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The relation between recently established asymmetry in Asymmetric Detrended Fluctuation Analysis (ADFA) and Heart Rate Asymmetry is studied. It is found that the ADFA asymmetric exponents are related both to the overall variability and to its asymmetric components at all studied time scales. We find that the asymmetry in scaling exponents, i.e., [Formula: see text] is associated with both variance-based and runs-based types of asymmetry. This observation suggests that the physiological mechanisms of both types are similar, even though their origins and mathematical methods are very different. The graphical abstract demonstrates strong, nonlinear association between the expression of Heart Rate Asymmetry measured using relative descriptors and the Asymmetric Detrended Fluctuation Analysis results. It is clear that there is a strong relation between the two theoretically disparate approaches to signal analysis. The technique to demonstrate the association is loess fit.
Assuntos
Eletrocardiografia , Eletrocardiografia/métodos , Frequência Cardíaca/fisiologiaRESUMO
We used the topological insulator (TI) Bi2Te3 and a high-temperature superconductor (HTSC) hybrid device for investigations of proximity-induced superconductivity (PS) in the TI. Application of the superconductor YBa2Cu3O7-δ (YBCO) enabled us to access higher temperature and energy scales for this phenomenon. The HTSC in the hybrid device exhibits emergence of a pseudogap state for T > Tc that converts into a superconducting state with a reduced gap for T < Tc. The conversion process has been reflected in Raman spectra collected from the TI. Complementary charge transport experiments revealed emergence of the proximity-induced superconducting gap in the TI and the reduced superconducting gap in the HTSC, but no signature of the pseudogap. This allowed us to conclude that Raman spectroscopy reveals formation of the pseudogap state but cannot distinguish the proximity-induced superconducting state in the TI from the superconducting state in the HTSC characterised by the reduced gap. Results of our experiments have shown that Raman spectroscopy is a complementary technique to classic charge transport experiments and is a powerful tool for investigation of the proximity-induced superconductivity in the Bi2Te3.
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Two polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers differing in molecular mass (49 and 78 kDa) but possessing the same PEO cylindrical morphology are examined to elucidate their molecular dynamics. Of particular interest here is the molecular motion of the PEO blocks involved in the rigid amorphous fraction (RAF). An analysis of complementary thermal calorimetry and X-ray scattering data confirms the presence of microphase-separated morphology as well as semicrystalline structure in each copolymer. Molecular motion within the copolymer systems is monitored by dielectric and nuclear magnetic resonance spectroscopies. The results reported herein reveal the existence of two local Arrhenius-type processes attributed to the noncooperative local motion of PEO segments involved in fully amorphous and rigid amorphous PEO microphases. In both systems, two structural relaxations governed by glass-transition phenomena are identified and assigned to cooperative segmental motion in the fully amorphous phase (the α process) and the RAF (the αc process). We measure the temperature dependence of the dynamics associated with all of the processes mentioned above and propose that these local processes are associated with corresponding cooperative segmental motion in both copolymer systems. In marked contrast to the thermal activation of the α process as discerned in both copolymers, the αc process appears to be a sensitive probe of the copolymer nanostructure. That is, the copolymer with shorter PEO blocks exhibits more highly restricted cooperative dynamics of PEO segments in the RAF, which can be explained in terms of the greater constraint imposed by the glassy PS matrix on the PEO blocks comprising smaller cylindrical microdomains.
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We simulate selective A1BA2-A and A1BA2-B triblock solutions (that is, mixtures of the A1BA2 triblock with a solvent of either type A or type B) using a lattice Monte Carlo method. Although the simulated triblock chains are compositionally symmetric in terms of the A to B volume ratio, the A1 block is significantly shorter than the A2 block. For the pure A1BA2 melt the phase behavior is relatively well known, including the existence and stability of the recently discovered interstitial micelles which were found at the very strong segregation limit. In this paper, we investigate the stability of the interstitial micelles as a function of triblock volume fraction in a selective solvent of either type A or type B. The main finding of this paper is that adding a selective solvent of type A shifts the stability of the interstitial micelles into significantly higher temperatures which may provide a pathway towards experimental studies of interstitial micelles in real triblock solutions. We also find that adding selective solvents to the A1BA2 melt gives rise to a variety of nonlamellar nanostructures for temperatures and compositions at which the interstitial micelles are stable.
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We report on the preparation method of nanocrystalline titanium dioxide modified with platinum by using nanosecond laser ablation in liquid (LAL). Titania in the form of anatase crystals has been prepared in a two-stage process. Initially, irradiation by laser beam of a titanium metal plate fixed in a glass container filled with deionized water was conducted. After that, the ablation process was continued, with the use of a platinum target placed in a freshly obtained titania colloid. In this work, characterization of the obtained nanoparticles, based on spectroscopic techniques--Raman, X-ray photoelectron and UV-vis reflectance spectroscopy--is given. High resolution transmission electron microscopy was used to describe particle morphology. On the basis of photocatalytic studies we observed the rate of degradation process of methylene blue (MB) (a model organic pollution) in the presence of Pt modified titania in comparison to pure TiO2--as a reference case. Physical and chemical mechanisms of the formation of platinum modified titania are also discussed here. Stable colloidal suspensions containing Pt modified titanium dioxide crystalline anatase particles show an almost perfect spherical shape with diameters ranging from 5 to 30 nm. The TiO2 nanoparticles decorated with platinum exhibit much higher (up to 30%) photocatalytic activity towards the degradation of MB under UV illumination than pure titania.
Assuntos
Coloides/química , Lasers , Nanopartículas Metálicas/química , Platina/química , Titânio/química , Água/química , Azul de Metileno/química , Microscopia Eletrônica de Transmissão , Espectroscopia Fotoeletrônica , Espectrofotometria UltravioletaRESUMO
This paper presents comprehensive studies on the molecular dynamics of a pharmaceutically important substance, posaconazole. In order to characterize relaxation dynamics in the supercooled liquid and glassy states, dielectric and mechanical spectroscopies were applied. Dielectric data have indicated multiple relaxation processes that appear above and below the glass transition temperature Tg (τα=100 s) of posaconazole. From the curvature of the dielectric log10(τα) versus inverse of temperature dependence, we determine so-called "fragility", being a very popular parameter for classifying the structural dynamics of supercooled liquids and polymers. From the calculations, we get m=150, which means that is one of the most fragile glass-forming liquids. In this paper, the relaxation dynamics of supercooled posaconazole extracted from the dielectric response function was also confronted with shear-mechanical relaxation. Finally, we have also presented a direct comparison of the fragility and the number of dynamically correlated molecules Nc determined from dynamic calorimetry curves and dielectric and mechanical spectroscopies, showing a clear deviation in the picture of glass-transition dynamics generated by calorimetric and spectroscopic techniques.
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Varredura Diferencial de Calorimetria/métodos , Simulação de Dinâmica Molecular , Análise Espectral/métodos , Triazóis/químicaRESUMO
In this Communication, we present experimental studies that put new insight into the puzzling nature of the Debye relaxation found in the supercooled liquid state of racemic ibuprofen. The appearance of D-relaxation in the loss spectra of non-hydrogen bonding methylated derivate of ibuprofen has proven that Debye relaxation is related solely with conformational changes of the carboxyl group, termed in this paper as synperiplanar-antiperiplanar. Our studies indicate that the presence of hydrogen bonding capabilities is not here the necessary condition to observe Debye process, however, their occurrence might strongly influence α- and D-relaxations dynamics. Interestingly, the activation energy of the D-process in ibuprofen methyl ester on approaching T(g) was found to be perfectly consistent with that reported for ibuprofen by Affouard and Correia [J. Phys. Chem. B 114, 11397-11402 (2010)] (~39 kJ/mol). Finally, IR measurements suggest that the equilibrium between conformers concentration depends on time and temperature, which might explain why the appearance of D-relaxation in supercooled ibuprofen depends on thermal history of the sample.
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Analgésicos não Narcóticos/química , Anti-Inflamatórios não Esteroides/química , Ibuprofeno/química , Ligação de Hidrogênio , Modelos Moleculares , Conformação MolecularRESUMO
Skeletal muscle satellite cells, which reside beneath the basal lamina of mature muscle fibers, function as myogenic precursors and are required for normal muscle growth and repair. Satellite cells share a common anatomical localization, yet they exhibit substantial phenotypic and functional heterogeneity. Recent efforts in the field of adult myogenesis have been aimed at dissecting this heterogeneity and reveal the presence of discrete cell lineages within the muscle that function independently and interactively to maintain muscle homeostasis and to determine the outcome of muscle damage. Normal developmental regulation of the frequency and function of these distinct tissue precursors, and pathological deregulation of their activity, may have an important role in age- and disease-dependent loss of muscle regenerative activity.
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Mioblastos Esqueléticos/citologia , Mioblastos Esqueléticos/fisiologia , Células-Tronco/citologia , Células-Tronco/fisiologia , Envelhecimento/patologia , Animais , Diferenciação Celular , Separação Celular , Humanos , Camundongos , Desenvolvimento Muscular , Doenças Musculares/etiologia , Doenças Musculares/patologia , Regeneração , Células Satélites de Músculo Esquelético/citologia , Células Satélites de Músculo Esquelético/fisiologiaRESUMO
The mechanical properties of polymer composites, reinforced with silica-coated multiwall carbon nanotubes (MWNTs), have been studied using the nanoindentation technique. The hardness and the Young's modulus have been found to increase strongly with the increasing content of these nanotubes in the polymer matrix. Similar experiments conducted on thin films containing MWNTs, but without a silica shell, revealed that the presence of these nanotubes does not affect the nanomechanical properties of the composites. While carbon nanotubes (CNTs) have a very high tensile strength due to the nanotube stiffness, composites fabricated with CNTs may exhibit inferior toughness. The silica shell on the surface of a nanotube enhances its stiffness and rigidity. Our composites, at 4 wt % of the silica-coated MWNTs, display a maximum hardness of 120 +/- 20 MPa, and a Young's modulus of 9 +/- 1 GPa. These are respectively 2 and 3 times higher than those for the polymeric matrix. Here, we describe a method for the silica coating of MWNTs. This is a simple and efficient technique, adaptable to large-scale production, and might lead to new advanced polymer based materials, with very high axial and bending strength.
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Spin-lattice relaxation times T1 and T1d as well as NMR second moment were employed to study molecular dynamics of pyridoxine (vitamin B6) in the temperature range 10-350 K. The T1 minimum observed at low temperatures at 200 MHz is attributed to a motion of methyl group. The motion is interpreted in terms of Haupt's theory, which takes into account the tunneling assisted relaxation. At low temperatures, where T1 is temperature independent, occupation of the ground state only is assumed. A motion of proton of the hydroxyl groups or CH2OH groups probably provides additional mechanism of relaxation, in the high-temperature region.
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Cristalização/métodos , Cristalografia/métodos , Movimento (Física) , Piridoxina/química , Cinética , Conformação Proteica , Desnaturação Proteica , Prótons , TemperaturaRESUMO
Penetration of water into low-density polyethylene-calcium lactate composite is studied with NMR techniques. The presence of filler speeds up the water uptake by the polymer matrix and facilitates polyethylene degradation. Spatial distribution of absorbed water molecules within the composite visualised with MRI corroborates differences in dynamical behaviour of the absorbed water molecules revealed by T2 measurements.
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Compostos de Cálcio/química , Lactatos/química , Espectroscopia de Ressonância Magnética/métodos , Manufaturas/análise , Polietileno/química , Água/química , Absorção , Difusão , Propriedades de SuperfícieRESUMO
Rheometry, 13C CP/MAS NMR spectra and 1H spin-lattice relaxation times T1 and T1rho have been employed to study the structure and molecular dynamics in composites of polyethylene (LDPE) with calcium carbonate filler. It has been found that the addition of the filler into the polymer leads to an increase in composite rigidity and a decrease in mobility in its crystalline regions. The presence of the filler affects the crystallization process making the crystal structure less perfect and reduces the size of the crystallites.
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Carbonato de Cálcio/química , Espectroscopia de Ressonância Magnética/métodos , Manufaturas/análise , Teste de Materiais/métodos , Polietileno/química , Reologia/métodos , Isótopos de Carbono , Elasticidade , Conformação Molecular , Prótons , Resistência ao Cisalhamento , Temperatura , ViscosidadeRESUMO
Molecular dynamics in n-dodecylammonium chloride/water solutions for concentrations of 34 and 45 wt% was studied by 2H NMR and by 1H NMR dispersion of spin-lattice relaxation in the 2 kHz-90 MHz frequency range. The system exhibits a number of lyotropic liquid crystalline phases, which differ in symmetry and involve motions characterized by a wide frequency scale. The analysis of 2H NMR lineshapes of selectively deuterated DDACl molecules gave us an evidence for local trans-gauche conformational changes in the chains, whereas the dispersion of spin-lattice relaxation times T1 explored by fast field cycling method revealed fast local motions, translational diffusion and collective molecular dynamics of the chains. In particular, we have found that the order director fluctuation mechanism in smectic and nematic phases dominates spin-lattice relaxation below 1 MHz and that local motions and translational diffusion are responsible for the spin-lattice relaxation in the higher Larmor frequency range.
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A lattice simulation of a model diblock copolymer melt is presented. In a series of simulation experiments an 8-8 diblock melt is quenched from an athermal state to 47 lower temperatures. A set of simulation boxes, 30 x 32 x 30, 40 x 32 x 60, 50 x 32 x 30, and 60 x 32 x 30, is used in order to explore the size effects. Energy, specific heat, copolymer end-to-end distance, lamellar spacing, and the degree of interfacial ordering are reported. For all sizes considered, the low-temperature interfacial ordering is noticeable.
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A set of computer simulations for three symmetric A-B-A triblock copolymer microarchitectures at varying temperatures is reported. By using the cooperative motion algorithm we obtain energy, specific heat, end-to-end distance, and bridging fraction as a function of the reduced temperature. The order-disorder transition temperatures are determined, an outline of a symmetric A-B-A triblock copolymer phase diagram is presented, and the visualization of different microstructures is given. A bicontinuous microstructure is reported at 67% fraction of A component.
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Spin-lattice relaxation times T1 and nuclear Overhauser effect (NOE) enhancement factors for the individual ring carbons in di-n-butyl phthalate (DBF) show that the reorientational correlation function corresponding to the global dynamics in supercooled liquid can be described by a Davidson-Cole distribution. Measurements of proton spin-lattice relaxation times T1 and T1p, as well as 1H NMR spectra at temperatures below the glass transition temperature, Tg, reveal that the same distribution holds also for description of local dynamics in glassy DBF. The activation parameters of the motions detected are derived.
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Dibutilftalato/química , Vidro/química , Espectroscopia de Ressonância Magnética , Isótopos de Carbono , Fenômenos Químicos , Físico-Química , Temperatura Baixa , Espectroscopia de Ressonância de Spin Eletrônica , Hidrogênio , Conformação Molecular , PrótonsRESUMO
Spin-lattice relaxation times T1 and T1p as well as 1H NMR spectra have been employed to study the dynamics of the glass-forming di-isobutyl phthalate in the temperature range extending from 100 K, through the glass transition temperature Tg, up to 340 K. Below Tg NMR relaxation is governed by local dynamics and may be attributed to rotation of methyl groups at low temperatures and to motion of isobutyl groups in the intermediate temperature interval. Above Tg the main relaxation mechanism is provided by overall molecular motion. The observed relaxation behavior is explained by motional models assuming asymmetrical distributions of correlation times. The motional parameters obtained from Davidson-Cole distribution, which yields the best fit of the data at all temperatures are given.
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Dibutilftalato/análogos & derivados , Dibutilftalato/química , Vidro , Espectroscopia de Ressonância MagnéticaRESUMO
Temperature dependences of proton and fluorine second moments and spin-lattice relaxation time T1 below glass transition were measured in glassy "I-Do,Pip-Me-BF4" ionene. The existence of motions of methyl groups and segments linking the cationic centers, namely piperidinium rings and trimethylene groups, for the polymeric part of ionene were established. Isotropic rotation of the counter-ion was evidenced and its limited diffusion suggested. To interpret the proton and fluorine relaxation data, a Davidson-Cole distribution of correlation times was assumed.