Shannon M. Notley

Highly concentrated aqueous suspensions of graphene through ultrasonic exfoliation with continuous surfactant addition.

Highly concentrated suspensions of graphene stabilized with surfactant were prepared using ultrasonic exfoliation. Concentrations of up to 1.5% w/w (15 mg/mL) were achieved through the continuous addition of the surfactant during the exfoliation process. Previous methods typically add the surfactant only once, prior to the commencement of sonication. The vast increase in the available solid-liquid interfacial area through delamination results in the rapid depletion of the surfactant from solution through adsorption. This leads to a change in the liquid-vapor surface tension outside of the optimum range for the efficient production of graphene sheets. By continuously replacing the surfactant to lower the surface tension during sonication and the production of the graphene surface area, the concentration of particles was significantly increased. Cationic, anionic, and nonionic surfactants were studied and all showed significant increases in the concentration of graphene produced using this continuous addition method.

Graphene Induces Formation of Pores That Kill Spherical and Rod-Shaped Bacteria

Pristine graphene, its derivatives, and composites have been widely reported to possess antibacterial properties. Most of the studies simulating the interaction between bacterial cell membranes and the surface of graphene have proposed that the graphene-induced bacterial cell death is caused either by (1) the insertion of blade-like graphene-based nanosheets or (2) the destructive extraction of lipid molecules by the presence of the lipophilic graphene. These simulation studies have, however, only take into account graphene-cell membrane interactions where the graphene is in a dispersed form. In this paper, we report the antimicrobial behavior of graphene sheet surfaces in an attempt to further advance the current knowledge pertaining to graphene cytotoxicity using both experimental and computer simulation approaches. Graphene nanofilms were fabricated to exhibit different edge lengths and different angles of orientation in the graphene sheets. These substrates were placed in contact with Pseudomonas aeruginosa and Staphylococcus aureus bacteria, where it was seen that these substrates exhibited variable bactericidal efficiency toward these two pathogenic bacteria. It was demonstrated that the density of the edges of the graphene was one of the principal parameters that contributed to the antibacterial behavior of the graphene nanosheet films. The study provides both experimental and theoretical evidence that the antibacterial behavior of graphene nanosheets arises from the formation of pores in the bacterial cell wall, causing a subsequent osmotic imbalance and cell death.

Aqueous dispersions of exfoliated molybdenum disulfide for use in visible-light photocatalysis.

Single and few layer molybdenum disulfide (MoS2) was exfoliated from the bulk form through a liquid phase exfoliation procedure. Highly concentrated suspensions were prepared that were stabilized against reaggregation through adsorption of nonionic polymers to the sheet surface. These exfoliated particles showed strong photoluminescence at an energy of 1.97 eV which is in the visible-light region. These exfoliated MoS2 sheets were then used to catalyze the degradation of a model dye upon exposure to visible light.

Surface Energy and Wettability of Spin-Coated Thin Films of Lignin Isolated from Wood

The surface energy of lignin films spin-coated onto oxidized silicon wafer has been determined from contact angle measurements of different test liquids with varying polar and dispersive components. Three different lignin raw materials were used, a kraft lignin from softwood, along with milled wood lignin from softwood and hardwood. Infrared and (31)P NMR spectroscopy was used to identify any major functional group differences between the lignin samples. No significant difference in the total solid-vapor surface energy for the different lignin films was observed; however, the polar component for the kraft lignin was much greater than for either of the milled wood lignin samples consistent with the presence of carboxyl groups and higher proportion of phenolic hydroxyl groups as shown by quantitative (31)P NMR on the phosphitylated samples. Furthermore, the total surface energy of lignin of 53-56 mJ m(-2) is of a similar magnitude to cellulose, also found in the wood cell wall; however, cellulose has a higher polar component leading to a lower contact angle with water and greater wettability than the milled wood lignin. Although lignin is not hydrophobic according to the strictest definition of a water contact angle greater than 90 degrees, water may only be considered a partially wetting liquid on a lignin surface. This supports the long-held belief that one of the functions of lignin in the wood cell wall is to provide water-proofing to aid in water transport. Furthermore, these results on the solid-vapor surface energy of lignin will provide invaluable insight for many natural and industrial applications including in the design and manufacture of many sustainable products such as paper, fiberboard, and polymer composite blends.

pH dependent stability of aqueous suspensions of graphene with adsorbed weakly ionisable cationic polyelectrolyte

Stable graphene suspensions were prepared through ultrasonic exfoliation followed by surface modification with the cationic polyelectrolyte poly(ethyleneimine) (PEI). The stability of the suspensions was found to be dependent upon the pH of the solution and the molecular weight of the PEI adsorbed. For the graphene sheets with adsorbed PEI with a molecular weigh of 600 Da, the particles were stabilised through an increased electrostatic repulsion at low pH inferred from in an increase in the measured zeta potential of the particles. However, the graphene with higher molecular weight PEI (70 kDa) was stable over a comparatively larger pH range through a combination of electrostatic repulsion at low pH and steric repulsion at elevated pH. Thus, solution conditions allowing the control of the colloidal sized graphene particles can be easily tuned through judicious management of solution conditions as well as polymer layer properties.

Extraordinary Adhesion of Phenylboronic Acid Derivatives of Polyvinylamine to Wet Cellulose: A Colloidal Probe Microscopy Investigation

Typically, the adhesion between cellulose surfaces under aqueous conditions is very poor. Often, adsorbed polymers such as polyvinylamine (PVAm) are used to increase the wet strength; however, this provides only a minimal increase in the adhesion energy. Here, the adhesion between cellulose surfaces with adsorbed layers of phenylboronic acid derivatized polyvinylamine has been studied using colloidal probe microscopy as a function of pH. The adhesion due to the phenylboronic acid (PBA) groups grafted on the polyvinylamine backbone is almost 30 times greater, providing a new, exciting class of polymers using covalent linkages to improve the strength of the joint between cellulose surfaces. The measured surface forces on approach provided key information on the molecular conformation of the polymers at the cellulose-solution interface. At low pH, the three polymers tested, PVAm, PVAm-Ph (with pendant phenol groups), and PVAm-PBA (with phenylboronic acid groups) all had a relatively flat conformation at the interface, which is in agreement with the predictions based upon theory for highly charged polyelectrolytes adsorbing to an oppositely charged interface. With increasing pH, the charge on the polymers is reduced, eventually resulting in a more expansive conformation at the interface at pH 10 and above with the development of a steric interaction force. The onset of this steric force correlates well with the observed significant increase in the pull-off force upon separation of the cellulose surfaces. Furthermore, a greater increase in the adhesion was observed for PVAm-PBA in agreement with previous studies using macroscopic cellulose surfaces. This is attributed to the formation of boronic acid esters between the polymer and the cis diol groups on the cellulose surface.

Adsorption of a strong polyelectrolyte to model lignin surfaces.

The adsorption of a strong, highly charged cationic polyelectrolyte to a kraft lignin thin film was investigated as a function of the adsorbing solution conditions using the quartz crystal microbalance. The polyelectrolyte, PDADMAC, with a molecular weight of 100 kDa and one cationic charge group per monomer, was adsorbed to the anionically charged lignin film in the pH range 3.5-9.5 in electrolyte solution of 0.1 to 100 mM NaCl. At low pH, the adsorbed amount of PDADMAC was minimal, however, this increased as a function of increasing pH. Indeed, the surface excess increased significantly at about pH 8.5, where ionization of the phenolic groups on the lignin macromolecule may be expected. Furthermore, at this elevated pH, the adsorbed amount of PDADMAC decreased as the ionic strength of the solution increased above 1 mM. This is due to the competitive adsorption of counterions to the lignin surface and indicates that the adsorption of PDADMAC to lignin is of a pure electrosorption nature.

Effect of introduced charge in cellulose gels on surface interactions and the adsorption of highly charged cationic polyelectrolytes

The interaction between cellulose surfaces in aqueous solution has been measured using colloidal probe microscopy. Cellulose thin films with varying charge through carboxyl group substitution were used in this study with the surface forces fit to DLVO theory. It was found that the surface potential increased, as expected, with increasing carboxyl substitution. Furthermore, for a given degree of substitution, the surface potential increased as a function of increasing pH. At low pH, the surface forces interaction were attractive and could be fit to the non-retarded Hamaker equation using a constant of 3 x 10(-21) J. At pH greater than 5, the force interactions were monotonically repulsive, regardless of the ionic strength of the solution for all charge densities of the cellulose thin films. The adsorption of polyDADMAC to these charged cellulose films was also investigated using the quartz crystal microbalance. It was found that for the low charge film, a low surface excess of PDADMAC was sensed and that the adsorbed conformation was essentially flat. However for the higher charged cellulose film, a spontaneous de-swelling was observed resulting in no possibility of quantitatively determining the sensed mass using QCM.

Adsorption of polyelectrolyte modified graphene to silica surfaces: monolayers and multilayers.

Exfoliated graphene particles stabilised by the cationic polyelectrolyte polyethyleneimine (PEI) were used in conjunction with an anionic polyelectrolyte, poly(acrylic acid), to construct multilayers using the layer-by-layer technique on a silica substrate. In the first adsorption step, the surface excess of the cationic graphene was dependent on the overall charge on the nanoparticle which in turn can be tuned through modifying solution pH as PEI has weakly ionisable charged amine groups. The adsorbed amount onto the silica surface increased as the solution pH increased. Subsequently, a layer of PAA was adsorbed on top of the cationic graphene through electrostatic interaction. The multilayer could be assembled through this alternate deposition, with the influence of solution conditions investigated. The pH of the adsorbing solutions was the chief determinant of the overall adsorbed amounts, with more mass added at the elevated pH of 9 in comparison with pH 4. Atomic force microscopy confirmed that the graphene particles were adsorbed to the silica interface and that the surface coverage of the disc-like nanoparticles was complete after the deposition of five graphene-polyelectrolyte bi-layers. Furthermore, the graphene nanoparticles themselves could be modified through the consecutive addition of the oppositely charged polymers. A multilayered assembly of negatively charged graphene sheets modified with a bi-layer of PEI and PAA was also deposited on a silica surface with adsorbed PEI.

Interaction between silica in the presence of adsorbed poly(ethyleneimine): correlation between colloidal probe adhesion measurements and yield stress

The interaction forces between silica surfaces with adsorbed layers of polyethyleneimine (PEI) were measured using colloidal probe microscopy as a function of solution conditions and PEI molecular weight. The surface coverage of polymer, as determined from optical reflectometry, was a significant factor influencing the extension of the chains away from the interface and also the development of adhesion between the surfaces. For the high molecular weight PEI (70 kDa), the adhesion passed through a maximum as a function of pH. The magnitude and position of this maximum was dependent on the surface excess of adsorbed PEI. The greatest adhesion was observed for the highest surface coverage of 0.88 mg m(-2) at pH 11 where the force-distance curves on approach indicated the presence of a significant steric layer. Furthermore, the forces on separation under these conditions indicated strong bridging of PEI chains across the interface contributing to the enhanced adhesion. However, at lower surface coverage, no bridging was observed but the adhesion was still significantly greater than in the absence of an adsorbed layer of PEI. The adhesion at lower surface coverage was indicative of a charge-patch mechanism. The measured values of adhesion correlated very well with the observed yield stress of concentrated dispersions of silica in the presence of adsorbed layers of PEI. Thus, the molecular mechanisms probed during surface forces measurements can be used to predict the ensemble behaviour of the many particles dispersed in an aqueous medium which is of particular importance in minerals processing.