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Understanding the interfacial structure–property relationship of complex fluid–fluid interfaces is increasingly important for guiding the formulation of systems with targeted interfacial properties, such as those found in multiphase complex fluids, biological systems, biopharmaceuticals formulations, and many consumer products. Mixed interfacial flow fields, typical of classical Langmuir trough experiments, introduce a complex interfacial flow history that complicates the study of interfacial properties of complex fluid interfaces. In this article, we describe the design, implementation, and validation of a new instrument capable of independent application of controlled interfacial dilation and shear kinematics on fluid interfaces. Combining the Quadrotrough with both in situ Brewster angle microscopy and neutron reflectometry provides detailed structural measurements of the interface at the mesoscale and nanoscale in relationship to interfacial material properties under controlled interfacial deformation histories. [ABSTRACT FROM AUTHOR]

The self-assembly of an end-functionalized PEO106-PPO70-PEO106 triblock copolymer (BCP) with acrylic end groups (Pluronic F127 diacrylate or FDA) in a protic ionic liquid (deuterated ethylammonium nitrate, dEAN) is studied using small-angle neutron scattering, shear rheology, and dielectric spectroscopy. This functionalization constitutes less than 1 wt % of the copolymer and has no effect on micelle formation in dEAN. The sol-gel transition and the supramolecular crystal structure of the concentrated FDA/dEAN solutions are also found to be unaffected by the acrylation of the end groups. Photo-cross-linking results in viscoelasticity enhancement of the FDA/dEAN solutions with FDA contents below the gel point. Cross-linking gels produces soft elastomers with exceptional elasticity and conductivity comparable to the un-cross-linked solutions. Tuning BCP microstructure via self-assembly in ionic liquids followed by chemical cross-linking is shown to be a promising route for the design of materials with specific mechanical properties and ionic conductivities. [ABSTRACT FROM AUTHOR]

In Paper I [J. W. Swan et al., J. Rheol. 58, 307-338 (2014)], we derived an exact theoretical description of medium amplitude oscillatory shear for a semidilute colloidal dispersion. Through solution of the Smoluchowski equation governing the spatial distribution of suspended particles in the semidilute limit, we calculated the stresses that arise from an oscillatory linear flow as an expansion in powers of the rate of deformation. Here, this is extended to calculation of the first departures from linearity in the first and third harmonics of the suspension stress driven by oscillatory deformation. The role of hydrodynamic interactions is investigated via the excluded-annulus model in which particles are given an impenetrable core with a radius larger than their hydrodynamic radius. The ratio of these length scales controls the strength of hydrodynamic interactions. The third harmonic of the suspension stress is predicted to be dominated by hydrodynamic stresses at high frequency, a result that is shown to be valid experimentally for the oscillatory shear response of concentrated near hard-sphere dispersions. The calculations anticipate recent experimental observations on model near hard-sphere colloidal dispersions, and quantitative agreement is demonstrated when the predictions are scaled appropriately to account for volume fraction effects. The first departures from linearity in harmonics of the suspension stress are separated into several material functions that are independent of the flow geometry. These functions are generated from detailed numerical solutions, while asymptotic analysis is shown to predict the values of these functions at high frequency. These exact calculations provide a basis for understanding the onset of nonlinear rheological behavior of colloidal suspensions under dynamic oscillatory flow. [ABSTRACT FROM AUTHOR]

The shear rate-dependent rheological properties of soft to rigid colloidal suspensions are studied using computational models. We show that a contact force defined based on an elastohydrodynamic deformation theory captures an important rheological behavior of colloidal suspensions: While near hard-sphere particles exhibit a strong and continuous shear thickening the evolves to a constant viscosity state, soft suspensions undergo a second shear-thinning regime at high Peclet numbers when the hydrodynamic stresses become larger than the modulus of the colloidal particles. We measure N1 and N2 to be large and negative in the shear-thickening regime; however, for soft spheres at the onset of second shear-thinning N2 reduces in magnitude and eventually becomes positive. We show that for near hard-sphere suspensions, colloidal pressure, shear stress, and normal stress difference coefficients tend to diverge near the maximum packing fraction while P > σ > N1 > N2. [ABSTRACT FROM AUTHOR]

The topology of self-assembled surfactant solutions includes varying degrees of micellar branching, ranging from linear wormlike micelles to a micellar network. Micellar branching acts as an effective attraction between micelles such that network condensation can lead to phase separation. Unlike chemical branching in polymers, micellar branches are labile. Movement of branches along a micelle contour has therefore been proposed as a mechanism of stress relaxation that leads to a reduction in the structural relaxation time and thus, the zero-shear viscosity. Branching is also thought to suppress flow alignment, and for lower levels of branching, may also suppress instabilities such as shear banding. The suppression of shear banding can lead to a lesser degree of shear-thinning in the apparent viscosity at higher shear rates, as well as a reduction in extensional thickening. However, for higher levels of branching, shear can induce branching for samples in proximity to such a phase transition, which can result in shear banding due to shear-induced phase separation. Recent modeling and simulations of the energetics of branching, as well as experiments on model systems, show that the reduction in zero-shear viscosity is due to micelle branching. Current research includes efforts to develop a more mechanistic, quantitative understanding of micellar branching and more generally, its effects on micellar solution rheology. [ABSTRACT FROM AUTHOR]

The microstructure and rheologicalproperties of micellar solutionsof Pluronic block copolymers (PEOx–PPOy–PEOx)in deuterated ethylammonium nitrate (dEAN, a protic ionic liquid)are studied by small- and ultrasmall-angle neutron scattering (SANSand USANS), fluorescence microscopy, and shear rheology. A homologousseries of three Pluronics with similar PPO block length (F127 (PEO106–PPO70–PEO106), P123(PEO20–PPO70–PEO20),and L121 (PEO5–PPO70–PEO5)) are examined to explore the effect of the relative balance ofsolvophilic to solvophobic block size on the self-assembled microstructure.Both F127 and P123 form spherical micelles in dEAN that assemble intoface-centered and body-centered cubic supramolecular crystals, respectively,upon increasing concentration or temperature. The transition fromdisordered to crystalline (ordered) structures manifests as a sol–gelrheological transition. A richer phase diagram is observed in theL121/dEAN system: due to its low solvophilicity in dEAN, L121 self-assemblesinto structures with low curvatures, namely, vesicles in the diluteregime, elongated (wormlike) micelles at intermediate concentrationsand low temperatures, a nematic phase in concentrated solutions, andmultilamellar phases at high temperatures. Highly viscoelastic solutionsare created by the self-assembly of entangled L121 wormlike micelles.Structural length scales of the three Pluronic/dEAN systems in thevarious mesophases are determined from SANS and USANS. [ABSTRACT FROM AUTHOR]

• Electrical properties of two saturated clays were investigated in the temperature range 25 °C down to 0 °C. • Impedance analyser measurements (mHz to kHz range) were combined with Vector Network Analyzer measurements (MHz to GHz range). • Temperature effect on typical geophysical quantities was modelled with a mixture approach. Impedance and vector network analyzer measurements are combined in order to measure frequency dependent conductivity and permittivity of two different saturated clays: montmorillonite and illite chlorite. In the low frequency range, the complex conductivity is determined over the 10 mHz to 45 kHz frequency range using a complex impedance analyzer with a 4-electrodes cell. In the high frequency range (50 MHz to 5 GHz), the complex permittivity is obtained from measured reflection factor of an open-ended probe. The ultrabroadband constitutive properties of the saturated clays were investigated in the temperature range 25 °C down to 0 °C. A mixture equation, based on a volume average approach, was applied to model the low and high frequency electrical properties based on the formation factor. The temperature dependency was considered in the following petrophysical quantities: low frequency conductivity, chargeability and high frequency permittivity. The modeled results are in reasonable agreement with measurements. [ABSTRACT FROM AUTHOR]

Recent work modeling the rheological behavior of human blood indicates that blood has all the hallmark features of a complex material, including shear-thinning, viscoelastic behavior, yield stress, and thixotropy. There is renewed interest in the modeling of human blood with thixo-elasto-visco-plastic rheological models. Previous work [Armstrong and Tussing, Phys. Fluids 32, 094111 (2020)] has led to the development of the enhanced thixotropic viscoelastic model for blood (ethixo-mHAWB; called here, after a minor modification, ETV) that incorporates viscoelasticity to a thixotropic model for the stress contributed by the rouleaux aggregates, in addition to describing using a nonlinear viscoelastic model the stress contributed by the individual red blood cells deforming under the action of the flow. This model has shown superior performance in fitting human blood steady state and transient rheological data from a strain-controlled rheometer [Horner et al., J. Rheol. 62, 577–591 (2018); 63, 799–813 (2019)] as compared to other alternate models. In the present work, we first develop another variant of the ETV model, the enhanced structural stress thixotropic-viscoelastic (ESSTV) model, and the modification patterned following an elastoviscoplastic model developed recently [Varchanis et al., J. Rheol. 63, 609–639 (2019)]. We develop full tensorial stress formulations of the rouleaux stresses for both the above-mentioned models, resulting in the t-ETV and t-ESSTV models. We use steady state and step-ups, and step-downs in shear rate data to independently fit the parameters of all before-mentioned models. We compare predictions against experimental data obtained on small, large, and unidirectional large amplitude oscillatory shear conditions. We find that the full tensor stress formulations t-ETV and t-ESSTV significantly improved the predictive capability of the earlier ETV model. [ABSTRACT FROM AUTHOR]

An extensive data set has been developed and used to further the progress of a model-informed design of controlled drug release. An improved drug-release model with mechanistic modeling of hydrolytic polymer degradation is used and validated by comparing model predictions to in vitro experiments. Combining parameter estimates from the literature with model fits to the data set, this study can aid in achieving a priori design of controlled drug release from a model PLGA release system. A systematic series of model release systems were formulated with FITC-labeled dextran, as a surrogate for biopharmaceuticals, in PLGA rods over a broad range of compositions. While general comparisons between the model and experiments were favorable, important discrepancies were identified for several formulations with significant first-phase drug release. Supported by cross-sectional fluorescence microscopy images of the FITC-dextran distribution within the rods, this first-phase release was attributed to a combination of two main factors: (1) percolation of the drug particles and (2) swelling of and pore formation in the rods due to water uptake. These observations indicate the importance of careful selection of the PLGA polymer grade when designing drug release systems but also reflect a need for better understanding of phenomena such as pore formation. Adapting model parameters, without modifying the physical processes included in the model, enabled accurate fitting of the experimental data for all formulations, highlighting the applicability of the model. [ABSTRACT FROM AUTHOR]

The adsorption of cationic polyelectrolytes (PEs) onto anionic silicone emulsion droplets, suspended in a sodium chloride solution is studied via electrophoretic mobility measurements and isothermal titration calorimetry. These model systems are studied to better understand the interactions governing PE adsorption-induced emulsion flocculation, which is relevant to many industrial applications. Electrophoretic mobility measurements provide critical information for rationalizing the effect of the PE charge density on the loss of stability of silicone emulsions. The interaction strength is calculated from a Langmuir adsorption isotherm determined by a ζ-potential titration measurement. Microcalorimetry measurements independently validate the adsorption free energy. Emulsion flocculation and coacervation are observed in the visual phase behavior as well as the ζ-potential titration measurements. The effect of PE charge density shows that PE-surfactant coacervation is the driving force in these PE-emulsion systems. [ABSTRACT FROM AUTHOR]

We study the medium amplitude oscillatory shear (MAOS) of a semi-dilute, hard-sphere colloidal dispersion. Through solution of the Smoluchowski equation governing the statistical distribution of suspended particles in the semi-dilute limit, we calculate the linear viscoelasticity and the normal stress differences that arise from oscillatory shear as an expansion in terms of small rates of deformation. The effects of hydrodynamic versus conservative interactions are studied via the excluded-annulus model for the hard-sphere interactions. This treats the hardsphere interactions as a steric barrier that resides beyond the hydrodynamic radius of the particles and allows for continuous variation of the strength of hydrodynamic interactions. We see remarkable distinctions between suspensions that are freely draining and those for which hydrodynamic lubrication among the particles dominate their motion. In oscillatory shear flow of a freely draining suspension at high-frequency, the normal stress differences are generated by hard-sphere stresses. In contrast, for a hydrodynamically interacting suspension at highfrequency, the first normal stress difference derives from Brownian stresses while the second normal stress difference is dominated by hydrodynamic stresses. When the first normal stress difference is plotted parametrically against the oscillatory rate of strain, the resulting Lissajous- Bowditch curves for freely draining suspensions and those with full hydrodynamic interactions take on distinct and disparate shapes. Additionally, we use an asymptotic analysis to predict that the third harmonic of the suspension stress for hard spheres is dominated by the hydrodynamic lubrication in the limit of high frequency oscillation. Our calculations demonstrate that under MAOS, hydrodynamic interactions play a central and qualitative role in the stress response of a semi-dilute colloidal dispersion. [ABSTRACT FROM AUTHOR]

Highlights: [•] An approach to describe ITC experiments on surfactant-polymer mixtures is presented. [•] The new formalism is compared to an approximated existing model. [•] The improvement is needed for a consistent description of ITC experiments. [•] The new formalism is tested on the binding of SDS to JR-400. [ABSTRACT FROM AUTHOR]

Structure-property relationships of alkali-activated aluminosilicate gels are studied using rheology, neutron scattering, solid-state NMR, and TEM to develop a pseudo-ternary state diagram. Empirical gel states are classified by the rheological behavior (sol-gel transition and scaling of storage modulus with aluminum concentration). The state boundaries are compared to alkali-activated materials from the literature including denser binders. This work focuses on two compositions of dilute gels, formulated to specifically quantify the effects of pH and aluminum concentration on gel microstructure and rheology. Gels formulated at constant pH of 12.5 show a change in morphology and silicon coordination, but consistent mass fractal dimension as aluminum concentration is increased. This microstructural behavior contrasts the characterization of gels previously formulated with a variable pH (range 3–11) which is dependent on aluminum concentration. These results inform the complicated interactions in the polycondensation reaction of alkali-activated binders and lead to a state diagram which unifies many structure-property observations reported for these materials. Structure-property relationships for two formulations of N-A-S-H gels are compared and plotted in a pseudo-ternary state diagram which includes other compositions of N-A-S-H gels and alkali-activated binders from the literature, shaded according to the scaling of the storage modulus where applicable. [Display omitted] [ABSTRACT FROM AUTHOR]

A new integrated experimental and theoretical framework to simultaneously measure mechanical, hydraulic and high frequency dielectric properties of soil during shrinkage was designed aiming at the development, verification and validation of constitutive electromagnetic material relationships. The electromagnetic response of a soil to a high frequency (radio to microwave) signal contains information that can be harvested to characterise soil including its state variables such as water content, density and soil suction. The developed framework allows decoding of this response. In the presented study on kaolin (i) shrinkage tests ii) shrinkage tests with non-destructive determination of dielectric spectra from 50 MHz to 3 GHz, and (iii) determination of the soil suction relationship over a broad range of water content, have been performed. The results of this investigation show a nonlinear evolution of the permittivity at 1 GHz as a function of water content with a sharp transition. None of the advanced mixture approaches that were applied in a forward approach could quantitatively characterize this relationship between the permittivity and the volumetric water content. With a recently developed advanced mixture equation (Augmented Broadband Complex dielectric Mixture model – ABCM) applied in an inverse scheme, the saturated part of the shrinkage curve was able to be estimated from the permittivity measurements. A quantitative relationship between the cementation exponent within this mixture equation and the soil suction have also been established. The conditions and reasons for the drop in permittivity remains subject of future research. • Linking soil shrinkage – soil water retention – high frequency electromagnetic (HF-EM) properties of soils. • 3 dimensional finite element modelling for vertical sensitivity of the open ended probe. • Forward and inverse approaches to link HF-EM and hydro-mechanical behaviour of kaolin during shrinkage. • Estimation of saturated part of the soil shrinkage curve using Augmented Broadband Complex dielectric Mixture model. • Linear relationship between cementation exponent and soil suction. [ABSTRACT FROM AUTHOR]

Protein salting‐out is a well established phenomenon that in many cases leads to amorphous structures and protein gels, which are usually not considered to be useful for protein structure determination. Here, microstructural measurements of several different salted‐out protein dense phases are reported, including of lysozyme, ribonuclease A and an IgG1, showing that salted‐out protein gels unexpectedly contain highly ordered protein nanostructures that assemble hierarchically to create the gel. The nanocrystalline domains are approximately 10–100 nm in size, are shown to have structures commensurate with those of bulk crystals and grow on time scales in the order of an hour to a day. Beyond revealing the rich, hierarchical nanoscale to mesoscale structure of protein gels, the nanocrystals that these phases contain are candidates for structural biology on next‐generation X‐ray free‐electron lasers, which may enable the study of biological macromolecules that are difficult or impossible to crystallize in bulk. [ABSTRACT FROM AUTHOR]

The assembly of ordered dicolloid monolayers is directedby anelectric field. The dicolloid particles are polystyrene latex witha maximum equatorial diameter 3.45 μm and length 4.63 μm.The monolayer structure is characterized using small-angle light scatteringand bright-field microscopy. With increasing field strength from 26.7to 200 VRMS/cm, a transition from a disordered monolayer,to first orientationally ordered, and then translationally orderedtwo-dimensional (2D) arrays occurs. A c2mmplane group symmetry dominates the ordered structure but is presentalongside structures with p2 symmetry, leading toa spread in the angular distribution of the light scattering peaks.The order–disorder transition dependence on field strengthand frequency is similar to that observed for colloidal spheres; athigher frequencies, stronger fields are required to assemble particles.Optimal ordered structures reflect a balance between inducing sufficientlystrong interparticle interactions while limiting the rate of formationto ensure the growth of large crystalline domains. [ABSTRACT FROM AUTHOR]

Abstract: Complex fluids with high concentrations of crystallizing fatty acids are important for consumer skin care products. These fluids exhibit solid-like elastic behavior at rest, but yield and flow under an applied strain. Such behavior is characteristic of isotropic, space-filling networks. The processing determines the microstructure of these systems, which in turn influences their macroscopic rheological properties. The kinetics of crystal growth in model system compositions, comprising (by weight) 9% sodium dodecyl sulfate, 3% cocamidopropyl betaine, and different specified amounts of palmitic acid in H2O or D2O, were studied by time domain nuclear magnetic resonance (TDNMR) and differential scanning calorimetry (DSC). The data were analyzed using the Avrami equation; both DSC and TDNMR gave consistent Avrami exponent values of approximately 1.5 for formulations with 11wt% and greater amounts palmitic acid content. The Avrami exponent is consistent with two-dimensional crystal growth limited both by diffusion and surface incorporation. The solids content at 25°C was found to be proportional to the concentration of palmitic acid level above its solubility limit of ca. 2wt%. TDNMR, combined with DSC, microscopy, and rheology provide valuable insights into the molecular structure and mechanism of crystallization in surfactant/fatty acid systems. [Copyright &y& Elsevier]

Abstract: Complex fluids with high concentrations of crystallizing fatty acids are important for consumer care products. The key features of these materials are their ability to support their weight under gravity and to yield or flow beyond a critical applied strain. To better understand the post-processing behavior of these systems, we have utilized a combination of Rheology, Differential Scanning Calorimetry, X-ray scattering, and Polarized Light Microscopy to study a model formulation consisting of two synthetic surfactants and a fatty acid (n-hexadecanoic acid) in water. Homogeneous samples with high storage modulus (G′) are realized due to the formation of a space filling solid fatty acid crystal network. A minimum of 5–7wt% of fatty acid is required to achieve the formation of a percolating crystal network. The storage modulus, yield stress and strain of these formulations show a non-monotonic increase with fatty acid content. This is attributed to the change in the fatty acid crystal habit from large to small aspect ratio plates. We hypothesize that the fatty acid crystal network consists of crystal aggregates linked by surfactant-fatty acid gels, rendering the desired paste-like characteristics to the formulation. The combination of methods utilized in this research provides a framework for understanding crystallizing systems. [Copyright &y& Elsevier]

Abstract: The split Hopkinson pressure bar experimental technique is used to evaluate the squeezing flow response of a concentrated, discontinuously thickening colloidal suspension of spherical silica particles loaded at high stresses/strain rates. These results provide insight into the transitional behavior of these materials, as well as the post-transitional response under compressive loading. A method of analyzing the strain and strain rate dependent behavior is presented to identify modes of material response (viscous, elastic, etc.). Experimental results are presented as stress–strain–strain rate plots and a surface fitting approach is used to develop a phenomenological model describing the overall response. From this model, it is possible to identify regions of elastic and viscous behavior using a gradient analysis approach. It was found that, after an initial period of viscous deformation, the suspension behaves like a viscoelastic material – this regime corresponds well with transition in which large clusters of particles percolate. This is followed by a third, viscous regime in which the material undergoes viscous deformation. At the highest stresses, a plateau region of plastic deformation has been identified. This approach and the conditions under which it may be applied are described in detail in the paper. [Copyright &y& Elsevier]

Abstract: Hydrogel materials are promising vehicles for the delivery of protein therapeutics. Proteins can impart physical interactions, both steric and electrostatic in nature, that influence their release from a given gel network. Here, model proteins of varying hydrodynamic diameter and charge are directly encapsulated and their release studied from electropositive fibrillar hydrogels prepared from the self-assembling peptide, MAX8. Hydrogelation of MAX8 can be triggered in the presence of proteins for their direct encapsulation with neither effect on protein structure nor the hydrogel’s mechanical properties. Bulk release of the encapsulated proteins from the hydrogels was assessed for a month time period at 37 °C before and after syringe delivery of the loaded gels to determine the influence of the protein structure on release. Release of positively charged and neutral proteins was largely governed by the sterics imposed by the network. Conversely, negatively charged proteins interacted strongly with the positively charged fibrillar network, greatly restricting their release to <10% of the initial protein load. Partition and retention studies indicated that electrostatic interactions dictate the amount of protein available for release. Importantly, when protein encapsulated gels were delivered via syringe, the release profiles of the macromolecules show the similar trends as those observed for non-sheared gels. This study demonstrates that proteins can be directly encapsulated in self assembled MAX8 hydrogels, which can then be syringe delivered to a site where subsequent release is controlled by protein structure. [Copyright &y& Elsevier]

Abstract: The behavior of a concentrated, hard-sphere colloidal suspension is evaluated using the split Hopkinson pressure bar (SHPB) experimental technique. The composition of the suspension is measured using thermograviometric analysis before and after loading. This, combined with recorded pressure distributions, result in the conclusion that the suspension undergoes high rate squeezing flow. Experimental results demonstrate that the suspension exhibits shear thickening consistent with that observed in standard rotational rheometry. At sufficiently high stresses the suspension exhibits a second regime of shear thinning behavior that is consistent with elastohydrodynamic theory that incorporates the shear modulus of the particles themselves. Further increases in stress result in irreversible behavior, i.e., rather than fracturing or crushing, the particles form non-reversible agglomerates during testing. This fact is demonstrated through the use of dynamic light scattering and electron microscopy. This behavior occurs within a regime of viscous material response which is seen to occur at normal strain rates and stresses over 104 s−1 and 40MPa, respectively. [Copyright &y& Elsevier]

The split Hopkinson pressure bar (SHPB) technique is implemented to evaluate the transient response of a colloidal suspension exhibiting shear thickening at strain rates and timescales never before explored in a laboratory instrument. These suspensions are shown to exhibit a discontinuous transition from fluid-like (shear thinning) to solid-like (shear thickening) behavior when evaluated using rotational rheometry. The effect of loading rate on this transition time is studied for a particle volume fraction of 0.54 using the SHPB technique. It is shown that the time required for transition to occur decreases logarithmically with loading rate. From these results, we conclude that transition is not triggered by a characteristic shear rate, but rather a critical shear strain is required. Results from SHPB experiments performed up to Peclet numbers of order 107 are presented and discussed for 0.50, 0.52, and 0.54 particle volume fraction suspensions. [ABSTRACT FROM AUTHOR]

Abstract: Self-assembling peptide hydrogels are used to directly encapsulate and controllably release model FITC–dextran macromolecules of varying size and hydrodynamic diameters. MAX1 and MAX8 are two peptide sequences with different charge states that have been designed to intramolecularly fold and self assemble into hydrogels at physiological buffer conditions (pH 7.4, 150mm NaCl). When self-assembly is initiated in the presence of dextran or protein probes, these macromolecules are directly encapsulated in the gel. Self-diffusion studies using fluorescence recovery after photobleaching (FRAP) and bulk release studies indicate that macromolecule mobility within, and release out of, these gels can be modulated by varying the hydrogel mesh size. The average mesh size can be modulated by simply varying the concentration of a given peptide used to construct the gel or by altering the peptide sequence. In addition, results suggest that electrostatic interactions between the macromolecules and the peptide network influence mobility and release. Depending on probe size, release half-lives can be varied from 8h to over a month. [Copyright &y& Elsevier]

Abstract: A microfluidic process for producing crystals of controlled size by confining the crystallization within drops is demonstrated. The process consists of a drop producing stage which segments the mother liquor into monodisperse drops followed by crystallization in a temperature controlled tubular crystallizer. The process is implemented to produce lactose crystals with significantly narrower crystal size distribution (CSD) as compared with crystals produced in a stirred bulk crystallizer. By controlling the drop size and initial supersaturation the mean crystal size can be controlled. The distribution of the number of crystals per drop and the CSD are measured as a function of supersaturation at temperatures between 20 and for 150 and drops. In the case where drops contain only one crystal, a very narrow CSD is obtained with a coefficient of variation of crystal size as low as 7%. The crystallization of lactose in a microfluidic tubular crystallizer is modeled by treating nucleation in drops as a Poisson process with a nucleation rate based on classical nucleation theory. Experimental results are in good agreement with predictions from a Poisson process model over the range of temperatures, supersaturations and drop sizes tested. [Copyright &y& Elsevier]

The rheology and particle alignment of suspensions of anisotropic-precipitated calcium carbonate particles of various aspect ratios is investigated using small-angle neutron scattering simultaneous with rheological measurement (Rheo-SANS). Rheo-SANS experiments were performed at concentrations from dilute to those exhibiting continuous and discontinuous shear thickening behavior. Long axis flow alignment is evident in all systems over the range of shear rates investigated. The flow alignment is shown to increase with particle aspect ratio, the applied shear stress (up to the point of shear thickening), and particle loading. For samples exhibiting shear thickening behavior, the highest degree of flow alignment occurs at the critical stress associated with the onset of shear thickening. Irrespective of particle aspect ratio, a gradual reduction in flow alignment with increasing applied stress is observed beyond the critical stress in continuously shear thickening samples, whereas discontinuously shear thickening samples maintain nearly the same degree of flow alignment within the shear thickening regime. The results are shown to be consistent with hydrocluster formation as the mechanism of shear thickening. The critical volume fraction for discontinuous shear thickening is shown to coincide with the equilibrium isotropic-nematic phase transition at higher aspect ratios. [ABSTRACT FROM AUTHOR]

Abstract: An algorithm has been developed to create structural models for amorphous carbons using Monte Carlo simulations in the canonical ensemble. The simulation method used follows the experimental preparation of nanoporous carbons (NPC) by pyrolysis from polyfurfuryl alcohol as a guideline. The resulting structure exhibits properties that compare favorably to those observed experimentally for real NPCs. These atomistic NPC models are approaching a realistic representation of NPCs used for gas separations and as such, are being used to study the diffusion of small gas molecules in these materials. Limitations of the method and possible improvements are discussed. [Copyright &y& Elsevier]

Abstract: A micromechanical model for the zero shear viscosity of polyampholyte-stabilized colloidal dispersions based on the osmotic overlap potential is proposed and tested against model system measurements. This model relates the shear viscosity of polyampholyte-stabilized colloidal dispersions to the oncotic pressure of polyampholyte solutions through an interparticle potential and an effective hard-sphere scaling. The results of viscosity calculations based on independently measured parameters compare favorably to experimental measurements on model, silica dispersions stabilized with adsorbed photographic grade gelatin. The results support a direct link between the capacity of polyampholytes and polyelectrolytes to stabilize dispersions and control dispersion viscosity and their solution oncotic pressure. The model is also demonstrated to provide a master curve for literature data for the zero shear viscosity of polyampholyte stabilized colloidal dispersions. [Copyright &y& Elsevier]

Small angle neutron scattering (SANS) studies of a model pharmaceutical formulation reveal how formulation stability depends on the compatibility of individual components. Solutions of two common protein formulation excipients, polysorbate 80 (PS80), a nonionic surfactant that prevents aggregation, and m-cresol, an antimicrobial agent for multi-dose injectable formulations, are investigated. The addition of m-cresol to PS80 solutions leads to solution turbidity and irreversibly alters PS80 micelle morphology. This slow preservative-induced destabilization of PS80 micelles progresses over days or even weeks, which highlights the essential role that aggregation kinetics plays in preservative-surfactant interactions. The temperature-dependence of PS80 micelle growth kinetics is quantified by SANS in the presence of m-cresol. Aggregation is a two-step process, where initial formation of small aggregates is followed by a period of monotonic power-law growth, providing evidence for the mechanism. Total aggregate mass stays constant after initial aggregate formation, and addition of a pH-regulating citrate buffer dramatically accelerates aggregation kinetics. [ABSTRACT FROM AUTHOR]

Two colloidal suspensions of paucidisperse, spherical silica particles with different surface chemistries leading to extreme limits of surface contact friction are studied to identify experimental differences in shear rheology and microstructure and quantitatively test theory and simulation models. The nonequilibrium microstructure in the plane of shear is measured by flow-small angle neutron scattering for steady shear states spanning the shear thinning and shear thickening regimes. The shear rheology and microstructure are compared against predictions from theory for Brownian hard sphere suspensions and state-of-the-art simulation methods that incorporate either contact friction or enhanced lubrication hydrodynamics. The first normal stress differences are confirmed to distinguish between these micromechanical mechanisms for stress enhancement in the shear thickened regime. The nonequilibrium microstructure in the plane of shear shows more anisotropy for the suspension with higher interparticle friction. A significant fourfold symmetry is confirmed and found to be amplified with increasing surface contact friction in the shear thickened state. The differences in shear-induced microstructures between suspensions with varying contact friction demonstrate that the nonequilibrium microstructure can distinguish between nanotribological interactions in the shear thickened state. Statistical comparison of experiments with simulations indicates that better resolution of microstructures in simulation models is required to be validated by the experimental data presented. Implications for the development of theories for colloidal suspension rheology are discussed. [ABSTRACT FROM AUTHOR]

The adsorption of monoclonal antibodies (mAbs) on hydrophobic surfaces is known to cause protein aggregation and degradation. Therefore, surfactants, such as Poloxamer 188, are widely used in therapeutic formulations to stabilize mAbs and protect mAbs from interacting with liquid-solid interfaces. Here, the adsorption of Poloxamer 188, one mAb and their competitive adsorption on a model hydrophobic siliconized surface is investigated with neutron scattering coupled with contrast variation to determine the molecular structure of adsorbed layers for each case. Small angle neutron scattering measurements of the affinity of Poloxamer 188 to this mAb indicate that there is negligible binding at these solution conditions. Neutron reflectometry measurements of the mAb show irreversible adsorption on the siliconized surface, which cannot be washed off with neat buffer. Poloxamer 188 can be adsorbed on the surface already occupied by mAb, which enables partial removal of some adsorbed mAb by washing with buffer. The adsorption of the surfactant introduces significant conformational changes for mAb molecules that remain on the surface. In contrast, if the siliconized surface is first saturated with the surfactant, no adsorption of mAb is observed. Competitive adsorption of mAb and Poloxamer 188 from solution leads to a surface dominantly occupied with surfactant molecules, whereas only a minor amount of mAb absorbs. These findings clearly indicate that Poloxamer 188 can protect against mAb adsorption as well as modify the adsorbed conformation of previously adsorbed mAb. [ABSTRACT FROM AUTHOR]

Molecular engineering facilitates the development of a complex fluid with contradictory requirements of yield stress and sprayability, while minimizing the amount of structuring material (<0.05 wt%). This unique system can be achieved by a biopolymer hydrogel with tunable inter- and intra-molecular interactions for microstructural robustness and molecular extensibility by the variation of chemical conformations that microstructure breaks up under shear followed by a low molecularly extensible response. Blends of xanthan and konjac glucomannan containing 99.95 wt% water are demonstrated to satisfy these contradictory requirements and formulated as a function of KCl concentrations. A systematic study was performed using shear and extensional rheology and compared to a reference solution of polyethylene oxide (PEO), a well-known, Boger fluid, highlights the role of molecular elasticity in controlling critical rheological properties. Static light scattering (SLS) and simultaneous rheology and small-angle neutron scattering (RheoSANS) are also used to elucidate the equilibrium structure and flow dynamics. The blends exhibit a lower yield stress and extensional resistance with added KCl, which leads to good spray characteristics in contrast to strain-hardening PEO. The results suggest that the inter-molecular attractions between the two gums leading to network formation with appropriate stiffness, that break up readily under shear, and low molecular elasticity are critical molecular design parameters necessary to achieve sprayable, yields stress fluids. [ABSTRACT FROM AUTHOR]

Colloidal dispersions with a short-range attraction and long-range repulsion can exhibit an intriguing intermediate range order, manifested in scattering experiments as a low-q peak in the structure factor. Monte Carlo simulations are performed on fluids that exhibit intermediate range order to explicitly determine its connection to a possible state of microphase separation, equilibrium clustering. This is accomplished by decomposing the structure factor into cluster-cluster, monomer-monomer, and cross-correlations that cannot be extracted from experimental scattering patterns. Our simulation results indicate that the intermediate range order arises from either monomeric or cluster species, depending on solution conditions, and reflects the presence of a preferred length scale that is not trivially related to the interparticle potential. Further, criteria are established to define monomer, cluster, and percolated states in these systems that facilitate further studies. Combining scattering techniques with simulations provides an effective method for identifying clustered states in complex fluids. [ABSTRACT FROM AUTHOR]

The chytrid fungus Batrachochytrium salamandrivorans (Bsal), recently introduced from Asia to Europe, causes mortality in numerous species of salamanders and newts and has led to catastrophic declines and local extinctions of the European fire salamander (Salamandra salamandra) in the Netherlands, Belgium, and Germany. Due to the continuous spread of the pathogen, Germany can be considered as the current 'hotspot' of Bsal-driven salamander declines. The pathogen was detected in 2015 in the Eifel Mountains where it probably has been present at least since 2004. Moreover, Bsal was found in 2017 in the Ruhr District where it also might occur since 2004. The Ruhr District is a heavily urbanized and industrialized region in western Germany, which offers an unprecedented opportunity to monitor range expansion and infection dynamics of Bsal in an area affected by intense human activities. We here review the current knowledge on Bsal in the Ruhr District where the pathogen by now has been recorded based on qPCR data from 18 sites distributed over eight cities. Transect counts (adult salamanders) and larval removal-sampling at two sites where Bsal was recorded in 2017 and 2018, confirm that fire salamander populations at the affected sites have declined dramatically. However, single negative-tested individuals were still observed and reproduction could be ascertained. Moreover, we successfully detected Bsal by analysing environmental DNA (eDNA) from samples obtained from a standing water body as well as a stream. Detailed monitoring of a site in Essen (Kruppwald) from January to May 2019 provided data on infection and disease dynamics during an acute Bsal-outbreak in a population of European fire salamanders. After initial observation of single dead infected salamanders in January and February 2019, the maximum Bsal loads in the population ranged from 7.90E+03 ITS copies in early March to 2.29E+09 ITS copies at the end of March. Prevalence of infection ranged from 4% to 50% and significantly increased over time; prevalence of externally visible disease symptoms peaked on May 2 and May 8. Single dead salamanders were encountered throughout the monitoring period. Recaptures of two infected salamanders indicated an increase of Bsal load by about one order of magnitude within one week. Infected salamanders showed small-sized regular round ulcerations usually of 0.25-1 mm but sometimes up to 2.5 mm in diameter, which gave the impression of outward growth from the centre of each ulceration. Among salamander individuals monitored in the Kruppwald, such ulcerations were only found in infected salamanders, but we found no significant correlation between the intensity of the ulcerations and Bsal load. Heat treatment proved effective to cure even deep ulcerations when salamanders were kept for 10 days at 25-27°C or 14 days at 25°C, but infection persisted and ulcerations reappeared six weeks after the end of the treatment; only heat treatment at 25°C for 21 days proved effective to reliably clear the infection in three tested salamanders. [ABSTRACT FROM AUTHOR]

• Application of a multiscale, population balance‐based thixotropy model to blood. • More physical description of the coin‐stack like rouleaux aggregate structures. • Meaningful microscopic structural information obtained by fitting bulk rheology. Modeling blood rheology remains challenging in part because of its multiphase, aggregating colloidal nature that gives rise to complex viscoplastic and time-dependent (thixotropic) behavior. Here, we demonstrate that a multiscale approach incorporating a direct coupling of coarse-graining particle-level modeling to the macroscopic phenomenological modeling can provide new insights and a promising methodology. Specifically, a general population balance-based, multiscale, thixotropic modeling approach, first proposed by Mwasame et al., AIChE J. 63 (2017) 517–531, is applied to account for the rouleaux-induced thixotropy in human blood in shear flow. Population balances offer a compelling alternative to previously proposed structure-based heuristic kinetics models of aggregating colloidal suspensions as they use a statistical approach to describe the aggregate size distribution with well-defined processes for either shear-induced or Brownian aggregation and breakup under shear flow. When applied to human blood, the population balance approach offers a first attempt to model the size evolution of predominantly coin-stack like rouleaux structures of the red blood cells that are the primary source behind the observed yield stress and thixotropy of blood at low shear rates. This microscopic information, suitably coarse-grained, is then introduced into a semi-phenomenological macroscopic model that expresses the total stress in terms of an elastic and viscous contribution. Shear thinning introduced due to the red blood cell deformation at high shear rates is accounted for by following Horner et al., J. Rheol. 62 (2018) 577–591. An advantage of this modeling approach is that the parameters have specific physical meaning that allows for independent estimates and/or evaluations through appropriately designed independent experiments. Conversely, parameters with specific microscopic interpretations, such as the fractal dimension of the aggregates, d f , are obtained fits of macroscopic shear experiments. Fitting and predictions use steady shear, and unidirectional large amplitude oscillatory shear (UD-LAOS) experiments on whole blood samples of two healthy donors, as reported in Horner et al. We obtain values for d f in the range of 1.5 ± 0.2 which is consistent with the rod-like shape of rouleaux structures reported in the literature. Furthermore, the shear predictions compare favorably against the experiments. While this approach is not as accurate as the fits of prior structure kinetics modeling of Horner et al., these promising results provide a pathway for model improvement by including independently verified physical properties of blood. This work demonstrates a new particle-level approach for describing and predicting the non-Newtonian, thixotropic rheology of human blood. [ABSTRACT FROM AUTHOR]

The chytrid fungus Batrachochytrium salamandrivorans (Bsal), recently introduced from Asia to Europe, causes mortality in numerous species of salamanders and newts and has led to catastrophic declines and local extinctions of the European fire salamander (Salamandra salamandra) in the Netherlands, Belgium, and Germany. Due to the continuous spread of the pathogen, Germany can be considered as the current 'hotspot' of Bsal-driven salamander declines. The pathogen was detected in 2015 in the Eifel Mountains where it probably has been present at least since 2004. Moreover, Bsal was found in 2017 in the Ruhr District where it also might occur since 2004. The Ruhr District is a heavily urbanized and industrialized region in western Germany, which offers an unprecedented opportunity to monitor range expansion and infection dynamics of Bsal in an area affected by intense human activities. We here review the current knowledge on Bsal in the Ruhr District where the pathogen by now has been recorded based on qPCR data from 18 sites distributed over eight cities. Transect counts (adult salamanders) and larval removal-sampling at two sites where Bsal was recorded in 2017 and 2018, confirm that fire salamander populations at the affected sites have declined dramatically. However, single negative-tested individuals were still observed and reproduction could be ascertained. Moreover, we successfully detected Bsal by analysing environmental DNA (eDNA) from samples obtained from a standing water body as well as a stream. Detailed monitoring of a site in Essen (Kruppwald) from January to May 2019 provided data on infection and disease dynamics during an acute Bsal-outbreak in a population of European fire salamanders. After initial observation of single dead infected salamanders in January and February 2019, the maximum Bsal loads in the population ranged from 7.90E+03 ITS copies in early March to 2.29E+09 ITS copies at the end of March. Prevalence of infection ranged from 4% to 50% and significantly increased over time; prevalence of externally visible disease symptoms peaked on May 2 and May 8. Single dead salamanders were encountered throughout the monitoring period. Recaptures of two infected salamanders indicated an increase of Bsal load by about one order of magnitude within one week. Infected salamanders showed small-sized regular round ulcerations usually of 0.25-1 mm but sometimes up to 2.5 mm in diameter, which gave the impression of outward growth from the centre of each ulceration. Among salamander individuals monitored in the Kruppwald, such ulcerations were only found in infected salamanders, but we found no significant correlation between the intensity of the ulcerations and Bsal load. Heat treatment proved effective to cure even deep ulcerations when salamanders were kept for 10 days at 25-27°C or 14 days at 25°C, but infection persisted and ulcerations reappeared six weeks after the end of the treatment; only heat treatment at 25°C for 21 days proved effective to reliably clear the infection in three tested salamanders. [ABSTRACT FROM AUTHOR]

Dense colloidal suspensions are processed in a wide variety of industries. Challenges for pumping suspensions and slurries at high concentrations include shear thickening and dilation, which can have deleterious consequences. These systems are shear sensitive close to the jamming point, meaning that a significant increase in high shear viscosity can be observed with just a few percent change in volume fractions. Therefore, accurate and rapid determination of the jamming point can greatly aid formulation. Typically, conventional rheometry identifies the jamming point by a time-consuming process, whereby multiple flow curves of suspensions of different volume fraction are measured and extrapolated to the volume fraction where the viscosity diverges. We present an alternative approach for rapid, one-step, experimental determination of the jamming point for aqueous suspensions. The procedure monitors the shear stress under constant shear stress or shear rate as the sample is dewatered using immobilization cell rheometry, until the viscosity diverges. The method is validated by comparing the results of this work with conventional rheometry for a model suspension. Then it is applied to examine the effect of grafting a short-chain polymer to particles, comprising an industrial suspension of silica-coated titania. Polymeric coating of the particles increases the jamming concentration and mitigates shear thickening, qualitatively consistent with predictions from simulations. [ABSTRACT FROM AUTHOR]

Surfactants are commonly used in therapeutic protein formulations in biopharmaceuticals to impart protein stability; however, their solution morphology and the role of the individual components in these structurally heterogeneous commercial grade surfactants at physiologically and pharmaceutically relevant temperatures have not been investigated systematically. The micellar morphologies of Polysorbate 20 and Polysorbate 80 and their primary components monoester fractions, as well as the diester fractions, are evaluated at 4, 22°C, 40°C, and 50°C using small-angle neutron scattering to determine the aggregation number, radius of gyration, core radius, critical micelle concentration, shell thickness, and shell hydration. The sizes and aggregation numbers of the diester fractions of PS20 above 80°C and PS80 above 50°C exhibit significant changes in shape. The analysis of the small-angle neutron scattering data of PS20 confirms that the critical micellar concentration of the monoester fraction is significantly higher at 4°C compared to the diester fraction and their original material, all-laurate PS20. Overall, these experiments identify the dominant components responsible for the temperature-dependent behavior of these surfactants in pharmaceutical protein formulations. [ABSTRACT FROM AUTHOR]

Rheological experiments on model and industrial colloidal dispersions that exhibit reversible shear thickening are compared to a recent model that correlates simulation results for the shear rheology of bidisperse suspensions of particles with varying levels of contact friction. Comparisons are presented with rheological results for a variety of colloidal dispersions varying from model systems to industrially relevant, commercial dispersions where both shear and first normal stress differences are available. Particle-scale measurements of particle friction coefficients are provided through a survey of the literature. The comparisons show under which conditions the model can quantitatively describe the measured rheology and how the model can be used to correlate data for systems with more complex interactions when allowances are made for effective volume fractions and adjustments in friction coefficients. Discrepancies evident in comparisons for the first normal stress differences highlight the importance of enhanced hydrodynamic friction in many systems, especially for continuous shear thickening, in qualitative agreement with recent simulations that incorporate enhanced lubrication hydrodynamics due to elastohydrodynamics or particle roughness. Finally, a literature survey of measurements of jamming volume fractions and particle friction coefficients indicates that the model overestimates the experimentally observed jamming volume fraction. The comparisons presented in this work provide quantitative information valuable for those modeling suspension processing as well as suggestions for further model improvement. [ABSTRACT FROM AUTHOR]

Mathematical modeling of drug release can aid in the design and development of sustained delivery systems, but the parameter estimation of such models is challenging owing to the nonlinear mathematical structure and complexity and interdependency of the physical processes considered. Highly parameterized models often lead to overfitting, strong parameter correlations, and as a consequence, inaccurate model predictions for systems not explicitly part of the fitting database. Here, we show that an efficient stochastic optimization algorithm can be used not only to find robust estimates of global minima to such complex problems but also to generate metadata that allow quantitative evaluation of parameter sensitivity and correlation, which can be used for further model refinement and development. A practical methodology is described through the analysis of a predictive drug release model on published experimental data sets. The model is then used to design a zeroth-order release profile in an experimental system consisting of an antibody fragment in a poly(lactic-co-glycolic acid) solvent depot, which is validated experimentally. This approach allows rational decision-making when developing new models, selecting models for a specific application, or designing formulations for experimental trials. [ABSTRACT FROM AUTHOR]

The use of enzymatic biomarkers constitutes a widely used approach in ecotoxicology. However, standard sampling procedures are invasive, requiring tissue, organ or blood extraction. This leads to concerns regarding conservation practice, animal welfare and restrictions in study design. New techniques are needed to avoid these problems, but still generate reliable data. Here, we aimed at validating the use of buccal swabs as a reliable method to detect pesticide exposure in reptiles. Common wall lizards (Podarcis muralis) were divided into control, dermal and oral treatment groups and exposed to different pesticide formulations. Subsequently, buccal swabs were taken and enzymatic activity was analyzed. We were able to confirm the suitability of the method to detect effects of pesticide exposure on the enzymatic level. While exposure to the formulation Roundup Ultramax® didn't match when compared to effects previously observed in situ when compared to other glyphosate based formulations, effects could still be detected. This can be seen as a strong indicator that the active ingredient of a formulation may not always be the mian driver for ecotoxicological effectsat the enzymatic level. At the same time, exposure towards the single formulation Vivando® didn't result in any effects. However, individuals residing in agricultural landscapes will mostly be exposed to pesticide mixes containing different formulations. Our results strongly advocate that buccal swabbing is a reliable minimal invasive method to generate samples for detecting effects of pesticide exposure in reptiles. Due to its easy handling, we believe it will provide new opportunities concerning study designs. • Buccal swabs are a reliable method to detect effects of pesticide exposure. • Dermal and oral exposure pathways can be detected separately. • The Method works well for pesticide mixes and herbicides. • No effects could be detected with very small amounts of pesticide. • Neurotoxic effects could not be observed. [ABSTRACT FROM AUTHOR]

Understanding the mechanisms of clustering in colloids, nanoparticles, and proteins is of significant interest in material science and both chemical and pharmaceutical industries. Recently, using an integral equation theory formalism, Bomont et al. [J. Chem. Phys. 132, 184508 (2010)] studied theoretically the temperature dependence, at a fixed density, of the cluster formation in systems where particles interact with a hard-core double Yukawa potential composed of a short-range attraction and a long-range repulsion. In this paper, we provide evidence that the low-q peak in the static structure factor, frequently associated with the formation of clusters, is a common behavior in systems with competing interactions. In particular, we demonstrate that, based on a thermodynamic self-consistency criterion, accurate structural functions are obtained for different choices of closure relations. Moreover, we explore the dependence of the low-q peak on the particle number density, temperature, and potential parameters. Our findings indicate that enforcing thermodynamic self-consistency is the key factor to calculate both thermodynamic properties and static structure factors, including the low-q behavior, for colloidal dispersions with both attractive and repulsive interactions. Additionally, a simple analysis of the mean number of neighboring particles provides a qualitative description of some of the cluster features. [ABSTRACT FROM AUTHOR]

Organismic drift in lotic waters can have major impact on population dynamics. It is influenced by a variety of interacting abiotic and biotic factors, and species often have evolved specific strategies for drift avoidance and compensation. We studied downstream and upstream movements of larval fire salamanders (Salamandra salamandra) within three first-order streams in Germany using up- and downstream traps. We tested several predictions related to the influence of body size, water flow and inclination on the number of upstream and downstream moving larvae. Larval fire salamanders actively moved upstream in all creeks, however, in much lower numbers than downstream. The total body lengths of upstream and downstream moving larvae did not differ significantly; in contrast, downstream drifting larvae were smaller compared to non-drifting larvae collected randomly from the creeks in-between traps. There was no negative effect of the amount of water flow on larval upward movements, but significantly more larvae drifted downstream with the increasing water flow volume. There was no effect of inclination on the amount of either upstream or downstream movements. Our results indicate that upstream movements are a side product of a principle rheotactic behaviour, which prevents larvae from being drifted downstream. [ABSTRACT FROM AUTHOR]

BACKGROUND: Research on hemorheology is driven in part by its significance in blood diseases and the possible use of hemorheology as a diagnostic tool. However, existing data on blood rheology are limited largely to measurements of steady shear behavior often with varying measurement protocols and insufficient characterization of the physiology. OBJECTIVE: The effects of ex vivo aging and environmental conditions on blood viscosity are investigated to improve standards for hemorheology measurements. METHODS: Measurements on the viscosity of blood from nine healthy donors are obtained and the physiological state of the blood determined. Steady and transient shear measurements are reported as a function of time from withdrawal. The effect of transportation temperature is also assessed. RESULTS: Blood transported at 4 °C may exhibit anomalous viscosity variations for short to intermediate times, as opposed to blood transported at room temperature. A time of approximately 3.0 hours was identified as the maximum time after the initial test that accurate rheological tests can be conducted on blood samples. CONCLUSIONS: Measurement protocol and time limit guidelines are established for conducting accurate rheological measurements on blood. [ABSTRACT FROM AUTHOR]

A broadband soil dielectric spectra retrieval approach (1MHz--2GHz) has been implemented for a layered half space. The inversion kernel consists of a two-port transmission line forward model in the frequency domain and a constitutive material equation based on a power law soil mixture rule (Complex Refractive Index Model--CRIM). The spatially-distributed retrieval of broadband dielectric spectra was achieved with a global optimization approach based on a Shuffled Complex Evolution (SCE) algorithm using the full set of the scattering parameters. For each layer, the broadband dielectric spectra were retrieved with the corresponding parameters thickness, porosity, water saturation and electrical conductivity of the aqueous pore solution. For the validation of the approach, a coaxial transmission line cell measured with a network analyzer was used. The possibilities and limitations of the inverse parameter estimation were numerically analyzed in four scenarios. Expected and retrieved layer thicknesses, soil properties and broadband dielectric spectra in each scenario were in reasonable agreement. Hence, the model is suitable for an estimation of in-homogeneous material parameter distributions. Moreover, the proposed frequency domain approach allows an automatic adaptation of layer number and thickness or regular grids in time and/or space. [ABSTRACT FROM AUTHOR]

In this paper, we propose a novel approach to broadband model relative effective complex permittivity of soils (augmented broadband complex dielectric mixture model). The approach involves a combination of mixture equation and relaxation model. The mixture equation is an extension in frequency domain developed from a volume average approach. The relaxation model aims at integrating polarization effects that would occur over the frequency range under interest. In this framework, the relative effective complex permittivity is computed from a set of parameters including water saturation, porosity, cementation exponent, and relaxation parameters. The proposed model was tested and validated on a new set of data measured over the 1-MHz–3-GHz frequency range on compacted kaolin. The model was fit to the measured spectra with satisfactory agreement in terms of root-square-mean error. Furthermore, the comparison between estimated and experimentally measured water saturation and porosity has shown a good correlation. This indicates the great potential of this new model for monitoring state parameters for applications in geophysics and geotechnics. [ABSTRACT FROM AUTHOR]

Understanding the adsorption of protein and surfactant molecules on hydrophobic surfaces is very important for storage stability and delivery of pharmaceutical liquid formulations as many commonly-used devices, such as drug containers and syringes, have hydrophobic surfaces. Neutron reflectometry is used here to investigate the structure information of the adsorption process of non-ionic surfactant (polysorbate 20) and proteins (monoclonal antibody (mAb) and lysozyme) on polystyrene surfaces. Thickness of adsorbed polysorbate 20 thin film is observed to be ≈21 Å, comparable to the radius of gyration of polysorbate 20 micelles in solution. Although no lysozyme adsorption is observed on the polystyrene surface in low solution pH condition, the mAb can be strongly absorbed on the polystyrene surface with a layer thickness of ≈145 Å. The mAb concentration near the surface is about 135 mg/ml significantly larger than the bulk protein concentration. The differences in adsorption behavior are attributed to different protein interactions with a hydrophobic surface. Further, both surfactants and proteins adsorbed on the polystyrene surfaces can not be rinsed off using pure water. [ABSTRACT FROM AUTHOR]

REFERENCES 1 Armstrong, M., A. Pincot, S. Jariwala, J. Horner, N. Wagner, and A. Beris, "Tensorial formulations for improved thixotropic viscoelastic modeling of human blood", J.: Rheol. 10.1122/8.0000346 2 Dataset 3: Armstrong, M. J., and J. S. Horner, "FEB20 human blood rheology " (2021). 10.17632/s672yykhf2.1 ACKNOWLEDGEMENTS The views expressed herein are those of the authors and do not reflect the position of the United States Military Academy, the Department of the Army, or the Department of Defense. [Extracted from the article]