Tuning the mechanical and morphological properties of self-assembled peptide hydrogels via control over the gelation mechanism through regulation of ionic strength and the rate of pH change

Hydrogels formed by the self-assembly of peptides are promising biomaterials. The bioactive and biocompatible molecule Fmoc-FRGDF has been shown to be an efficient hydrogelator via a π-β self-assembly mechanism. Herein, we show that the mechanical properties and morphology of Fmoc-FRGDF hydrogels can be effectively and easily manipulated by tuning both the final ionic strength and the rate of pH change. The increase of ionic strength, and consequent increase in rate of gelation and stiffness, does not interfere with the underlying π-β assembly of this Fmoc-protected peptide. However, by tuning the changing rate of the system's pH through the use of glucono-δ-lactone to form a hydrogel, as opposed to the previously reported HCl methodology, the morphology (nano- and microscale) of the scaffold can be manipulated.

The effect of water deprivation on the tonicity responsive enhancer binding protein (TonEBP) and TonEBP-regulated genes in the kidney of the spinifex hopping mouse, Notomys alexis

In desert rodents, the production of concentrated urine is essential for survival in xeric environments in order to conserve water. Reabsorption of water in the kidney is dependent on large osmotic gradients in the renal medulla. This causes the renal cells to be bathed in a hypertonic extracellular fluid that can compromise cellular function. In response to hypertonicity, kidney cells accumulate compatible, non-ionic osmolytes that lower the ionic strength within the cells to isotonic levels by replacing intracellular ionic electrolytes. The tonicity-responsive enhancer binding protein (TonEBP) is a transcription factor that regulates the expression of genes that encode proteins that catalyse the accumulation of compatible osmolytes. We investigated the expression of TonEBP mRNA and protein and compatible osmolyte genes in the Spinifex hopping mouse, Notomys alexis, an Australian desert rodent that produces a highly concentrated urine. TonEBP mRNA expression was unchanged after 3 days of water deprivation but was significantly increased after 7 and 14 days of water deprivation. Immunohistochemistry showed that during water deprivation TonEBP had translocated from the cytoplasm into the nucleus of cells in the renal medulla and papilla. In addition, 3, 7 and 14 days of water deprivation caused a significant increase in aldose reductase (AR), myo-inositol (SMIT), betaine/GABA (BGT-1) and taurine (TauT) transporter mRNA expression, which is indicative of an increase in TonEBP activity. In desert rodents, TonEBP regulation of gene transcription is probably an important mechanism to protect renal cells in the face of the large corticomedullary gradient that is required to concentrate urine and conserve water.

Trace metal speciation in the Pieman River catchment, western Tasmania

The Pieman River catchment has seen continuous mining of economic deposits of gold, silver, lead, copper, zinc and tin since the 1870’s. Tributaries of this river which receive mining effluent, either directly or from acid mine drainage (AMID), have total metal concentrations considerably above background levels and are of regulatory concern. The lower Pieman River is however classified as a State Reserve in which recreational fishing and tourism are the major activities. It is therefore important that water entering the lower Pieman River from upstream hydroelectric impoundments is of high quality. Metals in natural waters exist in a variety of dissolved, colloidal and particulate forms. The bioavailability and hence toxicity of heavy metal pollutants is very dependant on their physico form. Knowledge of the speciation of a metal in natural aquatic environments is therefore necessary for understanding its geochemical behaviour and biological availability. Complexation of metal ions by natural ligands in aquatic systems is believed to play a significant role in controlling their chemical speciation. This study has investigated temporal and spatial variation in complexation of metal ions in the Pieman River. The influence of pH, temperature, organic matter, salinity, ionic strength and time has been investigated in a series of field studies and in laboratory-based experiments which simulated natural and anthropogenic disturbances. Labile metals were measured using two techniques in various freshwater and estuarine environments. Diffusive gradients in thin-films (DGT) allowed in situ measurement of solution speciation whilst differential pulse anodic stripping voltammetry (DPASV) was used to measure labile metal species in water samples collected from the catchment. Organic complexation was found to be a significant regulating mechanism for copper speciation and the copper-binding ligand concentration usually exceeded the total copper concentration in the river water. Complexation was highly dependent on pH and at the river-seawater interface was also regulated by salinity, probably as a result of competitive complexation by major ions in seawater (eg. Ca 2+ ions). Zinc complexation was also evident, however total zinc concentrations in the water column often far exceeded the potential binding capacity of available ligands. In addition to organic complexation, Zn speciation may also be associated with adsorption by flocculated or resuspended colloidal Mn and/or Fe oxyhydroxides. Metal ion complexation and hence speciation was found to be highly variable within the Pieman River catchment. This presents major difficulties for environmental managers, as it is therefore not possible to make catchment-wide assumptions about the bioavailability of these metals. These results emphasise the importance of site-specific sampling protocols and speciation testing, ideally incorporating continuous, in situ monitoring.

Development of a novel micro-spray-assembly process for multilayer ultra-thin film formation

A novel micro-spray-assembly process and an automatic device to fabricate multilayer ultra-thin film are introduced. Employing self-assembly monolayer (SAM) technique, ultra-thin film can be assembled by utilizing the micro-spray-assembly device. The thickness and roughness of each monolayer can be controlled by varying various materials attributes, i.e., deposition time, ionic strength, pH value, molecular concentration and by selecting different manufacturing parameters of the automatic device such as spraying rate, size of micro-drop, N₂ flow rate, temperature of N₂ flow.

Influence of particle concentration on initial collection efficiency and surface coverage in porous media filtration

Four sizes (0.095, 0.53, 1.0 and 2.01 μm) of polystyrene latex particles were used to prepare monodispersed suspensions at three different ionic strengths (10−3, 10−2.5 and 10−2M KCl). Filtration experiments were conducted using those suspensions in a filter column with glass beads as porous medium. The filter bed depth and the filtration velocity were kept at 5 cm and 1 m/h, respectively. When suspensions with equal mass concentrations (0.2 mg/L) or equal surface area concentrations (0.12 cm2/mL) were filtered through the system, the largest particles exhibited higher initial single collector efficiency, η. The difference between the η of largest particles and the smaller particles was prominent for suspensions with equal surface area concentrations at higher ionic strengths. The collision efficiency, α of those particles exhibits higher values at higher ionic strengths. Both at equal mass concentration and equal surface area concentration, α is only slightly dependent on particle sizes when compared to its dependence on ionic strength. Further, it was found that the specific surface coverage was similar for 0.095 μm, 0.53 μm and 1.0 μm particles during the transient stage of filtration at any ionic strength when the surface area concentrations of those suspension were equal.

Surface coverage of filter medium in deep bed filtration : mathematical modelling and experiments

This paper highlights the importance of surface coverage in modeling the removal of particles in deep bed filtration. A model that considers the saturation of sites on which particle deposition occurs is used. Experimental results obtained with monodispersed suspensions of 0.46 and 0.816 μm latex particles at different influent concentrations and ionic strengths were used to calculate the fraction of filter grain surface (β1) on which actual particle deposition occurs. This will be useful in evaluating the filter performance in terms of the utilization of available surface area of the filter medium. Further, the level of dendrite formation of particles on filter grains during filtration is expressed in terms of β1 and the specific surface coverage, θT (the fraction of a filter grain surface that is covered by particles at time T, assuming that the filter grain is covered by a monolayer of particles). This can be used to compare the contribution of deposited particles in the removal efficiency of deep bed filtration for suspensions with different physical and chemical characteristics.

Deposition and wetting characteristics of polyelectrolyte multilayers on plasma-modified porous polyethylene

Hydrophilic and chemically reactive porous media were prepared by adsorbing functional polymers at the surface of sintered polyethylene membranes. Modification of the membrane was accomplished by first exposing the membrane to an oxygen glow discharge gas plasma to introduce an electrostatic charge at the membrane surfaces. Cationic polyelectrolyte polyethylenimine (PEI) was adsorbed from solution to the anionic-charged surface to form an adsorbed monolayer. The adsorption of a second anionic polyelectrolyte onto the PEI layer allows further modification of the membrane surface to form a polyelectrolyte-bilayer complex. The conformation and stability of the adsorbed monolayers and bilayers comprising the modified surface are probed as a function of the polymer structure, charge density, and solubility. Using X-ray photoelectron spectroscopy analysis, we demonstrate that the presence of the polyelectrolyte multilayers drastically increases the density and specificity of the functional groups at the surface, more than what can be achieved through the plasma modification alone. Also, using the wicking rate of deionized, distilled water through the porous membrane to gauge the interfacial energy of the modified surface, we show that the membrane wicking rate can be controlled by varying the chemistry of the adsorbing polyelectrolytes and, to a lesser extent, by adjusting the polarity or ionic strength of the polyelectrolyte solution.

Removal of ametryn through nanofiltration and reverse osmosis

 This study focused on the performance of nanofiltration (NF) and reverse osmosis (RO) in the removal of ametryn. Here, we investigated the effects of the applied pressure and ionic conditions on the removal of ametryn from water. It was found that the adsorption of ametryn onto NF membrane to decrease with the increase in ionic strength. Increased interaction between the NaCl electrolyte and the membrane surface is considered as the reason for the reduction in the adsorption. However, adsorption of ametryn onto the RO membrane did not show any trend. The removal of ametryn by NF and RO found to increase with the increase in the ionic strength. Retention of electrolyte salt (NaCl) on the membrane surface tends to decrease the membrane pore size which in turn increases the removal of ametryn at higher ionic strengths. It was found that up to 92% of ametryn could be removed using RO.

Geochemical changes during recharge with tertiary-treated wastewater at a coastal sandfill

Results of experiments investigating geochemical changes during artificial recharge of treated wastewater at a coastal sandfill, reclaimed with sand dredged from the seabed, are reported in this paper. Laboratory batch experiments were conducted using secondary effluent (SE) and SE treated with an additional ultrafiltration process (UF), and wastewater treated by reverse osmosis (RO) process, mixed with surface sand obtained from the sandfill. Experiments with RO showed a net increase of 0.41 meq/L, 0.12 meq/L and 0.31 meq/L for Ca(2 + ), Mg(2 + ) and HCO(3) (-), respectively. UF and SE also exhibited net increase in Ca(2 + ), Mg(2 + ) and HCO(3) (-) indicating carbonate mineral dissolution. All three waters were found to be over-saturated with respect to calcite. Carbonate dissolution reactions were observed in the field experiments. However, the presence of imported clays from the borrow source gave rise to ion exchange reactions where Na(+) attached to the clay particles were exchanged for Ca(2 + ) and Mg(2 + ) inducing mineral dissolution, driven by sub-saturation conditions. This resulted in an increase in pH with maximum values in excess of 9.0. It was also found that the sodium adsorption ratio remained high (>10) even after the groundwater had been diluted sufficiently to freshwater levels (ionic strength, I <0.015) indicating a potential for the dispersion of clay particles. This could have a deleterious consequence on porosity and hydraulic conductivity.

A parametric study of a monolithic microfluidic system for on-chip biomolecular separation

A microfabricated poly(dimethylsiloxane) (PDMS) chip containing channel filled with polymer monolith has been developed for on-chip biomolecule separation. Methacrylate monolithic polymers were prepared by photo-initiated polymerization within the channel to serve as a continuous stationary phase. The monolithic polymer was functionalized with a weak anion-exchange ligand, and key parameters affecting the binding characteristics of the system were investigated. The total binding capacity was unaffected by the flow rate of the mobile phase but varied significantly with changes in ionic strength and pH of the binding buffer. The binding capacity decreased with increasing buffer ionic strength, and this is due to the limited available binding sites for protein adsorption resulting from cationic shielding effect. Similarly, the binding capacity decreased with decreasing buffer pH towards the isoelectric point of the protein. A protein mixture, BSA and ovalbumin, was used to illustrate the capacity of the methacrylate-based microfluidic chip for rapid biomolecule separation.

Systematic approach to the quantitative voltammetric analysis of the Fe III /Fe II component of the [α 2 -Fe(OH 2 )P 2 W 17 O 61 ] 7-/8- reduction process in buffered and unbuffered aqueous media

The one-electron reduction of [α2-FeIII(OH2)P2W17O61]7- at a glassy carbon electrode was investigated using cyclic and rotating-disk-electrode voltammetry in buffered and unbuffered aqueous solutions over the pH range 3.45−7.50 with an ionic strength of approximately 0.6 M maintained. The behavior is well-described by a square-scheme mechanism P + e- ↔ Q (E10/ = −0.275 V, k10/ = 0.008 cm s-1, and α1 = 1/2), PH+ + e- ↔ QH+ (E20/ = −0.036 V, k20/ = 0.014 cm s-1, and α2 = 1/2), PH+ ↔ P + H+ (KP = 3.02 × 10-6 M), and QH+ ↔ Q + H+ (KQ = 2.35 × 10-10 M), where P, Q, PH+, and QH+ correspond to [α2-FeIII(OH)P2W17O61]8-, [α2-FeII(OH)P2W17O61]9-, [α2-FeIII(OH2)P2W17O61]7-, and [α2-FeII(OH2)P2W17O61]8-, respectively; E10‘ and E20‘ are the formal potentials, k10‘ and k20‘ are the formal (standard) rate constants, and KP and KQ are the acid dissociation constants for the relevant reactions. The analysis for the buffered media is based on the approach of Laviron who demonstrated that a square scheme with fully reversible protonations, reversible or quasi reversible electron transfers with the assumption that α1 = α2, can be well-described by the behavior of a simple redox couple, ox + e- ↔ red, whose formal potential, Eapp0‘, and standard rate constant, kapp0‘, are straightforwardly derived functions of pH, as are the values of E10‘, k10‘, E20‘, k20‘, and KP (only three of the four thermodynamic parameters in a square scheme can be specified). It was assumed that αapp = 1/2, and the simulation program DigiSim was used to determine the values of Eapp0‘ and kapp0‘, which are required to describe the cyclic voltammograms obtained in buffered media in the pH range from 3.45 to 7.52 (buffer-related reactions which effect general acid−base catalysis are included in the simulations). DigiSim simulations of cyclic voltammograms obtained in unbuffered media yielded the values of E10‘ and k10‘; KQ was then directly computed from thermodynamic constraints. These simulations included additional reactions between the redox species and H2O. The value of the diffusion coefficient of the [α2-FeIII(OH2)P2W17O61]7-, 2.92 × 10-6 cm2 s-1, was determined using DigiSim simulations of voltammograms at a rotating disk electrode in buffered and unbuffered media at pH 3.45. The diffusion coefficients of all redox species were assumed to be identical. When the pH is greater than 6, instability of P (i.e., [α2-FeIII(OH)P2W17O61]8-) led to the loss of the reactant and precluded lengthy experimentation.

Potential hydraulic barrier performance of cyclic organic carbonate modified bentonite complexes against hyper salinity

The effect of adding glycerol carbonate (GC) or propylene carbonate (PC) to sodium (Na)-bentonite on the hydraulic performance of geosynthetic clay liners (GCLs) under hypersaline conditions is examined. Fluid loss (FL), swell index (SI) and solution retention capacity (SRC) measurements were carried out to compare the potential hydraulic performance of these two cyclic organic carbonates (COCs) as bentonite modifiers. A modified FL test enabled quantitative measurement of both the water retention characteristics of untreated and COC modified bentonites as well as calculation of hydraulic conductivity values. Tests under aggressively saline conditions (ionic strength, I ≥ 1 M of NaCl and ≥3 M of CaCl2) showed that at a mass ratio of 1:1 (GC to bentonite), the FL of a GC-Na-bentonite was ≈40–104 mL in NaCl and ≈61–91 mL in CaCl2. This was about 10–20 mL and 70–200 mL, respectively, lower than that of a comparable PC-Na-bentonite (1:1 PC to bentonite) and untreated Na-bentonite. Greater swelling (SI) and greater solution retention capacity (SRC) was observed for the GC treated Na-bentonite compared to untreated Na-bentonite in all salt solutions, and for PC-Na-bentonite at high ionic strength of both NaCl and CaCl2 solutions, demonstrating the superior hydraulic barrier performance of COC-bentonites under severely saline conditions. Experiments conducted in flexible-wall permeameters with I = 3 M CaCl2 showed approximately one order of magnitude lower (∼10−11 m/s vs ∼1.9 × 10−10 m/s) hydraulic conductivity of GC treated bentonite cake compared to the k value of the untreated Na-bentonite cake. Calculated hydraulic conductivity from fluid loss tests estimated the measured values in a conservative way (overestimation).

Hydraulic performance of geosynthetic clay liners to sulfuric acid solutions

The ability of geosynthetic clay liners (GCLs) to contain acidic mining leachates is examined. The results of saturated hydraulic conductivity (k) of two GCLs permeated with sulfuric acid solutions (H2SO4) at 0.015M, 0.125M and 0.5M concentrations are reported. Also, the saturated k values of consolidated (35kPa) bentonite cakes made from sodium bentonite extracted from both GCLs were compared to a commonly used magnesium-sodium form bentonite. Chemical compatibility and effects of pre-hydration and effective stress were assessed as part of this study. Results indicated that an increased acid concentration (ionic strength) increased the k of all tested specimens. The ratio of the k0.5 values for non-prehydrated specimens permeated with 0.5M H2SO4 to the kw values for specimens permeated with deionized (DI) water (k0.5/kw) ranged from 10 to 110. Pre-hydration (50-140% water content) and increased effective stress (35-200kPa) improved the performance of GCLs (lower k). Strong correlations were observed between k and liquid limit and swell index parameters independent of pre-hydration and effective stress in this study. However, care should still be taken when using these correlations to evaluate hydraulic performance because the intrinsic micro-structure properties of bentonite, such as porosity, should also be considered. This work showed that, for example, high SI of bentonite does not translate necessarily to a better hydraulic performance of GCLs.

Thermal and physical properties of an archetypal organic ionic plastic crystal electrolyte

The thermal and mechanical properties of the ionic plastic crystal N-methyl-N-propylpyrrolidinium hexafluorophosphate have been investigated and the effect of adding a miscible polymer on the mechanical properties is reported. The physical properties of the pure plastic crystal are discussed in detail and for the first time the change in volume with temperature for an organic ionic plastic crystal is reported. An increase in volume in conjunction with increased conductivity supports the hypothesis that ion conduction within the plastic crystal proceeds via defects. For phase I and melting, the magnitude of the volume increase does not appear to be in accord with the subtle change in conductivity. This is suggested to be due to the presence of layer defects, which allow for correlated ionic motion, which does not increase the conductivity. Addition of polymer to the plastic crystal significantly increases the mechanical strength, decreases the conductivity, but has little effect on the phase behaviour, further supporting the hypothesis of vacancy-mediated conduction.

Blend films of natural wool and cellulose prepared from an ionic liquid

Natural wool/cellulose blends were prepared in an ionic liquid green solvent, 1-butyl-3-methylimidazolium chloride (BMIMCl) and the films were formed subsequently from the coagulated solutions. The wool/cellulose blend films show significant improvement in thermal stability compared to the coagulated wool and cellulose. Moreover, the blend films exhibited an increasing trend of tensile strength with increase in cellulose content in the blends which could be used for the development of wool-based materials with improved mechanical properties, and the elongations of the blends were considerably improved with respect to the coagulated films of wool and cellulose. It was found that there was hydrogen bonding interaction between hydroxyl groups of wool and cellulose in the coagulated wool/cellulose blends as determined by Fourier transform infrared (FTIR) spectroscopy. The ionic liquid was completely recycled with high yield and purity after the blend film was prepared. This work presents a green processing route for development of novel renewable blended materials from natural resource with improved properties.