Synthesis and characterisation of organo-beidellite

Today, there are growing concerns about the presence of environmental pollutants in many parts of the world. In particular, a lot of attention has been drawn to the levels of water and soil contaminants (de Paiva et al., 2008). The majority of these contaminants consist of NOCs (non-ionic organic compounds) and can enter our waterways through industrial activities, mining operations, crop and animal production, waste disposal and accidental leakage (de Paiva et al., 2008; Park et al., 2011). Therefore, there is an increased interest in the synthesis of new materials that can be used to remove potentially carcinogenic and toxic water contaminants. Smectite type organoclays are widely used in numerous applications, such as sorbent agents for environmental remediation, due to their unique properties (Jiunn-Fwu et al., 1990; Sheng et al., 1996; Zhou et al., 2007; Bektas et al., 2011; Park et al., 2011). This investigation focuses on beidellite (SBId-1), which belongs to the smectite clay family. Their properties include high cation exchange capacity (CEC), swelling properties, porous, high surface area and consequential strong adsorption/absorption capacity (Xi et al., 2007). However, swelling clays in general are not an effective sorbent agent in nature due to their hydrophilic properties. The hydrophilic properties of the clay can be changed to organophilic by intercalating a cationic surfactant. Many applications of organoclays are strongly dependent on their structural properties and hence, a better understanding of the configuration and structural change of organoclay is crucial. Organoclays were synthesised through ion exchange of 21CODTMA (MW: 392.5 g mol-1) and characterised using XRD and FTIR spectroscopy. This study investigates the structural and conformational changes of beidellite intercalated with octadecyltrimethylammonium bromide.

Self assembly of plasmonic core-satellite nano-assemblies mediated by hyperbranched polymer linkers

The morphology of plasmonic nano-assemblies has a direct influence on optical properties, such as localised surface plasmon resonance (LSPR) and surface enhanced Raman scattering (SERS) intensity. Assemblies with core-satellite morphologies are of particular interest, because this morphology has a high density of hot-spots, while constraining the overall size. Herein, a simple method is reported for the self-assembly of gold NPs nano-assemblies with a core-satellite morphology, which was mediated by hyperbranched polymer (HBP) linkers. The HBP linkers have repeat units that do not interact strongly with gold NPs, but have multiple end-groups that specifically interact with the gold NPs and act as anchoring points resulting in nano-assemblies with a large (~48 nm) core surrounded by smaller (~15 nm) satellites. It was possible to control the number of satellites in an assembly which allowed optical parameters such as SPR maxima and the SERS intensity to be tuned. These results were found to be consistent with finite-difference time domain (FDTD) simulations. Furthermore, the multiplexing of the nano-assemblies with a series of Raman tag molecules was demonstrated, without an observable signal arising from the HBP linker after tagging. Such plasmonic nano-assemblies could potentially serve as efficient SERS based diagnostics or biomedical imaging agents in nanomedicine.

Supramolecular organization in fluorene/indenofluorene-oligothiophene alternating conjugated copolymers

A series of conjugated copolymers containing fluorene or indenofluorene units alternating with oligothiophene segments, with potential interest for use as the active layer in field-effect transistors, is investigated. Atomic force microscopy analysis of the morphology of thin deposits shows either the formation of fibrillar structures, which are the signature of long-range π stacking, or the presence of untextured aggregates, resulting from disordered assembly. These morphologies are interpreted in terms of the supramolecular organization of the conjugated chains. Molecular modeling simulations indicate that the commensurability between the lengths of the monomer units and the presence of alkyl side groups are the two key structural factors governing the chain organization into highly ordered assemblies. The most favorable structures are those combining fluorene (indenofluorene) units with unsubstituted bithiophene (terthiophene) segments.

The effect of graphene oxide and its oxidized debris on the cure chemistry and interphase structure of epoxy nanocomposites

The influence of graphene oxide (GO) and its surface oxidized debris (OD) on the cure chemistry of an amine cured epoxy resin has been investigated by Fourier Transform Infrared Emission Spectroscopy (FT-IES) and Differential Scanning Calorimetry (DSC). Spectral analysis of IR radiation emitted at the cure temperature from thin films of diglycidyl ether of bisphenol A epoxy resin (DGEBA) and 4,4'-diaminodiphenylmethane (DDM) curing agent with and without GO allowed the cure kinetics of the interphase between the bulk resin and GO to be monitored in real time, by measuring both the consumption of primary (1°) amine and epoxy groups, formation of ether groups as well as computing the profiles for formation of secondary (2°) and tertiary (3°) amines. OD was isolated from as-produced GO (aGO) by a simple autoclave method to give OD-free autoclaved GO (acGO). It has been found that the presence of OD on the GO prevents active sites on GO surfaces fully catalysing and participating in the reaction of DGEBA with DDM, which results in slower reaction and a lower crosslink density of the three-dimensional networks in the aGO-resin interphase compared to the acGO-resin interphase. We also determined that OD itself promoted DGEBA homopolymerization. A DSC study further confirmed that the aGO nanocomposite exhibited lower Tg while acGO nanocomposite showed higher Tg compared to neat resin because of the difference in crosslink densities of the matrix around the different GOs.

Two-dimensional self-assembly of a symmetry-reduced tricarboxylic acid

Investigations of the self-assembly of simple molecules at the solution/solid interface can provide useful insight into the general principles governing supramolecular chemistry in two dimensions. Here, we report on the assembly of 3,4′,5-biphenyl tricarboxylic acid (H3BHTC), a small hydrogen bonding unit related to the much-studied 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA), which we investigate using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. STM images show that H3BHTC assembles by itself into an offset zigzag chain structure that maximizes the surface molecular density in favor of maximizing the number density of strong cyclic hydrogen bonds between the carboxylic groups. The offset geometry creates “sticky” pores that promote solvent coadsorption. Adding coronene to the molecular solution produces a transformation to a high-symmetry host–guest lattice stabilized by a dimeric/trimeric hydrogen bonding motif similar to the TMA flower structure. Finally, we show that the H3BHTC lattice firmly immobilizes the guest coronene molecules, allowing for high-resolution imaging of the coronene structure.

Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr

In a previous paper, we described the room temperature rapid, selective, reversible, and near quantitative Cu-activated nitroxide radical coupling (NRC) technique to prepare 3-arm polystyrene stars. In this work, we evaluated the Cu-activation mechanism, either conventional atom transfer or single electron transfer (SET), through kinetic simulations. Simulation data showed that one can describe the system by either activation mechanism. We also found through simulations that bimolecular radical termination, regardless of activation mechanism, was extremely low and could be considered negligible in an NRC reaction. Experiments were carried out to form 2- and 3-arm PSTY stars using two ligands, PMDETA and Me6TREN, in a range of solvent conditions by varying the ratio of DMSO to toluene, and over a wide temperature range. The rate of 2- or 3-arm star formation was governed by the choice of solvent and ligand. The combination of Me6TREN and toluene/DMSO showed a relatively temperature independent rate, and remarkably reached near quantitative yields for 2-arm star formation after only 1 min at 25 °C.

Ultrafast and reversible multiblock formation by the SET-Nitroxide radical coupling reaction

The single electron transfer-nitroxide radical coupling (SET-NRC) reaction has been used to produce multiblock polymers with high molecular weights in under 3 min at 50◦C by coupling a difunctional telechelic polystyrene (Br-PSTY-Br)with a dinitroxide. The well known combination of dimethyl sulfoxide as solvent and Me6TREN as ligand facilitated the in situ disproportionation of CuIBr to the highly active nascent Cu0 species. This SET reaction allowed polymeric radicals to be rapidly formed from their corresponding halide end-groups. Trapping of these carbon-centred radicals at close to diffusion controlled rates by dinitroxides resulted in high-molecular-weight multiblock polymers. Our results showed that the disproportionation of CuI was critical in obtaining these ultrafast reactions, and confirmed that activation was primarily through Cu0. We took advantage of the reversibility of the NRC reaction at elevated temperatures to decouple the multiblock back to the original PSTY building block through capping the chain-ends with mono-functional nitroxides. These alkoxyamine end-groups were further exchanged with an alkyne mono-functional nitroxide (TEMPO–≡) and ‘clicked’ by a CuI-catalyzed azide/alkyne cycloaddition (CuAAC) reaction with N3–PSTY–N3 to reform the multiblocks. This final ‘click’ reaction, even after the consecutive decoupling and nitroxide-exchange reactions, still produced high molecular-weight multiblocks efficiently. These SET-NRC reactions would have ideal applications in re-usable plastics and possibly as self-healing materials.

Rapid, selective, and reversible Nitroxide Radical Coupling (NRC) reactions at amibient temperature

High activation of polystyrene with bromine end groups (PSTY-Br) to their incipient radicals occurred in the presence of Cu(I)Br, Me6TREN, and DMSO solvent. These radicals were then trapped by nitroxide species leading to coupling reactions between PSTY-Br and nitroxides that were ultrafast and selective in the presence of a diverse range of functional groups. The nitroxide radical coupling (NRC) reactions have the attributes of a “click” reaction with near quantitative yields of product formed, but through the reversibility of this reaction, it has the added advantage of permitting the exchange of chemical functionality on macromolecules. Conditions were chosen to facilitate the disproportionation of Cu(I)Br to the highly activating nascent Cu(0) and deactivating Cu(II)Br2 in the presence of DMSO solvent and Me6TREN ligand. NRC at room temperature gave near quantitative yields of macromolecular coupling of low molecular weight polystyrene with bromine chain-ends (PSTY-Br) and nitroxides in under 7 min even in the presence of functional groups (e.g., −≡, −OH, −COOH, −NH2, =O). Utilization of the reversibility of the NRC reaction at elevated temperatures allowed the exchange of chain-end groups with a variety of functional nitroxide derivatives. The robustness and orthogonality of this NRC reaction were further demonstrated using the Cu-catalyzed azide/alkyne “click” (CuAAC) reactions, in which yields greater than 95% were observed for coupling between PSTY-N3 and a PSTY chain first trapped with an alkyne functional TEMPO (PSTY-TEMPO-≡).

Direct electrochemical formation of nanostructured amorphous Co(OH)2 on gold electrodes with enhanced activity for the oxygen evolution reaction.

The oxides of cobalt have recently been shown to be highly effective electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. In general species such as Co3O4 and CoOOH have been investigated that often require an elevated temperature step during their synthesis to create crystalline materials. In this work we investigate the rapid and direct electrochemical formation of amorphous nanostructured Co(OH)2 on gold electrodes under room temperture conditions which is a highly active precursor for the OER. During the OER some conversion to crystalline Co3O4 occurs at the surface, but the bulk of the material remains amorphous. It is found that the underlying gold electrode is crucial to the materials enhanced performance and provides higher current density than can be achieved using carbon, palladium or copper support electrodes. This catalyst exhibits excellent activity with a current density of 10 mA cm-2 at an overpotential of 360 mV with a high turnover frequency of 2.1 s-1 in 1 M NaOH. A Tafel slope of 56 mV dec-1 at low overpotentials and a slope of 122 mV dec-1 at high overpotentials is consistent with the dual barrier model for the electrocatalytic evolution of oxygen. Significantly, the catalyst maintains excellent activity for up to 24 hr of continuous operation and this approach offers a facile way to create a highly effective and stable material.

Dinuclear Ru-Cu complexes : electronic characterisation and application to dye-sensitised solar cells

Dye-sensitised solar cells have emerged as an important developing technology for low-cost solar energy conversion and a crucial element of these is the dye, responsible for light harvesting and control of interfacial electron-transfer processes.[1] A number of examples of dye exist in the literature which link a ruthenium polypyridyl complex to another platinum group metal complex such as Ru (II), Os (II), Re (I) or Rh (III) via a bridging ligand.[2-6] These systems are often referred to as heterosupramolecular triads when adsorbed on the surface of TiO2 as the semiconductor becomes an active component in the system. A number of problems can arise with these types of sensitisers, for example if a flexible linker, e.g. bis-pyridylethane, is used to couple the two complexes it can be hard to control the orientation of the whole dye. This may lead to the resultant dye cation hole being closer to the surface than desired, and hence the long-lived charge-separated state is not achieved. In addition the size of these dyes may be much larger than that of a mononuclear complex and can lead to poor pore filling on the TiO2 and lower dye coverage, leading to a lower efficiency cell.[7] Despite these issues, efficient charge-separation has been achieved with polynuclear complexes and a long-lived state on the millisecond timescale has been observed for a trinuclear ruthenium complex.[8]