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Journal of Chromatography. A Feb 2021Inverse gas chromatography was employed to investigate the sorption and diffusion of hydrocarbons into polydimethylsiloxane (PDMS) in the headspace-solid phase...
Investigation of sorption and diffusion of hydrocarbons into polydimethylsiloxane in the headspace-solid phase microextraction sampling process via inverse gas chromatography.
Inverse gas chromatography was employed to investigate the sorption and diffusion of hydrocarbons into polydimethylsiloxane (PDMS) in the headspace-solid phase microextraction (HS-SPME) sampling process. Six hydrocarbons as molecular probes and two types of non-cross-linked PDMS with different average molecular weights as stationary phases were used in this study. Experimental measurements with columns containing a PDMS stationary phase were carried out to obtain specific retention volumes, molar enthalpies of sorption, interaction parameters, diffusion coefficients, and activation energies of diffusion of hydrocarbon probes over temperatures ranging from 60 to 90°C. The primary driving force of the hydrocarbon sorption into the PDMS SPME fibers was found to be the molar enthalpy of sorption, which depended on the molecular size of the hydrocarbons. As the molecular size of the hydrocarbon increased, the molar enthalpies of sorption became more exothermic. Interaction parameters and diffusion coefficients indicated that both n-heptane and n-octane were diffused into the PDMS matrix and localized to form clusters or aggregates, which were responsible for more negative molar entropies of sorption. However, the diffusivities of n-nonane and aromatic probes were limited due to their large molecular size and lack in the structural flexibility, respectively. The molar enthalpies of hydrocarbon sorption were independent of the average molecular weight of PDMS. However, specific retention volumes, interaction parameters, diffusion coefficients, and activation energies of diffusion of the hydrocarbons depended on the molecular weight of PDMS as well as the molecular weights and structures of hydrocarbons, as shown by the results of the Wilcoxon signed-rank test.
Topics: Adsorption; Chromatography, Gas; Diffusion; Dimethylpolysiloxanes; Hydrocarbons; Molecular Weight; Solid Phase Microextraction; Temperature
PubMed: 33497832
DOI: 10.1016/j.chroma.2021.461894 -
Annual International Conference of the... 2014This paper reports diffusion weighted MRI measurements of cyclohexane in a novel diffusion tensor MRI phantom composed of hollow coaxial electrospun fibers (average...
This paper reports diffusion weighted MRI measurements of cyclohexane in a novel diffusion tensor MRI phantom composed of hollow coaxial electrospun fibers (average diameter 10.2 μm). Recent studies of the phantom demonstrated its potential as a calibration standard at low b values (less than 1000 s/mm<;sup>2<;/sup>) for mean diffusivity and fractional anisotropy. In this paper, we extend the characterization of cyclohexane diffusion in this heterogeneous, anisotropic material to high b values (up to 5000 s/mm<;sup>2<;/sup>), where the apparent diffusive motion of the cyclohexane exhibits anomalous behavior (i.e., the molecular mean squared displacement increases with time raised to the fractional power 2α/β). Diffusion tensor MRI was performed at 9.4 T using an Agilent imaging scanner and the data fit to a fractional order Mittag-Leffler (generalized exponential) decay model. Diffusion along the fibers was found to be Gaussian (2α/β=l), while diffusion across the fibers was sub-diffusive (2α/β<;l). Fiber tract reconstruction of the data was consistent with scanning electron micrograph images of the material. These studies suggest that this phantom material may be used to calibrate MR systems in both the normal (Gaussian) and anomalous diffusion regimes.
Topics: Algorithms; Anisotropy; Diffusion; Diffusion Tensor Imaging; Magnetic Resonance Imaging; Phantoms, Imaging; Time Factors
PubMed: 25570066
DOI: 10.1109/EMBC.2014.6943698 -
Soft Matter Feb 2016We experimentally investigate the effect of particle size on the motion of passive polystyrene spheres in suspensions of Escherichia coli. Using particles covering a...
We experimentally investigate the effect of particle size on the motion of passive polystyrene spheres in suspensions of Escherichia coli. Using particles covering a range of sizes from 0.6 to 39 microns, we probe particle dynamics at both short and long time scales. In all cases, the particles exhibit super-diffusive ballistic behavior at short times before eventually transitioning to diffusive behavior. Surprisingly, we find a regime in which larger particles can diffuse faster than smaller particles: the particle long-time effective diffusivity exhibits a peak in particle size, which is a deviation from classical thermal diffusion. We also find that the active contribution to particle diffusion is controlled by a dimensionless parameter, the Péclet number. A minimal model qualitatively explains the existence of the effective diffusivity peak and its dependence on bacterial concentration. Our results have broad implications on characterizing active fluids using concepts drawn from classical thermodynamics.
Topics: Diffusion; Escherichia coli; Models, Biological; Particle Size; Thermodynamics
PubMed: 26797039
DOI: 10.1039/c5sm02800k -
Environmental Monitoring and Assessment Oct 2021Landfills have been extensively used as waste deposits in most of the big cities in the world. Therefore, considerably large urban areas have contamination threats....
Landfills have been extensively used as waste deposits in most of the big cities in the world. Therefore, considerably large urban areas have contamination threats. Engineering solutions applied to prevent or contain soil, and water contamination often involve the application of liners, which are low permeability barriers made of materials such as compacted clay and geomembranes. In many liner applications, once reduced rates of seepage are expected, diffusion has proved to be relevant, if not dominant, to the process of contaminant transport. Normally, diffusivity parameters can be assessed by a single-reservoir pure diffusion test, where a contaminant solution is placed above a saturated soil sample and the solution's concentration is monitored over time. Once the temporal variation of concentration is measured, the process of back-calculating diffusivity parameters is not standardized. In this paper, an analytical model of the diffusive transport of contaminants is revisited considering the initial and boundary conditions of the pure diffusion test. In this model, the contaminant solution reservoir is included in the analysis domain as an equivalent contaminated soil layer. The analytical solution relies on a series evaluation, which may be a drawback to everyday engineering situations. Therefore, we build a high-accuracy exponential approximation to the solution. Expedited evaluation procedures are proposed to provide reasonable estimates for the fitting parameters. Also, in order to illustrate the applicability of the new solution, test datasets of a soil around the Jockey Club Landfill (JCL) site, one of the major landfills in Latin America, have been modeled. We discuss possible issues of considering linear isotherms to model the sorption characteristics of soils, indicating that convex isotherms, if linearly modeled, may lead to overestimated values of the diffusivity parameter.
Topics: Diffusion; Environmental Monitoring; Refuse Disposal; Waste Disposal Facilities; Water Pollution
PubMed: 34671846
DOI: 10.1007/s10661-021-09475-3 -
Enzyme and Microbial Technology Dec 1993Mass transfer limitations severely impede the performance of bioreactions involving large molecules by gel-entrapped microorganisms. This paper describes a quantitative... (Comparative Study)
Comparative Study
Mass transfer limitations severely impede the performance of bioreactions involving large molecules by gel-entrapped microorganisms. This paper describes a quantitative investigation of such diffusional limitations in agar gel membranes. Sucrose and commercial dextran fractions with (weight-average) molecular weights ranging from 10,000 to 2,000,000 Da were used as standard diffusants. For all tested solutes but sucrose, the values of the agar/water partition coefficients highlighted steric hindrance at the entrance of the membrane pores. The effective diffusivity of sucrose in agar was similar to that in water. All dextran fractions, however, displayed restricted diffusion in the agar membranes. Their effective diffusivities were a decreasing function of the agar content of the gel membrane (0.5, 1.0, or 1.5% w/v). The effective diffusivity in a given membrane decreased as the molecular weight of the diffusing molecule increased. T500 (Mw = 470,000 Da) and T2000 (Mw = 1,950,000 Da) fractions were unable to diffuse through 1.0 or 1.5% agar membranes. The diffusion data did not agree with the classical (Renkin) model for a hard sphere diffusing through a cylindrical pore. These results are discussed in terms of gel and diffusant characteristics.
Topics: Agar; Dextrans; Diffusion; Gels; Glucose; Membranes, Artificial; Models, Chemical; Molecular Weight; Solubility; Sucrose
PubMed: 7505595
DOI: 10.1016/0141-0229(93)90054-6 -
Protein Science : a Publication of the... Jan 2016When an enzyme modifies multiple sites on a substrate, the influence of the relative diffusive motion of the reactants cannot be described by simply altering the rate...
When an enzyme modifies multiple sites on a substrate, the influence of the relative diffusive motion of the reactants cannot be described by simply altering the rate constants in the rate equations of chemical kinetics. We have recently shown that, even as a first approximation, new transitions between the appropriate species must also be introduced. The physical reason for this is that a kinase, after phosphorylating one site, can rebind and modify another site instead of diffusing away. The corresponding new rate constants depend on the capture or rebinding probabilities that an enzyme-substrate pair, which is formed after dissociation from one site, reacts at the other site rather than diffusing apart. Here we generalize our previous work to describe both random and sequential phosphorylation by considering inequivalent modification sites. In addition, anisotropic reactive sites (instead of uniformly reactive spheres) are explicitly treated by using localized sink and source terms in the reaction-diffusion equations for the enzyme-substrate pair distribution function. Finally, we show that our results can be rederived using a phenomenological approach based on introducing transient encounter complexes into the standard kinetic scheme and then eliminating them using the steady-state approximation.
Topics: Diffusion; Kinetics; Phosphorylation; Phosphotransferases
PubMed: 26096178
DOI: 10.1002/pro.2722 -
Journal of Chromatography. A Aug 2020The aim of this study is to model, describe and predict the mass transfer of IgG as a function of the agarose concentration in the protein A stationary phase, taking...
The aim of this study is to model, describe and predict the mass transfer of IgG as a function of the agarose concentration in the protein A stationary phase, taking into account the influence of adsorption on the pore size. Therefore, particle size distribution, bed and bead porosities were examined by light microscopy, pressure-flow behavior and iSEC. Three agarose protein A stationary phases (2 wt%, 4 wt%, 6 wt%) were investigated. The pore size decreased from 116 nm for 2 wt% to 54 nm for 6 wt% and the porosity for the target molecule IgG was reduced by 25%. A shrinking core model approach was used to assess the influence of IgG adsorption on the pore size of the stationary phase and the diffusivity of IgG. Due to IgG adsorption, the pore diameter reduced by 24 nm, which is approximately two times its hydrodynamic diameter. Effective pore diffusivities of IgG were obtained by fitting the general rate model to breakthrough curves. They were in the range between 3.96·10m/s and 6.5·10m/s, decreasing as the agarose concentration increased. The DBC has a maximum for the 4 wt% agarose gel, showing optimal tradeoffs between accessibility, specific surface and diffusive mass transfer for IgG. A simple geometrical model was developed to describe the change in pore and filament diameters due to adsorption. The diffusion measured in protein A agarose beads can be described by a modification of the Ogston model. This enables the diffusion measured in protein A agarose networks to be predicted.
Topics: Adsorption; Chromatography, Gel; Chromatography, High Pressure Liquid; Diffusion; Immunoglobulin G; Particle Size; Porosity; Protein Binding; Sepharose; Staphylococcal Protein A
PubMed: 32797815
DOI: 10.1016/j.chroma.2020.461319 -
NMR in Biomedicine Jan 2012Diffusion tensor imaging (DTI) was used to study traumatic brain injury. The impact-acceleration trauma model was used in rats. Here, in addition to diffusivities (mean,...
Diffusion tensor imaging (DTI) was used to study traumatic brain injury. The impact-acceleration trauma model was used in rats. Here, in addition to diffusivities (mean, axial and radial), fractional anisotropy (FA) was used, in particular, as a parameter to characterize the cerebral tissue early after trauma. DTI was implemented at 7 T using fast spiral k-space sampling and the twice-refocused spin echo radiofrequency sequence for eddy current minimization. The method was carefully validated on different phantom measurements. DTI of a trauma group (n = 5), as well as a sham group (n = 5), was performed at different time points during 6 h following traumatic brain injury. Two cerebral regions, the cortex and corpus callosum, were analyzed carefully. A significant decrease in diffusivity in the trauma group versus the sham group was observed, suggesting the predominance of cellular edema in both cerebral regions. No significant FA change was detected in the cortex. In the corpus callosum of the trauma group, the FA indices were significantly lower. A net discontinuity in fiber reconstructions in the corpus callosum was observed by fiber tracking using DTI. Histological analysis using Hoechst, myelin basic protein and Bielschowsky staining showed fiber disorganization in the corpus callosum in the brains of the trauma group. On the basis of our histology results and the characteristics of the impact-acceleration model responsible for the presence of diffuse axonal injury, the detection of low FA caused by a drastic reduction in axial diffusivity and the presence of fiber disconnections of the DTI track in the corpus callosum were considered to be related to the presence of diffuse axonal injury.
Topics: Animals; Butadienes; Calibration; Corpus Callosum; Diffuse Axonal Injury; Diffusion; Diffusion Tensor Imaging; Disease Models, Animal; Elastomers; Male; Rats; Rats, Wistar; Spin Labels
PubMed: 21618304
DOI: 10.1002/nbm.1721 -
International Journal of Molecular... Jul 2023Intracellular environment includes proteins, sugars, and nucleic acids interacting in restricted media. In the cytoplasm, the excluded volume effect takes up to 40% of...
Intracellular environment includes proteins, sugars, and nucleic acids interacting in restricted media. In the cytoplasm, the excluded volume effect takes up to 40% of the volume available for occupation by macromolecules. In this work, we tested several approaches modeling crowded solutions for protein diffusion. We experimentally showed how the protein diffusion deviates from conventional Brownian motion in artificial conditions modeling the alteration of medium viscosity and rigid spatial obstacles. The studied tracer proteins were globular bovine serum albumin and intrinsically disordered α-casein. Using the pulsed field gradient NMR, we investigated the translational diffusion of protein probes of different structures in homogeneous (glycerol) and heterogeneous (PEG 300/PEG 6000/PEG 40,000) solutions as a function of crowder concentration. Our results showed fundamentally different effects of homogeneous and heterogeneous crowded environments on protein self-diffusion. In addition, the applied "tracer on lattice" model showed that smaller crowding obstacles (PEG 300 and PEG 6000) create a dense net of restrictions noticeably hindering diffusing protein probes, whereas the large-sized PEG 40,000 creates a "less restricted" environment for the diffusive motion of protein molecules.
Topics: Caseins; Serum Albumin, Bovine; Motion; Diffusion
PubMed: 37446325
DOI: 10.3390/ijms241311148 -
Journal of Biomechanics Jan 2019Developing effective therapeutics for osteoarthritis (OA) necessitates that such molecules can reach and target chondrocytes within articular cartilage. However,...
Developing effective therapeutics for osteoarthritis (OA) necessitates that such molecules can reach and target chondrocytes within articular cartilage. However, predicting how well very large therapeutic molecules diffuse through cartilage is often difficult, and the relationship between local transport mechanics for these molecules and tissue heterogeneities in the tissue is still unclear. In this study, a 150 kDa antibody diffused through the articular surface of healthy and enzymatically degraded cartilage, which enabled the calculation of local diffusion mechanics in tissue with large compositional variations. Local cartilage composition and structure was quantified with Fourier transform infrared (FTIR) spectroscopy and second harmonic generation (SHG) imaging techniques. Overall, both local concentrations of aggrecan and collagen were correlated to local diffusivities for both healthy and surface-degraded samples (0.3 > R < 0.9). However, samples that underwent surface degradation by collagenase exhibited stronger correlations (R > 0.75) compared to healthy samples (R < 0.46), suggesting that the highly aligned collagen at the surface of cartilage acts as a barrier to macromolecular transport.
Topics: Biological Transport; Cartilage, Articular; Chondrocytes; Diffusion; Humans; Macromolecular Substances; Surface Properties
PubMed: 30385000
DOI: 10.1016/j.jbiomech.2018.10.019