Flux-assisted self-assembly of monodisperse colloids

We have developed a novel method to grow ordered layers of monodisperse colloids on a flat substrate. The evaporation of the colloidal suspension in the presence of the inclined substrate is strengthened by an external gas flux directed on the meniscus. The meniscus oscillations caused by the gas flux have an evident effect on the ordering of the spheres on the substrate. Thick films (more than 150 layers in a single-step deposition) of large area single crystals (1 cm2) can be obtained in a very short time (~1 cm/h maximum growth rate) and from very diluted suspensions (up to 0.022% volume fraction).

Photostability of wool fabrics coated with pure and modified TiO2 colloids

The surface of wool fabrics was coated with TiO2 and TiO2-based nanocomposite colloids and the impact of this coating on the photostability of wool was investigated. TiO2 along with TiO2/Metal and TiO2/Metal/SiO2 sols were synthesized through a low-temperature sol-gel method and applied to fabrics. Composite colloids were synthesized through integrating the silica and three noble metals of silver (Ag), gold (Au) and platinum (Pt) into the synthesis process of sols. Four different molar ratios of Metal to TiO2 (0.01%, 0.1%, 0.5% and 1%) were used to elucidate the role of metal type and amount on the obtained features. Photostability and UV protection features of fabrics were evaluated through measuring the photo-induced chemiluminescence (PICL), photoyellowing rate and ultraviolet protection factor (UPF) of fabrics. PICL and photoyellowing tests were carried out under UVA and UVC light sources, respectively. PICL profiles demonstrated that the presence of pure and modified TiO2 nanoparticles on fabrics reduced the intensity of PICL peak indicating a lower amount of polymer free radicals in coated wool, compared to that of pristine fabric. Moreover, a higher PICL peak intensity as well as photoyellowing rate was observed on fabrics coated with modified colloids in comparison with pure TiO2. The surface morphology of fabrics was further characterized using FESEM images.

Reprint of: photostability of wool fabrics coated with pure and modified TiO2 colloids

The surface of wool fabrics was coated with TiO2 and TiO2-based nanocomposite colloids and the impact of this coating on the photostability of wool was investigated. TiO2 along with TiO2/Metal and TiO2/Metal/SiO2 sols were synthesized through a low-temperature sol-gel method and applied to fabrics. Composite colloids were synthesized through integrating the silica and three noble metals of silver (Ag), gold (Au) and platinum (Pt) into the synthesis process of sols. Four different molar ratios of Metal to TiO2 (0.01%, 0.1%, 0.5% and 1%) were used to elucidate the role of metal type and amount on the obtained features. Photostability and UV protection features of fabrics were evaluated through measuring the photo-induced chemiluminescence (PICL), photoyellowing rate and ultraviolet protection factor (UPF) of fabrics. PICL and photoyellowing tests were carried out under UVA and UVC light sources, respectively. PICL profiles demonstrated that the presence of pure and modified TiO2 nanoparticles on fabrics reduced the intensity of PICL peak indicating a lower amount of polymer free radicals in coated wool, compared to that of pristine fabric. Moreover, a higher PICL peak intensity as well as photoyellowing rate was observed on fabrics coated with modified colloids in comparison with pure TiO2. The surface morphology of fabrics was further characterized using FESEM images.

Effect of particle size on the photocatalytic activity of nanoparticulate zinc oxide

In this study, a three-stage process consisting of mechanical milling, heat treatment, and washing has been used to manufacture nanoparticulate ZnO powders with a controlled particle size and minimal agglomeration. By varying the temperature of the post-milling heat treatment, it was possible to control the average particle size over the range of 28–57 nm. The photocatalytic activity of these powders was characterized by measuring the hydroxyl radical concentration as a function of irradiation time using the spin-trapping technique with electron paramagnetic resonance spectroscopy. It was found that there exists an optimum particle size of approximately 33 nm for which the photocatalytic activity is maximized. The existence of this optimal particle size is attributable to an increase in the charge carrier recombination rate, which counteracts the increased activity arising from the higher specific surface area for a sufficiently small particle size.

Deployment of DGT units in marine waters to assess the environmental risk from a deep sea tailings outfall

Measurements of total, filterable and DGT-labile concentrations of nine metals (Al, Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn) have been made at five sites up to 4.2km from a deep sea tailings outfall operated by Lihir Gold Ltd. at Lihir Island, Papua New Guinea. At each site, pairs of DGT units (one containing a 0.4mm and the other a 0.8mm diffusive gel layer) were deployed at three depths (50–70; 105–130; 135–155m) for 4–7 days. Comparison of predicted water column DGT-labile metal concentrations in field deployments showed the 0.8mm DGT units were relatively enriched in metals, with the effect being greatest closer to the outfall for Pb and Mn and least for Fe, Cr, Ni and Zn. The most likely explanation for this is that in addition to simple ion diffusion, kinetic factors associated with ageing or desorption processes govern release of metals from iron and aluminium oxyhydroxide colloids which diffuse through the gels. The thicker gels have a longer residence time over which metals can be released for adsorption. This model explains why enrichment is most pronounced near the outfall; more distant sites have lower colloid concentrations because of the longer time for coagulation to increase particle sizes to the extent they cannot enter the gels. Total and filterable metal (FM) concentrations were frequently below the limits of detection (LOD) achievable by conventional ICP-AES (1–52gL⁻¹) and this limited their usefulness for assessing environmental risk and for metal speciation determination. Because of its pre-concentration step DGT gave metal concentrations above their LODs and these decreased exponentially with distance from the outfall. Concentrations of DGT–labile metal fell below Australian water quality guidelines for protection of 99% of marine organisms within 0.13km of the outfall for Cd, Cr and Ni and below that for protection of 95% of marine organisms within 0.4, 0.7 and 3.6km for lead, zinc and copper, respectively.

Comparative analysis of surface-enhanced Raman spectroscopy of daidzein and formononetin

Phytoestrogens daidzein (4′,7-dihydroxy-isoflavone) and formononetin (4′-methoxy-7-hydroxy-isoflavone) have been studied by surface-enhanced Raman (SER) spectroscopy. Spectra were acquired in the presence of citratereduced silver colloids, over a range of pH and concentrations. Density functional theory calculations were used to assist assignment of the normal Raman spectra and help determine the mode of interaction of isoflavones with the silver nanoparticles. Formononetin does not show SER activity unless the 7-OH group is deprotonated, and accordingly, the interaction with the silver surface occurs via the deprotonated site. Daidzein, on the other hand, appears to contain multiple species at the surface, interacting via both the hydroxyl groups at 7-OH and 4′-OH, after deprotonation. This is an important result that points to potential future SERS applications in phytoestrogen analysis and provides a foundation for understanding the SER spectra of isoflavones.

Analysis of 5-hydroxyisoflavones by surface-enhanced Raman spectroscopy : genistein and methoxy derivatives

A series of 5-hydroxy-isoflavones—genistein, biochanin A, prunetin, and 4′,7-dimethoxygenistein—have been studied by surface-enhanced Raman spectroscopy (SERS). Citrate reduced silver colloids were employed as a standard technique to measure SER spectra over a range of pH and concentrations. Density functional theory calculations were used to assist in determining the mode of interaction of isoflavones with the silver nanoparticles. It is revealed that biochanin A and prunetin interact with the silver nanoparticles upon deprotonation of the 7- and the 4′-OH groups, respectively, to show SERS activity. Correlations of their spectra with SERS of genistein strongly support the presence of multiple interaction modes involving both of the OH groups in genistein, in a similar manner to daidzein. Surprisingly, however, under these conditions, the 5-OH group was found to be noninteractive as revealed by attempts to measure SERS of 4′,7-dimethoxygenistein. This was attributed partly to the low solubility and, more importantly, to the influence of steric hindrance, caused by the position of the pendant phenyl ring, which prevented interaction with the Ag colloid surface. These results complement recent work on daidzein and formononetin and provide further insight into understanding the SER spectra of isoflavones.

Surface-enhanced raman scattering spectroscopy of resveratrol

We report here, for the first time, the surface-enhanced Raman scattering (SERS) spectra of resveratrol using KNO₃-aggregated citrate-reduced silver (Ag) colloids. The technique provided a substantial spectral enhancement and therefore good quality spectra of resveratrol at parts per million (ppm) concentrations. The detection limit was found to be <1 μM, equivalent to <0.2 ppm. The SERS profile additionally closely resembled its normal solid-state Raman spectrum with some changes in relative intensity. These intensity changes, together with a precise band assignment aided by density functional theory calculations at the B3LYP/6–31G(d) level, allowed the determination of the structural orientation of the adsorbed resveratrol on the surface of the metal nanoparticles. In particular, the SERS spectra obtained at different resveratrol concentrations exhibited concentration-dependent features, suggesting an influence of surface coverage on the orientation of the adsorbed molecules. At a high concentration, an adoption of close-to-upright orientation of resveratrol adsorbed on the metal surface through the p-OH phenyl ring is favoured. The binding structure is, however, altered at lower surface coverage when the concentration decreases to a tilted orientation with the trans-olefin C=C bond aligning closer to parallel to the surface of the Ag nanoparticles.

Removal of ametryn using membrane bioreactor process and its influence on critical flux

Compared to the Conventional Activated Sludge Process (ASP), Membrane Bioreactors (MBRs) have proven their superior performance in wastewater treatment and reuse during the past two decades. Further, MBRs have wide array of applications such as the removal of nutrients, toxic and persistent organic pollutants (POPs), which are impossible or difficult to remove using ASP. However, fouling of membrane is one of the main drawbacks to the widespread application of MBR technology and Extra-cellular Polymeric Substances (EPS) secreted by microbes are considered as one of the major foulants, which will reduce the flux (L/m2/h) through the membrane. Critical flux is defined as the flux above which membrane cake or gel layer formation due to deposition of EPS and other colloids on the membrane surface occurs. Thus, one of the operating strategies to control the fouling of MBRs is to operate those systems below the critical flux (at Sub-Critical flux). This paper discusses the critical flux results, which were obtained from short-term common flux step method, for a lab-scale MBR system treating Ametryn. This study compares the critical flux values that were obtained by operating the MBR system (consisting of a submerged Hollow-Fibre membrane with pore size of 0.4μm and effective area of 0.2m2) at different operating conditions and mixed liquor properties. This study revealed that the critical flux values found after the introduction of Ametryn were significantly lower than those of obtained before adding Ametryn to the synthetic wastewater. It was also revealed that the production of carbohydrates (in SMP) is greater than proteins, subsequent to the introduction of Ametryn and this may have influenced the membrane to foul more. It was also observed that a significant removal (40-60%) of Ametryn from this MBR during the critical flux determination experiments with 40 minutes flux-step duration.

Self-assembly behavior of colistin and its prodrug colistin methanesulfonate : implications for solution stability and solubilization

Colistin is an amphiphilic antibiotic that has re-emerged into clinical use due to the increasing prevalence of difficult-to-treat Gram-negative infections. The existence of self-assembling colloids in solutions of colistin and its derivative prodrug, colistin methanesulfonate (CMS), was investigated. Colistin and CMS reduced the air−water interfacial tension, and dynamic light scattering (DLS) studies showed the existence of 2.07 ± 0.3 nm aggregates above 1.5 mM for colistin and of 1.98 ± 0.36 nm aggregates for CMS above 3.5 mM (mean ± SD). Above the respective critical micelle concentrations (CMC) the solubility of azithromycin, a hydrophobic antibiotic, increased approximately linearly with increasing surfactant concentration (5:1 mol ratio colistin:azithromycin), suggestive of hydrophobic domains within the micellar cores. Rapid conversion of CMS to colistin occurred below the CMC (60% over 48 h), while conversion above the CMC was less than 1%. The formation of colistin and CMS micelles demonstrated in this study is the proposed mechanism for solubilization of azithromycin and the concentration-dependent stability of CMS.

Direct measurement of surface forces due to charging of solids immersed in a nonpolar liquid

Direct measurements of a long-range force between charged solid surfaces in a nonpolar liquid are presented for the first time. Measurements were made between mica surfaces in solutions of the anionic surfactant sodium di-2-ethylhexylsulfosuccinate (AOT) at millimolar concentrations in n-decane using a surface force apparatus which has been modified to improve its sensitivity for detecting a weak and long-range force. Modifications include a magnetic drive system, the use of a weak cantilever spring with the apparatus mounted in a vertical configuration, and a detailed consideration of the interference optics to allow accurate measurements of surface separations up to several micrometers. The results show a repulsion that is well fitted by theoretical curves based on a model in which only counterions enter the calculation, in other words, in the absence of a reservoir of ions in the solvent. Fitting the theory to the data allows an estimate of the mica surface charge density of ∼1 mC/m². A mechanism for surface charging of mica in this solution is proposed, which includes a role for trace amounts of water that are inevitably present and adsorbed surface aggregates of AOT. The relevance of the results to previously observed charge stabilization of colloids in nonaqueous solvents is discussed.

Measurement of forces due to structure in hydrocarbon liquids

Direct measurements of the force between two molecularly smooth mica sheets immersed in cyclohexane show not a monotonic van der Waals attraction, but an oscillatory function of distance, where the spacing between successive minima corresponds to the molecular diameter of cyclohexane. As surface separation increases the oscillations become less pronounced, and beyond 5 nm (typically seven or eight oscillations) they are no longer detected. These results accord with theoretical ideas on structural forces resulting from the inhomogeneous arrangement of molecules of the liquid near the solid surface. In n-octane the force law does not show the same pronounced oscillations, except at very small separations where repulsive barriers are found. These are attributed to the difficulty of removing the last layers of adsorbed molecules of the liquid from the mica surfaces, and they reduce the mice-mica adhesion significantly. Small amounts of water in the hydrocarbon liquids condense to form a bridge between the surfaces at small separations, causing a very strong adhesion between them. Some implications of these results for the stability of colloids in organic media are discussed.

Surface forces and their action in ceramic materials

A descriptive account is given of the surface forces acting between two solids. Different contributions to the force are outlined, with particular attention paid to the underlying mechanisms, and how they are affected by the nature of the medium between the surfaces. This is followed by a discussion of the areas of ceramic science and engineering in which surface forces play a role.

Forces between bilayers of cetyltrimethylammonium bromide in micellar solutions

A direct force-measuring technique has been used to study the interaction forces between adsorbed CTAB (cetyltrimethylammonium bromide) bilayers at concentrations well above the CMC (critical micelle concentration). An analysis of these results based on the Poisson-Boltzmann equations leads to the conclusion that CTAB micelles and adsorbed bilayers are about 22(±4)% dissociated. The apparent agreement of bilayer and micellar ion binding parameters raises an important challenge for theories of double-layer interactions. In addition, the double-layer decay lengths observed in these micellar solutions appear to be due entirely to the dissociated bromide and free CTA+ ions, with no apparent contribution from charged micelles.