886 resultados para Diffusion in liquids
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Objective: Abnormalities in the anterior interhemispheric connections provided by the corpus callosum (CC) have long been implicated in bipolar disorder (BID). In this study, we used complementary diffusion tensor imaging methods to study the structural integrity of the CC and localization of potential abnormalities in BD. Methods: Subjects included 33 participants with BID and 40 healthy comparison participants. Fractional anisotropy (FA) measures were compared between groups with region of interest (ROD methods to investigate the anterior, middle, and posterior CC and voxel-based methods to further localize abnormalities. Results: In ROI-based analyses, FA was significantly decreased in the anterior and middle CC in the BID group (p <.05). Voxel-based analyses similarly localized group differences to the genu, rostral body, and anterior midbody of CC (p <.05, corrected). Conclusion: The findings demonstrate abnormalities in the structural integrity of the anterior CC in BID that might contribute to altered interhemispheric connectivity in this disorder.
Abnormal anterior cingulum integrity in bipolar disorder determined through diffusion tensor imaging
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Background Convergent evidence implicates white matter abnormalities in bipolar disorder. The cingulum is an important candidate structure for study in bipolar disorder as it provides substantial white matter connections within the corticolimbic neural system that subserves emotional regulation involved in the disorder. Aims To test the hypothesis that bipolar disorder is associated with abnormal white matter integrity in the cingulum. Method Fractional anisotropy in the anterior and posterior cingulum was compared between 42 participants with bipolar disorder and 42 healthy participants using diffusion tensor imaging. Results Fractional anisotropy was significantly decreased in the anterior cingulum in the bipolar disorder group compared with the healthy group (P=0.003); however, fractional anisotropy in the posterior cingulum did not differ significantly between groups. Conclusions Our findings demonstrate abnormalities in the structural integrity of the anterior cingulum in bipolar disorder. They extend evidence that supports involvement of the neural system comprising the anterior cingulate cortex and its corticolimbic gray matter connection sites in bipolar disorder to implicate abnormalities in the white matter connections within the system provided by the cingulum.
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Contrary to expectations derived from preclinical studies of the effects of stress, and imaging studies of adults with posttraumatic stress disorder (PTSD), there is no evidence of hippocampus atrophy in children with PTSD. Multiple pediatric studies have reported reductions in the corpus callosum - the primary white matter tract in the brain. Consequently, in the present study, diffusion tensor imaging was used to assess white matter integrity in the corpus callosum in 17 maltreated children with PTSD and 15 demographically matched normal controls. Children with PTSD had reduced fractional anisotropy in the medial and posterior corpus, a region which contains interhemispheric projections from brain structures involved in circuits that mediate the processing of emotional stimuli and various memory functions - core disturbances associated with a history of trauma. Further exploration of the effects of stress on the corpus callosum and white matter development appears a promising strategy to better understand the pathophysiology of PTSD in children. (C) 2007 Elsevier Ireland Ltd. All rights reserved.
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The ionic liquids (ILs) 1-ethoxyethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [EtO-(CH(2))(2)MMI][Tf(2)N], and N-(ethoxyethyl)-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [EtO(CH(2))(2)MMor][Tf(2)N] were synthesized, and relevant properties, such as thermal stability, density, viscosity, electrochemical behavior, ionic conductivity, and self-diffusion coefficients for both ionic species, were measured and compared with those of their alkyl counterparts, 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [BMMI][Tf(2)N], and N-n-butyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide,[BMP][Tf(2)N] and N-n-butyl-N-methylmorpholinium bis(trilfuoromethanesulfonyl)imide [BMMor][Tf(2)N][. This comparison was done to evaluate the effects caused by the presence of the ether bond in either the side chain or in the organic cation ring. The salt, LiTf(2)N, was added to the systems to estimate IL behavior with regard to lithium cation transport. Pure [EtO(CH(2))(2)MMI][Tf(2)N] and their LiTf(2)N solutions showed low viscosity and the highest conductivity among the ILs studied. The H(R) (AC conductivity/NMR calculated conductivity ratio) values showed that, after addition of LiTf(2)N, ILs containing the ether bond seemed to have a greater number of charged species. Structural reasons could explain these high observed HR values for [EtO(CH(2))(2)MMor][Tf(2)N].
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Raman and electronic spectra of the [3,5-bis(dicyanomethylene)cyclopentane-1,2,4-trionate] dianion, the croconate violet (CV), are reported in solutions of ionic liquids based on imidazolium cations. Different normal modes of the CV anion, nu (C=O), nu (CO) + nu (CC) + nu (CCN), and nu(C N), were used as probes of solvation characteristics of ionic liquids, and were compared with spectra of CV in common solvents. The spectra of CV in ionic liquids are similar to those in dichloromethane solution, but distinct from those in protic solvents such as ethanol or water. The UV-vis spectra of CV in ionic liquids strongly suggest pi-pi interactions between the CV anion and the imidazolium cation. Copyright (C) 2009 John Wiley & Sons, Ltd.
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A new compact system encompassing in flow gas diffusion unit and a wall-jet amperometric FIA detector, coated with a supramolecular porphyrin film, was specially designed as an alternative to the time-consuming Monier-Williams method, allowing fast, reproducible and accurate analyses of free sulphite species in fruit juices. In fact, a linear response between 0.64 and 6.4 ppm of sodium sulphite. LOD = 0.043 ppm, relative standard deviation of +/- 1.5% (n = 10) and analytical frequency of 85 analyses/h were obtained utilising optimised conditions. That superior analytical performance allows the precise evaluation of the amount of free sulphite present in foods, providing an important comparison between the standard addition and the standard injection methods. Although the first one is most frequently used, it was strongly influenced by matrix effects because of the unexpected reactivity of sulphite ions with the juice matrixes, leading to its partial consumption soon after addition. In contrast, the last method was not susceptible to matrix effects yielding accurate results, being more reliable for analytical purposes. (C) 2011 Elsevier Ltd. All rights reserved.
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The electroformation of silicon oxide was performed in two room temperature ionic liquids (RTIL), 1-butyl-3-methyl-imidazolium bis(trifluoromethane sulfonyl) imide (BMITFSI) and N-n-butyl-N-methylpiperidinium bis(trifluoromethane sulfonyl) imide (BMPTFSI). This phenomenon was studied by electrochemical techniques and it was observed that the oxide growth follows a high-field mechanism. X-ray Photoelectron Spectroscopy experiments have shown that a non-stoichiometric oxide film was formed, related to the low water content present in both RTILs (< 30 ppm). The roughness values obtained by using AFM technique of the silicon surface after etching with HF was 1.5 nm (RMS). The electrochemical impedance spectroscopy at low frequencies range was interpreted as a resistance in parallel with a CPE element, the capacitance obtained was associated with the dielectric nature of the oxide formed and the resistance was interpreted considering the chemical dissolution of the oxide by the presence of the TFSI anion. The CPE element was associated with the surface roughness and the very thin oxide film obtained. (C) 2007 Elsevier Ltd. All rights reserved.
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The solvation of six solvatochromic probes in a large number of solvents (33-68) was examined at 25 degrees C. The probes employed were the following: 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (RB); 4-[(E)2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB; 2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenyl pyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), respectively. Of these, MePMBr is a novel compound. They can be grouped in three pairs, each with similar pK(a) in water but with different molecular properties, for example, lipophilicity and dipole moment. These pairs are formed by RB and MePM; QB and MePMBr; WB and MePMBr(2), respectively. Theoretical calculations were carried out in order to calculate their physicochemical properties including bond lengths, dihedral angles, dipole moments, and wavelength of absorption of the intramolecular charge-transfer band in four solvents, water, methanol, acetone, and DMSO, respectively. The data calculated were in excellent agreement with available experimental data, for example, bond length and dihedral angles. This gives credence to the use of the calculated properties in explaining the solvatochromic behaviors observed. The dependence of an empirical solvent polarity scale E(T)(probe) in kcal/mol on the physicochemical properties of the solvent (acidity, basicity, and dipolarity/polarizability) and those of the probes (pK(a), and dipole moment) was analyzed by using known multiparameter solvation equations. For each pair of probes, values of E(T)(probe) (for example, E(T)(MePM) versus E(T)(RB)) were found to be linearly correlated with correlation coefficients, r, between 0.9548 and 0.9860. For the mercyanine series, the values of E(T)(probe) also correlated linearly, with (r) of 0.9772 (MePMBr versus MePM) and 0.9919 (MePMBr(2) versus MePM). The response of each pair of probes (of similar pK(a)) to solvent acidity is the same, provided that solute-solvent hydrogen-bonding is not seriously affected by steric crowding (as in case of RB). We show, for the first time, that the response to solvent dipolarity/polarizability is linearly correlated to the dipole moment of the probes. The successive introduction of bromine atoms in MePM (to give MePMBr, then MePMBr(2)) leads to the following linear decrease: pK(a) in water, length of the phenolate oxygen-carbon bond, length of the central ethylenic bond, susceptibility to solvent acidity, and susceptibility to solvent dipolarity/polarizability. Thus studying the solvation of probes whose molecular structures are varied systematically produces a wealth of information on the effect of solute structure on its solvation. The results of solvation of the present probes were employed in order to test the goodness of fit of two independent sets of solvent solvatochromic parameters.
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Raman spectra of dilute solutions of acetonitrile in ionic liquids reveal the characteristic features of ionic liquids` polarity. This is accomplished by investigating the Raman bandshape of the nu (CN) band, corresponding to the CN stretching mode of CH(3)CN, which is a very sensitive probe of the local environment. The amphiphilic nature of the CH(3)CN molecule allows us to observe the effect of electron pair acceptor and electron pair donor characteristics on ionic liquids. It has been found that the overall polarity of nine different ionic liquids based on 1-alkyl-3-methylimidazolium cations is more dependent on the anion than cation. The observed wavenumber shift of the nu (CN) band of CH(3)CN in ionic liquids containing alkylsulfate anions agrees with the significant different values previously measured for the dielectric constant of these ionic liquids. The conclusions obtained from the analysis of the nu (CN) band were corroborated by the analysis of the symmetric nu(1) (CD(3)) stretching mode of deuterated acetonitrile in different ionic liquids. Copyright (C) 2010 John Wiley & Sons, Ltd.
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The Raman band assigned to the nu(C=O)mode in N,N-dimethylformamide (at ca. 1660 cm(-1)) was used as a probe to study a group of ionic liquids 1-alkyl-3-methylimidazolium bromide ([C(n)Mlm]Br) with different alkyl groups (n = 2, 4, 6, 8 and 10 carbons) in binary equimolar binary mixtures with dimethylformamide. Due to the high electric dipole moment of the group C=O, there is a substantial coupling between adjacent molecules in the solution, and the corresponding Raman band involves both vibrational and reorientational modes. Different chain lengths of the ILs lead to different extents of the uncoupling of adjacent molecules of dimethylformamide, resulting in different shifts for this band in the mixtures. Information about the organization of ionic liquids in solution was obtained and a model of aggregation for these systems is proposed. (C) 2010 Elsevier B.V. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Some photosensitizers (PSs) used for PACT (Antimicrobial Photodynamic Therapy) show an affinity for bacterial walls and can be photo-activated to cause the desired damage. However, on dentine bacterias may be less susceptible to PACT as a result of limited penetration of the PS. The aim of this study was to evaluate the diffusion of one PS based on hematoporphyrin on dentine structures. Twelve bovine incisors were used. Class III cavities (3 x 3 x 1 mm) were prepared on the mesial or distal surfaces using a diamond bur. Photogem (R) solution at 1 mg/mL (10 uL for each cavity) was used. The experimental Groups were divided according to thickness of dentine remaining and etched or no-etched before the PS application. The fluorescence excitation source was a VelScope (R) system. For image capture a scientific CCD color camera PixelFly (R) was coupled to VelScope. For image acquisition and processing, a computational routine was developed at Matlab (R). Fick's Law was used to obtain the average diffusion coefficient of PS. Differences were found between all Groups. The longitudinal temporal diffusion was influenced by the different times, thickness and acid etching.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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The mass transfer during osmotic dehydration of apple slices immersed in 40, 50 and 60% (w/w) aqueous sucrose solutions was investigated to evaluate the influence of solution concentration on diffusivities. In the mathematical model, the diffusion coefficients were functions of the local water and sucrose concentration. The mass transfer equations were, simultaneously, solved for water and sucrose using an implicit numerical method. Material coordinates following the shrinkage of the solid were used. The predicted concentration profiles were integrated and compared to experimental data, showing a reasonable agreement with the measured data. on average, the effective diffusion coefficients for water and sucrose decreased as the osmotic solution concentration increased; that is the behavior of the binary coefficients in water-sucrose solutions. However, the diffusivities expressed as a function of the local concentration in the slices varied between the treatments. Water diffusion coefficients showed a remarkable variation throughout the slice and unusual behavior, which was associated to the cellular structure changes observed in tissue immersed in osmotic solutions. Cell structure changes occurred in different ways: moderate plasmolysis at 40%, accentuated plasmolysis at 50% and generalized damage of the cells at 60%. Intact vacuoles were observed after a long time of exposure (30 h) to 40 and 50% solutions. Effects of the concentration on tissue changes make it difficult to generalize the behavior of diffusion coefficients.