Graphene oxides (GO) of highly polydisperse size distribution were prepared by the Brodie method and their dispersion stability was characterized. Exfoliation and fractionation led to well-defined particle populations in the Nano, classical Colloidal (submicron) and Micrometer size ranges, as revealed by atomic force microscopy and light scattering measurements. Time-resolved dynamic light scattering experiments revealed that aggregation processes are fully impeded in the intermediate pH regime of 3-13 in the absence of electrolytes. While the resistance against salt-induced aggregation increases with the pH due to the progressive ionization of the surface functional groups of GO sheets, their dispersions are inherently unstable at supramillimolar concentrations of strong acids and submolar concentrations of bases, in line with the DLVO theory. However, the aggregation behavior quantified by the critical coagulation concentrations (CCCs) shows surprisingly substantial platelet size dependence. The CCC of Nano Brodie-GO reaches 360 mM at pH =3D 12, which is one of the highest values ever reported for GO aqueous dispersions. These results provide useful quantitative information to design processable GO dispersions of pH- and size-tunable stability for future applications. (C) 2020 The Author(s). Published by Elsevier Ltd.

Using MP2, CCSD, and B3LYP methods of computational chemistry, we show length dependence in the intrinsic elastic properties of short alkane fragments. For isolated alkane fragments of finite length in the gas phase and zero temperature, the intrinsic elasticity constants are found to vary with the number of carbon atoms and its parity. From extrapolation of the elasticity constants calculations to infinite chain length, and by comparing with in-situ elasticity constant of single poly(ethylene) molecule obtained with atomic force microscopy, we estimate the softening effect of environment on the extension response of the polymer.

The colloidal probe technique was used to measure the inner layer capacitance of an electrical double layer. In particular, the forces were measured between silica surfaces and sulfate latex surfaces in solutions of monovalent salts of different alkali metals. The force profiles were interpreted with Poisson-Boltzmann theory with charge regulation, whereby the diffuse layer potential and the regulation properties of the interface were obtained. While the diffuse layer potential was measured in this fashion in the past, we are able to extract the regulation properties of the inner layer, in particular, its capacitance. We find systematic trends with the type of alkali metal ion and the salt concentration. The observed trends could be caused by difference in ion hydration, variation of the binding capacitance, and changes of the effective dielectric constant within the Stern layer. Our results are in agreement with recent experiments involving the water-silica interface based on a completely independent method using X-ray photoelectron spectroscopy in a liquid microjet. This agreement confirms the validity of our approach, which further provides a means to probe other types of interfaces than silica.

Direct force measurements between negatively charged colloidal particles were carried out using an atomic force microscope (AFM) in aqueous solutions containing monovalent organic cations, namely tetraphenylarsonium (Ph4As+), 1-hexyl-3-methylimidazolium (HMIM+), and 1-octyl-3-methylimidazolium (OMIM+). These ions adsorb to the particle surface, and induce a charge reversal. The forces become attractive at the charge neutralization point, but they are stronger than van der Waals forces. This additional and unexpected attraction decays exponentially with a decay length of a few nanometers, and is strikingly similar to the one previously observed in the presence of multivalent ions. This attractive force probably originates from coupled spontaneous charge fluctuations on the respective surfaces as initially suggested by Kirkwood and Shumaker.

The persistence length of cationic dendronized polymers adsorbed onto oppositely charged substrates was studied by atomic force microscopy (AFM) and quantitative image analysis. One can find that a decrease in the ionic strength leads to an increase of the persistence length, but the nature of the substrate and of the generation of the side dendrons influence the persistence length substantially. The strongest effects as the ionic strength is being changed are observed for the fourth generation polymer adsorbed on mica, which is a hydrophilic and highly charged substrate. However, the observed dependence on the ionic strength is much weaker than the one predicted by the Odijk, Skolnik, and Fixman (OSF) theory for semi-flexible chains. Low-generation polymers show a variation with the ionic strength that resembles the one observed for simple and flexible polyelectrolytes in solution. For high-generation polymers, this dependence is weaker. Similar dependencies are found for silica and gold substrates. The observed behavior is probably caused by different extents of screening of the charged groups, which is modified by the polymer generation, and to a lesser extent, the nature of the substrate. For highly ordered pyrolytic graphite (HOPG), which is a hydrophobic and weakly charged substrate, the electrostatic contribution to the persistence length is much smaller. In the latter case, we suspect that specific interactions between the polymer and the substrate also play an important role.

The present article offers an overview on the use of atomic force microscopy (AFM) to characterize the nanomechanical properties of polymers. AFM imaging reveals the conformations of polymer molecules at solid liquid interfaces. In particular, for polyelectrolytes, the effect of ionic strength on the conformations of molecules can be studied. Examination of force versus extension profiles obtained using AFM-based single molecule force spectroscopy gives information on the entropic and enthalpic elasticities in pN to nN force range. In addition, single molecule force spectroscopy can be used to trigger chemical reactions and transitions at the molecular level when force-sensitive chemical units are embedded in a polymer backbone.

Titanate nanowires (TiONWs) are synthesized through the hydrothermal method and characterized in acidic aqueous dispersions by using electrophoresis, dynamic light scattering, and atomic force microscopy. The TiONWs have a rodlike shape with an average length of about 600nm and a thickness of 35nm. They are positively charged under the conditions used. Their surface charge properties and aggregation are investigated in the presence of oppositely charged poly(styrene sulfonate) (PSS) polyelectrolyte. Charge neutralization followed by a subsequent charge reversal process is observed, which is attributed to the adsorption of PSS. The colloids are unstable near the charge neutralization point and stable at lower and higher PSS doses, in good qualitative agreement with the theory developed by Derjaguin, Landau, Verwey, and Overbeek (DLVO). The nanowires prefer to align along the walls, leading to spaghetti-like oriented aggregates. The aggregation processes of bare and PSS-coated TiONWs are monitored at different concentrations of an inert electrolyte; slow aggregation is found at low salt levels, whereas aggregation is rapid beyond the critical coagulation concentration, as predicted by the DLVO theory, which describes the colloid stability of the TiONWs adequately in all the systems investigated. Coating of the nanowires with the polyelectrolyte leads to a critical coagulation concentration 75 times higher than that of the bare titanates, indicating the enormous stabilizing effect of PSS.

We present a study of the adsorption of chitosan on silica. The adsorption behavior and the resulting layer properties are investigated by combining optical reflectometry and the quartz crystal microbalance. Exactly the same surfaces are used to measure the amount of adsorbed chitosan with both techniques, allowing the systematic combination of the respective experimental results. This experimental protocol makes it possible to accurately determine the thickness of the layers and their water content for chitosan adsorbed on silica from aqueous solutions of varying composition. In particular, we study the effect of pH in 10 mM NaCl, and we focus on the influence of electrolyte type and concentration for two representative pH conditions. Adsorbed layers are stable, and their properties are directly dependent on the behavior of chitosan in solution. In mildly acidic solutions, chitosan behaves like a weakly charged polyelectrolyte, whereby electrostatic attraction is the main driving force for adsorption. Under these conditions, chitosan forms rigid and thin adsorption monolayers with an average thickness of approximately 0.5 nm and a water content of roughly 60%. In neutral solutions, on the other hand, chitosan forms large aggregates, and thus adsorption layers are significantly thicker (10 nm) as well as dissipative, resulting in a large maximum of adsorbed mass around the pK of chitosan. These films are also characterized by a substantial amount of water, up to 95% of their total mass. Our results imply the possibility to produce adsorption layers with tailored properties simply by adjusting the solution chemistry during adsorption. =20

We report herein on the polymer-crystallization-assisted thiol-ene photosynthesis of an amphiphilic comb/graft DNA copolymer, or molecular brush, composed of a hydrophobic poly(2-oxazoline) backbone and hydrophilic short single-stranded nucleic acid grafts. Coupling efficiencies are above 60% and thus higher as compared with the straight solid-phase-supported synthesis of amphiphilic DNA block copolymers. The DNA molecular brushes self-assemble into sub-micron-sized spherical structures in water as evidenced by light scattering as well as atomic force and electron microscopy imaging. The nucleotide sequences remain functional, as assessed by UV and fluorescence spectroscopy subsequent to isoindol synthesis at the surface of the structures. The determination of a vesicular morphology is supported by encapsulation and subsequent spectroscopy monitoring of the release of a water-soluble dye and spectroscopic quantification of the hybridization efficiency (30% in average) of the functional nucleic acid strands engaged in structure formation: about one-half of the nucleotide sequences are available for hybridization, whereas the other half are hindered within the self-assembled structure. Because speciation between complementary and non complementary sequences in the medium could be ascertained by confocal laser scanning microscopy, the stable self-assembled molecular brushes demonstrate the potential for sensing applications. =20

Modification of solid substrates by poly-L-lysine (PLL) layers has been widely employed in order to improve their biocompatibility, for promoting protein and cell immobilization for fabrication of biosensor arrays and antibacterial coatings. However, despite many studies conducted in the literature, there is a deficiency in a quantitative description of PLL adsorption processes. It is postulated that this becomes feasible by applying direct experimental techniques combined with thorough theoretical modeling. In this work, the kinetics of PLL adsorption on silica for various ionic strengths was determined in situ under controlled flow conditions using the optical reflectometry and the streaming potential methods. Both the initial adsorption rates and longer time kinetic runs were acquired and quantitatively interpreted in terms of the convective diffusion and the random sequential adsorption theoretical modeling based on the coarse-grained Monte Carlo approach. This unique combination of experimental and theoretical approaches enabled us to gain new insight into the mechanism of macroion adsorption controlled by the electrostatic interactions, which affect both the molecule conformations and the blocking effects. Besides significance for basic science, the results obtained in this work can be exploited for developing reliable procedures for preparing stable PLL monolayers of well-controlled coverage and electrokinetic properties.

Various techniques to measure the force-extension relationship of individual polymer chains with the atomic force microscope (AFM) are compared. Reliable stretching force profiles can be obtained with the nano-handling technique, which involves imaging of the measured individual polymer molecules prior and after the force experiment. Results originating from the classical pulling technique, which relies on dense adsorbed polymer layers, must be interpreted with care. Comparison with the nano-handling technique reveals that the stretching response of individual molecules can be obtained with the pulling technique, provided the adsorbed polymer layer is dilute. For denser adsorbed layers, such experiments may not reflect the correct stretching response. The discrepancies seem to be related to polymer epolymer interactions and entanglements within the adsorbed layer. AFM imaging of the adsorbed layers can provide an indication concerning the relevance of such entanglement effects. Similar caveats apply to fishing experiments, where polymers are adsorbed to the AFM tip and not to the substrate. (C) 2016 Elsevier Ltd. All rights reserved.

Optical reflectometry was used to study adsorption behavior of poly(L-lysine) (PLL) on the water-silica interface for different pH and concentrations of the monovalent salt NaBr. At low salt level and low pH, the adsorbed amount increases with increasing salt concentration and pH This adsorption behavior can be qualitatively explained by electrostatic Interactions between the negatively charged substrate and the positively charged polyelectrolyte. At higher salt levels and pH, the adsorbed amount passes through a maximum. This maximum is probably related to the competition between adsorbing monovalent canons and the polyelectrolyte. The initial adsorption kinetics is mainly controlled by the mass transport to the surface (C) 2010 Elsevier B.V. All rights reserved

Reflectometry and quartz crystal microbalance are used to study the response of adsorbed polyelectrolyte monolayers to solutions of variable composition. These techniques respectively yield the dry and wet masses of the adsorbed layer, and by combing these results, one obtains the water content and the thickness of the polyelectrolyte films. The systems investigated are films of adsorbed poly(allyl amine) (PAH) and poly-L-lysine (PLL) on silica and films of poly(styrene sulfonate) (PSS) on amino-functionalized silica. When such films are adsorbed from concentrated polyelectrolyte solutions containing high levels of salt, they are found to swell reversibly up to a factor of 2 when incubated in solutions of low salt. This swelling is attributed to the strengthening of repulsive electrostatic interactions between the adsorbed polyelectrolyte chains. PAH films may also swell upon decrease of pH, and collapse upon a pH increase. This transition shows a marked hysteresis and can be rationalized by the competition of electrostatic repulsions between the chains and their attraction to the surface. The presently observed swelling phenomena are caused by a collective process driven by the electrostatic repulsion between the densely adsorbed polyelectrolyte chains. Such responsive layers are only obtained by adsorption from high polyelectrolyte and salt concentrations. Layers absorbed at low polyelectrolyte and salt concentrations show only minor swelling effects, since the adsorbed polyelectrolytes layers are dilute and the adsorbed polyelectrolyte chains interact only weakly.

Adsorption of poly(amido amine) (PAMAM) dendrimers at water-silica interfaces and the resulting self-organization on this type of substrate is discussed. Investigations with optical reflectivity and atomic force microscopy (AFM) reveal that dendrimers form monolayers of low coverage on such surfaces with liquid-like structure. The nearest neighbor separation distance in these layers is dictated by screened Coulomb repulsion forces between the adsorbing dendrimers. This effect rationalizes the strong increase of the adsorbed amount with the ionic strength and pH. These layers are stable for high dendrimer generations, while they can become unstable for lower generations.

Forces between individual colloidal particles can be measured with the atomic force microscope (AFM), and this technique permits the study of interactions between surfaces across aqueous solutions in great detail. The most relevant forces are described by the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, and they include electrostatic double-layer and van der Waals forces. In symmetric systems, the electrostatic forces are repulsive and depend strongly on the type and concentration of the salts present, while van der Waals forces are always attractive. In asymmetric systems, the electrostatic force can become attractive as well, even when involving neutral surfaces, while in rare situations van der Waals forces can become repulsive too. The enormous sensitivity of the double layer forces on additives present is illustrated with oppositely charged polyelectrolytes, which may induce attractions or repulsions depending on their concentrations.