1,699 research outputs found
Translational Diffusion of Small and Large Mesoscopic Probes in Hydroxypropylcellulose-Water in the Solutionlike Regime
Quasi-elastic light scattering spectroscopy was used to study the translational diffusion of monodisperse spheres in aqueous 1 MDa hydroxypropylcellulose (HPC) at 25 °C. Probe diameters d spanned 14â455 nm; HPC concentrations were 0⊽c⊽7g/L. Light scattering spectroscopy consistently found spectra having the form g(1)(t)=(1âAf)exp(âθtβ)+Af exp(âθftβf). Here θf and βf refer to the âfastâ mode; θ and β describe the âslowâ mode. We examine the dependence of θ, β, θf, βf, and Af on d, c, scattering vector q, and viscosity Ρ. β=1 for large probes; elsewise, β and βf are â(0,1). The slow mode, with short-lived memory function, is diffusive; for large probes θâ(dΡ)â1. The fast mode, with long-lived memory function, appears coupled to polymer chain internal dynamics. Probe behavior differs between âsmallâ and âlargeâ probes. Small probes have diameters
Relaxational Mode Structure for Optical Probe Diffusion in High Molecular Weight Hydroxypropylcellulose
We studied translational diffusion of dilute monodisperse spheres (diameters 14 \u3c d \u3c 455 nm) in aqueous 1 MDa hydroxypropylcellulose (0 ⤠c ⤠7 g/L) at 25°C using quasielastic light scattering. Spectra are highly bimodal. The two spectral modes (âslow,â âfastâ) have different physical properties. Probe behavior differs between small (d \u3c Rh) and large (d ⼠Rg) probes; Rh and Rg are the matrix polymer hydrodynamic radius and the radius of gyration, respectively. We examined the dependences of spectral lineshape parameters on d, c, scattering vector q, and viscosity Ρ for all four probe-size and mode-type combinations. We find three time scale-separated modes: (1) a large-probe slow mode has properties characteristic of particle motion in a viscous medium; (2) a large-probe fast mode and small-probe slow modes share the same time scale, and have properties characteristic of probe motion coupled to internal chain dynamics; and (3) a small-probe fast mode has properties that can be attributed to the probe sampling local chain relaxations. In the analysis, we also attempted to apply the coupling/scaling (CS) model of Ngai and Phillies [Ngai, K. L., Phillies, G. D. J. J. Chem. Phys.,105, 8385 (1996)] to analyze our data. We find that the second mode is described by the coupling/scaling model for probe diffusion; the first and third modes do not follow the predictions of this model
Translational Diffusion of Small and Large Mesoscopic Probes in Hydroxypropylcellulose-Water in the Solutionlike Regime
Quasi-elastic light scattering spectroscopy was used to study the translational diffusion of monodisperse spheres in aqueous 1 MDa hydroxypropylcellulose (HPC) at 25 °C. Probe diameters d spanned 14â455 nm; HPC concentrations were 0⊽c⊽7g/L. Light scattering spectroscopy consistently found spectra having the form g(1)(t)=(1âAf)exp(âθtβ)+Af exp(âθftβf). Here θf and βf refer to the âfastâ mode; θ and β describe the âslowâ mode. We examine the dependence of θ, β, θf, βf, and Af on d, c, scattering vector q, and viscosity Ρ. β=1 for large probes; elsewise, β and βf are â(0,1). The slow mode, with short-lived memory function, is diffusive; for large probes θâ(dΡ)â1. The fast mode, with long-lived memory function, appears coupled to polymer chain internal dynamics. Probe behavior differs between âsmallâ and âlargeâ probes. Small probes have diameters
Relaxational Mode Structure for Optical Probe Diffusion in High Molecular Weight Hydroxypropylcellulose
We studied translational diffusion of dilute monodisperse spheres (diameters 14 \u3c d \u3c 455 nm) in aqueous 1 MDa hydroxypropylcellulose (0 ⤠c ⤠7 g/L) at 25°C using quasielastic light scattering. Spectra are highly bimodal. The two spectral modes (âslow,â âfastâ) have different physical properties. Probe behavior differs between small (d \u3c Rh) and large (d ⼠Rg) probes; Rh and Rg are the matrix polymer hydrodynamic radius and the radius of gyration, respectively. We examined the dependences of spectral lineshape parameters on d, c, scattering vector q, and viscosity Ρ for all four probe-size and mode-type combinations. We find three time scale-separated modes: (1) a large-probe slow mode has properties characteristic of particle motion in a viscous medium; (2) a large-probe fast mode and small-probe slow modes share the same time scale, and have properties characteristic of probe motion coupled to internal chain dynamics; and (3) a small-probe fast mode has properties that can be attributed to the probe sampling local chain relaxations. In the analysis, we also attempted to apply the coupling/scaling (CS) model of Ngai and Phillies [Ngai, K. L., Phillies, G. D. J. J. Chem. Phys.,105, 8385 (1996)] to analyze our data. We find that the second mode is described by the coupling/scaling model for probe diffusion; the first and third modes do not follow the predictions of this model
Organic carbon compounds associated with deep soil carbon stores
Aims
Organic carbon has been reported in deep regolithic profiles to depths of tens of metres, but the composition of the carbon compounds is unknown.
Methods
Residual carbon in the form of non-volatile low molecular weight compounds (LMWC) was characterised in three deep soil profiles to a depth of 19 m under farmland in south-western Australia following extraction with ethyl acetate and analysis by GC/MS. Pyrolysis and off-line thermochemolysis were used to characterise macromolecular organic carbon (MOC) to a depth of 29 m at a fourth site.
Results
Three compound classes occurred across the three different field locations: (1) terpenes, (2) fatty acids, amides and alcohols, and (3) plant steroids; indicating the influence of input of the past and present vegetation. Compounds related to fatty acids were the predominant residual carbon species in deep soils, and may be derived from plants and microorganisms. Biomarkers such as lignin, polysaccharides, proteins and terpenes at 0â0.1 m implied influences of vegetation, fire events and microorganisms. Pyrolysis found that polysaccharides were distributed mainly from 0 to 0.1 m, while aromatic compounds were consistently detected down to 29 m.
Conclusions
Carbon was stabilised in the form of aromatic compounds in deep soil, whereas other carbon sources such as cellulose, chitin, and N-containing compounds were confined to the surface soil. LMWC (Z)-docos-13-enamide and bis(6-methylheptyl) phthalate, were the main components throughout the soil profiles representing 53â81% of the LMWC, and were a greater proportion of the organic matter at depths of 18â19 m
Study of The Crystallization of Zeolite NaA by Quasi-Elastic Light-Scattering Spectroscopy and Electron Microscopy
A study of the crystallization of the molecular sieve zeolite NaA from clear aluminosilicate solutions is reported. It was determined by powder X-ray diffraction that zeolite NaA was the only phase in the solid precipitate. The syntheses were monitored in situ by quasi-elastic light scattering spectroscopy. Characteristics of the products were examined by scanning and transmission electron microscopy. Our data show that nuclei formed from the clear aluminosilicate solution, that crystal growth occurred from the solution, that crystal growth was accelerated at elevated temperatures, and that aging the solution at room temperature before raising the synthesis temperature increased both the number of nuclei that formed and also the crystal growth rate for aging times up to a limit. Adding crushed seed crystal fragments to an unaged synthesis solution produced similar results to aging the solution, including reduced induction times, increased crystal growth rates, and polycrystalline product formation
Mode Structure of Diffusive Transport in Hydroxypropylcellulose:Water
A systematic analysis of the mode structure of diffusive relaxations in 1 MDa hydroxypropylcellulose(HPC):water is presented. New methods and data include (1) use of integral spectral moments to characterize nonexponential decays, (2) spectra of small probes in concentrated HPC solutions, (3) temperature dependence of the mode structure, and (4) comparison of optical probe spectra and spectra of probe-free polymer solutions. We find that (1) probe and polymer relaxations are in general not the same; (2) the apparent viscometric crossover near ctâ6 g/l is echoed by probe behavior; (3) our HPC solutions have a characteristic dynamic length, namely the 50 nm length that matches the polymerâs hydrodynamic radius; (4) characterization of spectral modes with their mean relaxation time affords simplifications relative to other characterizations; and (5) contrary to some expectations, StokesâEinsteinian behavior (diffusion rate determined by the macroscopic viscosity) is not observed, even for large probes in relatively concentrated solutions. We propose that the viscometric and light scattering effects found in HPC solutions at elevated concentrations reflect the incipient formation of a generalized Kivelson [S. A. Kivelson et al., J. Chem. Phys. 101, 2391 (1994)] glass
Study of The Effects of Initial-Bred Nuclei on Zeolite NaA Crystallization by Quasi-Elastic Light Scattering Spectroscopy and Electron Microscopy
Synthesis studies have been conducted at 25, 60, and 80 °C with a clear solution batch composition that produces zeolite NaA. Aluminosilicate precursor material was added to promote the synthesis and to evaluate the effects of adding initial-bred nuclei that were created by a precursor âseedâ reaction. It is shown that the initial-bred nuclei promoted the crystallization rate, that the crystalline mass produced was increased when using the initial-bred nuclei, and that the nucleation of a second population was not inhibited by the addition of initial-bred nuclei as seeds
Mode Structure of Diffusive Transport in Hydroxypropylcellulose:Water
A systematic analysis of the mode structure of diffusive relaxations in 1 MDa hydroxypropylcellulose(HPC):water is presented. New methods and data include (1) use of integral spectral moments to characterize nonexponential decays, (2) spectra of small probes in concentrated HPC solutions, (3) temperature dependence of the mode structure, and (4) comparison of optical probe spectra and spectra of probe-free polymer solutions. We find that (1) probe and polymer relaxations are in general not the same; (2) the apparent viscometric crossover near ctâ6 g/l is echoed by probe behavior; (3) our HPC solutions have a characteristic dynamic length, namely the 50 nm length that matches the polymerâs hydrodynamic radius; (4) characterization of spectral modes with their mean relaxation time affords simplifications relative to other characterizations; and (5) contrary to some expectations, StokesâEinsteinian behavior (diffusion rate determined by the macroscopic viscosity) is not observed, even for large probes in relatively concentrated solutions. We propose that the viscometric and light scattering effects found in HPC solutions at elevated concentrations reflect the incipient formation of a generalized Kivelson [S. A. Kivelson et al., J. Chem. Phys. 101, 2391 (1994)] glass
Trends in hepatocellular carcinoma incidence and survival among people with hepatitis C: An international study
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