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At least 1,225 records · Page 68Linked to original sources
PubMed1998

Influence of organic modifier concentration on plate number in micellar electrokinetic chromatography. 1. 2-propanol.

This paper establishes a physicochemical basis for the efficiency losses in micellar electrokinetic chromatography in buffers containing sodium dodecyl sulfate (SDS) and 2-propanol (2PN). Weakly, intermediately, and strongly retained analytes were separated in phosphate/borate buffers containing 50 mM SDS and from 0 to 10% 2PN by volume. Their plate numbers N generally agreed well with predictions of a theory for N based on longitudinal diffusion and instrumental contributions to dispersion. The N's of weakly and intermediately retained analytes were not affected strongly by 2PN over this concentration range, because their diffusion coefficients varied inversely with buffer viscosity and their retention times largely varied directly with viscosity. These combined effects on dispersion almost canceled. However, the N's of strongly retained analytes decreased with increasing 2PN, because their diffusion coefficients varied inversely with viscosity but their retention times increased more rapidly than did viscosity. These combined effects on dispersion did not cancel. These differences occurred because 2PN penetrated the micelles, caused bound counterions to be released, and increased the micellar charge and electrophoretic mobility. As 2PN concentration increased, the micelles electrophoresced increasingly rapidly against the electroosmotic flow. Consequently, strongly retained compounds required increasingly long times to elute.

2-Propanol↗
PubMed1988

Rotational dynamics of the single tryptophan of porcine pancreatic phospholipase A2, its zymogen, and an enzyme/micelle complex. A steady-state and time-resolved anisotropy study.

The rotational dynamics of the single tryptophan of porcine pancreatic phospholipase A2 and its zymogen (prophospholipase A2) have been studied by polarized fluorescence using steady-state and time-resolved single-photon counting techniques. The motion of Trp-3 in phospholipase A2 consists of a rapid subnanosecond wobble of the indole ring with an amplitude of about +/- 20 degrees accompanied by slower isotropic rotation of the entire protein. The rotational correlation times for overall particle rotational diffusion are consistent with conventional hydrodynamic theory. When phospholipase A2 binds to micelles of n-hexadecylphosphocholine, the amplitude of the fast ring rotation decreases. The whole particle rotational correlation time of the enzyme/micelle complex is smaller than the minimum value calculated from hydrodynamic theory. A similar result is obtained for the micelle itself by using the lipophilic probe transparinaric acid. These low values for the particle correlation times can be understood by postulating that an isotropic motion of the fluorophore in the small detergent particles contributes to the angular reorientation of the fluorophore. The internal reorientational motion of the tryptophan in the zymogen, prophospholipase A2, is of larger amplitude than that observed for the enzyme; specifically, the proenzyme exhibits a motion with a significant amplitude on the nanosecond time scale. This additional freedom of motion is attributed to segmental mobility of the N-terminal residues of prophospholipase A2. This demonstrates that this region of the protein is flexible in the zymogen but not in the processed enzyme. The implications of these findings for the mechanism of surface activation of phospholipase A2 are discussed by analogy with a trypsinogen-trypsin activation model.

Animals↗
PubMedDate not supplied

Characterization of the swelling of a size-exclusion gel.

The swelling of a dextran gel, Sephadex G-75, was observed in an aqueous environment at room temperature by a noninvasive technique that uses light microscopy coupled to an image analysis system via a video camera. The rate of swelling was found to follow the Tanaka and Fillmore theory, from which the overall gel diffusion coefficient was estimated as 6.3 x 10(-7) cm2/s. In addition to giving a quantitative measure of gel swelling that could be useful in the mechanical design of liquid chromatography columns, this approach provides data on wet particle size and particle size range, which is needed for the modeling of diffusional and mass transfer effects in size-exclusion chromatography. In this context, key observations are that the gel particles are nearly spherical with an elliptical shape factor of 0.98 (perfect sphere = 1) and that there is little difference between sizes of particles obtained in water, 50 mM Tris-glycine buffer (pH 10.2), and buffer containing 1 mg/mL protein. The diameter of the dry material ranged from 20 to 100 microns, while the hydrated particles had diameters of 40-350 microns. The rate of swelling is rapid, with 50% swelling occurring in about 10 s and swelling to 99% of the final wet particle size being obtained in less than 90 s.

Chemical Phenomena↗
PubMed2005

Density functional study of the conformational space of 4C1 D-glucuronic acid.

The conformational space of (4)C(1) alpha- and beta-d-glucuronic acid was scanned by HF/3-21G(p) calculations followed by optimization of the 15 most stable structures for each, using the B3LYP density functional theory method in conjunction with a diffuse polarized valence triple-zeta basis set. We found a general preference of the alpha anomers in the isolated molecules in agreement with the large endo-anomeric hyperconjugation effects in these structures. From the other intramolecular interactions (exo-anomeric hyperconjugation, hydrogen-bonding, dipole-dipole, and steric interactions), the effect of the hydrogen bonding is the most pronounced and plays a major role in determining the stability order within the alpha and beta series. The most stable conformer of both alpha and beta (4)C(1) d-glucuronic acid is the structure with the maximum number (5) of intramolecular hydrogen bonds. Introduction of solvent (water) effects by the SCI-PCM model resulted in two characteristic changes of the energetic properties: the gas-phase stability order changed considerably, and the energy range of the 15 most stable conformers decreased from 30 to 15 kJ/mol. The geometrical parameters reflect well the superimposed effects of hyperconjugation and hydrogen-bonding interactions. Most characteristics are the variations of the C-O bond distances (within a range of 0.04 A) upon the combined intramolecular effects.

Carbon↗
PubMed1997

Folding funnels and energy landscapes of larger proteins within the capillarity approximation.

The characterization of protein-folding kinetics with increasing chain length under various thermodynamic conditions is addressed using the capillarity picture in which distinct spatial regions of the protein are imagined to be folded or trapped and separated by interfaces. The quantitative capillarity theory is based on the nucleation theory of first-order transitions and the droplet analysis of glasses and random magnets. The concepts of folding funnels and rugged energy landscapes are shown to be applicable in the large size limit just as for smaller proteins. An ideal asymptotic free-energy profile as a function of a reaction coordinate measuring progress down the funnel is shown to be quite broad. This renders traditional transition state theory generally inapplicable but allows a diffusive picture with a transition-state region to be used. The analysis unifies several scaling arguments proposed earlier. The importance of fluctuational fine structure both to the free-energy profile and to the glassy dynamics is highlighted. The fluctuation effects lead to a very broad trapping-time distribution. Considerations necessary for understanding the crossover between the mean field and capillarity pictures of the energy landscapes are discussed. A variety of mechanisms that may roughen the interfaces and may lead to a complex structure of the transition-state ensemble are proposed.

Capillary Action↗
PubMed1994

Dissociation of duplexes formed by hybridization of DNA with gel-immobilized oligonucleotides.

The method of DNA sequencing by hybridization with oligonucleotides matrix (SHOM) developed in this laboratory (1.2) uses the matrix of oligonucleotides immobilized within polyacrylamide gel. The particular feature of this matrix is that the apparent thermostability of the duplexes depends on the concentration of gel-immobilized oligonucleotides. This dependence is specific for oligonucleotides immobilized in the gel volume (3-D-immobilization) rather than on a flat surface of a filter or glass (2-D-immobilization). The theory has been developed that provides a quantitative description of temperature-dependent duplex dissociation within gel. The theory takes into account that the diffusion of dissociated DNA out of the gel is retarded by multiple acts of association-dissociation of DNA with immobilized oligonucleotides. It allows to calculate the apparent dissociation temperature of duplexes and describes quantitatively its growth upon increase in the enthalpy of duplex dissociation, concentration of immobilized oligonucleotides, gel thickness and decrease of dissociation entropy and washing time. Concentration of gel-immobilized oligonucleotides can be calculated for a normalized matrix in which GC-rich and AT-rich duplexes exhibit the same apparent thermostabilities and are washed off at the same temperature. This simplifies identification of perfect duplexes formed on the matrix which can be carried out for all duplexes at the same temperature. The gel-immobilized oligonucleotide matrix provides also a higher capacity for immobilization and therefore a higher sensitivity of measurements, resulting in a higher discrimination power for identification of perfect duplexes as compared with matrixes of oligonucleotides immobilized on a surface.

Acrylic Resins↗
PubMed2006

Modeling dermal exposure--an illustration for spray painting applications.

This article presents a conceptual, mathematical model of dermal exposure resulting from aerosol deposition on human forearm hair. The model is applicable to exposure scenarios where dermal deposition is governed by aerosol impaction, interception, and diffusion mechanisms. The model employs filtration theory, single fiber efficiency equations, and a modified potential airflow approximation. The results are extended, using previously published results, for application to dermal deposition on the forearm during spray painting. The average (N = 8) predicted dermal deposition of 1,6-hexamethylene diisocyanate as collected on a 10-cm(2) tape strip is 108.9 (+/- 70.3) pmol, whereas field measurements indicated an average of 168.6 (+/- 82.0) pmol per strip. The corresponding measured average dermal flux was 3.63 pg/cm(2)s (+/- 1.34); the prediction was 2.24 pg/cm(2)sec (+/- 1.25). The study calls attention to the importance of body hair both for modeling and measuring dermal exposures.

Air Pollutants, Occupational↗
PubMed2000

Optical non-invasive technique for vessel imaging: II. A simplified photon diffusion analysis.

The purpose of this paper is to explain theoretically the origin of previously presented experimental results by an optical non-invasive method using NIR for imaging blood vessels based on a specific combination of several physical parameters. The theoretical model is based on the diffusion approximation derived from the transport theory deep in a bulk tissue. An analytical solution was obtained describing photon behaviour under certain conditions during vessel identification. The modelled results indicate that the vessel identification facility depends upon source-detector separation and vessel depth, and does not depend essentially on the radiant power from the light source. The solution offers a relatively simple theoretical explanation of the experimental results and can be applied to several other clinical applications using similar technical solutions.

Algorithms↗
PubMed1999

Droplet vaporization at critical conditions: long-time convective-diffusive profiles along the critical isobar.

The heating of a cold fluid package introduced, at critical conditions, in a hotter environment of the same fluid at the critical pressure is analyzed. Critical anomalies of the fluid transport properties as well as an arbitrary equation of state are taken into account. In unconfined microgravity conditions and for times much longer than the characteristic acoustic time, the heat transfer becomes a convective-diffusive isobaric transient process. An asymptotic theory valid in the limit of very small ratio between the fluid densities in the hot and cold regions is developed. The divergency of the thermal conductivity kappa at the critical temperature controls the heat transfer to the cold region. In the present model it is shown that there exists a well defined border, denoted by R(t), delimiting two distinguishable regions. The outer region extends from the far field down to R(t) where the critical temperature T(c) is reached. There, the temperature gradient vanishes due to the divergency of kappa. Thus, heat does not penetrate in the inner cold region where the temperature remains equal to T(c). The heating of the initially cold fluid package takes place by the recession of the border R(t). The model predicts a temperature profile in the outer region which is quasisteady in a reference system receding with R(t). It is shown that R2(t) decreases linearly with time. The recession velocity and thus the vaporization time are obtained as a function of the geometry and of the far-field conditions. Furthermore, the restrictions imposed by the long-time isobaric hypothesis are analyzed.

Journal Article↗
PubMed2005

Determination of the diffusion constant using phase-sensitive measurements.

We apply a pulsed-light interferometer to measure both the intensity and the phase of light that is transmitted through a strongly scattering disordered material. From a single set of measurements we obtain the time-resolved intensity, frequency correlations and statistical phase information simultaneously. We compare several independent techniques of measuring the diffusion constant for diffuse propagation of light. By comparing these independent measurements, we obtain experimental proof of the consistency of the diffusion model and corroborate phase statistics theory.

Journal Article↗
PubMed2006

Mechanisms in the size segregation of a binary granular mixture.

A granular mixture of particles of two sizes that is shaken vertically will in most cases segregate. If the larger particles accumulate at the top of the sample, this is called the Brazil-nut effect (BNE); if they accumulate at the bottom, it is called the reverse Brazil-nut effect (RBNE). While this process is of great industrial importance in the handling of bulk solids, it is not well understood. In recent years ten different mechanisms have been suggested to explain when each type of segregation is observed. However, the dependence of the mechanisms on driving conditions and material parameters and hence their relative importance is largely unknown. In this paper we present experiments and simulations where both types of particles are made from the same material and shaken under low air pressure, which reduces the number of mechanisms to be considered to seven. We observe both BNE and RBNE by varying systematically the driving frequency and amplitude, diameter ratio, ratio of total volume of small to large particles, and overall sample volume. All our results can be explained by a combination of three mechanisms: a geometrical mechanism called void filling, transport of particles in sidewall-driven convection rolls, and thermal diffusion, a mechanism predicted by kinetic theory.

Journal Article↗
PubMed2000

Changing shapes in the nanoworld

What are the mechanisms leading to the shape relaxation of three-dimensional crystallites? Kinetic Monte Carlo simulations of fcc clusters show that the usual theories of equilibration, via atomic surface diffusion driven by curvature, are verified only at high temperatures. Below the roughening temperature, the relaxation is much slower, kinetics being governed by the nucleation of a critical germ on a facet. We show that the energy barrier for this step linearly increases with the size of the crystallite, leading to an exponential dependence of the relaxation time.

Journal Article↗
PubMed2001

Coulomb blockade of tunneling between disordered conductors.

We determine the zero-bias anomaly of the conductance of tunnel junctions by an approach unifying the conventional Coulomb blockade theory for ultrasmall junctions with the diffusive anomalies in disordered conductors. Both electron-electron interactions within the electrodes and electron-hole interactions between the electrodes are taken into account nonperturbatively. Explicit results are given for one- and two-dimensional junctions, and the crossover to ultrasmall junctions is discussed.

Journal Article↗
PubMed2003

Site determination and thermally assisted tunneling in homogenous nucleation.

A combined low-temperature scanning tunneling microscopy and density functional theory study on the binding and diffusion of copper monomers, dimers, and trimers adsorbed on Cu(111) is presented. Whereas atoms in trimers are found in fcc sites only, monomers as well as atoms in dimers can occupy the fcc as well as the metastable hcp site. In fact the dimer fcc-hcp configuration is only 1.3 meV less favorable with respect to the fcc-fcc configuration. This enables a confined intracell dimer motion, which at temperatures below 5 K is dominated by thermally assisted tunneling.

Journal Article↗
PubMed2004

Tailoring Josephson coupling through superconductivity-induced nonequilibrium.

The distinctive quasiparticle distribution existing under nonequilibrium in a superconductor-insulator-normal metal-insulator-superconductor mesoscopic line is proposed as a novel tool to control the supercurrent intensity in a long Josephson weak link. We present a description of this system in the framework of the diffusive-limit quasiclassical Green-function theory and take into account the effects of inelastic scattering with arbitrary strength. Supercurrent enhancement and suppression, including a marked transition to a pi junction, are striking features leading to a fully tunable structure.

Journal Article↗
PubMed1966

A mechanism for the leaching of calcium from foliage.

Young bean plants (Phaseolus vulgaris) containing root-absorbed (45)Ca and (86)Rb were leached to determine the pathway and mechanism of cation loss by leaching. Calcium is leached from the exchangeable calcium fraction within the plant by a process of ion exchange and diffusion involving exchange sites both within the leaf and on the leaf surface. Leaching of cations is primarily a passive process, although some metabolites may be deposited upon leaf surfaces by active processes. The exchange and diffusion explanation is compatible with current theories of ion uptake and translocation and explains the results of numerous experiments on leaching reported in the literature.

Journal Article↗
PubMed2005

Migration and the diffusion of modern contraceptive knowledge and use in rural Guatemala.

This article uses the concept of social networks as it is employed in the research literature on family planning and migration to explore the impact of out-migration on modern contraceptive knowledge and use in rural Guatemala. Data for this study come from the 1995 Guatemalan Survey of Family Health. Results from multilevel regression models indicate that urban migration experience, having migrant kin in urban or international destinations, and living in a community where urban migration is common are all associated with greater contraceptive knowledge. Social ties to urban or international migrants are also associated with a greater likelihood of modern contraceptive use among married women, but this association works primarily through increased contraceptive knowledge. The findings of significant diffusion effects provide support for recent theories of fertility decline that emphasize the role of social interactions.

Adolescent↗
PubMed1998

Path integral description of light transport in tissue.

The early photons that arrive at a collector through a large thickness of tissue have potential for imaging internal organ structure, function, and status with improved image resolution relative to late arriving photons which have been diffusely scattered. Imaging algorithms require a theory to calculate early photon arrival for comparison with experimental data. The path integral description of light transport describes the movement of photons as particles undergoing collisions in a scattering medium based on the Brownian motion formalism of Feynman and Hibbs (unconstrained path) which applies the principle of least action. Including the additional constraint that photons have a constant velocity of c yields paths that conserve the speed of light (constrained path). This paper outlines the basic derivation of the path integral method and compares the constrained and unconstrained paths.

Animals↗