With a Gemini surfactant architecture and cationic 4-aminopyridinium headgroups, octenidine dihydrochloride (OCT) is one of the most potent antimicrobial actives. However, how its unique molecular architecture orchestrates interactions with lipopolysaccharides (LPS), a major constituent of the Gram-negative bacteria outer membrane, is not well understood. To probe OCT-LPS molecular interactions, we have studied the morphology and structure of nanoaggregates co-assembled between OCT and LPS. Furthermore, OCT was compared with Alkyl 8-10-8, an architecturally analogous Gemini surfactant with quaternary ammonium headgroups. Small-angle neutron scattering (SANS) revealed that, upon addition of 1.2 CMC OCT in the presence of 2.5 mM Ca2+, worm-like LPS-smooth micelles (of a radius ∼11.8 nm and a length ∼300 nm) transformed into longer rods with an ellipsoidal cross-section (9.4 nm × 29.3 nm) up to 3 µm in length. In contrast, co-assembly with 1.2 CMC Alkyl 8-10-8 led to a nano-aggregate mixture of lamellae and globules. Complementary cryo-TEM, dynamic light scattering, and zeta potential measurements further informed on the LPS-Gemini co-assembled nanostructures. To reconcile these observations, we suggest that the 4-aminopyridinium headgroups of OCT bind to anionic Lipid A phosphates in LPS through electrostatic, H-bonding, and π-system interactions, displacing bridging Ca2+ ions. In contrast, the dimethylammonium headgroups of Alkyl 8-10-8 would undergo dynamic exchange with the Ca2+ bridging between Lipid A phosphates, instead of binding to Ca2+, evident from disintegration of the worm-like aggregates. These findings provide mechanistic insights into the molecular interactions mediated by the OCT architecture, underpinning binding and subsequent disruption of the LPS-rich outer membrane leaflet in Gram-negative bacteria, with implications to future rational design of antimicrobial agents.
Erucamide is known to play a critical role in modifying polymer fiber surface chemistry and morphology. However, its effects on fiber crystallinity and mechanical properties remain to be understood. Here, synchrotron nanofocused X-ray Diffraction (nXRD) revealed a bimodal orientation of the constituent polymer chains aligned along the fiber axis and cross-section, respectively. Erucamide promoted crystallinity in the fiber, leading to larger and more numerous lamellae crystallites. The nXRD nanostructual characterization is complemented by single-fiber uniaxial tensile tests, which showed that erucamide significantly affected fiber mechanical properties, decreasing fiber tensile strength and stiffness but enhancing fiber toughness, fracture strain, and ductility. To correlate these single-fiber nXRD and mechanical test results, we propose that erucamide mediated slip at the interfaces between crystallites and amorphous domains during stress-induced single-fiber crystallization, also decreasing the stress arising from the shear displacement of microfibrils and deformation of the macromolecular network. Linking the single-fiber crystal structure with the single-fiber mechanical properties, these findings provide the direct evidence on a single-fiber level for the role of erucamide in enhancing fiber "softness".
We investigate the structure and interactions of a model anionic/amphoteric mixed surfactant micellar system, namely, sodium dodecyl sulfate (SDS) and N,N-dimethyl-dodecylamine N-oxide (DDAO), employing SANS, FTIR, DLS, and pH measurements, in the range 0.1-100 mM total surfactant concentration and 0-100% DDAO. Increasing surfactant concentration is found to elongate the prolate ellipsoid micelles (R-Polar similar to 25-40 angstrom), accompanied by up to a 6-fold increase in micellar charge. The surfactant synergy, in terms of micellar charge and size, diffusion coefficient, solution pH, and headgroup interactions, was found to vary with concentration. At lower concentrations (<= 50 mM), the SDS-DDAO ratio of maximum synergy is found to be asymmetric (at 65-85% DDAO), which is rationalized using regular solution theory, suggesting an equilibrium between Na+ dissociation, DDAO protonation, and counterion concentration. At higher concentrations, maximum synergy shifts toward the equimolar ratio. Overall, our study expands and unifies previous reports, providing a comprehensive understanding for this model, synergetic mixed micellar system.
We investigate the role of substrate surface energy on the removal of triacylglycerol (TAG) films by a model surfactant solution under laminar flow conditions. We select a mixture of 0.5:0.3:0.2 triolein:tripalmitin:tristearin mass fraction as a model TAG, yielding a solid 'fat' film, and expose it to a micellar aqueous surfactant solution, flowing at rate 250 μLmin−1 (corresponding to a velocity of 1.4 cms−1), within a microfluidic channel. We employ a combination of optical and atomic force microscopy, profilometry, X-ray photoelectron and infrared spectroscopy, and contact angle measurements to characterise a range of model substrates, the TAG films, and their removal over time. Our experimental data show a clear dependence of the TAG removal time with surface energy and, in particular, with the polar component of the surface energy, γSFEP. TAG films on very hydrophilic surfaces, with high γSFEP (>20 mJ/m2), are generally found to delaminate rapidly, while those on lower γSFEP surfaces are progressively eroded over longer timescales. An approximately inverse linear relation is found between γSFEP and removal time τ, which holds for a large range of surfaces including glass, silicon and plastics, and various surface treatments.
We report the coupling of dynamic light scattering (DLS) in microfluidics, using a contact-free fibre-optic system, enabling the under-flow characterisation of a range of solutions, dispersions, and structured fluids. The system is evaluated and validated with model systems, specifically micellar and (dilute) polymer solutions, and colloidal dispersions of different radii (∼1-100 nm). A systematic method of flow-DLS analysis is examined as a function of flow velocity (0-16 cm s-1), and considerations of the relative contribution of 'transit' and 'Brownian' terms enable the identification of regions where (i) a quiescent approximation suffices, (ii) the flow-DLS framework holds, as well as (iii) where deviations are found, until eventually (iv) the convection dominates. We investigate practically relevant, robust setups, namely that of a capillary connected to microdevice, as well as direct measurement on a glass microdevice, examining the role of capillary dimensions and challenges of optical alignment. We conclude with a demonstration of a continuous flow measurement of a binary surfactant/salt solution, whose micellar dimensions vary with composition, characterised with hundreds of data points (every ∼5 s) and adequate statistics, within a few minutes.
Hypothesis: Neutral amphiphilic PEG-g-PVAc co-polymer (a "tardigrade" polymer consisting of a hydrophilic polyethylene glycol, PEG, backbone with hydrophobic polyvinyl acetate, PVAc, grafts) can form complexes at the air-water interface with cationic dodecyltrimethylammonium bromide (DTAB) via self-assembly. Compared to anionic SDS, cationic DTAB headgroups are expected to interact strongly with the negatively charged OH- groups from the partial dissociation of the PVAc grafts. We anticipate a transition from synergistic to competitive behaviour, which is expected to be dependent on the surfactant structural characteristics and concentration. Experiments: DTAB/PEG-g-PVAc mixtures were investigated using a combination of dynamic and equilibrium surface tension measurements, neutron reflectivity (NR) at the air-water interface, and foaming tests. We varied the concentrations of both the DTAB (0.05 to 5 critical micelle concentration, cmc) and that of PEG-g-PVAc (0.2 and 2 critical aggregation concentration, cac). Findings: Our results show that the interfacial interactions between DTAB and PEG-g-PVAc were both synergistic and antagonistic, depending sensitively on the surfactant concentration. At DTAB concentrations below its cmc, a pronounced cooperative adsorption behaviour was likely driven by the hydrophobic interactions between the DTAB tail and the PVAc grafts and the attraction between the DTAB headgroups and the partially dissociated -O- groups in the partially hydrolysed PVAc grafts, forming a mixed layer. This synergistic adsorption behaviour transitioned to a competitive adsorption behaviour at DTAB concentrations above its cmc, leading to polymer-surfactant partition, forming a "hanging" polymer layer underlying a surfactant monolayer at the interface. We postulate that DTAB/PEG-g-PVAc complexation in the bulk contributed to partial depletion of the mixture from the interface. We therefore consider this polymer/surfactant system to be a moderately interacting system at the air-water interface. No discernible differences in the foaming behaviour were observed between the DTAB/PEG-g-PVAc systems and the pure surfactant. Our results suggest that surfactant headgroup characteristics (particularly charges) were crucial in determining the structure and composition of polymer-surfactant complexes at the air-water interface, as well as the foamability and foam stability, whilst the coexistence of the synergistic and competitive adsorption behaviour is attributed to the unique architecture of the tardigrade polymer with amphiphilicity and partial charge, facilitating different surfactant-polymer interactions at different DTAB concentrations. (C) 2021 Elsevier Inc. All rights reserved.
Usually, to characterize bacterial cells’ susceptibility to antimicrobials, basic microbiology techniques such as serial dilutions or disk assays are used. In this work, we present an approach focused on combining static light scattering (SLS) and ultra-/small angle X-ray scattering (USAXS/SAXS). This approach was used to support microbiology techniques, with the aim of understanding the structural changes caused to bacteria when they are exposed to different stresses like pH, oxidation, and surfactants. Using USAXS/SAXS and SLS data, we developed a detailed multiscale model for a Gram-positive bacterium, S. epidermidis, and we extracted information regarding changes in the overall size and cell thickness induced by different stresses (i.e., pH and hydrogen peroxide). Increasing the concentration of hydrogen peroxide leads to a progressive reduction in cell wall thickness. Moreover, the concomitant use of pH and hydrogen peroxide provides evidence for a synergy in inhibiting the S. epidermidis growth. These promising results will be used as a starting base to further investigate more complex formulations and improve/refine the data modeling of bacteria in the small angle scattering regime.
We investigate the phase behavior of model ternary triacylglycerol blends, comprising triolein (C57H104O6, OOO), tripalmitin (C51H98O6, PPP) and tristearin (C57H110O6, SSS), building upon extensive characterisation of single and binary mixtures, in order to rigorously map the thermal transitions of model natural 'fats'. A combination of calorimetry, X-ray diffraction, and FTIR spectroscopy is employed to determine crystallisation and melting temperatures and identify the corresponding phases in the complex ternary system. We recover the eutectic behaviour of SSS-PPP blends and the invariability of OOO neat transitions, and resolve the complex β' + β ternary surface, reflecting the roles of unsaturation and polymorphism of its constituents. Our results provide a representation of the OOO:PPP:SSS:temperature phase behaviour into a triangular prism, consistent with binary pair-wise data, which can inform a range of food science, cosmetic, pharmaceutical and cleaning applications that depend strongly on the physical-chemistry of such multicomponent 'triglycerides'.
We investigate the effect of micrometer-scale surface wrinkling on the attachment and proliferation of model bacteria (Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli K12) and fungi (Candida albicans). Specifically, sinusoidal (1D), checkerboard (C), and herringbone (H) patterns were fabricated by mechanical wrinkling of plasma-oxidized polydimethylsiloxane (PDMS) bilayers and contrasted with flat (F) surfaces. Microbial deformation and orientation were found to correlate with the aspect ratio and commensurably with surface pattern dimensions and local pattern order. Significantly, the proliferation of P. aeruginosa could be described by a linear scaling between bacterial area coverage and available surface area, defined as a fraction of the line integral along each profile with negative curvature. However, in the early stages of proliferation (up to 6 h examined), that C and H patterns disrupt the spatial arrangement of bacteria, impeding proliferation for several hours and reducing it (by ∼50%) thereafter. Our findings suggest a simple framework to rationalize the impact of micrometer-scale topography on microbial action and demonstrate that multiaxial patterning order provides an effective strategy to delay and frustrate the early stages of bacterial proliferation.
We examine the solution structures in a mixed surfactant system of sodium dodecyl sulfate (SDS) and N,N-dimethyldodecylamine N-oxide (DDAO) in water, on both sides of the two-phase boundary, employing dynamic light scattering, small-angle neutron scattering, and Fourier transform infrared spectroscopy. The precipitate phase boundary was accessed by lowering pH to 8, from its floating pH 9.5 value, and was experimentally approached from the monomeric and micellar regions in three ways: at fixed DDAO or SDS concentrations and at a fixed (70:30) SDS:DDAO molar ratio. We characterize the size, shape, and interactions of micelles, which elongate approaching the boundary, leading to the formation of disk-like aggregates within the biphasic region, coexisting with micelles and monomers. Our data, from both monomeric and micellar solutions, indicate that the two phase structures formed are largely pathway-independent, with dimensions influenced by both pH and mixed surfactant composition. Precipitation occurs at intermediate stoichiometries with a similar SDS:DDAO ratio, whereas asymmetric stoichiometries form a re-entrant transition, returning to the mixed micelle phase. Overall, our findings demonstrate the effect of stoichiometry and solution pH on the synergistic interaction of mixed surfactants and their impact on phase equilibrium and associated micellar and two-phase structures.
Spray-dried detergent granules have a complex and multi-scale structure, in which submicron sized crystals of inorganic salts along with multi-lamellar stacks of surfactant molecules are dispersed within a matrix phase. In this study, two model formulations based on sodium linear alkylbenzene sulphonate (NaLAS) and sodium sulphate were used to investigate the molecular structure of stacked lamellae. The parameters of lamellar d-spacing, bilayer thickness (dHH) and water layer thickness (dW) were determined using small-angle X-ray scattering. Four sets of lamellae were detected in nil-silicate detergent powders conditioned at 33 % RH (relative humidity). The exposure of these samples to a higher RH level (75 %) resulted in a reduced number of coexisting lamellar phases by two. This was accompanied by an increase in lamellar d-spacings and a considerable reduction in bilayer thicknesses (dHH). The reduction in number of sets of lamellae was explained by an increase in the fluidity of the lamellar phases and disappearance of water-poor solid polymorphs. This was consistent with the results of FTIR for nil-silicate samples, indicating an increase in the conformational disorder of the alkyl chains at a higher RH value. Interestingly, in the presence of sodium silicate the lamellar phases display a greater degree of swelling at a relatively low RH value (33 % RH) as compared with those in the absence of sodium silicate. Nonetheless, the thickness of water layer was found to slightly decrease at a higher RH (75 %), which was attributed to the moisture-induced glass transition and kosmotropic effect of sodium silicates.
The interactions between a model anionic and amphoteric surfactant pair in aqueous solution are examined as a function of composition, at floating and fixed pH, employing a combination of tensiometry, regular solution theory analysis, and FTIR spectroscopy. An extensive series of pure and mixed ratios of sodium dodecyl sulfate (SDS) and N,N-dimethyldodecylamine N-oxide (DDAO), ranging from 0.0016 to 100 mM, yielding 77 data points below and above the critical micelle concentrations (CMC), is investigated. Compared to either pure surfactant solutions, the CMC of mixed SDS:DDAO solutions is found to decrease by up to 20-fold, and the surface tension (?) at CMC down to <^> 23 mN/m. At all concentrations, the most prominent effects are observed at equimolar SDS:DDAO ratios. Further, the pH of mixed micellar solutions is found to increase with respect to the pure surfactant solutions (from <^> 7 up to <^> 9.5), which is attributed to the enhanced protonation of DDAO in the presence of SDS, and supported by FTIR frequency shifts of isolated O-H stretching vibrations. Vibrational responses from CH2 stretching of the methylene tails, and the S-O stretching modes for the sulfate headgroups indicate strong lateral interaction and enhanced packing between SDS and DDAO. From regular solution theory analysis of tensiometry data, the molecular interaction parameters are found to have a larger magnitude (i.e., more negative) at the interface as compared to within micelles. At fixed solution pH, a decrease from pH 9.5 to 7.5 results in minimal changes in both interfacial and micellar parameters, indicating the intrinsic origin of these pairwise interactions. Overall, our findings demonstrate a pronounced synergistic interaction between SDS and DDAO, arising from diminished electrostatic and steric repulsions in, respectively, SDS and DDAO, accompanied by enhanced lateral surfactant packing.
Hypothesis: Despite the widespread industrial usage of erucamide as a slip additive to modify polymer surface properties, a controversy appears to have persisted regarding the nanostructure of erucamide surface layers, particularly the molecular orientation at the outermost layer. The erucamide nanostructure and molecular orientation, along with its surface coverage, hydrophobicity, and adhesive response, can be tuned by simply varying the erucamide concentration in the solution from which the spin coated layer is prepared. Experiments: Synchrotron X-ray reflectivity (XRR) allowed a comprehensive characterisation of the out of-plane structural parameters (e.g. molecular packing and thickness) of the erucamide layers prepared via spin coating from nonaqueous solution on silica. Complementary Atomic Force Microscopy (AFM) imaging with high lateral resolution revealed localised in-plane structures. Contact angle measurements provided information on the wettability of erucamide-coated surfaces. Peak Force Quantitative Nanomechanical Mapping (QNM) allowed a correlation between the erucamide nanostructure with the surface nanomechanical properties (i.e. adhesive response). Findings: Our results reveal erucamide surface nanostructures on silica as patchy monolayers, isolated circular bilayers/rounded rectangle-like aggregates and overlapping plate-like multilayers as the erucamide concentration in the spin coating solution was varied. In all the cases, XRR and AFM results were consistent with the picture that the erucamide tails were oriented outwards. The QNM adhesion force mapping of all the observed morphologies also supported this molecular orientation at the outermost erucamide monolayer. The wettability study further confirmed this conclusion with the observed increase in the surface hydrophobicity and coverage upon increasing erucamide concentration, with the macroscopic water contact angle 0 = 92.9 degrees +/- 2.9 degrees at the highest erucamide concentration of 2 wt%. (c) 2021 Elsevier Inc. All rights reserved.
The applications of polymeric sponges are varied, ranging from cleaning and filtration to medical applications. The specific properties of polymeric foams, such as pore size and connectivity, are dependent on their constituent materials and production methods. Nuclear magnetic resonance imaging (MRI) and X-ray micro-computed tomography (µCT) offer complementary information about the structure and properties of porous media. In this study, we employed MRI, in combination with µCT, to characterize the structure of polymeric open-cell foam, and to determine how it changes upon compression, µCT was used to identify the morphology of the pores within sponge plugs, extracted from polyurethane open-cell sponges. MRI T2 relaxation maps and bulk T2 relaxation times measurements were performed for 7° dH water contained within the same polyurethane foams used for µCT. Magnetic resonance and µCT measurements were conducted on both uncompressed and 60% compressed sponge plugs. Compression was achieved using a graduated sample holder with plunger. A relationship between the average T2 relaxation time and maximum opening was observed, where smaller maximum openings were found to have a shorter T2 relaxation times. It was also found that upon compression, the average maximum opening of pores decreased. Average pore size ranges of 375–632 ± 1 µm, for uncompressed plugs, and 301–473 ± 1 µm, for compressed plugs, were observed. By determining maximum opening values and T2 relaxation times, it was observed that the pore structure varies between sponges within the same production batch, as well as even with a single sponge.
Understanding the nanostructure and nanomechanical properties of surface layers of erucamide, in particular the molecular orientation of the outermost layer, is important to its widespread use as a slip additive in polymer materials. Extending our recent observations of nanomorphologies of erucamide layers on a hydrophilic silica substrate, here we evaluate its nanostructure on a more hydrophobic polypropylene surface. Atomic force microscopy (AFM) imaging revealed the molecular packing, thickness, and surface coverage of the erucamide layers, while peak force quantitative nanomechanical mapping (QNM) showed that erucamide reduced the adhesive response on polypropylene. Synchrotron X-ray reflectivity (XRR) was used to probe the out-of-plane structure of the surface layers. Static contact angle measurements further corroborated on the resulting wettability, also demonstrating the efficacy of erucamide physisorption in facilitating control over polypropylene surface wetting. The results show the formation of erucamide monolayers, bilayers and multilayers, depending on the concentration in the spin-cast solution. Correlation of AFM, XRR and wettability results consistently points to the molecular orientation in the outermost layer, i.e. with the erucamide tails pointing outward for the surface nanostructures with different morphologies (i.e., bilayers and multilayers). Rare occurrence of monolayers with exposed hydrophilic head groups were observed only at the lowest erucamide concentration. Compared with our previous observations on the hydrophilic surface, the erucamide surface coverage was much higher on the more hydrophobic propylene surface at similar erucamide concentrations in the spin-cast solution. Furthermore, the structure, molecular orientation and nanomechanical properties of the spin-cast erucamide multilayers atop polypropylene were also similar to those on industrially relevant polypropylene fibers coated with erucamide via blooming. These findings shed light on the nanostructural features of the erucamide surface layer underpinning its nanomechanical properties, relevant to many applications in which erucamide is commonly used as a slip additive.
Linear alkylbenzene sulfonate (NaLAS) surfactant is often combined with polycarboxylate polymers in detergent formulations. However, the behavior of these aqueous surfactant-polymer systems in the absence of an added electrolyte is unreported. This work investigates the behavior of such systems using polarized light microscopy, small-angle X-ray scattering (SAXS), centrifugation, and 2H NMR techniques. A phase diagram at 50 °C is reported for 0-50 wt % NaLAS concentrations and 0-10 wt % polycarboxylate concentrations. The NaLAS-water system is micellar at concentrations <35 wt %, and a 2-phase micellar-lamellar system is seen at higher NaLAS levels, consistent with that reported by previous studies. As polymers are added at low surfactant concentrations (∼10 to 20 wt % NaLAS), a second optically isotropic phase is formed; this is thought to be a polymer-rich phase. Further addition of polycarboxylate leads to the formation of a lamellar phase. At high surfactant concentrations (>20 wt % NaLAS), the addition of a polymer induces a second lamellar phase. These observed behaviors are thought to arise as a result of depletion flocculation and salting-out effects. The observed lamellar phases adopt colloidal multilamellar vesicle (MLV) structures, and the average MLV radii were estimated using 2H NMR by probing the diffusion and anisotropy of D2O within the bilayers of the vesicles. The NMR results show that as the polymer concentration was increased from 0 to 10 wt %, an increase in the average multilamellar vesicle size from ∼200 to ∼500 nm was observed. This increase in the calculated average MLV radius likely results from depletion flocculation-induced MLV fusion.
We investigate the shape, dimensions, and transformation pathways of micelles of linear sodium alkylbenzenesulfonate (NaLAS), a common anionic surfactant, in aqueous solution. Employing Small Angle Neutron Scattering (SANS) and surface tensiometry, we quantify the effects of surfactant concentration (0.6-15 wt%), temperature (5-40 °C) and added salt (≤0.35 M Na2SO4). Spherical micelles form at low NaLAS (≤2.6 wt%) concentration in water, and become elongated with increasing concentration and decreasing temperature. Addition of salt reduces the critical micelle concentration (CMC) and thus promotes the formation of micelles. At fixed NaLAS concentration, salt addition causes spherical micelles to grow into cylindrical micelles, and then multilamellar vesicles (MLVs), which we examine by SANS and cryo-TEM. Above a threshold salt concentration, the MLVs reach diameters of 100 s of nm to few μm, eventually causing precipitation. While the salt concentrations associated with the micelle-to-cylinder transformation increase only slightly with temperature, those required for the cylinder-to-MLV transformation exhibit a pronounced, linear temperature dependence, which we examine in detail. Our study establishes a solution structure map for this model anionic surfactant in water, quantifying the combined roles of concentration, temperature and salt, at practically relevant conditions.
In the present study, the early stage of bacteria biofilm formation has been studied as a function of different nutrients. Infrared spectra of Pseudomonas fluorescens (PF) and Staphylococcus epidermidis (SE), on germanium ATR crystal, were collected under deionized water H2O, phosphate buffered solution (PBS) and PBS with glucose (PBS-G). In H2O, protein bands of PF increased while, no difference in PBS and PBS-G were observed until 135 min. SE strain showed a low sensitivity to PBS composition starting to expose proteins on surfaces after 120 min. SE shows a low polysaccharides increase in H2O while, in bare and enriched PBS their intensity increases after 120 and 75 min. in PBS and PBS-G respectively. PF exhibits a peculiar behavior in H2O where the saccharide bands increased strongly after 100 min, while under all the other conditions, the intensity of polysaccharide bands increased up to the plateau probably because the layer of the biofilm exceeded the penetration capability of FTIR technique. All data suggest that, under lack of nutrients, both the bacteria tend to firmly anchor themselves to the support using proteins.
Aqueous mixtures of anionic and nonionic/cationic surfactants can form non-trivial self-assemblies in solution and exhibit macroscopic responses. Here, we investigate the micellar phase of pure and mixed aqueous solutions of Sodium Dodecyl Sulfate (SDS) and Dimethyldodecyl Amine Oxide (DDAO) using a combination of Small Angle Neutron Scattering (SANS), Fourier-Transform Infrared Spectroscopy (FTIR) and rheological measurements. We examine the effect of temperature (0-60 °C), on the 20 wt% SDS micellar solutions with varying DDAO (⩽5 wt%), and seek to correlate micellar structure with zero-shear solution viscosity. SANS establishes the formation of prolate ellipsoidal micelles in aqueous solutions of pure SDS, DDAO and SDS/DDAO mixtures, whose axial ratio is found to increase upon cooling. Elongation of the ellipsoidal micelles of pure SDS is also induced by the introduction of the non-anionic DDAO, which effectively reduces the repulsive interactions between the anionic SDS head-groups. In FTIR measurements, the formation of elongated mixed ellipsoidal micelles is confirmed by the increase of ordering in the hydrocarbon chain tails and interaction between surfactant head-groups. We find that the zero-shear viscosity of the mixed surfactant solutions increases exponentially with decreasing temperature and increasing DDAO content. Significantly, a master curve for solution viscosity can be obtained in terms of micellar aspect ratio, subsuming the effects of both temperature and DDAO composition in the experimental range investigated. The intrinsic viscosity of mixed micellar solutions is significantly larger than the analytical and numerical predictions for Brownian suspensions of ellipsoidal colloids, highlighting the need to consider interactions of soft micelles under shear, especially at high concentrations.
Investigation of biofilms and visualization using non-destructive imaging techniques like X-ray μCT has recently gained interest. Biofilms are congregations of microorganisms that attach to surfaces and comprise of microbial cells embedded in extracellular polymeric substances (EPS). They are ubiquitous entities that are commonly found in any non-sterile setting and have direct implications on human health. Methods to visualize them in-situ are highly needed to understand their behaviour (attachment and detachment) inside a substrate. Contrast-enhanced X-ray μCT is a 3D imaging technique that is capable of visualising objects that have very low attenuation contrast. The use of contrast agents in X-ray μCT has been an evolving process, however, the possible toxic effect of these chemical compounds against biofilms has not been studied in detail. In this study, we focus on the toxic effect of contrast agents and study the diffusion and drainage of contrast agents in biofilms. We propose using water-soluble potassium bromide (KBr) as a suitable contrast agent for enhancement of the attenuation coefficient of a monoculture of Pseudomonas fluorescens biofilms inside a porous substrate. At the given concentration, KBr proved to be less bactericidal compared to other commonly used contrast agents and at 5% w/v concentration we were able to clearly distinguish between the biofilm and the porous substrate.