Adsorption, lubrication, and wear of lubricin on model surfaces : polymer brush-like behavior of a glycoprotein

Using a surface force apparatus, we have measured the normal and friction forces between layers of the human glycoprotein lubricin, the major boundary lubricant in articular joints, adsorbed from buffered saline solution on various hydrophilic and hydrophobic surfaces: i), negatively charged mica, ii), positively charged poly-lysine and aminothiol, and iii), hydrophobic alkanethiol monolayers. On all these surfaces lubricin forms dense adsorbed layers of thickness 60–100 nm. The normal force between two surfaces is always repulsive and resembles the steric entropic force measured between layers of end-grafted polymer brushes. This is the microscopic mechanism behind the antiadhesive properties showed by lubricin in clinical tests. For pressures up to ∼6 atm, lubricin lubricates hydrophilic surfaces, in particular negatively charged mica (friction coefficient μ = 0.02–0.04), much better than hydrophobic surfaces (μ > 0.3). At higher pressures, the friction coefficient is higher (μ > 0.2) for all surfaces considered and the lubricin layers rearrange under shear. However, the glycoprotein still protects the underlying substrate from damage up to much higher pressures. These results support recent suggestions that boundary lubrication and wear protection in articular joints are due to the presence of a biological polyelectrolyte on the cartilage surfaces.

Granular Activated Carbon (GAC) adsorption in tertiary wastewater treatment : experiments and models

Wastewater treatment has always been a major concern in the developed countries. Over the last few decades, activated carbon adsorption has gained importance as an alternative tertiary wastewater treatment and purification process. In this study, granular activated carbon (GAC) adsorption was evaluated in terms of total organic carbon (TOC) removal from low strength synthetic wastewater. This paper provides details on adsorption experiments conducted on synthetic wastewater to develop suitable adsorption isotherms. Although the inorganics used in the synthetic wastewater solution had an overall unfavourable effect on adsorption of organics, the GAC adsorption system was found to be effective in removing TOC from the wastewater. This study showed that equation of state (EOS) theory was able to fit the adsorption isotherm results more precisely than the most commonly used Freundlich isotherm. Biodegradation of the organics with time was the most crucial and important aspect of the system and it was taken into account in determining the isotherm parameters. Initial organic concentration of the wastewater was the determining factor of the model parameters, and hence the isotherm parameters were determined covering a wide range of initial organic concentrations of the wastewater. As such, the isotherm parameters derived using the EOS theory could predict the batch adsorption and fixed bed adsorption results of the multi-component system successfully. The isotherm parameters showed a significant effect on the determination of the mass transfer coefficients in batch and fixed bed systems.

Benzene adsorption at the aqueous (011) α-quartz interface : is surface flexibility important?

Atomistic simulations of molecular adsorption onto inorganic substrates under aqueous conditions can be used to guide the rational design of new materials, fabricated using biomimetic methods. The success of such work depends critically on the model used. Here, we investigate the impact of using a rigid structural model of the (0 1 1) ?-quartz surface, over a fully flexible model, on the calculated free energy change in the adsorption of a single molecule of benzene (a simple analogue of the amino acid phenylalanine) from liquid water. Subtle differences in the mobility of the adsorbate close to the surface result in the free energy of adsorption being overestimated by the rigid model, relative to the fully flexible case. Moreover, we find that the distribution of bound configurations of the adsorbate at their respective free energy minima is different between the two models.

Efficient simulations of the aqueous bio-interface of graphitic nanostructures with a polarisable model.

To fully harness the enormous potential offered by interfaces between graphitic nanostructures and biomolecules, detailed connections between adsorbed conformations and adsorption behaviour are needed. To elucidate these links, a key approach, in partnership with experimental techniques, is molecular simulation. For this, a force-field (FF) that can appropriately capture the relevant physics and chemistry of these complex bio-interfaces, while allowing extensive conformational sampling, and also supporting inter-operability with known biological FFs, is a pivotal requirement. Here, we present and apply such a force-field, GRAPPA, designed to work with the CHARMM FF. GRAPPA is an efficiently implemented polarisable force-field, informed by extensive plane-wave DFT calculations using the revPBE-vdW-DF functional. GRAPPA adequately recovers the spatial and orientational structuring of the aqueous interface of graphene and carbon nanotubes, compared with more sophisticated approaches. We apply GRAPPA to determine the free energy of adsorption for a range of amino acids, identifying Trp, Tyr and Arg to have the strongest binding affinity and Asp to be a weak binder. The GRAPPA FF can be readily incorporated into mainstream simulation packages, and will enable large-scale polarisable biointerfacial simulations at graphitic interfaces, that will aid the development of biomolecule-mediated, solution-based graphene processing and self-assembly strategies.

Adsorption and desorption characteristics of fluoride in the calcareous and siliceous sand sheet aquifers of south-west Victoria, Australia

This study assessed the sustainability of utilising groundwater systems to manage an aluminium smelters fluoridated trade wastewater stream. Replacing ocean discharge of the wastewater with land irrigation is one option. Using a groundwater model (developed using MODFLOW incorporating parameter estimation software (PEST-ASP)), we found that most of the groundwater flow takes place through surface sands. Fluoride is adsorbed in these sands during the drier summer months, but desorption is rapid when winter rain flushes the aquifer. Underlying clays and other layers prevent significant contamination of the deeper aquifer.

Adsorption kinetics and optimum conditions for Cr(VI) removal by activated carbon prepared from luffa sponge

Activated carbon (AC) prepared from luffa sponge was firstly used as an adsorbent to remove Cr(VI) from aqueous solution. The Cr(VI) adsorption behaviors of AC under different conditions, including initial Cr(VI) concentration, quantity of AC, solution pH, and temperature were investigated. The optimal conditions for adsorption of Cr(VI) by AC were pH = 1, initial Cr(VI) concentration = 80 mg/L, T = 303 K, and AC content = 1.6 g/L. The adsorption kinetics could be described by the pseudo-second-order model. Fourier transform infrared spectroscopy was used to investigate the sorption mechanism. Some functional groups such as C–O and O–H were formed on the carbon surface, which could then react with Cr(VI). The surface structure of AC before and after adsorption was analyzed by scanning electronic microscopy. Adsorbed ions choked some of the pores in AC after adsorption. The Brunauer–Emmett–Teller surface area and average pore size of the AC were 834.13 m2/g and 5.17 nm, respectively. The maximum adsorption of Cr(VI) by AC was 149.06 mg/g, which makes AC prepared from luffa sponge promising for removing Cr(VI) from wastewater.

Preparation and adsorption of phosphorus by new heteropolyacid salt–lanthanum oxide composites

In this article, we reported a new method in which molybdenum heteropolyacid salt was selected to mix with lanthanum oxide and bentonite, respectively, and the dipping method was used to prepare the new composites of heteropolyacid salt–lanthanum oxide, heteropolyacid salt–bentonite, and heteropolyacid salt–lanthanum oxide–bentonite. We observed that the composites have a better removal effect for phosphorus by control of the ratio and calcination temperature. The effect of quantity, adsorption time, phosphorus wastewater concentration, and pH value of composites on phosphorus adsorption was studied. We also found that the removal rate of phosphorus by the composite of heteropolyacid salt–lanthanum oxides increases up to 99.1% under the condition of 1:1 mass ratio and 500°C of calcination temperature. IR and XRD studies suggest that molybdenum heteropolyacid salt has been loaded to lanthanum oxide carrier successfully and heteropolyacid salt keeps the original Keggin structure. Heteropolyacid salt–lanthanum oxide has a good adsorption effect on phosphorus under the condition of 0.15 g of the composite, 90 min of adsorption time, phosphorus concentration of 50 mg L−1, and pH value of 3. The adsorption of phosphorus corresponds with the Langmuir isotherm model and Lagergren first-order kinetics equation. Therefore, the composite has excellent absorption ability and was competent in removing phosphorus with a low concentration from aqueous solution. It could be a great potential adsorbent for the removal of phosphorus in lakes, rivers, and reservoirs.

Liquid phase adsorption kinetics and equilibrium of toluene by novel modified-diatomite

The adsorption equilibria of toluene from aqueous solutions on natural and modified diatomite were examined at different operation parameters such as pH, contact time, initial toluene concentration was evaluated and optimum experimental conditions were identified. The surface area and morphology of the nanoparticles were characterized by SEM, BET, XRD, FTIR and EDX analysis. It was found that in order to obtain the highest possible removal of toluene, the experiments can be carried out at pH 6, temperature 25°C, an agitation speed of 200 rpm, an initial toluene concentration of 150 mg/L, a centrifugal rate of 4000 rpm, adsorbent dosage = 0.1 g and a process time of 90 min. The results of this work show that the maximum percentage removal of toluene from aqueous solution in the optimum conditions for NONMD was 96.91% (145.36 mg/g). Furthermore, under same conditions, the maximum adsorption of natural diatomite was 71.45% (107.18 mg/g). Both adsorption kinetic and isotherm experiments were carried out. The experimental data showed that the adsorption follows the Langmuir model and Freundlich model on natural and modified diatomite respectively. The kinetics results were found to conform well to pseudo-second order kinetics model with good correlation. Thus, this study demonstrated that the modified diatomite could be used as potential adsorbent for removal of toluene from aqueous solution.

Use of optical interferometry to measure gold nanoparticle adsorption on silica

Adsorption of metal nanoparticles is at the heart of many chemical and biosensor techniques, but there are few approaches that can provide quantitative characterisation of individual nanoparticle films fabricated at different times and/or under different conditions. Using synthesised gold nanoparticles (Au NPs) as a model, the nanoparticle films were investigated using an optical interferometry technique known as fringes of equal chromatic order (FECO), which was further systematically validated against both in situ quartz crystal microbalance (QCM) and ex situ atomic force microscopy (AFM) measurements. The results indicate that the FECO wavelengths has a quantifiable red shift with increasing particle densities, making it possible to quantify the degree of surface coverage via the analysis of the fringe shift at a fixed fringe order. Moreover, the calculated formula between the FECO shifts and the surface coverage allows quantitative analysis of the whole adsorption kinetics investigated. Particularly, the as-proposed FECO technique can successfully monitor the Au NP adsorption in situ, which could be a new versatile technology platform for “online” monitoring method, for example in biosensor applications using Au NP-tagged analytes.