Physicochemical surface properties of Chlorella vulgaris: a multiscale assessment, from electrokinetic and proton uptake descriptors to intermolecular adhesion forces.

Given the growing scientific and industrial interests in green microalgae, a comprehensive understanding of the forces controlling the colloidal stability of these bioparticles and their interactions with surrounding aqueous microenvironment is required. Accordingly, we addressed here the electrostatic and hydrophobic surface properties of Chlorella vulgaris from the population down to the individual cell levels. We first investigated the organisation of the electrical double layer at microalgae surfaces on the basis of electrophoresis measurements. Interpretation of the results beyond zeta-potential framework underlined the need to account for both the hydrodynamic softness of the algae cells and the heterogeneity of their interface formed with the outer electrolyte solution. We further explored the nature of the structural charge carriers at microalgae interfaces through potentiometric proton titrations. Extraction of the electrostatic descriptors of interest from such data was obscured by cell physiology processes and dependence thereof on prevailing measurement conditions, which includes light, temperature and medium salinity. As an alternative, cell electrostatics was successfully evaluated at the cellular level upon mapping the molecular interactions at stake between (positively and negatively) charged atomic force microscopy tips and algal surface via chemical force microscopy. A thorough comparison between charge-dependent tip-to-algae surface adhesion and hydrophobicity level of microalgae surface evidenced that the contribution of electrostatics to the overall interaction pattern is largest, and that the electrostatic/hydrophobic balance can be largely modulated by pH. Overall, the combination of multiscale physicochemical approaches allowed a drawing of some of the key biosurface properties that govern microalgae cell-cell and cell-surface interactions.

Photodegradation of disposable polypropylene face masks: Physicochemical properties of debris and implications for the toxicity of mask-carried river biofilms.

COVID-19 outbreak led to a massive dissemination of protective polypropylene (PP) face masks in the environment, posing a new environmental risk amplified by mask photodegradation and fragmentation. Masks are made up of a several kilometres long-network of fibres with diameter from a few microns to around 20 µm. After photodegradation, these fibres disintegrate, producing water dispersible debris. Electrokinetics and particle stability observations support that photodegradation increases/decreases the charge/hydrophobicity of released colloidal fragments. This change in hydrophobicity is related to the production of UV-induced carbonyl and hydroxyl reactive groups detectable after a few days of exposure. Helical content, surface roughness and specific surface area of mask fibres are not significantly impacted by photodegradation. Fragmentation of fibres makes apparent, at the newly formed surfaces, otherwise-buried additives like TiO2 nanoparticles and various organic components. Mortality of gammarids is found to increase significantly over time when fed with 3 days-UV aged masks that carry biofilms grown in river, which is due to a decreased abundance of microphytes therein. In contrast, bacteria abundance and microbial community composition remain unchanged regardless of mask degradation. Overall, this work reports physicochemical properties of pristine and photodegraded masks, and ecosystemic functions and ecotoxicity of freshwater biofilms they can carry.

Kinetics of metal detection by luminescence-based whole-cell biosensors: connecting biosensor response to metal bioavailability, speciation and cell metabolism.

Luminescent whole-cell metal biosensors are genetically engineered cells used for the detection of metals in e.g. aqueous solutions. Herein, we detail the quantitative connections between time-response of luminescent bacterial metal sensors and the bioavailability of free and complexed metal species. To that end, we formulate the biophysicochemical dynamics of metal partitioning at a biosensor/solution interface and integrate the required metabolism contribution to cell response. The formalism explains the ways in which cell signal depends on: coupled Eigen kinetics of metal complexation and diffusion of metal species to/from the interface; kinetics of metal excretion, Michaelis-Menten bioaccumulation and ensuing metal depletion from bulk solution; and kinetics of bioluminescence production following intracellular metal sequestration by regulatory metalloproteins. In turn, an expression is derived for the time-dependent cell signal as a function of interrelated (bioavai)lability of metal species and (thermo)dynamic descriptors of extra/intracellular metal complexation. Quantitative criteria are elaborated to identify scenarios where equilibrium modeling of metal speciation is incorrect, bulk metal depletion is operative, metal biouptake kinetics is governed by metal diffusion, or labile metal complexes fully contribute to cell response. Remarkably, in agreement with experiments, the theory predicts time-shifts of bioluminescence peaks with increasing concentration of biosensor and/or metal ligand in solution. We show that these shifts originate from the crosstalk between activation kinetics of cell photoactivity and speciation-dependent kinetics of bulk metal depletion. Overall, the work paves the way for the elaboration of new strategies to exploit the bioluminescence response of metal lux-biosensors at a dynamic level and evaluate metal bioavailability properties in environmental or biological aqueous samples.

Effect of Polymer Aging on Uptake/Release Kinetics of Metal Ions and Organic Molecules by Micro- and Nanoplastics: Implications for the Bioavailability of the Associated Compounds.

The main driver of the potential toxicity of micro- and nanoplastics toward biota is often the release of compounds initially present in the plastic, i.e., polymer additives, as well as environmentally acquired metals and/or organic contaminants. Plastic particles degrade in the environment via various mechanisms and at different rates depending on the particle size/geometry, polymer type, and the prevailing physical and chemical conditions. The rate and extent of polymer degradation have obvious consequences for the uptake/release kinetics and, thus, the bioavailability of compounds associated with plastic particles. Herein, we develop a theoretical framework to describe the uptake and release kinetics of metal ions and organic compounds by plastic particles and apply it to the analysis of experimental data for pristine and aged micro- and nanoplastics. In particular, we elucidate the contribution of transient processes to the overall kinetics of plastic reactivity toward aquatic contaminants and demonstrate the paramount importance of intraparticulate contaminant diffusion.

Bacterial capsular polysaccharides with antibiofilm activity share common biophysical and electrokinetic properties.

Bacterial biofilms are surface-attached communities that are difficult to eradicate due to a high tolerance to antimicrobial agents. The use of non-biocidal surface-active compounds to prevent the initial adhesion and aggregation of bacterial pathogens is a promising alternative to antibiotic treatments and several antibiofilm compounds have been identified, including some capsular polysaccharides released by various bacteria. However, the lack of chemical and mechanistic understanding of the activity of these polymers limits their use to control biofilm formation. Here, we screen a collection of 31 purified capsular polysaccharides and first identify seven new compounds with non-biocidal activity against Escherichia coli and/or Staphylococcus aureus biofilms. We measure and theoretically interpret the electrophoretic mobility of a subset of 21 capsular polysaccharides under applied electric field conditions, and we show that active and inactive polysaccharide polymers display distinct electrokinetic properties and that all active macromolecules share high intrinsic viscosity features. Despite the lack of specific molecular motif associated with antibiofilm properties, the use of criteria including high density of electrostatic charges and permeability to fluid flow enables us to identify two additional capsular polysaccharides with broad-spectrum antibiofilm activity. Our study therefore provides insights into key biophysical properties discriminating active from inactive polysaccharides. The characterization of a distinct electrokinetic signature associated with antibiofilm activity opens new perspectives to identify or engineer non-biocidal surface-active macromolecules to control biofilm formation in medical and industrial settings.

Electrostatics of soft (bio)interfaces: Corrections of mean-field Poisson-Boltzmann theory for ion size, dielectric decrement and ion-ion correlations.

HYPOTHESIS: Electrostatics of soft (ion-permeable) (bio)particles (e.g. microorganisms, core/shell colloids) in aqueous electrolytes is commonly formulated by the mean-field Poisson-Boltzmann theory and integration of the charge contributions from electrolyte ions and soft material. However, the effects connected to the size of the electrolyte ions and that of the structural charges carried by the particle, to dielectric decrement and ion-ion correlations on soft interface electrostatics have been so far considered at the margin, despite the limits of the Gouy theory for condensed and/or multivalent electrolytes. EXPERIMENTS: Accordingly, we modify herein the Poisson-Boltzmann theory for core/shell (bio)interfaces to include the aforementioned molecular effects considered separately or concomitantly. The formalism is applicable for poorly to highly charged particles in the thin electric double layer regime and to unsymmetrical multivalent electrolytes. FINDINGS: Computational examples of practical interests are discussed with emphasis on how each considered molecular effect or combination thereof affects the interfacial potential distribution depending on size and valence of cations and anions, size of particle charges, length scale of ionic correlations and shell-to-Debye layer thickness ratio. The origins of here-evidenced pseudo-harmonic potential profile and ion size-dependent screening of core/shell particle charges are detailed. In addition, the existence and magnitude of the Donnan potential when reached in the shell layer are shown to depend on the excluded volumes of the electrolyte ions.

Comparative Analysis of Cell Metabolic Activity Sensing by Escherichia coli rrnB P1-lux and Cd Responsive-Lux Biosensors: Time-Resolved Experiments and Mechanistic Modelling

Whole-cell bacterial sensors are used in medical/environmental applications to detect chemicals, and to assess medium toxicity or stress. Non-specific constitutive biosensors generally serve the latter purpose, whereas chemical detection is performed with biosensors involving a specific chemical-inducible promoter. Herein, we show that functioning principles of specific and non-specific whole-cell biosensors are not exclusive as both can probe modulations of cell metabolic activity under stressing conditions. The demonstration is based on (i) time-resolved measurements of bioluminescence produced by constitutive rrnB P1-luxCDABE Escherichia coli biosensor in media differing with respect to carbon source, (ii) theoretical reconstruction of the measured signals using a here-reported theory for bioluminescence generated by constitutive cells, (iii) comparison between time-dependent cell photoactivity (reflecting metabolic activity) retrieved by theory with that we reported recently for cadmium-inducible PzntA-luxCDABE E. coli in media of similar compositions. Whereas signals of constitutive and non-constitutive biosensors differ in terms of shape, amplitude and peak number depending on nutritional medium conditions, analysis highlights the features shared by their respective cell photoactivity patterns mediated by the interplay between stringent response and catabolite repressions. The work advocates for the benefits of a theoretical interpretation for the time-dependent response of biosensors to unravel metabolic and physicochemical contributions to the bioluminescence signal.

Absolute and Relative Positioning of Natural Organic Matter Acid-Base Potentiometric Titration Curves: Implications for the Evaluation of the Density of Charged Reactive Sites.

Potentiometric acid-base titration curves collected on humic (nano)particles as a function of pH and salt concentration reflect the electrostatics of the particles and the amount of chemical charges (Q) they carry. In turn, the interpretation of titration data helps quantify their reactivity toward metals provided that both intrinsic chemical and nonspecific electrostatic contributions to proton binding are correctly unraveled. Establishing a titration curve requires several steps, i.e., blank subtraction, relative curve positioning with respect to the electrolyte concentration, and absolute curve positioning achieved by the estimation of particle charge Q0 at low pH. Failure to properly establish each step may lead to the misevaluation of nanoparticle charging behavior. Here, we report (i) a simple procedure to measure and position titration curves for humic substances (HS) versus salt concentration and (ii) an original approach for absolute curve positioning upon the exploitation of proton affinity spectra. The latter do not depend on Q0 and they thus constrain the titration data analysis using the soft Poisson-Boltzmann-based titration (SPBT) formalism for nanoparticles in the thick electric double-layer regime. We illustrate the benefits of our approach by analyzing titration measurements for a large range of humic nanoparticles and by comparing the outcome with results from the literature.

Exploiting Catabolite Repression and Stringent Response to Control Delay and Multimodality of Bioluminescence Signal by Metal Whole-Cell Biosensors: Interplay between Metal Bioavailability and Nutritional Medium Conditions.

The time-dependent response of metal-detecting whole-cell luminescent bacterial sensors is impacted by metal speciation/bioavailability in solution. The comprehensive understanding of such connections requires the consideration of the bacterial energy metabolism at stake and the effects of supplied food on cells' capability to convert bioaccumulated metals into light. Accordingly, we investigated the time response (48 h assay) of PzntA-luxCDABE Escherichia coli Cd biosensors in media differing with respect to sources of amino acids (tryptone or Lysogeny Broth) and carbon (glucose, xylose and mixtures thereof). We show that the resulting coupling between the stringent cell response and glucose/xylose-mediated catabolite repressions lead to well-defined multimodalities and shapes of the bioluminescence signal over time. Based on a recent theory for the time-response of metal-sensing luminescent bacteria, successful theoretical reconstructions of the bioluminescence signals are reported under all Cd concentrations (0-20 nM) and nutritive conditions examined. This analysis leads to the evaluation of time-dependent cell photoactivity and qualitative information on metal speciation/bioavailability in solution. Biosensor performance and the position, shape, number, and magnitude of detected peaks are discussed in relation to the metabolic pathways operative during the successive light emission modes identified here over time. Altogether, the results clarify the contributions of metal/nutrient bio-availabilities and food quality to cell response typology.

Surface Properties of Parabacteroides distasonis and Impacts of Stress-Induced Molecules on Its Surface Adhesion and Biofilm Formation Capacities.

The gut microbiota is a complex and dynamic ecosystem whose balance and homeostasis are essential to the host's well-being and whose composition can be critically affected by various factors, including host stress. Parabacteroides distasonis causes well-known beneficial roles for its host, but is negatively impacted by stress. However, the mechanisms explaining its maintenance in the gut have not yet been explored, in particular its capacities to adhere onto (bio)surfaces, form biofilms and the way its physicochemical surface properties are affected by stressing conditions. In this paper, we reported adhesion and biofilm formation capacities of 14 unrelated strains of P. distasonis using a steam-based washing procedure, and the electrokinetic features of its surface. Results evidenced an important inter-strain variability for all experiments including the response to stress hormones. In fact, stress-induced molecules significantly impact P. distasonis adhesion and biofilm formation capacities in 35% and 23% of assays, respectively. This study not only provides basic data on the adhesion and biofilm formation capacities of P. distasonis to abiotic substrates but also paves the way for further research on how stress-molecules could be implicated in P. distasonis maintenance within the gut microbiota, which is a prerequisite for designing efficient solutions to optimize its survival within gut environment.

Osmotic stress and vesiculation as key mechanisms controlling bacterial sensitivity and resistance to TiO2 nanoparticles.

Toxicity mechanisms of metal oxide nanoparticles towards bacteria and underlying roles of membrane composition are still debated. Herein, the response of lipopolysaccharide-truncated Escherichia coli K12 mutants to TiO2 nanoparticles (TiO2NPs, exposure in dark) is addressed at the molecular, single cell, and population levels by transcriptomics, fluorescence assays, cell nanomechanics and electrohydrodynamics. We show that outer core-free lipopolysaccharides featuring intact inner core increase cell sensitivity to TiO2NPs. TiO2NPs operate as membrane strippers, which induce osmotic stress, inactivate cell osmoregulation and initiate lipid peroxidation, which ultimately leads to genesis of membrane vesicles. In itself, truncation of lipopolysaccharide inner core triggers membrane permeabilization/depolarization, lipid peroxidation and hypervesiculation. In turn, it favors the regulation of TiO2NP-mediated changes in cell Turgor stress and leads to efficient vesicle-facilitated release of damaged membrane components. Remarkably, vesicles further act as electrostatic baits for TiO2NPs, thereby mitigating TiO2NPs toxicity. Altogether, we highlight antagonistic lipopolysaccharide-dependent bacterial responses to nanoparticles and we show that the destabilized membrane can generate unexpected resistance phenotype.

Chemodynamic features of nanoparticles: Application to understanding the dynamic life cycle of SARS-CoV-2 in aerosols and aqueous biointerfacial zones.

We review concepts involved in describing the chemodynamic features of nanoparticles and apply the framework to gain physicochemical insights into interactions between SARS-CoV-2 virions and airborne particulate matter (PM). Our analysis is highly pertinent given that the World Health Organisation acknowledges that SARS-CoV-2 may be transmitted by respiratory droplets, and the US Center for Disease Control and Prevention recognises that airborne transmission of SARS-CoV-2 can occur. In our theoretical treatment, the virion is assimilated to a core-shell nanoparticle, and contributions of various interaction energies to the virion-PM association (electrostatic, hydrophobic, London-van der Waals, etc.) are generically included. We review the limited available literature on the physicochemical features of the SARS-CoV-2 virion and identify knowledge gaps. Despite the lack of quantitative data, our conceptual framework qualitatively predicts that virion-PM entities are largely able to maintain equilibrium on the timescale of their diffusion towards the host cell surface. Comparison of the relevant mass transport coefficients reveals that virion biointernalization demand by alveolar host cells may be greater than the diffusive supply. Under such conditions both the free and PM-sorbed virions may contribute to the transmitted dose. This result points to the potential for PM to serve as a shuttle for delivery of virions to host cell targets. Thus, our critical review reveals that the chemodynamics of virion-PM interactions may play a crucial role in the transmission of COVID-19, and provides a sound basis for explaining reported correlations between episodes of air pollution and outbreaks of COVID-19.

On the strong connection between nanoscale adhesion of Yad fimbriae and macroscale attachment of Yad-decorated bacteria to glycosylated, hydrophobic and hydrophilic surfaces.

Yad fimbriae are currently viewed as versatile bacterial adhesins able to significantly mediate host or plant-pathogen recognition and contribute to the persistence of Escherichia coli in both the environment and within hosts. To date, however, the underlying adhesion process of Yad fimbriae on surfaces defined by controlled coating chemistries has not been evaluated on the relevant molecular scale. In this work, the interaction forces operational between Yad fimbriae expressed by genetically modified E. coli and self-assembled monolayers (SAM) differing in terms of charge, hydrophobicity or the nature of decorating sugar units are quantified by Single Molecule Force Spectroscopy (SMFS) on the nanoscale. It is found that the adhesion of Yad fimbriae onto probes functionalized with xylose is as strong as that measured with probes decorated with anti-Yad antibodies (ca. 80 to 300 pN). In contrast, the interactions of Yad with galactose, lactose, mannose, -OH, -NH2, -COOH and -CH3 terminated SAMs are clearly non-specific. Interpretation of SMFS measurements on the basis of worm-like-chain modeling for polypeptide nanomechanics further leads to the estimates of the maximal extension of Yad fimbriae upon stretching, of their persistence length and of their polydispersity. Finally, we show for the first time a strong correlation between the adhesion properties of Yad-decorated bacteria determined from conventional macroscopic counting methods and the molecular adhesion capacity of Yad fimbriae. This demonstration advocates the effort that should be made to understand on the nanoscale level the interactions between fimbriae and their cognate ligands. The results could further help the design of potential anti-adhesive molecules or surfaces to better fight against the virulence of bacterial pathogens.

Impacts of Mechanical Stiffness of Bacteriophage-Loaded Hydrogels on Their Antibacterial Activity.

The elaboration of efficient hydrogel-based materials with antimicrobial properties requires a refined control of defining their physicochemical features, which includes mechanical stiffness, so as to properly mediate their antibacterial activity. In this work, we design hydrogels consisting of polyelectrolyte multilayer films for the loading of T4 and φX174 bacteria-killing viruses, also called bacteriophages. We investigate the antiadhesion and bactericidal performances of this biomaterial against Escherichia coli, with a specific focus on the effects of chemical cross-linking of the hydrogel matrix, which, in turn, mediates the hydrogel stiffness. Depending on the latter and on phage replication features, it is found that the hydrogels loaded with the bacteria-killing viruses make both contact killing (targeted bacteria are those adhered at the hydrogel surface) and release killing (planktonic bacteria are the targets) possible with ca. 20-80% efficiency after only 4 h of incubation at 25 °C as compared to cases where hydrogels are free of viruses. We further demonstrate the lack of dependence of virus diffusion within the hydrogel and of the maximal viral storage capacity on the hydrogel mechanical properties. In addition to the evidenced bacteriolytic activity of the phages loaded in the hydrogels, the antimicrobial property of the phage-loaded materials is shown to be partly controlled by the chemistry of the hydrogel skeleton and, more specifically, by the mobility of the peripheral free polycationic components, known for their ability to weaken and permeabilize membranes of bacteria, the latter then becoming "easier" targets for the viruses.

Addressing the electrostatic component of protons binding to aquatic nanoparticles beyond the Non-Ideal Competitive Adsorption (NICA)-Donnan level: Theory and application to analysis of proton titration data for humic matter.

HYPOTHESIS: Charge descriptors of aquatic nanoparticles (NPs) are evaluated from proton titration curves measured at different salt concentrations and routinely analysed by the Non-Ideal Competitive Adsorption-Donnan (NICAD) model. This model, however, suffers from approximations regarding particle electrostatics, which may bias particle charge estimation. Implementation of Poisson-Boltzmann (PB) theory within consistent treatment of NPs protolytic data is expected to address NICAD shortcomings. EXPERIMENTS: An alternative to NICAD is elaborated on the basis of nonlinearized PB equation for soft particle electrostatics to properly unravel the electrostatic and chemical components of proton binding to NPs. A numerical package is developed for automated analysis of proton titration curves and proton affinity spectra at different salt concentrations. The performance of the method is illustrated for humic matter nanoparticles with different charge and size, and compared to that of NICAD. FINDINGS: Unlike NICAD, PB-based treatment successfully reproduces particle charge dependence on pH for practical salt concentrations from the thin to thick electric double layer limit. Donnan representation in NICAD leads to moderate to dramatic misestimations of proton affinity and binding heterogeneity depending on particle size to Debye layer thickness ratio. Interpretation of NPs protolytic properties with PB theory further avoids adjustment of the 'particle Donnan volume' empirically introduced in NICAD.

Fast automated processing of AFM PeakForce curves to evaluate spatially resolved Young modulus and stiffness of turgescent cells.

Atomic Force Microscopy (AFM) is a powerful technique for the measurement of mechanical properties of individual cells in two (x × y) or three (x × y × time) dimensions. The instrumental progress makes it currently possible to generate a large amount of data in a relatively short time, which is particularly true for AFM operating in so-called PeakForce tapping mode (Bruker corporation). The latter corresponds to an AFM probe that periodically hits the sample surface while the pico-newton level interaction force is recorded from cantilever deflection. The method provides unprecedented high-resolution (a few tens of nm) imaging of the mechanical features of soft biological samples (e.g. bacteria, yeasts) and of hard abiotic surfaces (e.g. minerals). The rapid conversion of up to several tens of thousands spatially resolved force curves typically collected in AFM PeakForce tapping mode over a given cell surface area into comprehensive nanomechanical information requires the development of robust data analysis methodologies and dedicated numerical tools. In this work, we report an automated algorithm for (i) a rapid and unambiguous detection of the indentation regimes corresponding to non-linear and linear deformations of bacterial surfaces upon compression by the AFM probe, (ii) the subsequent evaluation of the Young modulus and cell surface stiffness, and (iii) the generation of spatial mappings of relevant nanomechanical properties at the single cell level. The procedure involves consistent evaluation of the contact point between the AFM probe and sample biosurface and that of the threshold indentation value marking the transition between non-linear and linear deformation regimes. For comparison purposes, the former regime is here analyzed on the basis of Hertz and Sneddon models corrected or not for effects of finite sample thickness. Analysis of AFM measurements performed on a selected Escherichia coli strain is detailed to demonstrate the feasibility, rapidity and robustness of the here-proposed PeakForce data treatment process. The flexibility of the algorithm allows consideration of force curve parameterizations other than that detailed here, which may be desired for investigation of e.g. eukaryotes nanomechanics. The performance of the adopted Hertz-based and Sneddon-based contact mechanics formalisms in recovering experimental data and in identifying nanomechanical heterogeneities at the bacterium scale is further thoroughly discussed.

Electrophoresis of composite soft particles with differentiated core and shell permeabilities to ions and fluid flow.

Within the framework of analytical theories for soft surface electrophoresis, soft particles are classically defined by a hard impermeable core of given surface charge density surrounded by a polyelectrolyte shell layer permeable to both electroosmotic flow and ions from background electrolyte. This definition excludes practical core-shell particles, e.g. dendrimers, viruses or multi-layered polymeric particles, defined by a polyelectrolytic core where structural charges are distributed and where counter-ions concentration and electroosmotic flow velocity can be significant. Whereas a number of important approximate expressions has been derived for the electrophoretic mobility of hard and soft particles, none of them is applicable to such generic composite core-shell particles with differentiated ions- and fluid flow-permeabilities of their core and shell components. In this work, we elaborate an original closed-form electrophoretic mobility expression for this generic composite particle type within the Debye-Hückel electrostatic framework and thin double layer approximation. The expression explicitly involves the screening Debye layer thickness and the Brinkman core and shell hydrodynamic length scales, which favors so-far missing analysis of the respective core and shell contributions to overall particle mobility. Limits of this expression successfully reproduce results from Ohshima's electrophoresis theory solely applicable to soft particles with or without hard core.

Coupling between electrokinetics and electrode kinetics by bipolar faradaic depolarisation processes in microfluidic channels.

This article is concerned with the nature and impact of bipolar faradaic electron transfer processes in the context of measuring electrokinetic parameters at the interface between an electronically conductive substrate such as a solid metal layer, and a liquid medium. More specifically, it analyses the steady state electric current through the electrodic substrate layer in terms of its short-circuiting effect on the system's electrokinetic quantities, such as the streaming potential. Ample attention is paid to the electrodic behaviour of the chosen metal and its electron transfer characteristics with respect to redox functions in the medium. The electrochemical reversibility of redox couple species is expressed in terms of their oxidation and reduction rate constants as compared to their diffusive transport rates under lateral flow conditions. High values for rate constants lead to high reversibilities and large bipolar leaking currents through the metal substrate. In turn, high electron transfer rate constants generate large reductions in measured values for electrokinetic quantities such as streaming potentials that further become a non-linear function of the pressure gradient applied through the fluidic chamber. The present article presents an overview of theoretical and experimental approaches of this intricate coupling between bipolar electrode kinetics and electrokinetics and the impact from Hans Lyklema's contributions. It highlights not only the implications of bipolar faradaic depolarisation processes in electrokinetics but also the importance of bipolar electrochemistry principles in various electroanalytical applications reported for e.g. the control of microfluidic flows, for surfaces functionalisation, particles manipulation or for the wireless detection of electroactive analytes.

Rigorous Physicochemical Framework for Metal Ion Binding by Aqueous Nanoparticulate Humic Substances: Implications for Speciation Modeling by the NICA-Donnan and WHAM Codes.

Latest knowledge on the reactivity of charged nanoparticulate complexants toward aqueous metal ions is discussed in mechanistic detail. We present a rigorous generic description of electrostatic and chemical contributions to metal ion binding by nanoparticulate complexants, and their dependence on particle size, particle type (i.e., reactive sites distributed within the particle body or confined to the surface), ionic strength of the aqueous medium, and the nature of the metal ion. For the example case of soft environmental particles such as fulvic and humic acids, practical strategies are delineated for determining intraparticulate metal ion speciation, and for evaluating intrinsic chemical binding affinities and heterogeneity. The results are compared with those obtained by popular codes for equilibrium speciation modeling (namely NICA-Donnan and WHAM). Physicochemical analysis of the discrepancies generated by these codes reveals the a priori hypotheses adopted therein and the inappropriateness of some of their key parameters. The significance of the characteristic time scales governing the formation and dissociation rates of metal-nanoparticle complexes in defining the relaxation properties and the complete equilibration of the metal-nanoparticulate complex dispersion is described. The dynamic features of nanoparticulate complexes are also discussed in the context of predictions of the labilities and bioavailabilities of the metal species.

Pleiotropic effects of rfa-gene mutations on Escherichia coli envelope properties.

Mutations in the rfa operon leading to severely truncated lipopolysaccharide (LPS) structures are associated with pleiotropic effects on bacterial cells, which in turn generates a complex phenotype termed deep-rough. Literature reports distinct behavior of these mutants in terms of susceptibility to bacteriophages and to several antibacterial substances. There is so far a critical lack of understanding of such peculiar structure-reactivity relationships mainly due to a paucity of thorough biophysical and biochemical characterizations of the surfaces of these mutants. In the current study, the biophysicochemical features of the envelopes of Escherichia coli deep-rough mutants are identified from the molecular to the single cell and population levels using a suite of complementary techniques, namely microelectrophoresis, Atomic Force Microscopy (AFM) and Isobaric Tag for Relative and Absolute Quantitation (iTRAQ) for quantitative proteomics. Electrokinetic, nanomechanical and proteomic analyses evidence enhanced mutant membrane destabilization/permeability, and differentiated abundances of outer membrane proteins involved in the susceptibility phenotypes of LPS-truncated mutants towards bacteriophages, antimicrobial peptides and hydrophobic antibiotics. In particular, inner-core LPS altered mutants exhibit the most pronounced heterogeneity in the spatial distribution of their Young modulus and stiffness, which is symptomatic of deep damages on cell envelope likely to mediate phage infection process and antibiotic action.