with nitrified synthetic domestic sewage and different sulfide concentrations. The intrinsic kinetic parameters of nitrogen removal were determined when the mass transfer resistance was negligible. This bioprocess could be described by a half-order kinetic model for biofilms. The half-order kinetic coefficients ranged from 0.425 to 0.658 mg N-1/2 L-1/2 h(-1) for denitrification via nitrite and from 0.190 to 0.609 mg N-1/2 L-1/2 h(-1) for denitrification via nitrate. In this latter, the lower value was due to the use of electrons donated from intermediary sulfur compounds whose formation and subsequent consumption were detected. (C) 2011 Elsevier Ltd. All rights reserved.
Resumo:
Gas-phase reactions of model carbosulfonium ions (CH3-S+?=?CH2; CH3CH2-S+?=?CH2 and Ph-S+?=?CH2) and an O-analogue carboxonium ion (CH3-O+?=?CH2) with acyclic (isoprene, 1,3-butadiene, methyl vinyl ketone) and cyclic (1,3-cyclohexadiene, thiophene, furan) conjugated dienes were systematically investigated by pentaquadrupole mass spectrometry. As corroborated by B3LYP/6-311?G(d,p) calculations, the carbosulfonium ions first react at large extents with the dienes forming adducts via simple addition. The nascent adducts, depending on their stability and internal energy, react further via two competitive channels: (1) in reactions with acyclic dienes via cyclization that yields formally [4?+?2+] cycloadducts, or (2) in reactions with the cyclic dienes via dissociation by HSR loss that yields methylenation (net CH+ transfer) products. In great contrast to its S-analogues, CH3-O+?=?CH2 (as well as C2H5-O+?=?CH2 and Ph-O+?=?CH2 in reactions with isoprene) forms little or no adduct and proton transfer is the dominant reaction channel. Isomerization to more acidic protonated aldehydes in the course of reaction seems to be the most plausible cause of the contrasting reactivity of carboxonium ions. The CH2?=?CH-O+?=?CH2 ion forms an abundant [4?+?2+] cycloadduct with isoprene, but similar to the behavior of such alpha,beta-unsaturated carboxonium ions in solution, seems to occur across the C?=?C bond. Copyright (c) 2012 John Wiley & Sons, Ltd.
Resumo:
The efficiency of the charge-carrier photogeneration processes in poly(2,5-bis(3',7'-dimethyl-octyloxy)-1,4-phenylene vinylene) (OC(1)OC10-PPV) has been analyzed by the spectral response of the photocurrent of devices in ITO/polymer/Al structures. The symbatic response of the photocurrent action spectra of the OC1OC10-PPV devices, obtained for light-excitation through the ITO electrode and for forward bias, has been fitted using a phenomenological model which considers that the predominant transport mechanism under external applied electric field is the drift of photogenerated charge-carriers, neglecting charge-carrier diffusion. The proposed model takes into account that charge-carrier photogeneration occurs via intermediate stages of bounded pairs (excitonic states), followed by dissociation processes. Such processes result in two different contributions to the photoconductivity: The first one, associated to direct creation of unbound polaron pairs due to intrinsic photoionization; and the second one is associated to secondary processes like extrinsic photoinjection at the metallic electrodes. The results obtained from the model have shown that the intrinsic component of the photoconductivity at higher excitation energies has a considerably higher efficiency than the extrinsic one, suggesting a dependence on the photon energy for the efficiency of the photogeneration process.
Resumo:
Yolk color and egg white (albumen) cleanliness and viscosity are important parameters by which consumers judge the quality of eggs. This study aimed to investigate changes in albumen viscosity during storage of eggs for up to 36 days from two different commercial laying hen strains (Carijo Barbada and Isa Brown) fed a diet containing annatto (1.5 and 2.0%) or a synthetic additive without synthetic colorants (control). Analyses of humidity, albumen height, pH, viscosity, foam formation, and stability were carried out on eggs. Carijo Barbada strain had smaller albumen, lower humidity and higher egg white viscosity than Isa Brown strain; however, with storage, viscosity lowered significantly on both strains. Initially, the addition of 2.0% of annatto or a synthetic additive increased viscosity in both strains, but with storage only the control maintained longer viscosity. Lower viscosity did not change foam density and stability.
Resumo:
The suprachiasmatic nucleus (SCN), which is the main circadian biological clock in mammals, is composed of multiple cells that function individually as independent oscillators to express the self-sustained mRNA and protein rhythms of the so-called clock genes. Knowledge regarding the presence and localization of the proteins and neuroactive substances of the SCN are essential for understanding this nucleus and for its successful manipulation. Although there have been advances in the investigation of the intrinsic organization of the SCN in rodents, little information is available in diurnal species, especially in primates. This study, which explores the pattern of expression and localization of PER2 protein in the SCN of capuchin monkey, evaluates aspects of the circadian system that are common to both primates and rodents. Here, we showed that PER2 protein immunoreactivity is higher during the light phase. Additionally, the complex organization of cells that express vasopressin, vasoactive intestinal polypeptide, neuron-specific nuclear protein, calbindin and calretinin in the SCN, as demonstrated by their immunoreactivity, reveals an intricate network that may be related to the similarities and differences reported between rodents and primates in the literature.