Structure of Cellulose Ether Affected by Ionic Surfactant and Solvent: A Small-Angle Neutron Scattering Investigation.

Polysaccharides and their derivatives are commonly used in pharmaceutical and agricultural formulations as rheology modifiers. Their performance is related to their conformation in solution, which in turn is affected by other ingredients present in the formulation. This study focuses on modulating the conformation of relatively rigid cellulose chains in aqueous solutions. In particular, we have investigated the nonionic cellulose derivative ethyl(hydroxyethyl)cellulose (EHEC) in water in the presence of the ionic surfactant sodium dodecyl sulfate (SDS) and/or ethanol acting as modulating agents. We have used small angle neutron scattering (SANS) with contrast variation to determine the EHEC chain conformation in the presence of (but not masked by) ethanol and SDS. In dilute and semidilute aqueous solutions, EHEC exhibits worm-like chain conformation due to the rigid cellulose backbone. Addition of ethanol does not impact the polymer conformation to a great extent. Addition of SDS alters the EHEC chain conformation, resulting in polyelectrolyte-like scattering behavior due to repulsive interactions between bound charged micelles which show similar structure as the free SDS micelles in solution (in the absence of polymers). Ethanol affects the polymer + surfactant system primarily by acting on the surfactant (bound on polymer) which, in turn, affects the polymer conformation. At higher ethanol concentrations (20 wt %), EHEC regains the worm-like chain conformation because of the detachment of the bound SDS micelles. To the best of our knowledge, this is the only study providing details on chain conformation of the rigid polymer EHEC in dilute or semidilute aqueous solutions in the presence of surfactant and alcohol and one of very few papers utilizing SANS for the characterization of polymer + surfactant + water + alcohol interactions. Such fundamental understanding of interactions and structure in multicomponent mixtures supports the design of industrial formulations.

Salt and Temperature Effects on Xanthan Gum Polysaccharide in Aqueous Solutions.

Xanthan gum (XG) is a carbohydrate polymer with anionic properties that is widely used as a rheology modifier in various applications, including foods and petroleum extraction. The aim was to investigate the effect of Na+, K+, and Ca2+ on the physicochemical properties of XG in an aqueous solution as a function of temperature. Huggins, Kraemer, and Rao models were applied to determine intrinsic viscosity, [η], by fitting the relative viscosity (ηrel) or specific viscosity (ηsp) of XG/water and XG/salt/water solutions. With increasing temperature in water, Rao 1 gave [η] the closest to the Huggins and Kraemer values. In water, [η] was more sensitive to temperature increase (~30% increase in [η], 20-50 °C) compared to salt solutions (~15-25% increase). At a constant temperature, salt counterions screened the XG side-chain-charged groups and decreased [η] by up to 60% over 0.05-100 mM salt. Overall, Ca2+ was much more effective than the monovalent cations in screening charge. As the salt valency and concentration increased, the XG coil radius decreased, making evident the effect of shielding the intramolecular and intermolecular XG anionic charge. The reduction in repulsive forces caused XG structural contraction. Further, higher temperatures led to chain expansion that facilitated increased intermolecular interactions, which worked against the salt effect.

Phase Behavior and Structure of Poloxamer Block Copolymers in Protic and Aprotic Ionic Liquids.

Ionic liquids are promising media for self-assembling block copolymers in applications such as energy storage. A robust design of block copolymer formulations in ionic liquids requires fundamental knowledge of their self-organization at the nanoscale. To this end, here, we focus on modeling two-component systems comprising a Poly(ethylene oxide)-poly (propylene oxide)-Poly(ethylene oxide) (PEO-PPO-PEO) block copolymer (Pluronic P105: EO37PO58EO37) and room temperature ionic liquids (RTILs): protic ethylammonium nitrate (EAN), aprotic ionic liquids (1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), or 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4). Rich structural polymorphism was exhibited, including phases of micellar (sphere) cubic, hexagonal (cylinder), bicontinuous cubic, and lamellar (bilayer) lyotropic liquid crystalline (LLC) ordered structures in addition to solution regions. The characteristic scales of the structural lengths were obtained using small-angle X-ray scattering (SAXS) data analysis. On the basis of phase behavior and structure, the effects of the ionic liquid solvent on block copolymer organization were assessed and contrasted to those of molecular solvents, such as water and formamide.

Rhamnolipid Micellization and Adsorption Properties.

Biosurfactants are naturally occurring amphiphiles that are being actively pursued as alternatives to synthetic surfactants in cleaning, personal care, and cosmetic products. On the basis of their ability to mobilize and disperse hydrocarbons, biosurfactants are also involved in the bioremediation of oil spills. Rhamnolipids are low molecular weight glycolipid biosurfactants that consist of a mono- or di-rhamnose head group and a hydrocarbon fatty acid chain. We examine here the micellization of purified mono-rhamnolipids and di-rhamnolipids in aqueous solutions and their adsorption on model solid surfaces. Rhamnolipid micellization in water is endothermic; the CMC (critical micellization concentration) of di-rhamnolipid is lower than that of mono-rhamnolipid, and both CMCs decrease upon NaCl addition. Rhamnolipid adsorption on gold surface is mostly reversible and the adsorbed layer is rigid. A better understanding of biosurfactant self-assembly and adsorption properties is important for their utilization in consumer products and environmental applications.

Structure and Interactions in Perfluorooctanoate Micellar Solutions Revealed by Small-Angle Neutron Scattering and Molecular Dynamics Simulations Studies: Effect of Urea.

The self-assembly of surfactants in aqueous solution can be modulated by the presence of additives including urea, which is a well-known protein denaturant and also present in physiological fluids and agricultural runoff. This study addresses the effects of urea on the structure of micelles formed in water by the fluorinated surfactant perfluoro-n-octanoic acid ammonium salt (PFOA). Analysis of small-angle neutron scattering (SANS) experiments and atomistic molecular dynamics (MD) simulations provide consensus strong evidence for the direct mechanism of urea action on micellization: urea helps solvate the hydrophobic micelle core by localizing at the surface of the core in the place of some water molecules. Consequently, urea decreases electrostatic interactions at the micelle shell, changes the micelle shape from prolate ellipsoid to sphere, and decreases the number of surfactant molecules associating in a micelle. These findings inform the interactions and behavior of surface active per- and polyfluoroalkyl substances (PFAS) released in the aqueous environment and biota.

Controlling the self-assembly of perfluorinated surfactants in aqueous environments.

Surface active per- and polyfluoroalkyl substances (PFAS) released in the environment generate great concern in the US and worldwide. The sequestration of PFAS amphiphiles from aqueous media can be limited by their strong tendency to form micelles that plug the pores in the adsorbent material, rendering most of the active surface inaccessible. A joint experimental and simulation approach has been used to investigate the structure of perfluorooctanoate ammonium (PFOA) micelles in aqueous solutions, focusing on the understanding of ethanol addition on PFOA micelle formation and structure. Structurally compact and slightly ellipsoidal in shape, PFOA micelles in pure water become more diffuse with increasing ethanol content, and break into smaller PFOA clusters in aqueous solutions with high ethanol concentration. A transition from a co-surfactant to a co-solvent behavior with the increase of ethanol concentration has been observed by both experiments and simulations, while the latter also provide insight on how to achieve co-solvent conditions with other additives. An improved understanding of how to modulate PFAS surfactant self-assembly in water can inform the fate and transport of PFAS in the environment and the PFAS sequestration from aqueous media.

Perfluorooctanoate in Aqueous Urea Solutions: Micelle Formation, Structure, and Microenvironment.

Fluorinated surfactants are used in a wide range of applications that involve aqueous solvents incorporating various additives. The presence of organic compounds such as urea is expected to affect the self-assembly of fluorinated surfactants, however, very little is known about this. We investigated the effect of urea on the micellization in water of the common fluorinated surfactant ammonium perfluorooctanoate (APFO), and on the structure and microenvironment of the micelles that APFO forms. Addition of urea to aqueous APFO solution decreased the critical micellization concentration (CMC) and increased the counterion dissociation. The observed increase in surface area per APFO headgroup and decrease in packing density at the micelle surface suggest the localization of urea at the micelle surface in a manner that reduces headgroup repulsions. Micropolarity data further support this picture. The results presented here indicate that significant differences exist between urea effects on fluorinated surfactant and on hydrocarbon surfactant micellization in aqueous solution. For example, the CMC of sodium dodecyl sulfate (SDS) increased with urea addition, while the increase in surface area per headgroup and packing density of SDS with urea addition are much lower than those observed for APFO. This study informs fluorinated surfactant fate and transport in the environment, and also applications involving aqueous media in which urea or similar additives are present.

Dissolution of Cellulosic Fibers: Impact of Crystallinity and Fiber Diameter.

With the aim of informing the selection of biomass pretreatment options and to assist in interpreting experimental results from different biomass/solvent combinations, this study addresses the impact of crystallinity and size on the kinetics of semicrystalline cellulose fiber swelling and dissolution. To this end, a newly developed phenomenological model is utilized that accounts for the role of decrystallization and disentanglement as two rate-determinant steps in the cellulose dissolution process. Although fibers with lower crystallinity swell more and faster, the degree of crystallinity does not affect the dissolution rate. Fibers of smaller diameter swell more and become amorphous faster. When decrystallization is important, the solubility of thinner fibers increases more with a reduction in the crystallinity compared to the diameter. However, when the dissolution is controlled by chain disentanglement, or in the case of dissolution of fibers having larger diameters, milling the fibers to reduce the particle size could increase the solubility.

Nanoparticles in ionic liquids: interactions and organization.

Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.

Effects of Ionic Liquids on the Cylindrical Self-Assemblies Formed by Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Block Copolymers in Water.

Aiming at the fundamental understanding of solvent effects in amphiphilic polymer systems, we considered poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers in water mixed with an ionic liquid-ethylammonium nitrate (EAN), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), or 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4)-and we investigated the hexagonal lyotropic liquid crystal structures by means of small-angle X-ray scattering (SAXS). At 50% polymer, the hexagonal structure (cylinders of self-assembled block copolymer) was maintained across the solvent mixing ratio. The effects of the ionic liquids were reflected in the characteristic length scales of the hexagonal structure and were interpreted in terms of the location of the ionic liquid in the self-assembled block copolymer domains. The protic ionic liquid EAN was evenly distributed within the aqueous domains and showed no affinity for the interface, whereas BMIMPF6 preferred to swell PEO and was located at the interface so as to reduce contact with water. BMIMBF4 was also interfacially active, but to a lesser extent.

Carboxymethyl hydroxypropyl guar gum physicochemical properties in dilute aqueous media.

We investigate carboxymethyl hydroxypropyl guar gum (CMHPG) solution properties in water and NaCl, KCl, and CaCl2 aqueous solutions. The Huggins, Kraemer, and Rao models were applied by fitting specific and relative viscosity of CMHPG/water and CMHPG/salt/water to determine the intrinsic viscosity [η]. The Rao models yielded better results (R2 = 0.779-0.999) than Huggins and Kraemer equations. [η] decreased up to 84% in salt solution over the range 0.9-100 mM compared to water. Salt effects screened the CMHPG charged side groups chains leading to a compacted structure. In 0.9 mM NaCl(aq), the hydrodynamic coil radius (Rcoil) was 28% smaller and 45% smaller in 100 mM NaCl solution relative to water. Similar decreases were seen in KCl and CaCl2 solutions. KCl and CaCl2 were more effective than NaCl. CMHPG is salt-tolerant and shows comparatively less viscosity change than native guar gum, with modest reduced viscosity increases with CMHPG dilution at all salt concentrations. The electrostatic interactions were effective up to 100 mM salt. The activation energy of viscous flow for CMHPG solutions was computed and compared to measured xanthan gum and several literature values. These data show that the barrier to CMHPG flow is higher than for xanthan gum.

Self-assembled block copolymer-nanoparticle hybrids: interplay between enthalpy and entropy.

The dispersion of nanoparticles in ordered block copolymer nanostructures can provide control over particle location and orientation, and pave the way for engineered nanomaterials that have enhanced mechanical, electrical, or optical properties. Fundamental questions pertaining to the role of enthalpic and entropic particle-polymer interactions remain open and motivate the present work. We consider here a system of 10.6 nm silica nanoparticles (NPs) dispersed in ordered cylinders formed by hydrated poly(ethylene oxide)-poly(propylene oxide) block copolymers (Pluronic P105: EO(37)PO(56)EO(37)). Protonation of silica was used to vary the NP-polymer enthalpic interactions, while polar organic solvents (glycerol, DMSO, ethanol, and DMF) were used to modulate the NP-polymer entropic interactions. The introduction of deprotonated NPs in the place of an equal mass of water did not affect the lattice parameter of the PEO-PPO-PEO block copolymer hexagonal lyotropic liquid crystalline structures. However, the dispersion of protonated NPs led to an increase in the lattice parameter, which was attributed to stronger NP-polymer hydrogen bonding (enthalpic) interactions. Dispersion of protonated NPs into cylindrical structures formed by Pluronic P105 in 80/20 water/organic solvents does not influence the lattice parameter, different from the case of protonated NP in plain water. Organic solvents appear to screen the NP-polymer hydrogen bonding interactions.

Xanthan gum in aqueous solutions: Fundamentals and applications.

Xanthan gum is a naturally occurring polysaccharide obtained from Xanthomonas campestris. The xanthan gum backbone consists of ß-d-glucose linked like in cellulose. The trisaccharide ß-d-mannose-(1-4)-α-d-glucuronic acid-(1-2)-α-d-mannose is linked to O(3) position of every other glucose residue. Ketal bonds link pyruvic acid residues to approximately half of the terminal mannose residues. The terminal mannose residues also carry acetate groups. Xanthan gum is used as a thickening, stabilizing, or suspending agent in various applications, e.g., food, pharmaceutical, cosmetic, and petroleum extraction. The performance of xanthan gum is based on its macromolecular conformation and association in solution and at interfaces. In water, xanthan gum undergoes conformational transitions from helix to random coil, in response to stimuli such as pH, ionic strength, temperature, and shear. This review presents fundamental information on the behavior of xanthan gum in aqueous media, at conditions and in the presence of additives which are of interest to applications that benefit from viscosity changes such as in oil and gas extraction. Effects on xanthan gum aqueous solutions of pH, electrolytes, changes in temperature, and added natural polysaccharides or synthetic polymers are highlighted. Such information is useful in the formulation of products and the design of processes involving xanthan gum and related polysaccharide polymers.

Structure and composition of mixed micelles formed by nonionic block copolymers and ionic surfactants in water determined by small-angle neutron scattering with contrast variation.

HYPOTHESIS: Complex fluids comprising polymers and surfactants exhibit interesting properties which depend on the overall composition and solvent quality. The ultimate determinants of the macroscopic properties are the nano-scale association domains. Hence it is important to ascertain the structure and composition of the domains, and how they respond to the overall composition. EXPERIMENTS: The structure and composition of mixed micelles formed in aqueous solution between poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers (Pluronics or Poloxamers) and the ionic surfactant sodium dodecylsulfate (SDS) are determined from an analysis of small-angle neutron scattering (SANS) intensity data obtained at different contrasts. Different polymers and concentrations have been probed. FINDINGS: The SDS + Pluronic mixed micelles include polymer and some water in the micelle core that is formed primarily by alkyl chains. This is different than what was previously reported, but is consistent with a variety of experimental observations. This is the first report on the structure of SDS + Pluronic P123 (EO19PO69EO19) assemblies. The effects on the mixed micelle structure and composition of the surfactant concentration and the polymer hydrophobicity are discussed here in the context of interactions between the different components.

GenX in water: Interactions and self-assembly.

2,3,3,3-tetrafluoro-2-(heptafluoropropoxy) propanoate, a.k.a. "GenX", is a surfactant introduced as a safer alternative to replace perfluorooctanoate (PFOA) in the manufacturing of fluorinated polymers, however, GenX is shown to cause adverse health effects similar to, or even worse than, those of the legacy PFOA. With an overarching goal to understand the behavior of GenX molecules in aqueous media, we report here on GenX micelle formation and structure in aqueous solutions, on the basis of results obtained from a combination of experimental techniques such as surface tension, fluorescence, viscosity, and small-angle neutron scattering (SANS), and molecular dynamics (MD) simulations. To our best knowledge, this is the first report on GenX micelles. The critical micelle concentration (CMC) of GenX ammonium salt in water is 175 mM. GenX forms small micelles with association number 6-8 and 10 Å radius. GenX molecules prefer to align along the micelle surface, and the ether oxygen of GenX has very little interaction with and exposure to water. Information on the surfactant and interfacial properties of GenX is crucial, since such properties are manifestations of interactions between GenX molecules and between GenX and water molecules and, in turn, the amphiphilic character of GenX dictates its fate and transport in the aqueous environment, its interactions with various biomolecules, and its binding to adsorbent materials.

Well-defined homopolypeptides, copolypeptides, and hybrids of poly(l-proline).

l-Proline is the only, out of 20 essential, amino acid that contains a cyclized substituted α-amino group (is formally an imino acid), which restricts its conformational shape. The synthesis of well-defined homo- and copolymers of l-proline has been plagued either by the low purity of the monomer or the inability of most initiating species to polymerize the corresponding N-carboxy anhydride (NCA) because they require a hydrogen on the 3-N position of the five-member ring of the NCA, which is missing. Herein, highly pure l-proline NCA was synthesized by using the Boc-protected, rather than the free amino acid. The protection of the amine group as well as the efficient purification method utilized resulted in the synthesis of highly pure l-proline NCA. The high purity of the monomer and the use of an amino initiator, which does not require the presence of the 3-N hydrogen, led for the first time to well-defined poly(l-proline) (PLP) homopolymers, poly(ethylene oxide)-b-poly(l-proline), and poly(l-proline)-b-poly(ethylene oxide)-b-poly(l-proline) hybrids, along with poly(γ-benzyl-l-glutamate)-b-poly(l-proline) and poly(Boc-l-lysine)-b-poly(l-proline) copolypeptides. The combined characterization (NMR, FTIR, and MS) that results for the l-proline NCA revealed its high purity. In addition, all synthesized polymers exhibit high molecular and compositional homogeneity.

Micellization of alkyl-propoxy-ethoxylate surfactants in water-polar organic solvent mixtures.

The effects of cosolvents (glycerol, ethanol, and isopropanol) on the self-assembly of novel alkyl-propoxy-ethoxylate surfactants in aqueous solutions have been investigated with a focus on the (i) quantification of solvent effects on the critical micelle concentration (cmc), (ii) free-energy contributions to micellization, (iii) local environment in the micellar solution, and (iv) structure of the micelles. The introduction of the polar organic solvents considered in this work into water decreases cohesive forces in the solvent mixture, resulting in an increase in the solubility of the surfactant molecules. As a result, micelle formation becomes less favorable and the cmc increases. The contribution of the cosolvent to the free energy of micellization is positive, and the data for different mixed solvents collapse onto a single straight line when plotted versus a function of the solubility parameters of the surfactant alkyl chains and the mixed solvents. The behavior of the poly(propylene oxide) part of the alkyl-propoxy-ethoxylate surfactants is hydrophilic, albeit less so in the ethanol-water mixed solvent than in plain water. Pyrene fluorescence emission I(1)/I(3) data suggest that the microenvironment in micellar solutions is affected mainly by the cosolvent concentration, not the surfactant degree of ethoxylation. Small-angle X-ray scattering data for both water and ethanol-water surfactant solutions are consistent with oblate ellipsoid micelles and reveal that the introduction of 20% ethanol decreases the micelle long axis by 10-15%.

Biosurfactants, natural alternatives to synthetic surfactants: Physicochemical properties and applications.

Biosurfactants comprise a wide array of amphiphilic molecules synthesized by plants, animals, and microbes. The synthesis route dictates their molecular characteristics, leading to broad structural diversity and ensuing functional properties. We focus here on low molecular weight (LMW) and high molecular weight (HMW) biosurfactants of microbial origin. These are environmentally safe and biodegradable, making them attractive candidates for applications spanning cosmetics to oil recovery. Biosurfactants spontaneously adsorb at various interfaces and self-assemble in aqueous solution, resulting in useful physicochemical properties such as decreased surface and interfacial tension, low critical micellization concentrations (CMCs), and ability to solubilize hydrophobic compounds. This review highlights the relationships between biosurfactant molecular composition, structure, and their interfacial behavior. It also describes how environmental factors such as temperature, pH, and ionic strength can impact physicochemical properties and self-assembly behavior of biosurfactant-containing solutions and dispersions. Comparison between biosurfactants and their synthetic counterparts are drawn to illustrate differences in their structure-property relationships and potential benefits. Knowledge of biosurfactant properties organized along these lines is useful for those seeking to formulate so-called green or natural products with novel and useful properties.

Association between Nonionic Amphiphilic Polymer and Ionic Surfactant in Aqueous Solutions: Effect of Polymer Hydrophobicity and Micellization.

The interaction in aqueous solutions of surfactants with amphiphilic polymers can be more complex than the surfactant interactions with homopolymers. Interactions between the common ionic surfactant sodium dodecyl sulfate (SDS) and nonionic amphiphilic polymers of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) type have been probed utilizing a variety of experimental techniques. The polymer amphiphiles studied here are Pluronic F127 (EO100PO65EO100) and Pluronic P123 (EO19PO69EO19), having the same length PPO block but different length PEO blocks and, accordingly, very different critical micellization concentrations (CMC). With increasing surfactant concentration in aqueous solutions of fixed polymer content, SDS interacts with unassociated PEO-PPO-PEO molecules to first form SDS-rich SDS/Pluronic assemblies and then free SDS micelles. SDS interacts with micellized PEO-PPO-PEO to form Pluronic-rich SDS/Pluronic assemblies, which upon further increase in surfactant concentration, break down and transition into SDS-rich SDS/Pluronic assemblies, followed by free SDS micelle formation. The SDS-rich SDS/Pluronic assemblies exhibit polyelectrolyte characteristics. The interactions and mode of association between nonionic macromolecular amphiphiles and short-chain ionic amphiphiles are affected by the polymer hydrophobicity and its concentration in the aqueous solution. For example, SDS binds to Pluronic F127 micelles at much lower concentrations (~0.01 mM) when compared to Pluronic P123 micelles (~1 mM). The critical association concentration (CAC) values of SDS in aqueous PEO-PPO-PEO solutions are much lower than CAC in aqueous PEO homopolymer solutions.

Application of fluorescence spectroscopy to quantify shear-induced protein conformation change.

Rapid and robust methods are required to quantify the effect of hydrodynamic shear on protein conformation change. We evaluated such strategies in this work and found that the binding of the fluorescent probe 4,4'-dianilino-1,1'-binaphthyl-5,5'-disulfonic acid (bis-ANS) to hydrophobic pockets in the blood protein von Willebrand factor (VWF) is enhanced upon the application of fluid shear to the isolated protein. Significant structural changes were observed when the protein was sheared at shear rates >or= 6000/s for approximately 3.5 min. The binding of bis-ANS to multimeric VWF, but not dimeric VWF or control protein bovine serum albumin, was enhanced upon fluid shear application. Thus, high-molecular-weight VWF is more susceptible to conformation change upon tensile loading. Although bis-ANS itself did not alter the conformation of VWF, it stabilized protein conformation once it bound the sheared molecule. Bis-ANS binding to VWF was reduced when the sheared protein was allowed to relax before dye addition. Taken together with functional data in the literature, our results suggest that shear-induced conformation changes in VWF reported by bis-ANS correlate well with the normal function of the protein under physiological/pathological fluid flow conditions. Further, this study introduces the fluorescent dye bis-ANS as a tool that may be useful in studies of shear-induced protein conformation change.