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The influence of oligosaccharides (α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin), and a polysaccharide, sodium hyaluronate (NaHy), on the diffusion of aqueous solutions of cobalt and chromium chlorides has been investigated. Cobalt and chromium are constituents of metal alloys for biomedical use, including dental prostheses. Thus, the release of these ions in the human body can lead to harmful biological effects. The interaction of metal ions with saccharides might have information on the role of mouthwashes in preventing these effects. This interaction has been assessed by measuring multicomponent intermolecular diffusion coefficients at 298.15 K. It has been found that β-cyclodextrin has the highest interaction towards cobalt and chromium ions. This work will contribute to unveiling the mechanisms responsible for transport by diffusion in aqueous solutions, and, therefore, mitigating the potential toxicity inherent to those metal ions.

The dispersive spreading of microscopic particles in shear flows is influenced both by advection and thermal motion. At the nanoscale, interactions between such particles and their confining boundaries become unavoidable. We address the roles of electrostatic repulsion and absorption on the spatial distribution and dispersion of charged nanoparticles in near-surface shear flows, observed under evanescent illumination. The electrostatic repulsion between particles and the lower charged surface is tuned by varying electrolyte concentrations. Particles leaving the field of vision can be neglected from further analysis, such that the experimental ensemble is equivalent to that of Taylor dispersion with absorption. These two ingredients modify the particle distribution, deviating strongly from the Gibbs-Boltzmann one at the nanoscale studied here. The overall effect is to restrain the accessible space available to particles, leading to a striking, ten-fold reduction in the spreading dynamics as compared to the non-interacting case.

A theoretical analysis is developed to investigate the effects of gas expansion due to heat release on unsteady diffusion flames evolving in a pipe flow in which the mixing of reactants is controlled by Taylor's dispersion processes thereby extending a previously developed theory based on the thermo-diffusive model. It is first shown that at times larger than radial diffusion times, the pressure gradient induced by the gas expansion is, in the first approximation, small in comparison with the prevailing pressure gradient driving the flow, indicating that corrections to the background velocity profile are small. The corrections to the velocity components along with the leading-order mixing variables such as the concentrations, temperature and density are solved for a Burke–Schumann flame. Due to the dependence of the effective Taylor diffusion coefficients on the gas density, quantitative and sometimes qualitative departures in predictions from the thermo-diffusive model are observed.

Microfluidic systems under laminar flow conditions provide in-solution information about species size and binding affinities at very modest sample costs. Flow-induced dispersion analysis directly measures the spread of the analyte profile using Taylor dispersion analysis, whereas microfluidic diffusional sizing quantifies the transfer of analyte from one phase to another. Species of sizes between 0.5 and 1000 nm can be analyzed, and different populations resolved. Both techniques also allow analysis in complex media and medium throughput analysis. These properties make them valuable complements to existing approaches to measure biomolecular interactions.

We investigate the effect of Taylor dispersion on the thermo-diffusive instabilities of premixed flames. This is a physically interesting and analytically tractable problem within a relatively unex...

Consider a particle whose drift velocity fluctuates due to transitions among discrete states or due to diffusion in a confined moving fluid. At long times, the dynamics of the particle in the direction of transport can be described in terms of the average drift velocity and an effective diffusivity. For both types of fluctuations, we show that the effective diffusivity is the sum of the average intrinsic diffusivity and the time integral of the velocity correlation function of the deviation of the fluctuating velocity from its mean value. For nearest-neighbor interstate transitions and for one-dimensional diffusion in a perpendicular direction, the time integral can be found in closed form. Our analytical expressions for the effective diffusivity recover the classic results for Taylor dispersion in the laminar flow of viscous fluid and for cargo transport along microtubules by molecular motors.

International audience; Vaccine adjuvants are immunostimulatory substances used to improve and modulate the immune response induced by antigens. A better understanding of the antigen-adjuvant interactions is necessary to develop future effective vaccine. In this study, Taylor dispersion analysis (TDA) was successfully implemented to characterize the interactions between a polymeric adjuvant (poly(acrylic acid), SPA09) and a vaccine antigen in development for the treatment of Staphylococcus aureus. TDA allowed one to rapidly determine both (i) the size of the antigen-adjuvant complexes under physiological conditions and (ii) the percentage of free antigen in the adjuvant/antigen mixture at equilibrium and finally get the interaction parameters (stoichiometry and binding constant). The complex sizes obtained by TDA were compared to the results obtained by transmission electron microscopy, and the binding parameters were compared to results previously obtained by frontal analysis continuous capillary electrophoresis.

International audience; Aggregation mechanisms of amyloid β peptides depend on multiple intrinsic and extrinsic physicochemical factors (e.g., peptide chain length, truncation, peptide concentration, pH, ionic strength, temperature, metal concentration, etc.). Due to this high number of parameters, the formation of oligomers and their propensity to aggregate make the elucidation of this physiopathological mechanism a challenging task. From the analytical point of view, up to our knowledge, few techniques are able to quantify, in real time, the proportion and the size of the different soluble species during the aggregation process. This work aims at demonstrating the efficacy of the modern Taylor dispersion analysis (TDA) performed in capillaries (50 μm i.d.) to unravel the speciation of β-amyloid peptides in low-volume peptide samples (∼100 μL) with an analysis time of ∼3 min per run. TDA was applied to study the aggregation process of Aβ(1-40) and Aβ(1-42) peptides at physiological pH and temperature, where more than 140 data points were generated with a total volume of ∼1 μL over the whole aggregation study (about 0.5 μg of peptides). TDA was able to give a complete and quantitative picture of the Aβ speciation during the aggregation process, including the sizing of the oligomers and protofibrils, the consumption of the monomer, and the quantification of different early- and late-formed aggregated species.

Ternary diffusion coefficient matrices [D] were measured using the Taylor dispersion method, for crowded aqueous solutions of decaethylene glycol monododecyl ether (C12E10) with either decane or limonene solute. The matrix [D], for both systems, was found to be highly non-diagonal, and concentration dependent, over a broad domain of solute to surfactant molar ratios and micelle volume fractions. A recently developed theoretical model, based on Batchelor's theory for gradient diffusion in dilute, polydisperse mixtures of interacting spheres, was simplified by neglecting local polydispersity, and effectively used to predict [D] with no adjustable parameters. Even though the model originates from dilute theory, the theoretical results were in surprisingly good agreement with experimental data for concentrated mixtures, with volume fractions up to ϕ ≈ 0.47. In addition, the theory predicts eigenvalues D− and D+ that correspond to long-time self and gradient diffusion coefficients, respectively, for monodisperse spheres, in reasonable agreement with experimental data.

The two-dimensional laminar flow of a viscous fluid induced by peristalsis due to a moving wall wave has been studied previously for a rectangular channel, a circular tube and a concentric circular annulus. Here, we study peristaltic flow in a non-axisymmetric annular tube: in this case, the flow is three-dimensional, with motions in the azimuthal direction. This type of geometry is motivated by experimental observations of the pulsatile flow of cerebrospinal fluid along perivascular spaces surrounding arteries in the brain, which is at least partially driven by peristaltic pumping due to pulsations of the artery. These annular perivascular spaces are often eccentric and the outer boundary is seldom circular: their cross-sections can be well matched by a simple, adjustable model consisting of an inner circle (the outer wall of the artery) and an outer ellipse (the outer edge of the perivascular space), not necessarily concentric. We use this geometric model as a basis for numerical simulations of peristaltic flow: the adjustability of the model makes it suitable for other applications. We concentrate on the general effects of the non-axisymmetric configuration on the flow and do not attempt to specifically model perivascular pumping. We use a finite-element scheme to compute the flow in the annulus driven by a propagating sinusoidal radial displacement of the inner wall. Unlike the peristaltic flow in a concentric circular annulus, the flow is fully three-dimensional: azimuthal pressure variations drive an oscillatory flow in and out of the narrower gaps, inducing an azimuthal wiggle in the streamlines. We examine the dependence of the flow on the elongation of the outer elliptical wall and the eccentricity of the configuration. We find that the time-averaged volumetric flow is always in the same direction as the peristaltic wave and decreases with increasing ellipticity or eccentricity. The additional shearing motion in the azimuthal direction will increase mixing and enhance Taylor dispersion in these flows, effects that might have practical applications.

The miscible process between carbon dioxide (CO2) and oil in nanopore multiphase flow is essential for CO2-enhanced oil recovery (CO2-EOR) techniques, especially in low permeability oil reservoirs....

An analysis is presented for the Burke–Schumann flame established when a fuel tank discharges with mean velocity U along a circular duct of radius a filled initially with air. Attention is focused ...

This theoretical work addresses the characterization of polymer-coated nanoparticles via the analysis of Taylor dispersion experiments. Our focus is on determining the apparent hydrodynamic radius and the related accuracy bias, which results from polydispersity and optical-absorption-weighted averages. To that end, we construct a statistical model addressing joint distributions of particle core size and ligand surface density, which determine the hydrodynamic radius and optical absorption of such nanoparticles. Our model predicts that a polymer shell that is thick compared with the core radius results in a smaller bias than a thin shell, and the bias may become even negative when ligand surface density is sufficiently high.

Passive micromixers are of great importance in biomedical engineering (lab-on-chips) and chemical processing (microreactors) fields. Various hydrodynamic principles such as lamination, flow separation, and chaotic advection were employed previously to improve mixing in passive mixers. However, mixing enhancement due to velocity gradients in the flow, which is known as the Taylor dispersion effect, has been seldom studied. In the present study, thin rectangular slabs oriented in the flow direction are placed in the mixing channel of a T-micromixer. The thin rectangular slabs are referred to as Taylor Dispersion Obstructions (TDOs) as they are designed to create velocity gradients in the flow. The mixing performance of T-micromixer with and without TDOs is estimated in the Re range of 0 to 350. It is observed that there is no effect on mixing in the presence of TDOs in the low Re (0 < Re < 100), as the velocity gradients created in the flow are considerably small. The vortex formed in the flow for Re of 100 to 220 damped the gradients of velocity created in the flow (due to the presence of TDOs) which resulted in negligible improvement in the quality of mixing. However, considerable enhancement in mixing performance is obtained at high Re (250 to 350) with the presence of TDOs in the mixer. The increase in inertial effects at higher Recreated larger gradients of velocity near the walls of TDOs and mixing channel walls and thereby a significant enhancement in mixing performance is obtained due to Taylor dispersion.

The wave-induced Stokes drift plays a significant role on mass/tracer transport in the ocean and the evolution of coastal morphology. The tracer advection diffusion equation needs to be modified for Eulerian ocean models to properly account for the surface wave effects. The Eulerian description of Stokes drift effect on the tracer transport is derived in this study to show that this effect can be accounted for automatically in the wave-averaged advection-diffusion equation. The advection term in this equation is the wave-averaged concentration flux produced by the interaction between fluctuations of linear wave orbital velocity and tracer concentration, and the advection velocity is the same as the Stokes drift velocity. Thus, the effective dispersion of tracers by surface gravity waves is calculated due to the Stokes drift effect and the corresponding dispersion coefficient in the depth-integrated equation is then derived. The Eulerian description of Stokes drift effect of tracer concentration is illustrated by the direct numerical simulation of the advection–diffusion equation under simple linear waves. The equivalence between both the Eulerian and Lagrangian descriptions is also verified by particle tracking method. The theoretical analysis is found to agree well with the wave-induced dye drift velocity observed outside the surf zone in a longshore current experiment.

The Richardson-scaling law states that the mean square separation of a fluid particle pair grows according to t3 within the inertial range and at intermediate times. The theories predicting this scaling regime assume that the pair separation is within the inertial range and that the dispersion is local, which means that only eddies at the scale of the separation contribute. These assumptions ignore the structural organization of the turbulent flow into large-scale shear layers, where the intense small-scale motions are bounded by the large-scale energetic motions. Therefore, the large scales contribute to the velocity difference across the small-scale structures. It is shown that, indeed, the pair dispersion inside these layers is highly non-local and approaches Taylor dispersion in a way that is fundamentally different from the Richardson-scaling law. Also, the layer's contribution to the overall mean square separation remains significant as the Reynolds number increases. This calls into question the validity of the theoretical assumptions. Moreover, a literature survey reveals that, so far, t3 scaling is not observed for initial separations within the inertial range. We propose that the intermediate pair dispersion regime is a transition region that connects the initial Batchelor- with the final Taylor-dispersion regime. Such a simple interpretation is shown to be consistent with observations and is able to explain why t3 scaling is found only for one specific initial separation outside the inertial range. Moreover, the model incorporates the observed non-local contribution to the dispersion, because it requires only small-time-scale properties and large-scale properties.

$A+B\ensuremath{\rightarrow}C$ reaction fronts describe a wide variety of natural and engineered dynamics, according to the specific nature of reactants and product. Recent works have shown that the properties of such reaction fronts depend on the system geometry, by focusing on one-dimensional plug flow radial injection. Here, we extend the theoretical formulation to radial deformation in two-dimensional systems. Specifically, we study the effect of a Poiseuille advective velocity profile on $A+B\ensuremath{\rightarrow}C$ fronts when A is injected radially into B at a constant flow rate in a confined axisymmetric system consisting of two parallel impermeable plates separated by a thin gap. We analyze the front dynamics by computing the temporal evolution of the average over the gap of the front position, the maximum production rate, and the front width. We further quantify the effects of the nonuniform flow on the total amount of product, as well as on its radial concentration profile. Through analytical and numerical analyses, we identify three distinct temporal regimes, namely (i) the early-time regime where the front dynamics is independent of the reaction, (ii) the transient regime where the front properties result from the interplay of reaction, diffusion that smooths the concentration gradients and advection, which stretches the spatial distribution of the chemicals, and (iii) the long-time regime where Taylor dispersion occurs and the system becomes equivalent to the one-dimensional plug flow case.

When a mixture of viscous oil and non-colloidal particles displaces air between two parallel plates, the shear-induced migration of particles leads to the gradual accumulation of particles on the advancing oil–air interface. This particle accumulation results in the fingering of an otherwise stable fluid–fluid interface. While previous works have focused on the resultant instability, one unexplored yet striking feature of the experiments is the self-similarity in the concentration profile of the accumulating particles. In this paper, we rationalise this self-similar behaviour by deriving a depth-averaged particle transport equation based on the suspension balance model, following the theoretical framework of Ramachandran (J. Fluid Mech., vol. 734, 2013, pp. 219–252). The solutions to the particle transport equation are shown to be self-similar with slight deviations, and in excellent agreement with experimental observations. Our results demonstrate that the combination of the shear-induced migration, the advancing fluid–fluid interface and Taylor dispersion yield the self-similar and gradual accumulation of particles.

Mutual diffusion coefficients of chloroquine diphosphate (CDP) in aqueous solutions both without and with β-cyclodextrin (β-CD) were measured at concentrations from (0.0000 to 0.0100) mol dm−3 and 298.15 K, using the Taylor dispersion technique. Ternary mutual diffusion coefficients (Dik) measured by the same technique are reported for aqueous CDP + β-CD solutions at 298.15 K. The presence of β CD led to relevant changes in the diffusion process, as showed by nonzero values of the cross-diffusion coefficients, D12 and D21 . β-CD concentration gradients produced significant co-current coupled flows of CDP. In addition, the effects of β-CD on the transport of CDP are assessed by comparing the binary diffusion coefficient of aqueous CDP solutions with the main diffusion coefficient (D11 ) measured for ternary {CDP(1) + β-CD(2)} solutions. These observations are supported by viscosity analysis. All data allow to have a better interpretation on the effect of cyclodextrin on the transport behavior of CDP. © 2021 by the authors. Licensee MDPI, Basel, Switzerland., Coimbra Chemistry Centre - FundacAo para a Ciencia e a Tecnologia (FCT), Portuguese Agency for Scientific Research [UID/QUI/UI0313/2019]; COMPETE; Ministry of Education, Youth and Sports of the Czech Republic DKRVO [RP/CPS/2020/003]; University of Alcala (Spain), RP/CPS/2020/003; UID/QUI/UI0313/2019; Fundação para a Ciência e a Tecnologia, FCT; Universidad de Alcalá, UAH; Programa Operacional Temático Factores de Competitividade, POFC

We consider Taylor dispersion for tracer particles in micro-fluidic planar channels with strong confinement. In this context, the channel walls modify the local diffusivity tensor and also interactions between the tracer particles and the walls become important. We provide a simple and general formula for the effective diffusion constant along the channel as well as the first non-trivial finite time correction for arbitrary flows along the channel, arbitrary interaction potentials with the walls and arbitrary expressions for the diffusion tensor. The formula are in particular amenable to a straightforward numerical implementation, rendering them extremely useful for comparison with experiments. We present a number of applications, notably for systems which have parabolically varying diffusivity profiles, to systems with attractive interactions with the walls as well as electroosmotic flows between plates with differing surface charges within the Debye-H\"uckel approximation., Comment: 33 pages, 7 figures

Modeling contaminant transport in fractured-rock matrix systems often approximates the effect of the parabolic flow field in the fractures (i.e., Poiseuille flow) on transport by adding a dispersion term to the uniform flow field. In this study, an analytical solution is derived to model contaminant transport in a parallel-plate fractured-rock matrix that explicitly simulates Poiseuille flow in the fractures, eliminating the need for the dispersion approximation. In addition to simulating Poiseuille flow in the fracture, the contaminant transport model developed here includes: (1) two-dimensional contaminant diffusion in the fractures and matrix, (2) first-order decay in the aqueous phase, and (3) rate-limited sorption onto matrix solids. It should be noted, however, that this model, much like the commonly employed Taylor dispersion approximation, neglects macro dispersion, thereby limiting the model’s applicability to systems having wide fracture apertures with extremely high flow velocities ( P e > 104). Model equations are analytically solved in the Laplace domain and numerically inverted. In addition, analytical expressions for the zeroth, first, and second spatial moments of the concentration profiles along the fractures are derived for both the new Poiseuille flow model as well as a model that approximates the effect of Poiseuille flow on transport by using a dispersion term. The first and second moment expressions are used to quantify how well the dispersion term approximates the effect of Poiseuille flow. Simulations confirm that the dispersion approximation will be adequate for natural fractures at long times. However, if a modeler is concerned with short-time transport behavior or transport behavior in systems with relatively wide-aperture fractures and high groundwater velocities where macro dispersion can be ignored, such as may be found at engineered geothermal systems and carbon capture and storage sites, there may be significant differences between model simulations that explicitly incorporate Poiseuille flow and those that approximate Poiseuille flow with a dispersion term. The model presented here allows the modeler to analytically quantify these differences, which, depending on the modeling objective, may cause the dispersion approximation to be inadequate. Simulations were also run to examine the effect of adsorption rate on remediation of fractured-rock matrix systems. It was shown that moderate adsorption rate constants could lead to very long remediation times, if remediation success is quantified by achieving low concentrations within the fracture.

Taylor dispersion is used to measure the binary mutual diffusion coefficient (D) of aqueous solutions of sodium salicylate (NaSal), a non-steroidal anti-inflammatory drug (NSAID). The D° value estimated by extrapolation to zero NaSal concentration is used to calculate the limiting mobility of the Sal− ion for comparison with the value determined previously from conductivity data. Salt effects on NSAID diffusion are studied by measuring the ternary mutual diffusion coefficients (Dik) of aqueous NaSal(C1) + NaCl(C2) solutions, including results for the diffusion of NaSal in physiological saline solutions with C2 = 0.15 mol dm−3. As the NaCl:NaSal ratio increases, NaSal diffusion coefficient D11 changes from the binary diffusion coefficient of aqueous NaSal (a weighted average of the Na+ and Sal− diffusion coefficients) to the tracer diffusion coefficient of the Sal− ion in NaCl solutions. Coupled diffusion in the solutions is analysed by using Nernst-Planck equations to calculate the fluxes of ions migrating in the electric field (diffusion potential) generated by NaSal and NaCl concentration gradients.

Diffusivities of nonassociated aromatic compounds at infinite dilution in methanol and in cyclohexane were measured by the Taylor dispersion method. At constant temperatures, the diffusivity recipr...

Scalar transport in an open channel with irreversible first-order absorption boundaries is investigated through random walk particle tracking method (RWPT). We provide the pre-asymptotic behavior of scalar transport as well as a comparison with existing asymptotic formulations. The RWPT method is based on the development of the probability that a particle is absorbed at the boundary. The random walk model is applied to simulate three main parameters of the scalar transport in the laminar flow with sorption boundaries. The three parameters are (1) the attenuation coefficient reflecting the depletion rate of the total mass; (2) the effective velocity coefficient representing the effective advection of the total mass; and (3) the effective longitudinal dispersion coefficient expressing the effective spreading rate of the solute plume. When the Peclet number is large, numerical results agree well with previous theoretical solutions. Results show that (1) the three coefficients reach their asymptotic values when the dimensionless time τ (= Dt/H2) is about 0.5, where t is the time, H is the water depth, and D is the molecular diffusion coefficient and (2) when the Damkohler number reaches a value around 100, the boundary can be treated as a totally absorptive boundary.

Taylor dispersion and dynamic light scattering techniques were used to measure the ternary diffusivity matrix [D] and the micelle gradient diffusion coefficient, respectively, in crowded aqueous solutions of decaethylene glycol monododecyl ether (C12E10) and decane. The results indicate that C12E10 diffused down its own gradient with the micelle gradient diffusivity while decane diffused down a decane gradient at a much slower rate. Furthermore, strong diffusion coupling, comprising decane diffusion down a surfactant gradient and surfactant diffusion up a decane gradient, was also observed with cross diffusivities that were on the order of or larger than the main diffusivities. Measurements of the micelle aggregation number, hydration index, and the hydrodynamic radius, obtained using both static and dynamic light scattering methods, indicate that decane-containing micelles interacted as hard spheres and had radii and aggregation numbers that increased linearly with the molar ratio of solute to surfactant. A theoretical model, developed using Batchelor's theory for gradient diffusion in a polydisperse system of interacting hard spheres, was effectively used to predict [D] with no adjustable parameters. A comparison with the theory indicates that decane diffused down its own gradient by micelle self-diffusion while surfactant diffused down a surfactant gradient by micelle gradient diffusion. It is also shown that intermicellar interactions drove decane diffusion down a C12E10 gradient by a volume exclusion effect while an increase in the micelle aggregation number and hydrodynamic radius with decane was necessary to drive surfactant diffusion up a decane gradient.

Recent extensive and important studies have provided detailed information and compelling evidence on how the presence of waves influences the vertical diffusivity/dispersivity in the coastal environment, which can affect various water quality considerations such as the distribution of suspended sediments in the water column as well as the potential of eutrophication. Comparatively, how the presence of waves influences the horizontal diffusivity/dispersivity has received only scant attention in the literature. Our previous works investigated the role played by the Taylor mechanism due to the wave-induced drift profile which leads to the longitudinal dispersion of contaminants in the horizontal direction, under regular sinusoidal waves and random waves with single-peak spectra. Natural waves in the coastal environment, however, often possess dual-peak spectra, comprising both higher frequency wind waves and lower frequency swells. In this study, the Taylor dispersion of contaminants under random waves with dual-peak spectra is examined through analytical derivation and numerical calculations. The effects of various dual-peak spectral parameters on the horizontal dispersion, including the proportion of lower frequency energy, peak frequency ratio and spectral shape parameter, are investigated. The results show that the relative energy distribution between the dual peaks has the most significant effect. Compared with single-peak spectra with equivalent energy, the Taylor dispersion with dual-peak spectra is stronger when the lower frequency is close to the peak frequency of the single-peak spectrum, and weaker with the higher frequency instead. Thus, it can be concluded that with a dual-peak wave spectrum, wind-dominated seas with higher frequency lead to stronger dispersion in the horizontal direction than swell-dominated seas with lower frequency.

This paper is addressing the challenge related to understanding the experimental results obtained by Taylor dispersion technique when working under high pressure with supercritical carbon dioxide (CO2). We discuss typical experimental problems that arise when using the Taylor dispersion method for measuring diffusion coefficients in the supercritical fluids. The diffusion coefficients of the two samples in supercritical carbon dioxide were measured along the isobars at different temperatures. The diffusion coefficients of ethanol in supercritical CO2 have been measured in the temperature range from 304.15 to 343 K along the isobar p = 12.0 MPa. Experiments with the gaseous CH4/CO2 mixture with a mole fraction of CH4 = 0.2052 mol mol− 1 have been conducted in the temperature range from 317.85K to 343.15 K along the isobar p = 12.5 MPa. A comparative analysis of a diffusion behavior of these very different mixtures is presented., SCOPUS: ar.j, info:eu-repo/semantics/published

Transport of micro-organisms in confined flows can be characterized by a one-dimensional overall dispersion mechanism, of importance to various biotechnological applications. Based on Brenner’s generalized Taylor dispersion theory, an overall dispersion model is analytically studied in the present work for a dilute suspension of active particles in confined unidirectional flows. With the confined section of the channel and the swimming orientation space taken together as the local space and the longitudinal coordinate standing for the one-dimensional global space, this model is analytically accurate and possessed of wide adaptability in terms of the swimming Péclet number. The Robin boundary condition is introduced to account for wall accumulation of active particles, and compared with a typical reflection boundary condition. Complications associated with the boundary conditions for analytical derivation are removed respectively by a decomposition of the distribution function and an extension of the flow field. Interesting solutions are concretely found and intensively illustrated. Detailed case studies on the transport of spherical and rod-like particles to illustrate the dispersion mechanism are presented with respect to a Couette flow and a plane Poiseuille flow. Associated with the local distribution of particles, extensive descriptions are given for the dynamical system behaviours such as accumulation near both stable points/lines and boundaries, symmetric polarization structure, closed orbits, trapping effect, nematic alignments and bimodalization of swimming direction. For spherical particles, the accumulation is shown leading to a reduction of the overall dispersivity in both of the flows, while for rod-like active particles in the Couette flow, the accumulation can result in an enhancement of dispersion, due to the nematic alignments of particles towards streamlines.

Taylor diffusion (or dispersion) refers to a phenomenon discovered experimentally by Taylor in the 1950s where a solute dropped into a pipe with a background shear flow experiences diffusion at a rate proportional to $1/\nu$, which is much faster than what would be produced by the static fluid if its viscosity is $0 < \nu \ll 1$. This phenomenon is analyzed rigorously using the linear PDE governing the evolution of the solute. It is shown that the solution can be split into two pieces, an approximate solution and a remainder term. The approximate solution is governed by an infinite-dimensional system of ODEs that possesses a finite-dimensional center manifold, on which the dynamics correspond to diffusion at a rate proportional to $1/\nu$. The remainder term is shown to decay at a rate that is much faster than the leading order behavior of the approximate solution. This is proven using a spectral decomposition in Fourier space and a hypocoercive estimate to control the intermediate Fourier modes., Comment: 37 pages, 0 figures

Assessment of protein stability and function is key to the understanding of biological systems and plays an important role in the development of protein-based drugs. In this work, we introduce an integrated approach based on Taylor dispersion analysis (TDA), flow induced dispersion analysis (FIDA), and in-line intrinsic fluorescence which enables rapid and detailed assessment of protein stability and unfolding. We demonstrate that the new platform is able to efficiently characterize chemically induced protein unfolding of human serum albumin (HSA) in great detail. The combined platform enables local structural changes to be probed by monitoring changes in intrinsic fluorescence and loss of binding of a low-molecular weight ligand. Simultaneously, the size of the unfolding HSA is obtained by TDA on the same samples. The integration of the methodologies enables a fully automated characterization of HSA using only a few hundred nanoliters of sample. We envision that the presented methodology will find applications in fundamental biophysics and biology as well as in stability screens of protein-based drug candidates.

Non-Fickian solute transport is observed across many scales, which has motivated development of numerous non-Fickian-based models. Assuming that local fluid flow was estimable from the Modified Local Cubic Law, this study determined whether the local ADE better simulated non-Fickian transport through rough (3-D) fractures when local dispersion was described using either the Taylor dispersion coefficient (DTaylor) or the molecular diffusion coefficient (Dm). The assessment was based on how well the local ADE compared to particle-tracking solutions for solute transport across a range of Peclet numbers (Pe) through two simulated fractures. Even though the local ADE is based on local Fickian transport processes, it was able to reproduce non-Fickian transport characteristics through these heterogeneous fractures. When supplying DTaylor to the local ADE, it extended the applicability of the local ADE to a threshold of Pe

Fully resolved simulations of flow and mass transfer in a unit cell of structured open-cell foam catalysts are presented. Numerical studies are conducted on a uniform three-dimensional Cartesian grid where the fluid-solid interface coupling is enforced via a sharp interface Immersed Boundary technique. Several validation cases for the numerical method are presented followed by extensive calculations to quantify hydrodynamic dispersion in open-cell foams. In our study five different porosities of the idealized foam structure, represented by the spatially periodic Kelvin’s unit cell, were considered. Dimensionless dispersion coefficients were calculated for varying Peclet numbers and flow directions using volume-averaging theory. Our numerical studies indicate that Taylor dispersion is the dominant mechanism for structured porous media in the Darcy-Brinkman flow regime.

The integration of Taylor dispersion analysis (TDA) into mobility capillary electrophoresis allows protein separation, effective charge and hydrodynamic radius measurements., Measuring the conformations and effective charges of proteins in solution is critical for investigating protein bioactivity, but their rapid analysis remains a challenging problem. Here we report a mobility capillary electrophoresis (MCE) based method for the rapid analysis of protein stereo-structures and effective charges in different solution environments. With the capability of mixture separation, MCE measures the hydrodynamic radius of a protein through Taylor dispersion analysis and its effective charge through ion mobility analysis. The experimental results acquired from MCE are then utilized to restrain molecular dynamics simulations, so that the most probable conformation of that protein can be obtained. As proof-of-concept demonstrations, the charge states and structures of five proteins were analyzed under close to native environments. The conformation transitions and charge state variations of bovine serum albumin and lysozyme under different pH conditions were also investigated. This method is promising for high-throughput protein analysis, which could potentially be coupled with mass spectrometry for investigating protein stereo-structures and functions in top-down proteomics.

Biological and pharmaceutical analytes like liposomes, therapeutic proteins, nanoparticles, and drug-delivery systems are utilized in applications, such as pharmaceutical formulations or biomimetic models, in which controlling their size is often critical. Many of the common techniques for sizing these analytes require method development, significant sample preparation, large sample quantities, and lengthy analysis times. In other cases, such as DLS, sizing can be biased towards the largest constituents in a mixture. Therefore, there is a need for more rapid, sensitive, accurate, and straightforward analytical methods for sizing macromolecules, especially those of biological origin which may be sample-limited. Taylor dispersion analysis (TDA) is a sizing technique that requires no calibration and consumes only nL to pL sample volumes. In TDA, average diffusion coefficients are determined via the Taylor–Aris equation by characterizing band broadening of an analyte plug under well-controlled laminar flow conditions. Diffusion coefficient can then be interpreted as hydrodynamic radius (RH) via the Stokes–Einstein equation. Here, we offer a tutorial review of TDA, intended to make the method better understood and more widely accessible to a community of analytical chemists and separations scientists who may benefit from the unique advantages of this versatile sizing method. We first provide a tutorial on the fundamental principles that allow TDA to achieve calibration-free sizing of analytes across a wide range of RH, with an emphasis on the reduced sample consumption and analysis times that result from utilizing fused silica capillaries. We continue by highlighting relationships between operating parameters and critically important flow conditions. Our discussion continues by looking at methods for applying TDA to sample mixtures via algorithmic approaches and integration of capillary electrophoresis and TDA. Finally, we present a selection of reports that demonstrate TDA applied to complex challenges in bioanalysis and materials science.

We conduct an asymptotic analysis to derive a macrotransport equation for the long-time transport of a chemotactic/diffusiophoretic colloidal species in a uniform circular tube under a steady, laminar, pressure-driven flow and transient solute gradient. The solute gradient drives a ‘log-sensing’ advective flux of the colloidal species, which competes with Taylor dispersion due to the hydrodynamic flow. We demonstrate excellent agreement between the macrotransport equation and direct numerical solution of the full advection–diffusion equation for the colloidal species transport. In addition to its accuracy, the macrotransport equation requires times less computational runtime than direct numerical solution of the advection–diffusion equation. Via scaling arguments, we identify three regimes of the colloidal species macrotransport, which span from chemotactic/diffusiophoretic-dominated macrotransport to the familiar Taylor dispersion regime, where macrotransport is dominated by the hydrodynamic flow. Finally, we discuss generalization of the macrotransport equation to channels of arbitrary (but constant) cross-section and to incorporate more sophisticated models of chemotactic fluxes. The macrotransport framework developed here will broaden the scope of designing chemotactic/diffusiophoretic transport systems by elucidating the interplay of macrotransport due to chemotaxis/diffusiophoresis and hydrodynamic flow.

International audience; Sucrose is among the main products of photosynthesis that are deemed necessary for plant growth and survival. It is produced in the mesophyll cells of leaves and translocated to different parts of the plant through the phloem. Progress in understanding this transport process remains fraught with experimental difficulties, thereby prompting interest in theoretical approaches and laboratory studies. The Munch pressure and mass flow model is one of the accepted hypotheses describing the physics of sucrose transport in the phloem. It is based on osmosis creating an energy potential difference between the source and the sink. The flow responding to this energy potential is assumed laminar and described by the Hagen-Poiseuille equation. This study revisits such osmotically driven flows in tubes with membrane walls by including the effects of Taylor dispersion on mass transport. This effect has been overlooked in phloem flow studies. Taylor dispersion can increase the effective transport of solutes by increasing the apparent diffusion coefficient. It is shown that, in addition to the conventional diffusive correction derived for impermeable tube walls, a new adjustment to the mean advective terms arises because of osmotic effects. Because the molecular Schmidt number is very large for sucrose in water, the sucrose front speed and travel times have a direct dependence on the Peclet number for different ranges of the Munch number. This study establishes upper limits on expected Taylor dispersion enhancement of sucrose transport.

The present article discusses the solute transport process in unsteady laminar blood flow through\ud a non-Darcy porous medium, as a model for drug movement in blood vessels containing deposits.\ud The Darcy-Brinkman-Forchheimer drag force formulation is adopted to mimic a sparsely packed\ud porous domain, and the vessel is approximated as an impermeable cylindrical conduit. The\ud conservation equations are implemented in an axisymmetric system (R,Z) with suitable boundary\ud conditions, assuming constant tortuosity and porosity of the medium. Newtonian flow is assumed,\ud which is physically realistic for large vessels at high shear rates. The velocity field is expanded\ud asymptotically, and the concentration field decomposed. Advection and dispersion coefficient\ud expressions are rigorously derived. Extensive visualization of the influence of effective Péclet\ud number, Forchheimer number, reaction parameter on velocity, asymptotic dispersion coefficient,\ud mean concentration, and transverse concentration at different axial locations and times are\ud provided. Increasing reaction parameter and Forchheimer number both decrease the dispersion\ud coefficient, although the latter exhibits a linear decay. The maximum mean concentration is\ud enhanced with greater Forchheimer numbers, although the centre of the solute cloud is displaced\ud in the backward direction. Peak mean concentration is suppressed with the reaction parameter,\ud although the centroid of the solute cloud remains unchanged. Peak mean concentration\ud deteriorates over time since the dispersion process is largely controlled by diffusion at the large\ud time, and therefore the breakthrough curve is more dispersed. A similar trend is computed with\ud increasing Péclet number (large Péclet numbers imply diffusion-controlled transport). The\ud computations provide some insight into a drug (pharmacological agents) reacting linearly with\ud blood.

International audience; Intrinsic viscosity is a key hydrodynamic parameter to understand molecular structure and hydration, as well as intramolecular interactions. Commercially available instruments measure intrinsic viscosity by recording the macromolecular mobility in a capillary. These instruments monitor Taylor dispersion using an absorbance or fluorescence detector. By design, these instruments behave like U-tube viscometers. To our knowledge, there are no studies to date showing that the Viscosizer TD instrument (Malvern-Panalytical) is able to measure the intrinsic viscosity of macromolecules. In this study, we then performed our assays on the Poly(ethylene oxide) polymer (PEO), used classically as a standard for viscometry measurements and on three model proteins: the bovine serum albumin (BSA), the bevacizumab monoclonal antibody, and the RTX Repeat Domain (RD) of the adenylate cyclase toxin of Bordetella pertussis (CyaA). The presence of P20 in the samples is critical to get reliable results. The data obtained with our in-house protocol show a strong correlation with intrinsic viscosity values obtained using conventional techniques. However, with respect to them, our measurements could be performed at relatively low concentrations, between 2 and 5 mg/ml, using only 7 µL per injection. Altogether, our results show that the Viscosizer TD instrument is able to measure intrinsic viscosities in a straightforward manner. This simple and innovative approach should give a new boost to intrinsic viscosity measurements and should reignite the interest of biophysicists, immunologists, structural biologists and other researchers for this key physicochemical parameter.

Active particles often swim in confined environments. The transport mechanisms, especially the global one as reflected by the Taylor dispersion model, are of great practical interest to various applications. For active dispersion process in confined flows, previous analytical studies focused on the long-time asymptotic values of dispersion characteristics. Only several numerical studies preliminarily investigated the temporal evolution. Extending recent studies of Jiang & Chen (J. Fluid Mech., vol. 877, 2019, pp. 1--34; J. Fluid Mech., vol. 899, 2020, A18), this work makes the first analytical attempt to investigate the transient process. The temporal evolution of the local distribution in the confined-section--orientation space, drift, dispersivity and skewness, is explored based on moments of distributions. We introduce the biorthogonal expansion method for solutions because the classic integral transform method for passive transport problems is not applicable due to the self-propulsion effect. Two types of boundary condition, the reflective condition and the Robin condition for wall accumulation, are imposed respectively. A detailed study on spherical and ellipsoidal swimmers dispersing in a plane Poiseuille flow demonstrates the influences of the swimming, shear flow, wall accumulation and particle shape on the transient dispersion process after a point-source release. The swimming-induced diffusion makes the local distribution reach its equilibrium state faster than that of passive particles. Though the wall accumulation significantly affects the evolution of the local distribution and the drift, the time scale to reach the Taylor regime is not obviously changed. The shear-induced alignment of ellipsoidal particles can enlarge the dispersivity but has less influence on the drift and the skewness., 34 pages,21 figures

The effect of traces of ethanol in supercritical carbon dioxide on the mixture's thermodynamic properties is studied by molecular simulations and Taylor dispersion measurements. This mixture is investigated along the isobar p = 10 MPa in the temperature range between T = 304 and 343 K. Along this path, the mixture undergoes two transitions: First, the Widom line is crossed, marking the transition from liquid-like to gas-like conditions. A second transition occurs from the supercritical gas-like domain to a subcritical gas. The Widom line crossover entails inflection points for most of the studied properties, i.e. density, enthalpy, shear viscosity, Maxwell–Stefan and intradiffusion coefficients. On the other hand, the transition between the super- and subcritical regions is found to be generally smooth, an observation that is qualitatively confirmed by experimental Taylor dispersion measurements. Dedicated atomistic simulations show the presence of microheterogeneities due to ethanol self-association along the investigated path, which lead to the mixture's anomalous behavior in its extended critical region.

The understanding and characterization of protein interactions is crucial for elucidation of complicated biomolecular processes as well as for the development of new biopharmaceutical therapies. Often, protein interactions involve multiple binding, avidity, oligomerization, and are dependent on the local environment. Current analytical methodologies are unable to provide a detailed mechanistic characterization considering all these parameters, since they often rely on surface immobilization, cannot measure under biorelevant conditions, or do not feature a structurally-related readout for indicating formation of multiple bound species. In this work, we report the use of flow induced dispersion analysis (FIDA) for in-solution characterization of complex protein interactions under in vivo like conditions. FIDA is an immobilization-free ligand binding methodology employing Taylor dispersion analysis for measuring the hydrodynamic radius (size) of biomolecular complexes. Here, the FIDA technology is utilized for a size-based characterization of the interaction between TNF-α and adalimumab. We report concentration-dependent complex sizes, binding affinities (Kd), kinetics, and higher order stoichiometries, thus providing essential information on the TNF-α–adalimumab binding mechanism. Furthermore, it is shown that the avidity stabilized complexes involving formation of multiple non-covalent bonds are formed on a longer timescale than the primary complexes formed in a simple 1 to 1 binding event.

During past decade, special focus has been laid on ultrasmall nanoparticles for nanomedicine and eventual clinical translation. To achieve such translation, a lot of challenges have to be solved. Among them, size determination is a particularly tricky one. In this aim, we have developed a simple hyphenation between Taylor dispersion analysis and inductively coupled plasma-mass spectrometry (ICP-MS). This method was proven to allow the determination of the hydrodynamic radius of metal-containing nanoparticles, even for sizes under 5 nm, with a relative standard deviation below 10% (with a 95% confidence interval) and at low concentrations. Moreover, its specificity provides the opportunity to perform measurements in complex biological media. This was applied to the characterization of an ultrasmall gadolinium-containing nanoparticle used as a theranostic agent in cancer diseases. Hydrodynamic radii measured in urine, cerebrospinal fluid, and undiluted serum demonstrated the absence of interaction between the particle and biological compounds such as proteins.

Diffusion coefficients, D, for ethanol in supercritical carbon dioxide (scCO2) were measured in the temperature range 306.15–331.15 K and along the 10.5 MPa isobar, using the Taylor dispersion technique. The obtained diffusivities ranged from 1.49 × 10−8 to 2.98 × 10−8 m2 s−1, an order of magnitude higher than in usual liquids. The dependence of D on temperature and solvent density was examined. Various correlation models based in the hydrodynamic theory were assessed to estimate the diffusion coefficients, with reasonable results obtained for the Wilke–Chang and Lai–Tan models.

While near-surface geothermal energy applications for the heating and cooling of buildings have been in use for decades, their practical adoption is limited by the energy transport rates through soils. Aquifers provide a means to use convective heat transport to improve heat transfer between the building and the aquifer. However, the solid matrix in the aquifer is carbonaceous in nature, and calcification prevention techniques in the heat exchangers for the building also lead to dissolution of the aquifer matrix. Due to the Arrhenius nature of the reaction, dissolution rates may decrease with increasing temperature. An effective medium model is derived for the energy, calcium species, and fluid transport through a dynamic calcite porous medium which undergoes a reaction between the matrix and fluid. To better discern how these competing phenomena affect thermal transport in the aquifer, a two-dimensional Cartesian system is considered, where the vertical axis is parallel to the borehole axis, and flow is in the horizontal direction. An effective medium model is derived for the energy, calcium species, and fluid transport through a dynamic calcite porous medium which undergoes a reaction between the matrix and fluid. Since the fluid velocity decays algebraically with radial distance from the borehole axis, two flow regimes are considered. In one regime, far from the borehole where flow rates are small, conductive thermal transport acts faster than the species transport, leading to a case where precipitation dominates and regions of the smallest porosity contract to limit energy recovery. In regions with larger porosity, moderate advection of the species is sufficient to prevent significant pore closures over the time scale of exploration. The second regime, closer to the borehole, larger flow rates reduce species concentrations sufficiently to dissolve the solid phase between pores. In this second regime, Taylor dispersion effects in both energy and species transport compete, but thermal conduction acts more slowly than advection, promoting dissolution. The critical limitation in modeling the long-term evolution of the aquifer structure is the in situ dissolution rate.

This study aims at contributing to quinine extraction using supercritical CO2 and ethanol as a co-solvent. The diffusion coefficients of quinine in supercritical CO2 are measured using the Taylor dispersion technique when quinine is pre-dissolved in ethanol. First, the diffusion coefficients of pure ethanol in the supercritical state of CO2 were investigated in order to get a basis for seeing a relative change in the diffusion coefficient with the addition of quinine. We report measurements of the diffusion coefficients of ethanol in scCO2 in the temperature range from 304.3 to 343 K and pressures of 9.5, 10 and 12 MPa. Next, the diffusion coefficients of different amounts of quinine dissolved in ethanol and injected into supercritical CO2 were measured in the same range of temperatures at p = 12 Mpa. At the pressure p = 9.5 MPa, which is close to the critical pressure, the diffusion coefficients were measured at the temperature, T = 343 K, far from the critical value. It was found that the diffusion coefficients are significantly dependent on the amount of quinine in a small range of its content, less than 0.1%. It is quite likely that this behavior is associated with a change in the spatial structure, that is, the formation of clusters or compounds, and a subsequent increase in the molecular weight of the diffusive substance., info:eu-repo/semantics/published

The transport and association of the dipeptide glycyl-L-phenylalanine (Gly-L-Phen) in solutions containing cyclodextrins are of prime importance given its relevance in different areas, from biochemistry to wastewater treatment. We have investigated the interaction between aqueous Gly-L-Phen and β-cyclodextrin (β-CD) by NMR, DFT calculations in parallel with UV/visible absorption, luminescence spectral measurements and diffusion experiments. Ternary mutual diffusion coefficients of aqueous {Gly-L-Phen + β-CD} solutions have been measured by using the Taylor dispersion technique. The results show that the association of Gly-L-Phen and β-CD has a significant effect on the diffusion coefficients, consistent with an association constant of about 50 to 100, assuming a 1:1 (Gly-L-Phen):(β-CD) stoichiometry. This stoichiometry has been assessed by the continuous variation (Job's plot) method and the association constant was determined by using the Hildebrand-Benesi equation modified for NMR applications. The association constant was estimated to be equal to 40. This association constant is in close agreement with that obtained by fluorescence measurements (K = 43). Additionally, from NMR, detailed structural information on the complex has been obtained. This has been complemented by DFT and TD-DFT studies.

In the experiment that first demonstrated gyrotactic behaviour of bottom-heavy swimming microalgae (e.g. Chlamydomonas), Kessler (Nature, vol. 313, 1985, pp. 218-220) showed that a beam-like structure, often referred to as a gyrotactic plume, would spontaneously appear from a suspension of gyrotactic swimmers in a downflowing pipe. Such a plume is prone to an instability to form blips. This work models the gyrotactic plume as a steady parallel basic state and its subsequent breakdown into blips as an instability, employing both the Generalised Taylor Dispersion (GTD) theory and the Fokker-Planck model for comparison. Upon solving for the basic state, it is discovered that the steady plume solution undergoes sophisticated bifurcations. When there is no net flow, there exists a non-trivial solution of the plume structure other than the stationary uniform suspension, stemming from a transcritical bifurcation with the average cell concentration. When a net downflow is prescribed, there exists a cusp bifurcation. Furthermore, there is a critical concentration, at which the cell concentration at the centre would blow up for the GTD model. The subsequent stability analysis using the steady plume solution shows that the Fokker-Planck model is inconsistent with what was experimentally observed, as it predicts stabilisation of axisymmetric blips at high concentration of the plume and destabilisation of the first non-axisymmetric mode at low flow rates.

We consider the injection of a buoyant low viscosity fluid into an aquifer saturated with a higher viscosity fluid. The nose region of the flow, where the thickness of the injected fluid is less than the thickness of the aquifer, grows in proportion to time and as a result fluid continually migrates further into the nose where it has a progressively smaller vertical extent. We explore how the flow in the nose influences the migration of a pulse of tracer. The growth of the nose stretches a pulse of tracer of initial length, , longitudinally to have a length proportional to , where is the nose entry time. Diffusion acts at the same rate and the combination of the two processes results in an tracer spreading longitudinally with a length proportional to at long times after entering the nose, where D is the coefficient of diffusion. The results are generalised to consider the case in which the permeability in the aquifer varies with depth. At early times, the tracer is sheared. As the tracer migrates into continually thinner regions of the growing nose, the permeability contrast sampled by the tracer rapidly decays. The role of the shear becomes dominated by the stretching of the nose and ultimately the late-time behaviour is as in a uniform aquifer. However, the effective pulse length of the tracer upon asymptoting to the stretching regime is now given by , where is the magnitude of the shear. The spreading in the stretching regime then has a length scale of , which may be much faster than in the case of a uniform aquifer. If the diffusion is sufficiently fast, there may be an intermediate regime in which Taylor dispersion is important prior to the stretching dominating.

Dissertação de Mestrado em Química apresentada à Faculdade de Ciências e Tecnologia Esta dissertação de Mestrado em Química tem como objetivo principal o estudo estrutural da interação de ciclodextrinas e surfactantes com o péptido glicil-L-fenilalanina. Quer as ciclodextrinas, quer os surfactantes são profusamente utilizados em formulações farmacêuticas e agroquímicas com o objetivo de melhorar a eficiência do princípio ativo.Os estudos centram-se no estudo comparativo da interação do péptido glicil-L-fenilalanina (Gly-L-Phe) com β-ciclodextrina (β-CD) e dodecilsulfato de sódio (SDS).Para ambos os sistemas (péptido/ciclodextrina e péptido/surfactante), pretende-se a determinação dos locais de interação dos péptidos com as respetivas moléculas de aditivo, as alterações conformacionais e as respetivas constantes de associação e sua relação com a hidrofobicidade do péptido. Adicionalmente, este projeto tem também como objetivo a compreensão da química-física de fenómenos de transporte desses sistemas multicomponente. Assim, propomos um estudo experimental e computacional abrangente da difusão mútua isotérmica do péptido e transportadores isolados e do péptido em combinação com moléculas transportadoras (ciclodextrinas e surfactantes), visando avaliar in situ constantes de ligação termodinâmicas para possíveis complexos péptido / transportadores e fornecer informações abrangentes detalhadas tanto de ordem cinética como termodinâmica para esses sistemas com interesse biológico.As técnicas experimentais utilizadas foram o estudo da difusão mútua multicomponente pelo método de dispersão de Taylor; a espectroscopia de RMN uni- e bidimensional de 1H, 13C e, adicionalmente, a espectroscopia de RMN de 23Na, em paralelo com o estudo da espectroscopia de absorção de UV/Vis, espectroscopia de fluorescência e estudos teóricos computacionais. The objective of this project for my Master’s thesis in Chemistry is the structural study of the interaction of cyclodextrins and surfactants with the peptide glycyl-L-phenylalanine. Both cyclodextrins and surfactants are commonly used in pharmaceutical and agrochemical formulations in order to improve the efficiency of the active ingredient.The studies have been focused on the comparative study of the interaction of the peptide glycyl-L-phenylalanine (Gly-L-Phe) with β-cyclodextrin (β-CD) and sodium dodecyl sulfate (SDS).For both systems (peptide / cyclodextrin and peptide / surfactant), it is intended to determine the sites of interaction of the peptides with the respective additive molecule, the conformational changes and the respective association constants and their relationship with the hydrophobicity of the peptide. Additionally, this project also has in view the understanding of the physical-chemistry of transport phenomena of these multicomponent systems. With this, we propose a comprehensive experimental and computational study of the isothermal mutual diffusion of the peptide and isolated transporters and of the peptide in combination with the carrier molecules (cyclodextrins and surfactants), aiming to evaluate in situ thermodynamic binding constants for possible peptide / carrier complexes and provide comprehensive and detailed information on both kinetics and thermodynamic details for these systems of biological interest.The experimental techniques used are the study of multicomponent mutual diffusion by Taylor dispersion; the 1H, 13CNMR spectroscopy and, in addition, the 23NaNMR spectroscopy; in parallel, we also used UV/Vis absorption and fluorescence spectroscopy; and complemented by DFT and TD-DFT studies. Universidade de Coimbra - Os dados de RMN foram obtidos na unidade de RMN da UC, que é parcialmente suportada pelo FEDER - Fundo Europeu de Desenvolvimento Regional através do COMPETE (Programa Operacional de Competitividade) e pelo Programa Nacional Fundos através da FCT - Fundação para a Ciência e Tecnologia através de doações REEQ / 481 / QUI / 2006, RECI / QEQ-QFI / 0168/2012, CENTRO-07-CT62-FEDER-002012 e Rede Nacional de Ressonância Magnética Nuclear (RNRMN)

International audience; Advection-diffusion coupling can enhance particle and solute dispersion by orders of magnitude as compared to pure diffusion, with a steady state being reached for confined flow regions such as a nanopore or blood vessel. Here, by using evanescent wave microscopy, we measure for the first time the full dynamics of Taylor dispersion, highlighting the crucial role of the initial concentration profile. We make time-dependent, nanometrically-resolved particle dispersion measurements varying nanoparticle size, velocity gradient, and viscosity in sub-micrometric near-surface flows. Such resolution permits a measure of the full dynamical approach and crossover into the steady state, revealing a family of master curves. Remarkably, our results show that the dynamics depend sensitively on the initial spatial distribution of the nanoparticles. These observations are in quantitative agreement with existing analytical models and numerical simulations performed herein. We anticipate that our study will be a first step toward observing and modelling more complex situations at the nanoscale, such as target finding and chemical reactions in nanoconfined flows, dynamical adsorption and capture problems, as well as nanoscale drug delivery systems.