Synthesis, characterization, and multilayer assembly of pH sensitive graphene−polymer nanocomposites

pH sensitive graphene−polymer composites have been prepared by the modification of graphene basal planes with pyrene-terminated poly(2-N,N′-(dimethyl amino ethyl acrylate) (PDMAEA) and poly(acrylic acid) (PAA) via π−π stacking. The pyrene-terminal PDMAEA and PAA were synthesized using reversible addition−fragmentation chain transfer (RAFT) polymerization with a pyrene-functional RAFT agent. The graphene−polymer composites were found to demonstrate phase transfer behavior between aqueous and organic media at different pH values. Atomic force microscopy (AFM) analysis revealed that the thicknesses of the graphene−polymer sheets were approximately 3.0 nm when prepared using PDMAEA (M_n: 6800 and PDI: 1.12). The surface coverage of polymer chains on the graphene basal plane was calculated to be 5.3 × 10⁻¹¹ mol cm⁻² for PDMAEA and 1.3 × 10⁻¹⁰ mol cm⁻² for PAA. The graphene−polymer composites were successfully characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR-IR) spectroscopy, and thermogravimetric analysis (TGA). Self-assembly of the two oppositely charged graphene−polymer composites afforded layer-by-layer (LbL) structures as evidenced by high-resolution scanning electron microscopy (SEM) and quartz crystal microbalance (QCM) measurements.

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.

Anion recognition and sensing in organic and aqueous media using luminescent and colorimetric sensors

This review article focuses primarily on the work carried in our laboratories over the last few years using luminescent and colorimetric sensors, where the anion recognition occurs through hydrogen bonding in organic or aqueous solvents. This review begins with the story of the discovery of fluorescent photoinduced electron transfer (PET) sensors for anions using charged neutral urea or thiourea receptors where both fluorescent and NMR spectroscopic methods monitored anion recognition. This work led to the development of dual luminescent and colorimetric anion sensors based on the use of the ICT based naphthalimide chromophore, where ions such as fluoride gave rise to changes in both the fluorescence and the absorption spectra of the sensors, but at different concentrations. Here, the former changes were due to hydrogen bonding interactions, whereas the latter was due to the deprotonation of acidic protons, giving rise to the formation of the bifluoride anion (HF2−). Modification of the 4-amino-l,8-naphthalimide moiety has facilitated the formation of colorimetric anion sensors that work both in organic or aqueous solutions. Such charge neutral receptor motifs have also been incorporated into organic scaffolds with norbomyl and calixarene backbones, which have enabled us to produce anion directed self-assembled structures.

Use of plastic and textile media in polishing primary treated effluent

The majority of on-site sewage management systems in Australia fail to perform to expectations. About 60% to 80% of on-site systems reportedly fail to produce acceptable effluent quality, and there is an increaed concern about the risks associated with public health and environmental pollution. In Victoria, a large proportion of septic tank installations have been reported to discharge highly polluted waste to drains and streams. Users, often considered by regulators as operators, have to bear the costs of upgrade/replacement of their old systems to meet stringent water quality guidelines. Some of the common problems include clogging of the disposal fields due to solids and organic overloading and surfacing of highly polluted effluent. Large land application area is subsequently required for irrigating the effluent and/or installation of upgraded disposal fields.
This paper investigates the effectiveness of various types of textile and plastic media, in polishing primary tank effluent, downstream from a typical two-compartment septic tank system. Results to date show that high biochemical oxygen demand removal rates are achieved from the textile and plastic media (up to 86% and 83% respectively). At these removal levels, the performance of a combined conventional septic tank system and plastic/textile filters is comparable to that of an advanced aerated wastewater treatment system. This approach, subject to further investigation, could provide a less costly upgrade.

Evaluating the performance of different media in a horizontal subsurface flow constructed wetland

The treatment efficiency of a wetland system requires a balance between pollutant loading rate and hydraulic retention time (HRT), hydraulic loading rate (HLR) and the suitable substrate to be used. The aim of this study was to investigate the treatment efficiency of horizontal subsurface flow constructed wetland planted with phragmites australis and scirpus maritimus containing three different substrates to treat agricultural wastewater under short term operation. Alum sludge and zeolite were used as substrates and gravel was used as a control for a laboratory-scale horizontal flow constructed wetland (CW) units that were made of high-density Polyethylene. The units were operated under 2, 3 and 4 days of HRTs and at different HLR for each substrate. Each beds received 0.012 m3/d to 0.08 m3/d of synthetic wastewater corresponding to a HLR of 0.035 to 0.243 m/d and a COD loading rate of 0.0148 kg COD (m2.d)-1 to 0.026 kg COD (m2.d)-1. The relationships between the substrate, retention time and removal efficiency, especially of organic matter and nutrient removal were investigated. All units showed relatively stable removal for COD during the entire operational period. The COD removal for all units and HRT were in ranged from 67% to 93%. The zeolite unit achieved significantly higher removal of TN, NH4-N and TSS compared to alum sludge and gravel unit at all HRT. The unit with zeolite was highly effective in removing TN (54 to 96%), NH4-N (50 to 99%) and TSS (91 to 96%) respectively, at 2, 3 and 4 days of HRT. Meanwhile, alum sludge was highly effective in removing phosphate. The removal of phosphate from alum sludge unit was ranged from 94 to 97% for all HRT. Compared to gravel CW unit, zeolite and alum sludge CW were proved to be tolerant to high organic loadings and nutrients, suggesting these substrates as viable options for biological treatment of agricultural wastewater.

Microbial lipases : at the interface of aqueous and non-aqueous media: a review

In recent times, biotechnological applications of microbial lipases in synthesis of many organic molecules have rapidly increased in non-aqueous media. Microbial lipases are the working horses' in biocatalysis and have been extensively studied when their exceptionally high stability in non-aqueous media has been discovered. Stability of lipases in organic solvents makes them commercially feasibile in the enzymatic esterification reactions. Their stability is affected by temperature, reaction medium, water concentration and by the biocatalyst's preparation. An optimization process for ester synthesis from pilot scale to industrial scale in the reaction medium is discussed. The water released during the esterification process can be controlled over a wide range and has a profound effect on the activity of the lipases. Approaches to lipase catalysis like protein engineering, directed evolution and metagenome approach were studied. This review reports the recent development in the field of non-aqueous microbial lipase catalysis and factors controlling the esterification/transesterification processes in organic media.

Removal of natural organic matter though membrane filtration and subsequent effect on disinfectant decay

This study aims to evaluate the effectiveness of membrane filtration in removing natural organic matters (NOMs) from four different source waters and the subsequent effect that it has on total chlorine (TC) demand of these waters. Source water samples were filtered sequentially through membranes with molecular weight cut-off of 3,500, 1,000 and 200 Da as well as RO membrane. The source waters and sequentially filtered samples were dosed with chlorine and the residual chlorine data were used to estimate the TC demand of these waters. A robust chlorine decay model constructed in AQUASIM software was used to do so. More than 80% of the chlorine demand in untreated surface water sources was found to be contributed mainly by NOMs that were larger than 3,500 Da. However, for water treated by granular filtration, the chlorine demand was found to be contributed by NOMs which were down to 200 Da. Sequential filtration through all four membranes reduced chlorine demand by more than 94% in surface waters and 84% in waters treated by granular filtration. Significant reduction in the formation of trihalomethane can be achieved if water is treated by appropriate membranes after granular media filtration. © 2014 © 2014 Balaban Desalination Publications. All rights reserved.

Structure and thickness optimization of active layer in nanoscale organic solar cells

 This paper presents the development of a two-dimensional model of multilayer bulk heterojunction organic nanoscale solar cells, consisting of the thickness of active layer and morphology of the device. The proposed model is utilized to optimize the device parameters in order to achieve the best performance using particle swarm optimization algorithm. The organic solar cells under research are from poly (3-hexylthiophene) and [6,6]-phenyl C61-butyric acid methyl ester type which are modelled to be investigated for performance enhancement. A three-dimensional fitness function is proposed involving domain size and active layer thickness as variables. The best results out of 20 runs of optimization show that the optimized value for domain size is 17 nm, while the short-circuit current vs. voltage characteristic shows a very good agreement with the experimental results obtained by previous researchers. © 2014 Springer Science+Business Media New York

New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).

Solvate ionic liquids as reaction media for electrocyclic transformations

Solvate ionic liquids (SILs) consisting of lithium bis(trifluoromethylsulfonyl)imide dissolved in tri-or tetraglyme have recently emerged as a novel class of ionic liquids. Herein, the first use of solvate ionic liquids as a replacement for molecular solvents in electrocyclization reactions is reported. The SILs promoted both Diels-Alder and [2+2] cycloaddition reactions, compared to an appropriate molecular solvent, and 5 M lithium perchlorate in diethyl ether. The Gutmann acceptor number (AN) of these solvate ionic liquids has also been determined by 31P NMR spectroscopy to be 26.5, thus being modest Lewis acids.

Optical actuation of inorganic/organic interfaces: comparing peptide-azobenzene ligand reconfiguration on gold and silver nanoparticles

Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au. These results demonstrate differences in binding and switching behavior between the Au and Ag surfaces. These molecules can also produce and stabilize Au and Ag nanoparticles in aqueous media where the biointerface can be reproducibly and reversibly switched by optically triggered azobenzene isomerization. Comparisons of switching rates and reversibility on the nanoparticles reveal differences that depend upon whether the azobenzene is attached at the peptide N- or C-terminus, its isomerization state, and the nanoparticle composition. Our integrated experimental and computational investigation shows that the number of ligand anchor sites strongly influences the nanoparticle size. As predicted by our molecular simulations, weaker contact between the hybrid biomolecules and the Ag surface, with fewer anchor residues compared with Au, gives rise to differences in switching kinetics on Ag versus Au. Our findings provide a pathway toward achieving new remotely actuatable nanomaterials for multiple applications from a single system, which remains difficult to achieve using conventional approaches.

Optical actuation of inorganic/organic interfaces: comparing peptide-azobenzene ligand reconfiguration on gold and silver nanoparticles

Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au. These results demonstrate differences in binding and switching behavior between the Au and Ag surfaces. These molecules can also produce and stabilize Au and Ag nanoparticles in aqueous media where the biointerface can be reproducibly and reversibly switched by optically triggered azobenzene isomerization. Comparisons of switching rates and reversibility on the nanoparticles reveal differences that depend upon whether the azobenzene is attached at the peptide N- or C-terminus, its isomerization state, and the nanoparticle composition. Our integrated experimental and computational investigation shows that the number of ligand anchor sites strongly influences the nanoparticle size. As predicted by our molecular simulations, weaker contact between the hybrid biomolecules and the Ag surface, with fewer anchor residues compared with Au, gives rise to differences in switching kinetics on Ag versus Au. Our findings provide a pathway toward achieving new remotely actuatable nanomaterials for multiple applications from a single system, which remains difficult to achieve using conventional approaches.