Ion Coupling, Bonding, and Transfer in Narrow Carbon Nanotubes.

Narrow carbon nanotubes (nCNT) are unique mimics of biological channels with water-ion selectivity attractive for applications such as water purification and osmotic energy harvesting, yet their understanding is still incomplete. Here, an ab initio computation is employed to develop the full picture of ion transfer in nCNT including specificity and coupling between ions. The thermodynamic costs of ion transfer are computed for single ions and ion pairs and used to evaluate different local coupling scenarios including strong (pairing) and weak (free-ion) coupling as well as "electroneutrality breakdown" (EB), possible for cations only due to their chemisorption-like interaction with nCNT. The results also indicate that nCNT behaves as a highly polarizable metal-like shell, which eliminates the dielectric energy when CNT accommodates coupled cation and anion. This allows facile computation and comparison of the full transfer costs, including translation entropy, for different ions in different coupling modes to identify the dominant regime. EB transfer appears most favorable for K+, while anions strongly favor transfer as pairs, except for chloride which favors weak coupling and, at neutral pH, transfers as a trace ion coupled to both cation and OH-. The results demonstrate that, in general, observed ion permeation and conduction in nCNT, especially for anions, reflect a complex ion-specific and composition-dependent interplay between different ions.

Degradation of Polyamide Membranes Exposed to Chlorine: An Impedance Spectroscopy Study.

Polyamide is the key material in modern membrane desalination; however, its well-known and incompletely understood drawback is its low tolerance to chlorine, the most efficient in-line disinfectant. Here we report a first investigation of the mechanism and kinetics of chlorine attack using electrochemical impedance spectroscopy (EIS) that directly probes changes in ion permeation upon chlorination at different pH values, focusing on its early stages and low chlorine concentrations (15-197 ppm). EIS results partly conform to an established two-stage mechanism that proceeds as N-chlorination followed by either C-chlorination in acidic conditions or amide bond scission in alkaline conditions. However, early time kinetics in acidic conditions shows inconsistencies with this model, explained by possible effects of direct ring chlorination and finite polymer relaxation rates. The findings indicate that (a) N-chlorination reduces membrane polarity and ion permeability, while C-chlorination has an opposite effect; (b) chlorination in acidic conditions must involve other reactions, such as direct ring chlorination, in addition to N-chlorination and Orton rearrangement; and (c) the ultimate chemical transformations (C-chlorination or amide bond scission) result in an irreversible increase in membrane polarity and loss of ion rejection. The results highlight the potential of EIS as a powerful and sensitive tool for studying chemical degradation of ion-selective materials that may assist in developing new chlorine-resistant membranes.

Modeling QCM-D Response to Deposition and Attachment of Microparticles and Living Cells.

Quartz crystal microbalance with dissipation monitoring (QCM-D) is a powerful tool for studying adhesion, yet its use for analyzing the deposition of microparticles and living cells on surfaces has been hampered by difficulties in interpretation. Here we report a new quantitative model of QCM-D response, presented as an equivalent acoustic impedance circuit. As an essential feature, the particle interaction with surrounding fluid is modeled by relations for a freely oscillating rotating and translating sphere in an unbounded fluid, which is a valid approximation for microparticles. This helps deduce from the measured reponse the parameters pertinent to the contact mechanics. We use the model to analyze deposition of different microparticles as well as Pseudomonas fluorescens bacteria on several substrates using QCM-D combined with real-time microscopy. The parameter space is increased by varying particle type and size, substrate surface chemistry and rigidity, and ionic strength of the solution, which allows observation of diverse responses and transition from inertial to elastic loading, including rarely observed resonant regimes. Ultimately, we find that the model describes reasonably well the observed response for different microparticles and substrates, as well as for bacteria, and enables extraction of the contact characteristics in elastic and mixed loading regimes. It also reveals discrepancies between measured and anticipated parameters for large particles. The new model can be a useful tool for interpreting and quantifying QCM-D data on the adhesion of particles and living cells to surfaces, including time-dependent adhesion phenomena.

Selectivity and polarization in water channel membranes: lessons learned from polymeric membranes and CNTs.

Water channels are employed by nature to move pure water across cell membranes while selectively rejecting salts. At present, synthetic channels successfully mimic water permeation, yet even the best channels, such as carbon nanotubes (CNTs) and graphene oxide stacks, still fall short of the selectivity target. The present paper analyzes factors that may help to enhance and control salt rejection based on the lessons learned from conventional membranes and CNTs. First, it highlights the importance of raising the ion self-energy (dielectric mechanism), which suggests that having the channels both narrow and surrounded by a low-dielectric environment is key to high selectivity. In contrast, pore charge alone is insufficient, yet it may help to enhance and tune ion rejection, provided that non-mean-field effects enhanced in low-dielectric pores, such as ion association and sorption, especially of H+ and OH- ions, are properly understood and addressed in the channel design. Second, the role of concentration polarization (CP) is analyzed, which shows that the CP level is apparently low in isolated channels or microscopically small membranes. However, the geometry of the diffusion field should change and CP should increase drastically in macroscopic membranes incorporating densely spaced channel arrays. If not properly addressed in membrane design, the increased CP level in scaled-up channel-based membranes may significantly compromise the observed selectivity and require that target of selectivity be re-set to an even more challenging value. These points may help guide the future development of high-performance artificial water channels and their scale-up towards utilization in next-generation water purification membranes.

When Salt-Rejecting Polymers Meet Protons: An Electrochemical Impedance Spectroscopy Investigation.

Polymeric membranes are widely used for salt removal, but mechanism of ion permeation is still insufficiently understood. Here we analyze ion transport in polymers relevant to desalination, dense aromatic polyamide Nomex and cellulose acetate (CA), using impedance spectroscopy, focusing on the effects of the salt type, concentration and pH. The results highlight the role of proton uptake in ion permeation. For Nomex the exceptionally high affinity to proton results in a power-low scaling of conductivity with salt concentrations with an unusual exponent 1/2. The results for CA suggest dominance of pore transport, with pore charge increasing with decreasing pH, which contradicts previous view of CA as a weakly acidic polymer and points to proton uptake as possible pore-charging mechanism. The observed effects may have far-reaching consequences in desalination, as even at neutral pH they may both enhance and suppress salt permeation and affect pH changes.

Facile Modification of Reverse Osmosis Membranes by Surfactant-Assisted Acrylate Grafting for Enhanced Selectivity.

The top polyamide layer of composite reverse osmosis (RO) membranes has a fascinatingly complex structure, yet nanoscale nonuniformities inherently present in polyamide layer may reduce selectivity, e.g., for boron rejection. This study examines improving selectivity by in situ "caulking" such nonuniformities using concentration polarization-enhanced graft-polymerization with a surfactant added to the reactive solution. The surfactant appears to enhance both polarization (via monomer solubilization in surfactant micelles) and adherence of graft-polymer to the membrane surface, which facilitates grafting and reduces monomer consumption. The effect of surfactant was particularly notable for a hydrophobic monomer glycidyl methacrylate combined with a nonionic surfactant Triton X-100. With Triton added at an optimal level, close to critical micellization concentration (CMC), monomer gets solubilized and highly concentrated within micelles, which results in a significantly increased degree of grafting and uniformity of the coating compared to a procedure with no surfactant added. Notably, no improvement was obtained for an anionic surfactant SDS or the cationic surfactant DTAB, in which cases the high CMC of surfactant precludes high monomer concentration within micelles. The modification procedure was also up-scalable to membranes elements and resulted in elements with permeability comparable to commercial brackish water RO elements with superior boric acid rejection.

Predicting the Rejection of Major Seawater Ions by Spiral-Wound Nanofiltration Membranes.

Seawater nanofiltration (SWNF) generates a softened permeate stream and a retentate stream in which the multivalent ions accumulate, offering opportunities for practical utilization of both streams. This study presents an approach to simulation of SWNF including all major seawater ions (Na(+), Cl(-), Ca(2+), Mg(2+), and SO4(2-)) based on the Nernst-Planck equation, and uses it for permeate and retentate streams composition prediction. The number of degrees of freedom in the system was reduced by assuming a very high ionic permeability for Na(+), which only weakly affected the other parameters in the system. Two alternatives were examined to analyze the importance of concentration dependence of ion permeabilities: The assumption of constant ion permeabilities resulted in a reasonable fit with experimental data. However, for the permeate composition the overall fit was significantly improved (P < 0.0001) when the permeabilities of Ca(2+) and Mg(2+) were allowed to depend on the ratio of their total concentration to Na(+). This type of dependence emphasizes the strong interaction of divalent ions with the membrane and its effect on the membrane fixed charge through screening or charge reversal. When this effect was included, model predictions closely matched the experimental results obtained, corroborating the phenomenological approach proposed in this study.

Interactions of glycosphingolipids and lipopolysaccharides with silica and polyamide surfaces: adsorption and viscoelastic properties.

Bacterial outer membrane components play a critical role in bacteria-surface interactions (adhesion and repulsion). Sphingomonas species (spp.) differ from other Gram-negative bacteria in that they lack lipopolysaccharides (LPSs) in their outer membrane. Instead, Sphingomonas spp. outer membrane consists of glycosphingolipids (GSLs). To delineate the properties of the outer membrane of Sphingomonas spp. and to explain the adhesion of these cells to surfaces, we employed a single-component-based approach of comparing GSL vesicles to LPS vesicles. This is the first study to report the formation of vesicles containing 100% GSL. Significant physicochemical differences between GSL and LPS vesicles are reported. Composition-dependent vesicle adherence to different surfaces using quartz crystal microbalance with dissipation monitoring (QCM-D) technology was observed, where higher GSL content resulted in higher mass accumulation on the sensor. Additionally, the presence of 10% GSL and above was found to promote the relative rigidity of the vesicle obtaining viscoelastic ratio of 30-70% higher than that of pure LPS vesicles.

Does hindered transport theory apply to desalination membranes?

As reverse osmosis (RO) and nanofiltration polyamide membranes become increasingly used for water purification, prediction of pollutant transport is required for membrane development and process engineering. Many popular models use hindered transport theory (HTT), which considers a spherical solute moving through an array of fluid-filled rigid cylindrical pores. Experiments and molecular dynamic simulations, however, reveal that polyamide membranes have a distinctly different structure of a "molecular sponge", a network of randomly connected voids widely distributed in size. In view of this disagreement, this study critically examined the validity of HTT by directly measuring diffusivities of several alcohols within a polyamide film of commercial RO membrane using attenuated total reflection-FTIR. It is found that measured diffusivities deviate from HTT predictions by as much as 2-3 orders of magnitude. This result indicates that HTT does not adequately describe solute transport in desalination membranes. As a more adequate alternative, the concept of random resistor networks is suggested, with resistances described by models of activated transport in "soft" polymers without a sharp size cutoff and with a proper address of solute partitioning.

'Should I stay or should I go?' Bacterial attachment vs biofilm formation on surface-modified membranes.

A number of techniques are used for testing the anti-biofouling activity of surfaces, yet the correlation between different results is often questionable. In this report, the correlation between initial bacterial deposition (fast tests, reported previously) and biofilm growth (much slower tests) was analyzed on a pristine and a surface-modified reverse osmosis membrane ESPA-1. The membrane was modified with grafted hydrophilic polymers bearing negatively charged, positively charged and zwitter-ionic moieties. Using three different bacterial strains it was found that there was no general correlation between the initial bacterial deposition rates and biofilm growth on surfaces, the reasons being different for each modified surface. For the negatively charged surface the slowest deposition due to the charge repulsion was eventually succeeded by the largest biofilm growth, probably due to secretion of extracellular polymeric substances (EPS) that mediated a strong attachment. For the positively charged surface, short-term charge attraction by quaternary amine groups led to the fastest deposition, but could be eventually overridden by their antimicrobial activity, resulting in non-consistent results where in some cases a lower biofilm formation rate was observed. The results indicate that initial deposition rates have to be used and interpreted with great care, when used for assessing the anti-biofouling activity of surfaces. However, for a weakly interacting 'low-fouling' zwitter-ionic surface, the positive correlation between initial cell deposition and biofilm growth, especially under flow, suggests that for this type of coating initial deposition tests may be fairly indicative of anti-biofouling potential.

Pseudo-bottle-brush decorated thin-film composite desalination membranes with ultrahigh mineral scale resistance.

High water recovery is crucial to inland desalination but is impeded by mineral scaling of the membrane. This work presents a two-step modification approach for grafting high-density zwitterionic pseudo-bottle-brushes to polyamide reverse osmosis membranes to prevent scaling during high-recovery desalination of brackish water. Increasing brush density, induced by increasing reaction time, correlated with reduced scaling. High-density grafting eliminated gypsum scaling and almost completely prevented silica scaling during desalination of synthetic brackish water at a recovery ratio of 80%. Moreover, scaling was effectively mitigated during long-term desalination of real brackish water at a recovery ratio of 90% without pretreatment or antiscalants. Molecular dynamics simulations reveal the critical dependence of the membrane's silica antiscaling ability on the degree to which the coating screens the membrane surface from readily forming silica aggregates. This finding highlights the importance of maximizing grafting density for optimal performance and advanced antiscaling properties to allow high-recovery desalination of complex salt solutions.

Bacterial attachment and viscoelasticity: physicochemical and motility effects analyzed using quartz crystal microbalance with dissipation (QCM-D).

This investigation is focused on the combined effect of bacterial physicochemical characteristics and motility on cell adhesion and deposition using a flow-through quartz crystal microbalance with dissipation (QCM-D). Three model flagellated strains with different degrees of motility were selected, including a highly motile Escherichia coli K12 MG1655, an environmental strain Sphingomonas wittichii RW1, and a nonmotile (with paralyzed flagella) Escherichia coli K12 MG1655 ΔmotA that is incapable of encoding the motor torque generator for flagellar movement. Of the three strains, S. wittichii RW1 is highly hydrophobic, while E. coli strains are equally hydrophilic. Consideration of the hydrophobicity provides an alternative explanation for the bacterial adhesion behavior. QCM-D results show that motility is a critical factor in determining bacterial adhesion, as long as the aquatic chemical conditions are conducive for motility and the substratum and bacterial surface are similarly hydrophobic or hydrophilic. Once their properties are not similar, the contribution of hydrophobic interactions becomes more pronounced. QCM-D results suggest that during adhesion of the hydrophobic bacterium, S. wittichii RW1, the initial step of adhesion and maturation of bacteria-substratum interaction on hydrophilic surface includes a dynamic change of the viscoelastic properties of the bond bacterium-surface becoming more viscously oriented.

Modeling and analysis of hydrodynamic and physico-chemical effects in bacterial deposition on surfaces.

The parallel-plate flow chamber (PFC) is often used for characterizing the propensity of microorganisms to attachment to surfaces. The model presented quantitatively analyzes the complex interplay of diffusion, convection, inertial lift, buoyancy, and surface forces in the PFC, which make it difficult to separate the surface- and microorganism-specific effects from the hydrodynamics. An empirical dimensionless factor K entering the boundary condition expresses enhancement of adhesion diffusion of microorganisms across a thin fluid layer adjacent to the surface by adhesion forces. The model examines the role of various factors (e.g., shear rate, size of bacterium, and strength of adhesion) on the rate of bacterial deposition. Using no adjustable parameter for strongly adhesive surfaces and K as the only adjustable parameter for repulsive or weakly adhesive surfaces, the model explains the observed decrease in deposition flux at high flow rates and compares reasonably with reported experimental results. The results suggest that the fitted value of K may be used for 'rating' the propensity of bacteria to deposit on surfaces and separating this from hydrodynamic effects.

Dielectric exclusion, an éminence grise.

Dielectric exclusion has long been well-established as the key mechanism in membrane desalination, critical for delivering the required levels of salt rejection, also playing important role in electro-membrane processes, nanofluidics, and biomimetics. Unfortunately, its elusive nature and many features, such as dependence on the pore size, membrane hydration, and ion size and charge, make it deceivingly similar to the other ion exclusions mechanisms, steric and Donnan, which has led to much controversy and misconceptions. Starting from the Born model and the concept of self-energy, the present paper reviews and highlights the physical basis of dielectric exclusion, its main features and the ways it may be looked at. It discusses what makes the dielectric exclusion both similar and distinctly different from the other mechanism and its synergy and intimate connection with other phenomena, such as Donnan exclusion, permeability-selectivity upper-bound, and selectivity of charged membranes towards uncharged solutes. The paper also addresses subjects that still cause much controversy at present, such as appropriate measures of ionic radii and the subtle distinction between the dielectric exclusion and primary ion hydration. It also points to gaps that need to be bridged towards more complete theory. The points addressed here are important for understanding, modeling and development of various next-generation separation technologies including water purification, resource recovery and reuse, and green energy generation and storage.

Dynamics of underwater microparticle adhesion to soft hydrated surfaces: Modeling and analysis by time-dependent AFM force spectroscopy.

HYPOTHESIS: Understanding the attachment and detachment of microparticles and living cells to surfaces is crucial for developing antifouling strategies. Hydrogel coatings have shown promise in reducing fouling and particle adhesion due to their softness and high water content, yet the mechanisms involved are dynamic and complex, and relevant parameters are not easily accessible. AFM-based force spectroscopy (FS) experiments with colloidal probe particles is a direct way of evaluating adhesive and mechanical relaxational dynamics, yet their interpretation and modeling has been challenging. The present study proposes and examines several dynamic models, suitable for quantitative analysis of FS results with model probe particle on hydrogels surfaces. EXPERIMENTS: FS were performed using polyethylene glycol (PEG) hydrogels and polystyrene microspheres including particle attachement to the hydrogel surface (loading), holding the particle on the surface with a constant force for variable times (dwell) and pulling the particle away from the surface (unloading) FINDINGS: It was found that a viscoelastic extension of the classical JKR model with energy of adhesion unevenly distributed over the contact area and vanishing at its circumferences accurately described all FS experiments and yielded physically consistent viscoelastic and adhesive dynamic parameters, steadily changing with dwell time and applied force. The observed time evolution and force dependence were rationalized as combination of osmotic and osmo-mechnical relaxation in the contact region.

Pseudomonas aeruginosa attachment on QCM-D sensors: the role of cell and surface hydrophobicities.

While biofilms are ubiquitous in nature, the mechanism by which they form is still poorly understood. This study investigated the process by which bacteria deposit and, shortly after, attach irreversibly to surfaces by reorienting to create a stronger interaction, which leads to biofilm formation. A model for attachment of Pseudomonas aeruginosa was developed using a quartz crystal microbalance with dissipation monitoring (QCM-D) technology, along with a fluorescent microscope and camera to monitor kinetics of adherence of the cells over time. In this model, the interaction differs depending on the force that dominates between the viscous, inertial, and elastic loads. P. aeruginosa, grown to the midexponential growth phase (hydrophilic) and stationary phase (hydrophobic) and two different surfaces, silica (SiO(2)) and polyvinylidene fluoride (PVDF), which are hydrophilic and hydrophobic, respectively, were used to test the model. The bacteria deposited on both of the sensor surfaces, though on the silica surface the cells reached a steady state where there was no net increase in deposition of bacteria, while the quantity of cells depositing on the PVDF surface continued to increase until the end of the experiments. The change in frequency and dissipation per cell were both positive for each overtone (n), except when the cells and surface are both hydrophilic. In the model three factors, specifically, viscous, inertial, and elastic loads, contribute to the change in frequency and dissipation at each overtone when a cell deposits on a sensor. On the basis of the model, hydrophobic cells were shown to form an elastic connection to either surface, with an increase of elasticity at higher overtones. At lower overtones, hydrophilic cells depositing on the hydrophobic surface were shown to also be elastic, but as the overtone increases the connection between the cells and sensor becomes more viscoelastic. In the case of hydrophilic cells interacting with the hydrophilic surface, the connection is viscous at each overtone measured. It could be inferred that the transformation of the viscoelasticity of the cell-surface connection is due to changes in the orientation of the cells to the surface, which allow the bacteria to attach irreversibly and begin biofilm formation.