Hydrotalcite intercalated siRNA:computational characterization of the interlayer environment

Using molecular dynamics (MD) simulations, we explore the structural and dynamical properties of siRNA within the intercalated environment of a Mg:Al 2:1 Layered Double Hydroxide (LDH) nanoparticle. An ab initio force field (Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies: COMPASS) is used for the MD simulations of the hybrid organic-inorganic systems. The structure, arrangement, mobility, close contacts and hydrogen bonds associated with the intercalated RNA are examined and contrasted with those of the isolated RNA. Computed powder X-ray diffraction patterns are also compared with related LDH-DNA experiments. As a method of probing whether the intercalated environment approximates the crystalline or rather the aqueous state, we explore the stability of the principle parameters (e.g., the major groove width) that differentiate both A- and A'- crystalline forms of siRNA and contrast this with recent findings for the same siRNA simulated in water. We find the crystalline forms remain structurally distinct when intercalated, whereas this is not the case in water. Implications for the stability of hybrid LDH-RNA systems are discussed.

A novel Mo-W interlayer approach for CVD diamond deposition on steel

Steel is the most widely used material in engineering for its cost/performance ratio and coatings are routinely applied on its surface to further improve its properties. Diamond coated steel parts are an option for many demanding industrial applications through prolonging the lifetime of steel parts, enhancement of tool performance as well as the reduction of wear rates. Direct deposition of diamond on steel using conventional chemical vapour deposition (CVD) processes is known to give poor results due to the preferential formation of amorphous carbon on iron, nickel and other elements as well as stresses induced from the significant difference in the thermal expansion coefficients of those materials. This article reports a novel approach of deposition of nanocrystalline diamond coatings on high-speed steel (M42) substrates using a multi-structured molybdenum (Mo) - tungsten (W) interlayer to form steel/Mo/Mo-W/W/diamond sandwich structures which overcome the adhesion problem related to direct magnetron sputtering deposition of pure tungsten. Surface, interface and tribology properties were evaluated to understand the role of such an interlayer structure. The multi-structured Mo-W interlayer has been proven to improve the adhesion between diamond films and steel substrates by acting as an effective diffusion barrier during the CVD diamond deposition.

Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

The adsorption of phenolic and organotin compounds by clays and cation exchanged clays

Quaternary ammonium exchanged laponites (Quat-laponites) show selectivity in the adsorption of phenols and chlorinated phenols. Strong adsorbate-adsorbent interactions are indicated by adsorption isotherms. Adsorption of phenols and chlorinated phenols by Quat-smectites is greater than that by the Bi Quat-Smectites prepared in this study. It is thought that the quaternary ammonium exchanged smectite components of the Bi Quat-smectites interact with each other (adsorbent-adsorbent interactions) reducing the number of sites available for adsorbate-adsorbent interactions. Solidification/stabilisation studies of 2-chlorophenol show that a blend of ground granulated blast furnace slag and ordinary Portland cement attenuates 2-chlorophenol more effectively than ordinary Portland cement alone. Tetramethyl ammonium- (TMA-) and tetramethyl phosphonium- (TMP-) montmorillonites were exposed to solutions of phenol or chlorinated phenols. TMP- montmorillonite was the better adsorbent and preferentially adsorbed 4-chlorophenol over phenol. Hydration of the interlayer cations occurs to a greater extent in the TMA-montmorillonite than the TMP-montmorillonite restricting interlayer adsorption. Contrary to that observed for phenols and chlorinated phenols, the Quat-smectites were ineffective as adsorbents for triphenyltin hydroxide and bis(tributyltin) oxide at room temperature. Under microwave conditions, only bis(tributyltin) oxide was adsorbed by the quaternary ammonium exchanged smectites. Bis(tributyltin) oxide was adsorbed from ethanol on the surface of the smectite clays at room temperature and under microwave conditions. The adsorbate-adsorbent interactions were weak. Adsorption is accompanied by conversion of bis(tributyltin) oxide to a different tin(IV) species and the release of sodium cations from the montmorillonite interlayer region. Attempts to introduce conditions suitable for charge transfer interactions between synthesised quaternary ammonium compounds and 2,4,6-trichlorophenol are documented. Transition metal complex exchanged clays adsorb 2,4,6-trichlorophenol and phenol. Strong adsorbate-adsorbent interactions (Type I isotherms) occur when the adsorbate is 2,4,6-trichlorophenol and when the adsorbent is [Fe(bipy)3]2+ exchanged montmorillonite or [Co(bipy)3]3+ exchanged montmorillonite. The 2,2'-bipyridyl ligands of the adsorbents are electron rich and the 2,4,6-trichlorophenol is electron deficient. This may have enhanced adsorbate-adsorbent interactions.

Studies in clay chemistry

A study of clay chemistry has been approached with three aims: - to modify the conducting properties by intercalation of tetrathiafulvalene, - to study the electrochemistry of redox-active coordination compounds immobilised on clay coated electrodes, and - to study the role of clays as reagents in inorganic glass forming reactions using mainly solid-state magic-angle-spinning NMR. TTF was intercalated by smectites containing different interlayer and lattice cations. Evidence from ESR and 57Fe Mossbauer indicated charge-transfer from TTF to structural iron in natural montmorillonite, and to interlayer Cu2+ in Cu2+ exchanged laponite. No charge transfer was observed for laponite (Na+ form) itself. Ion exchange of TTF3(BF4)2 with laponite was found to proceed quantitatively. The intercalated species were believed to be (TTF)2+ dimers. Conductivity data showed an order of magnitude increase for the intercalated clays. The mechanism is thought to be ionic rather than CT as Na+ laponite showed a similar enhancement in conductivity. Mechanically robust colloidal clay films were prepared on platinum electrodes. After immersion in solutions containing redox active complexes [Co(bpy)3]3+ and [Cr(bpy)3]3+, the films became electroactive when a potential was applied. Cyclic voltammograms obtained for both complexes were found to be of the diffusion controlled type. For [Co(bpy)3]3+ immobilised on clay coated electrodes, a one-step oxidation and four-step reduction wave was observed corresponding to a one electron stepwise reversible reduction of Co(III), through Co(II), Co(I), Co(O) to Co(I) oxidation state. For [Cr(bpy)3]3+ the electrochemistry was complicated by the presence of additional waves corresponding to the dissociation of [Cr(bpy)3]3+ into the diaquo complex. ESR and diffuse reflectance data supported such a mechanism. 29Si, 27Al and 23Na MAS NMR spectroscopy, supported by powder XRD and FTIR, was used to probe the role of clays as reagents in glass forming reactions. 29Si MAS NMR was found to be a very sensitive technique for identifying the presence and relative abundance of crystalline and non-crystalline phases. In thermal reactions of laponite formation of new mineral phases such as forsterite, akermanite, sillimanite and diopside were detected. The relative abundance of each phase was dependent on thermal history, chemical nature and concentration of the modifier oxide present. In continuing work, the effect of selected oxides on the glass forming reactions of a model feldspar composition was investigated using solid state NMR alone. Addition of network modifying oxides generally produced less negative 29Si chemical shifts and larger linewidths corresponding to a wider distribution of Si-O-Si bond angles and lengths, and a dominant aluminosilicate phase with a less polymerised structure than the starting material. 29Si linewidths and 27Al chemical shifts were respectively correlated with cationic potential and Lewis acidity of the oxide cations. Anomalous Al(4) chemical shifts were thought to be due to precipitation of aluminate phases rather than a breakdown in Lowenstein's aluminium avoidance principle.

Organometallic precursors for pillared clay synthesis

The synthetic hectorite, laponite has been used within the paper industry to produce mildly conducting paper for use in electrographic printing. The aim of this research was to modify laponite in order to improve the electrical conductivity. In a continuation of a previous investigation involving organotin intercalation of laponite, the organotin precursor (p-CH3,OC6H4)4Sn was synthesised and characterised using Mass Spectroscopy, Infrared Spectroscopy and elemental analysis. Results of intercalation with this compound and a range of organobismuth and organoantimony compounds suggested that a halide content within the precursor was necessary for improvement in conductivity to be observed. Organometallic intercalation of a range of organotellurium compounds with laponite provided evidence that a hydrolysis reaction on the clay surface followed by the release of hydrochloric acid was an important first step if a reaction was to occur with the clay. Atomic Absorption Spectroscopy studies have shown that the acid protons underwent exchange with the interlayer sodium ions in the clay to varying degrees. Gas-liquid Chromatography and Infrared Spectroscopy revealed that the carbon-tellurium bond remained intact. Powder X-ray diffraction revealed that there had been no increase in the basal spacing. The a.c. conductivity of the modified clays in the form of pressed discs was studied over a frequency range of 12Hz - 100kHz using two electrode systems, silver paste and stainless steel. The a.c. conductivity consists of two components, ionic and reactive. The conductivity of laponite was increased by intercalation with organometallic compounds. The most impressive increase was gained using the organotellurium precursor (p-CH3OC6H4)2TeCl2. Conductivity investigations using the stainless steel electrode where measurements are made under pressure showed that in the case of laponite, where poor particle-particle contact exists at ambient pressure, there is a two order of magnitude increase in the measured a.c. conductivity. This significant increase was not seen in modified laponites where the particle-particle contact had already been improved upon. Investigations of the clay surface using Scanning Electron Microscopy suggested that the improvement in particle-particle contact is the largest factor in the determination of the conductivity. The other important factor is the nature and the concentration of the interlayer cations. A range of clays were synthesised in order to increase the concentration of sodium interlayer cations. A sol-gel method was employed to carry out these syntheses. A conductivity evaluation showed that increasing the concentration of the sodium cations within the clay led to an increase in the conductivity.

Chemical modification of smectite clays

Today, speciality use organoclays are being developed for an increasingly large number of specific applications. Many of these, including use in cosmetics, polishes, greases and paints, require that the material be free from abrasive impurities so that the product retains a smooth `feel'. The traditional `wet' method preparation of organoclays inherently removes abrasives naturally present in the parent mineral clay, but it is time-consuming and expensive. The primary objective of this thesis was to explore the alternative `dry' method (which is both quicker and cheaper but which provides no refining of the parent clay) as a process, and to examine the nature of the organoclays produced, for the production of a wide range of commercially usable organophilic clays in a facile way. Natural Wyoming bentonite contains two quite different types of silicate surface (that of the clay mineral montmorillonite and that of a quartz impurity) that may interact with the cationic surfactant added in the `dry' process production of organoclays. However, it is oil shale, and not the quartz, that is chiefly responsible for the abrasive nature of the material, although air refinement in combination with the controlled milling of the bentonite as a pretreatment may offer a route to its removal. Ion exchange of Wyoming bentonite with a long chain quaternary ammonium salt using the `dry' process affords a partially exchanged, 69-78%, organoclay, with a monolayer formation of ammonium ions in the interlayer. Excess ion pairs are sorbed on the silicate surfaces of both the clay mineral and the quartz impurity phases. Such surface sorption is enhanced by the presence of very finely divided, super paramagnetic, Fe2O3 or Fe(O)(OH) contaminating the surfaces of the major mineral components. The sorbed material is labile to washing, and induces a measurable shielding of the 29Si nuclei in both clay and quartz phases in the MAS NMR experiment, due to an anisotropic magnetic susceptibility effect. XRD data for humidified samples reveal the interlamellar regions to be strongly hydrophobic, with the by-product sodium chloride being expelled to the external surfaces. Many organic cations will exchange onto a clay. The tetracationic cyclophane, and multipurpose receptor, cyclobis(paraquat-p-phenylene) undergoes ion exchange onto Wyoming bentonite to form a pillared clay with a very regular gallery height. The major plane of the cyclophane is normal to the silicate surfaces, thus allowing the cavity to remain available for complexation. A series of group VI substituted o-dimethoxybenzenes were introduced, and shown to participate in host/guest interactions with the cyclophane. Evidence is given which suggests that the binding of the host structure to a clay substrate offers advantages, not only of transportability and usability but of stability, to the charge-transfer complex which may prove useful in a variety of commercial applications. The fundamental relationship between particle size, cation exchange capacity and chemical composition of clays was also examined. For Wyoming bentonite the extent of isomorphous substitution increases with decreasing particle size, causing the CEC to similarly increase, although the isomorphous substitution site: edge site ratio remains invarient throughout the particle size range studied.

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH 3OD and (CH2OD)2 in deuterated clay allows us to measure the diffusion of the CH3- and CH2-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.

Synthesis and characterization of nanoporous phospho-tungstate organic-inorganic hybrid materials

Nanoporous phospho-tungstate organic-inorganic hybrid materials have been synthesized from sodium tungstate and mono-n-dodecyl phosphate (MDP), which was used as both surfactant and phosphorus precursor. These hybrid materials were thoroughly characterized by N2 adsorption, elemental analysis, powder XRD, FTIR, Raman, TG, TEM and XPS and possess lamellar structures with interlayer spacings of 3.2 nm. A plausible method for formation of hybrid materials comprised of lacunary Keggin anions and micelles of surfactants is proposed. © The Royal Society of Chemistry 2008.

Cost-effective and eco-friendly synthesis of novel and stable N-doped ZnO/g-C3N4 core-shell nanoplates with excellent visible-light responsive photocatalysis

N-doped ZnO/g-C3N4 hybrid core–shell nanoplates have been successfully prepared via a facile, cost-effective and eco-friendly ultrasonic dispersion method for the first time. HRTEM studies confirm the formation of the N-doped ZnO/g-C3N4 hybrid core–shell nanoplates with an average diameter of 50 nm and the g-C3N4 shell thickness can be tuned by varying the content of loaded g-C3N4. The direct contact of the N-doped ZnO surface and g-C3N4 shell without any adhesive interlayer introduced a new carbon energy level in the N-doped ZnO band gap and thereby effectively lowered the band gap energy. Consequently, the as-prepared hybrid core–shell nanoplates showed a greatly enhanced visible-light photocatalysis for the degradation of Rhodamine B compare to that of pure N-doped ZnO surface and g-C3N4. Based on the experimental results, a proposed mechanism for the N-doped ZnO/g-C3N4 photocatalyst was discussed. Interestingly, the hybrid core–shell nanoplates possess high photostability. The improved photocatalytic performance is due to a synergistic effect at the interface of the N-doped ZnO and g-C3N4 including large surface-exposure area, energy band structure and enhanced charge-separation properties. Significantly, the enhanced performance also demonstrates the importance of evaluating new core–shell composite photocatalysts with g-C3N4 as shell material.

Efficient 1,4-addition of enones and boronic acids catalyzed by a Ni-Zn hydroxyl double salt-intercalated anionic rhodium(III) complex

Intercalation of an in situ prepared [Rh(OH)6]3- complex into an anion exchangeable Ni-Zn layered hydroxy double salt (Rh/NiZn) was demonstrated. The resulting Rh/NiZn effectively catalyzed the 1,4-addition of diverse enones and phenylboronic acids to their corresponding β-substituted carbonyl compounds. In the case of 2-cyclohexen-1-one and phenylboronic acid, a turnover frequency (TOF) of 920 h-1 based on Rh was achieved. The [Rh(OH)6]3- complex maintained its original monomeric trivalent state within the NiZn interlayer following catalysis, attributable to a strong electrostatic interaction between the NiZn host and anionic Rh(III) complex.

Identification of the degradation mechanisms of organic solar cells:active layer and interfacial layers

Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.