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Carbon Capture, Utilisation and Storage (CCUS) technologies are utilised to minimise net CO2 emissions and hence mitigate the impact of anthropogenic emissions on the global climate. One example of CO2 utilisation is the production of carbon-neutral methane fuel via catalytic CO2 reduction with H2 (methanation). Thermal activation of a metal impregnated metal-organic framework (MOF), 1 wt%Ru/UiO-66 in the presence of H2 and CO2 provides in situ synthesis of a highly active methanation catalyst: H2 promotes the formation of Ru0 nanoparticles, and CO2 behaves as a mild oxidant to remove framework carbon and promote ZrO2 crystallisation. The nature of the active MOF-derived Ru0/ZrO2 catalyst was studied by PXRD, TEM, and XAS, and the evolution of the parent 1 wt%Ru/UiO-66 during thermal activation monitored in operando by synchrotron PXRD. The Ru impregnated Zr-based MOF collapses on heating in H2 and CO2 to form an amorphous C and Zr containing phase that subsequently crystallises as tetragonal (t-) ZrO2 nanoparticles. These t-ZrO2 nanoparticles undergo a subsequent phase transition to the more stable monoclinic (m-) ZrO2 polymorph. In situ activation of Ru/UiO-66 generates a highly active catalyst for CO2 methanation by transforming the MOF precursor into a (carbon-free) crystalline t-ZrO2 support that stabilises highly dispersed metallic Ru nanoparticles. This insight may guide the rational design of future MOF-derived catalysts.

Understanding the structure–performance relationship for Fe-based Fischer–Tropsch synthesis (FTS) catalysts is crucial for the design of improved FTS catalysts. Herein, catalysts derived from four ...

Enhanced T1 MRI contrast was observed in mesoporous gadolinosilicates co-doped with aluminium. The effect of gadolinium and aluminium dopant concentration was explored using a high-throughput workflow. The T1 relaxivity increases with lower gadolinium and higher aluminium loadings.

The conversion of CO2 into chemicals of commercial interest is a rapidly expanding area of research. Here, we present a highly active and stable CO2 methanation catalyst that is derived from a Ru-impregnated zirconium-based metal–organic framework (MOF) material. The Ru-doped MOF is transformed, under reaction conditions, into an active catalyst which yields CO2 conversions of 96% and a CH4 selectivity of 99%. We demonstrate that the final catalyst was composed of a mixture of Ru-nanoparticles supported on monoclinic and tetragonal ZrO2 nanoparticles. Notably, such catalytic activity has only been achieved using the MOF templating strategy. Catalysts of the same composition were synthesized via different methods but were less active for CO2 methanation.

The rate constant for the reaction between hexan-1-amine and 4-methoxybenzaldehyde was determined in ionic liquids containing an imidazolium cation. The effect on the rate constant of increasing the length of the alkyl substituent on the cation was examined in a number of ionic liquid/acetonitrile mixtures. In general it was found that there was no significant effect of changing the alkyl substituent on the rate constant of this process, suggesting that any nanodomains in these mixtures do not have a significant effect on the outcome of this process. A series of small-angle X-ray scattering and wide-angle X-ray scattering experiments were performed on mixtures of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim][N(CF3SO2)2]) and acetonitrile; this work indicated that the main structural changes in the mixtures occur by about a 0.2 mole fraction of ionic liquid in the mixture (χIL). This region at which the main changes in the solvent structuring occurs corresponds to ...

Natural lifeforms specialize to their environmental niches across many levels, from low-level features such as DNA and proteins, through to higher-level artefacts including eyes, limbs and overarching body plans. We propose ‘multi-level evolution’, a bottom-up automatic process that designs robots across multiple levels and niches them to tasks and environmental conditions. Multi-level evolution concurrently explores constituent molecular and material building blocks, as well as their possible assemblies into specialized morphological and sensorimotor configurations. Multi-level evolution provides a route to fully harness a recent explosion in available candidate materials and ongoing advances in rapid manufacturing processes. We outline a feasible architecture that realizes this vision, highlight the main roadblocks and how they may be overcome, and show robotic applications to which multi-level evolution is particularly suited. By forming a research agenda to stimulate discussion between researchers in related fields, we hope to inspire the pursuit of multi-level robotic design all the way from material to machine.

Fabricating high-quality transparent conductors using inexpensive and industrially viable techniques is a major challenge toward developing low cost optoelectronic devices such as solar cells, light emitting diodes, and touch panel displays. In this work, highly transparent and conductive ZnO thin films are prepared from a low-temperature, aqueous deposition method through the careful control of the reaction chemistry. A robotic synthetic platform is used to explore the wide parameter space of a chemical bath system that uses only cheap and earth abundant chemicals for thin film deposition. As-deposited films are found to be highly resistive, however, through exposure to several millisecond pulses of high-intensity, broadband light, intrinsically doped ZnO films with sheet resistances as low as 40 Ω □-1 can be readily prepared. Such values are comparable with state-of-the-art-doped transparent conducting oxides. The mild processing conditions (

Fluorous protic ionic liquids (FPILs) which consist of a hydrocarbon cation and fluorocarbon anion can possess a complex liquid nanostructure, consisting of segregated polar, hydrocarbon and fluorocarbon domains. FPILs are an interesting series of compounds of relevence to the fields of ionic liquids (Ils), fluorinated amphiphiles and mixed hydrocarbon/fluorocarbon amphiphile systems. Here we show the self-assembly of FPIL ethylammonium perfluorooctanoate (EOAF)–water solutions, which transitions from a low water content L 3 sponge structure in EOAF, to a L α lamellar mesophase and then to dispersed lamellar vesicles. The robust lamellar mesophase was present between 10 and 85 wt.% EAOF, and retained up to 91 °C. This phase underwent significant swelling on addition of water. In contrast, the addition of water to the hydrocarbon analogue, ethylammonium octanoate (EAO) swelled the sponge-like liquid nanostructure, with no other lyotropic liquid crystal mesophases observed.

This work reports a facile and efficient seed-mediated method for the synthesis of dendritic platinum (Pt) nanoparticles (NPs) at low temperatures of 55–60 °C in water, using L-ascorbic acid as a reducing agent and sodium citrate as a capping agent.It is found that the dendritic Pt NPs (10–150 nm) are composed of tiny Pt nanocrystals, which nucleate and grow through the introduced smaller Pt seeds with diameters of 3–5 nm. Further investigation shows that the dendritic Pt nanostructures display excellent catalytic performance in an aqueous-phase aromatic ketone hydrogenation reaction, including: (i) acetophenone conversion rate of > 90%, with smaller dendritic Pt NPs (10–46 nm) offering a higher conversion efficiency; (ii) high chemoselectivity toward carbonyl group (90.6%–91.5%), e.g., the selectivity to 1-phenylethanol is ∼90.1% with nearly 100% acetophenone conversion for 10 nm dendritic Pt NPs within 60 min, under mild reaction conditions (20 °C, 1.5 bar H 2 pressure, and 1.5 mol% catalyst). The high catalytic activity, selectivity and stability of the dendritic Pt nanostructures under the organic solvent-free conditions make them promising for many potential applications in green catalytic conversion of hydrophilic biomass derived compounds.

Carbon dioxide, an energy waste by-product with significant environmental consequences can be utilized and converted into useful chemical products such as formic acid, formaldehyde, methanol or methane, but more energy and cost efficient catalytic processes are required. Here we develop the methodology for the intelligent selection of porous zeolites for dual-adsorption of hydrogen and carbon dioxide as templates for preparing the optimal catalytic environment for carbon dioxide reduction. Useful zeolite catalysts were computationally screened from over 300 thousand zeolite structures using a combination of molecular simulation and machine-learning techniques. Several of the top candidates were very promising energy-efficient templates for catalysis with the potential to perform at 50% above conventional reactors. It is also found that an optimal cavity size of around 6 A is required to maximize the change in entropy–enthalpy upon adsorption with a maximum void space >30% to boost product formation per volume of material.

Manganese-based metal–organic frameworks (MOFs) metalated with Rh were used as pre-catalysts for CO2 hydrogenation. Activated insitu (80% H2, 20% CO2, 350°C), the resulting templated catalysts displayed CO2 conversion of up to 20%, with CH4 as the main product. Used catalysts were compared with samples templated in 5% H2/Ar at 350°C using powder X-ray diffraction, electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. It was found that under reducing atmosphere Rh0 nanoparticles formed and organic MOF components decomposed, which allowed growth of MnO or MnCO3 and the formation of a mesh of catalytic Rh0 nanoparticles.

Solvothermal reactions of an anthracene-based tetracarboxylic acid ligand, 5,5′-(anthracene-9,10-diyl)diisophthalic acid (H4ADIP) with Zn(NO3)2·6H2O afforded three novel metal–organic frameworks with unusual coordination geometries compared to the Cu analogue, PCN-14.

The mesoporous structure of sol-gel prepared gadolinium and europium doped silicate nanoparticles has been found to be highly dependent on the formulated composition, with synthesised samples displaying both disordered and hexagonally ordered mesoporous packing symmetry. The degree of pore ordering within the nanoparticles has a strong correlation with the total lanthanide (Gd(3+) and Eu(3+) ) concentration. The gadolinosilicates are excellent magnetic resonance imaging (MRI) longitudinal (T1 ) agents. The longitudinal relaxivity (r1 ) and transverse (r2 ) relaxivity, a measure of MRI contrast agent efficiency, were up to four times higher than the clinically employed Omniscan (gadodiamide); with r1 up to 20.6 s(-1) mM(-1) and r2 of 66.2 s(-1) mM(-1) compared to 5.53 and 4.64 s(-1) mM(-1) , respectively, for Omniscan. In addition, the europium content of all the samples studied is below the self-quenching limit, which results in a strong luminescence response from the nanoparticles on excitation at 250 nm. The Eu-Gd silicate nanoparticles act as bimodal imaging agents for MRI and luminescence. These mesoporous nanoparticles also have the potential to serve as encapsulation and controlled release matrices for pharmaceuticals. They are therefore a promising multimodal theranostic platform.

The development of biomedical nanoparticulate materials for use in diagnostics is a delicate balance between performance, particle size, shape, and stability. To identify materials that satisfy all of the criteria it is useful to employ automated high-throughput (HT) techniques for the study of these materials. The structure and performance of surfactant templated mesoporous silica is very sensitive to a wide number of variables. Variables, such as the concentration of the structure-directing agent, the cosolvent and dopant ions and also the temperature and concentration of quenching all have an influence on the structure, surface chemistry, and therefore, the performance of the mesoporous silica nanoparticles generated. Using an automated robotic synthetic platform, a technique has been developed for the high-throughput preparation of mesoporous silica and gadolinium-doped silicate (gadoliniosilicate) nanoparticulate MRI contrast agents. Twelve identical repeats of both the mesoporous silica and gadolinosilicate were synthesized to investigate the reproducibility of the HT technique. Very good reproducibility in the production of the mesoporous silica and the gadolinosilcate materials was obtained using the developed method. The performance of the gadolinosilicate materials was comparable as a T(1) agent to the commercial MRI contrast agents. This HT methodology is highly reproducible and an effective tool that can be translated to the discovery of any sol-gel derived nanomaterial.

The development of improved, low toxicity, clinically viable nanomaterials that provide MRI contrast have tremendous potential to form the basis of translatable theranostic agents. Herein we describe a class of MRI visible materials based on lyotropic liquid crystal nanoparticles loaded with a paramagnetic nitroxide lipid. These readily synthesized nanoparticles achieved enhanced proton-relaxivities on the order of clinically used gadolinium complexes such as Omniscan™ without the use of heavy metal coordination complexes. Their low toxicity, high water solubility and colloidal stability in buffer resulted in them being well tolerated in vitro and in vivo. The nanoparticles were initially screened in vitro for cytotoxicity and subsequently a defined concentration range was tested in rats to determine the maximum tolerated dose. Pharmacokinetic profiles of the candidate nanoparticles were established in vivo on IV administration to rats. The lyotropic liquid crystal nanoparticles were proven to be effective liver MRI contrast agents. We have demonstrated the effective in vivo performance of a T1 enhancing, biocompatible, colloidally stable, amphiphilic MRI contrast agent that does not contain a metal.

Protic ionic liquids (PILs) have been evaluated as additives in protein crystallization trials. Ten ionic liquids were incorporated as additives along with the JCSG+ sparse matrix screen for the crystallization of lysozyme, glucose isomerase, and trypsin. When used as additives, the PILs were identified to influence the crystallization of these globular proteins. Crystal structures obtained for lysozyme with each of the 10 PILs under identical conditions showed no change in the crystal structure of the protein; however, in three of the ten cases fragments of the ionic liquids were observed to be incorporated within the protein.

Protic ionic liquids (PILs) have been shown to provide media for small amphiphilic molecule self-assembly into periodic 3D geometries. The ability of phytantriol and monoolein to self-assemble into ordered 3D nanostructures analogous to structures observed in aqueous solvents has been demonstrated. Monoolein in ethanolammonium formate (EOAF) formed the double diamond lyotropic liquid crystalline cubic mesophase, and phytantriol formed the gyroid cubic mesophase at 25 °C. The monoolein cubic mesophase was successfully dispersed in excess PIL, forming nanostructured nanoparticles, and imaged by cryo-transmission electron microscopy. The self-assembled materials reported herein can be considered for soft-templating of material structures during synthesis, as encapsulation and controlled release media, as carrier particles in transport phenomena, and as supports for catalysts where the process conditions require a nonaqueous environment.

The nanostructure of a series of 20 protic ionic liquids (PILs) has been investigated using small- and wide-angle X-ray scattering (SAXS and WAXS). The PILs contained alkylammonium, dialkylammonium, trialkylammonium, and cyclic ammonium cations combined with organic or inorganic anions. The presence of hydroxyl and methoxy substituents on the alkyl chains of the cations was also explored. Many of the PILs showed a nanostructure resulting from segregation of the polar and nonpolar components of the ionic liquid. It was found that this segregation was enhanced for longer alkyl chains, with a corresponding increase in the length scale, whereas the presence of hydroxyl groups on the alkyl chains led to much less ordered liquids. The broad range of protic ionic liquids studied allowed several structure-property relationships to be established. The solvophobic effect was shown to be dependent on the nanostructure of the PILs. These PILs support amphiphile self-assembly, and it was shown that the less structured PILs had more "water-like" behavior in the diversity of lyotropic liquid-crystal phases supported, and the thermal stability ranges for these phases.

Lanthanide salts of phytanic acid, an isoprenoid-type amphiphile, have been synthesized and characterized. Elemental analysis and FTIR spectroscopy were used to confirm the formed product and showed that three phytanate anions are complexed with one lanthanide cation. The physicochemical properties of the lanthanide phytanates were investigated using DSC, XRD, SAXS, and cross-polarized optical microscopy. Several of the hydrated salts form a liquid-crystalline hexagonal columnar mesophase at room temperature, and samarium(III) phytanate forms this phase even in the absence of water. Select lanthanide phytanates were dispersed in water, and cryo-TEM images indicate that some structure has been retained in the dispersed phase. NMR relaxivity measurements were conducted on these systems. It has been shown that a particulate dispersion of gadolinium(III) phytanate displays proton relaxivity values comparable to those of a commercial contrast agent for magnetic resonance imaging and a colloidal dispersion of europium(III) phytanate exhibits the characteristics of a fluorescence imaging agent.

Two solvent-modified MEKC methods were developed for the quantitative analysis of heterocyclic amines synthesised using intramolecular ring closure via catalysed hydroamination. The first method was capable of resolving six of the amines (precursors and products) with a sample-to-sample injection time of 2 min employing a 20 mM borate buffer, pH 9.2 with 20 mM SDS and 5% v/v n-butanol (n-BuOH). A second low-pH method using 20 mM phosphate buffer, 100 mm SDS, 5% v/v n-BuOH and 20% v/v iso-propanol (i-PrOH) was able to resolve an additional pair of compounds with a sample-to-sample time of 3.5 min. Application of the first method to the analysis of a sample containing catalyst as well as amines placed directly in a 96-well plate showed excellent performance, with migration time and peak height and area reproducibility being less than 0.9 and 9.6%, respectively. The quantity of conversion by catalyst was calculated to be 68 +/- 7%, which was in excellent agreement with the 67 +/- 5% obtained by more conventional (1)H NMR experiments, with the added advantage that this method is also cheaper, quicker and more amendable to high-throughput screening of combinatorial libraries.

Complexes of the type [Cp*MCl(N–N)][X] (M = Rh and Ir) have been synthesised, where N–N is a series of bidentate ligands with sp2 N-donors: bis(pyrazol-1-yl)methane (bpm), bis(1-methylimidazol-2-yl)methane (bim), bis(3,5-dimethylpyrazol-1-yl)methane (dmbpm), bis(1-methylimidazol-2-yl) ketone (bik), bis(2,4,6-trimethylphenylimino)acenapthene (mesBIAN), 2,4,6-trimethylphenylimino-(1-methyl-2-imidazolyl)methane (mesim–mim), and X = Cl–, BF4– and the unusual anion [Cp*MCl3]–. All of these complexes were synthesised by treatment of [Cp*MCl2]2 with 2 equivalents of ligand and were isolated as air stable solids. The solid-state structures of [Cp*MCl(bpm)][Cp*MCl3] (M = Rh and Ir) and [Cp*IrCl(bim)][Cp*IrCl3] have been determined by single-crystal X-ray diffraction analysis. All of the structures of the bimetallic species displayed a “piano stool” configuration about the both the anionic and cationic metal centre. The solid-state structures of the monometallic iridium species [Cp*IrCl(N–N)][BF4], where N–N = bim, mesBIAN, and mesim-mim, were also determined using single-crystal X-ray diffraction analysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Porosity loss, also known as physical aging, in glassy polymers hampers their long term use in gas separations. Unprecedented interactions of porous aromatic frameworks (PAFs) with these polymers offer the potential to control and exploit physical aging for drastically enhanced separation efficiency. PAF-1 is used in the archetypal polymer of intrinsic microporosity (PIM), PIM-1, to achieve three significant outcomes. 1) hydrogen permeability is drastically enhanced by 375% to 5500 Barrer. 2) Physical aging is controlled causing the selectivity for H2 over N2 to increase from 4.5 to 13 over 400 days of aging. 3) The improvement with age of the membrane is exploited to recover up to 98% of H2 from gas mixtures with N2 . This process is critical for the use of ammonia as a H2 storage medium. The tethering of polymer side chains within PAF-1 pores is responsible for maintaining H2 transport pathways, whilst the larger N2 pathways gradually collapse.

Amphiphile self-assembly materials, which contain both a hydrophilic and a hydrophobic domain, have great potential in high-throughput and combinatorial approaches to discovery and development. However, the materials chemistry community has not embraced these ideas to anywhere near the extent that the medicinal chemistry community has. While this situation is beginning to change, extracting the full potential of high-throughput approaches in the development of self-assembling materials will require further development in the synthesis, characterization, formulation, and application domains. One of the key factors that make small molecule amphiphiles prospective building blocks for next generation multifunctional materials is their ability to self-assemble into complex nanostructures through low-energy transformations. Scientists can potentially tune, control, and functionalize these structures, but only after establishing their inherent properties. Because both robotic materials handling and customized rapid characterization equipment are increasingly available, high-throughput solutions are now attainable. These address traditional development bottlenecks associated with self-assembling amphiphile materials, such as their structural characterization and the assessment of end-use functional performance. A high-throughput methodology can help streamline materials development workflows, in accord with existing high-throughput discovery pipelines such as those used by the pharmaceutical industry in drug discovery. Chemists have identified several areas that are amenable to a high-throughput approach for amphiphile self-assembly materials development. These allow an exploration of not only a large potential chemical, compositional, and structural space, but also material properties, formulation, and application variables. These areas of development include materials synthesis and preparation, formulation, characterization, and screening performance for the desired end application. High-throughput data analysis is crucial at all stages to keep pace with data collection. In this Account, we describe high-throughput advances in the field of amphiphile self-assembly, focusing on nanostructured lyotropic liquid crystalline materials, which form when amphiphiles are added to a polar solvent. We outline recent progress in the automated preparation of amphiphile molecules and their nanostructured self-assembly systems both in the bulk phase and in dispersed colloidal particulate systems. Once prepared, we can structurally characterize these systems by establishing phase behavior in a high-throughput manner with both laboratory (infrared and light polarization microscopy) and synchrotron facilities (small-angle X-ray scattering). Additionally, we provide three case studies to demonstrate how chemists can use high-throughput approaches to evaluate the functional performance of amphiphile self-assembly materials. The high-throughput methodology for the set-up and characterization of large matrix in meso membrane protein crystallization trials can illustrate an application of bulk phase self-assembling amphiphiles. For dispersed colloidal systems, two nanomedicine examples highlight advances in high-throughput preparation, characterization, and evaluation: drug delivery and magnetic resonance imaging agents.

A porous treasure: Porous aromatic framework PAF‐1 (see picture, blue structure) has been lithiated, giving a reduced framework with an increased gas storage capacity compared to native PAF‐1 (by 22, 71, and 320 % for H2, CH4, and CO2, respectively). The reduced framework was examined spectroscopically, and the potential hydrogen storage capacity was calculated. Refereed/Peer-reviewed

The aqueous gelation of an amphiphilic ammonium oligoether-based ionic liquid (AMMOENG 102) is addressed and compared to the gelation of a similar compound (AMMOENG 100) recently reported (J. Casamada Ribot, C. Guerrero-Sanchez, R. Hoogenboom and U. S. Schubert, J. Mater. Chem., 2010, 20, 8279.).(1) The comparison is based on proton nuclear magnetic resonance spectroscopy, rheological, ionic conductivity, water uptake, differential scanning calorimetry, surface tension and small angle X-ray scattering investigations. The results demonstrate that slight changes in the chemical structure of these ionic liquids can have an important effect on the properties of their corresponding ion gels. Hence, this contribution provides an insight into the stability and formation mechanism of these new ion gels solely consisting of ionic liquid and water and expands the range of amphiphilic ionic liquids which can be utilized for the straightforward and inexpensive preparation of thermoresponsive materials with tunable properties (i.e., ionic conductivity and melting point) and high mechanical moduli

The effect of adding primary n-alcohols with aliphatic chains and hexane on the nanostructure of a series of 14 protic ionic liquids (PILs) was explored using small and wide angle X-ray scattering (SAXS and WAXS). PILs were investigated with primary, secondary and tertiary ammonium cations containing different alkyl chain lengths, with and without hydroxyl substitution of the alkyl chain. Formate or nitrate anions were paired with these cations. The PILs which had no identified intermediate range order between 5–16 A had very low solubilities of the solutes. The other PILs, which had non-polar domains present, were mostly miscible with the primary alcohols of ethanol, propanol and butanol. When the alkyl chain length of the alcohols was similar to the PILs then the alcohols co-partitioned with the alkylammonium cation components of the PILs and caused either an increase or decrease in the size of the non-polar domains, depending on whether the alcohol chain length was longer or shorter than that of the cation in the PIL respectively. For ethylammonium nitrate (EAN) with propanol or butanol and propylammonium nitrate (PAN) with butanol, the difference between the alcohol chain length and the alkyl chain length was too great to lead to a modified nanostructure, and instead large aggregates were present. The solubility of hexane in the alkylammonium nitrate PILs had a very strong correlation to the alkyl chain length. The addition of hexane had very little effect on the non-polar domain sizes, which was attributed to it not being orientated in alignment with the alkylammonium cations in the non-polar domains. Lastly, seven binary PIL–PIL solution series were investigated using SAXS and WAXS to show how the nanostructure of these systems can be fine tuned to control the size and structure of the non-polar domains.

Small- and wide-angle X-ray scattering (SWAXS) has been used to investigate the effect that water has on the nanoscale structure of protic ionic liquids (PILs) along with their precursor Bronsted acids and bases. The series of PILs consisted of primary, secondary, and tertiary alkylammonium cations in conjunction with formate, nitrate, or glycolate anions. Significant differences were observed for these systems. The nanoscale aggregates present in neat protic ionic liquids were shown to be stable in size on dilution to high concentrations of water, indicating that the water is localized in the ionic region and has little effect on the nonpolar domains. The Bronsted acid-water solutions did not display nanostructure at any water concentration. Primary amine Bronsted bases formed aggregates in water, which generally displayed characteristics of poorly structured microemulsions or a form of bicontinuous phase. Exceptions were butyl- and pentylamine with high water concentrations, for which the SWAXS patterns fitted well to the Teubner-Strey model for microemulsions. Bronsted base amines containing multiple alkyl chains or hydroxyl groups did not display nanostructure at any water concentration. IR spectroscopy was used to investigate the nature of water in the various solutions. For low PIL concentrations, the water was predominately present as bulk water for PIL molar fractions less than 0.4-0.5. At high PIL concentrations, in addition to the bulk water, there was a significant proportion of perturbed water, which is water influenced in some way by the cations and anions. The molecular state of the water in the studied amines was predominately present as bulk water, with smaller contributions from perturbed water than was seen in the PILs.

Three nucleoside lipids have been synthesized: 30 -oleoylthymidine, 30 ,50 -dioleoylthymidine, and 30 -phytanoylthymidine. Differential scanning calorimetry and X-ray diffraction have been employed to characterize the physical properties of these neat lipids. Polarizing optical microscopy, small-angle X-ray scattering, and cryo-transmission electron microscopy techniques have been used to investigate the phase behavior in aqueous systems. Both oleoyl-based nucleoside lipids adopted a lamellar crystalline phase in the neat form at room temperature, and the phytanoyl derivative exhibited a fluid isotropic phase. Under excess water conditions, the presence of one branched (phytanoyl) or one unsaturated (oleoyl) chain promoted the formation of a liquid-crystalline lamellar phase at physiological temperatures. In contrast, the 30 ,50 -dioleoylthymidine derivative is nonswelling and does not exhibit lyotropic liquid-crystalline phase behavior. The nucleolipids' propensity for DNA-type binding and recognition has been evaluated by using a monolayer system to measure surface pressure-area isotherms in a Langmuir trough and indicates that the nucleoside base is available for nonspecific hydrogen bonding in the monolayer liquid expanded state for the single-chain nucleolipids but not for the dual-chain amphiphile.

This paper reports on a systematic method – called PLUXter – developed for screening and data mining of large numbers of potential metal-organic framework compounds that have been synthesized then subsequently analyzed with high throughput synchrotron radiation X-ray powder diffraction. The first part of the method utilizes principal components analysis (PCA), which allows materials to be ranked in order of crystallinity so that undesirable amorphous materials may be identified and eliminated. The second part allows structural grouping within and between samples to be observed using hierarchical cluster analysis (HCA). Classification using a single linkage distance produced unsatisfactory clusters however the dendrograms structural relationships were used to establish and guide the boundaries of groups. The resultant grouping identities allowed further structure-property studies to be undertaken on representative structures from the clusters, significantly reducing time and the use of resources.

The preparation, characterisation and assessment of drug delivery vehicles is typically a slow and complex process. Here we present a nanostructured nanoparticle system that can be prepared and characterised in a high-throughput fashion. In particular we use phytantriol and Myverol to prepare inverse bicontinuous cubic and inverse hexagonal liquid crystalline nanoparticles loaded with 10 commonly used therapeutic agents at increasing concentration. The dispersions are prepared using automated apparatus to create different concentrations and phases using novel protocols. We are able to characterise each stabilised nanoparticle dispersion using a range of methodologies including small angle X-ray scattering, particle sizing and drug partitioning. With this information we are able to assess which drug delivery vehicle is preferred for each drug and at which concentration the drug should be loaded to ensure maximum payload and to retain particle integrity.

The reaction of 2-(2-phenylethynyl)aniline with acetone in presence of [IrCp*Cl(2)](2) has previously been found to yield a vinyl indole derivative and not the indole expected to form following a hydroamination reaction. Experimental data, including labelling studies, isolation and solid state structure determination of a reaction intermediate together with DFT calculations were used to develop a mechanism for the formation of the vinyl indole. In the mechanism proposed, acetone plays a significant role in several steps of the reaction path, participating in the fragmentation of the dinuclear Ir complex and the formation of the reactive form of the catalyst as well as blocking the formation of the expected hydroamination product by coordination to the Ir catalyst. Coordinated acetone reacts with the aniline to form an imine derivative, which yields the final product following proton transfer promoted by acetone. The proposed mechanism is in good agreement with the experimental data.

Large aggregated parent ions, for example, C(8)A(7)(+) (C = cation and A = anion), have been observed within some protic ionic liquids (PILs) using electrospray ionization mass spectrometry (ESI-MS). We have shown that the formation and size of aggregates is dependent on the nature of the anion and cation. Solvent structuring in select PILs through aggregation can contribute to their classification as "poor ionic liquids" and can also strongly influence the entropic component to the free energy of amphiphile self-assembly in select PILs.

Parallel factor analysis (PARAFAC) was used to analyze data from the high throughput screening of an array of organometallic rhodium and iridium complexes as catalysts for the intramolecular hydroamination of 2-(2-phenylethynyl)aniline to give 2-phenylindole. The progress of the hydroamination reactions was monitored using UV-visible spectroscopy. The overlapped UV-visible spectra of the mixture of starting material, product and solvent in the samples taken at different times were deconvoluted using PARAFAC. Unique PARAFAC models led to close approximations of the actual UV-visible spectra of the compounds in the mixture. The performance of the catalysts was then compared by estimating the final concentration of the starting material and product using PARAFAC loadings. A library of 63 complexes generated in situ was examined in a single experiment using this methodology. The complexes were generated from combinations of seven ligands (bis(N-methyl2-imidazolyl)methane, bis(1-pyrazolyl)methane, 1,10-phenanthroline, N,N'-bis(p-tolyl)diazabutadiene, N,N'-bis(p-tolyl)1,2-dimethyldiazabutadiene, N,N'-bis(mesityl)1,2-dimethyldiazabutadiene and bis(2,4,6-trimethylphenylimino)acenapthene) and nine metal precursors ([Ir(COD)Cl](2) (COD = 1,5-cyclooctadiene), [Ir(CO)(2)Cl](n), [Ir(COE)(2)Cl](2), [IrCp*Cl(2)](2) (Cp* = 1,2,3,4,5-pentamethylcyclopentadiene), [Rh(COD)Cl](2), [Rh(CO)(2)Cl](2), [Rh(COE)(2)Cl](2), [RhCp*Cl(2)](2) and [RhCpCl(2)](2)) (Cp = cyclopentadiene)). The proposed method can be used for the fast screening of arrays of metal complexes for identifying effective catalysts, providing information that can augment traditional methods used for the analysis of catalyzed reactions.

A series of 11 new protic ionic liquids with fluorous anions (FPILs) have been identified and their self-assembled nanostructure, thermal phase transitions and physicochemical properties were investigated. To the best of our knowledge this is the first time that fluorocarbon domains have been reported in PILs. The FPILs were prepared from a range of hydrocarbon alkyl and heterocyclic amine cations in combination with the perfluorinated anions heptafluorobutyrate and pentadecafluorooctanoate. The nanostructure of the FPILs was established by using small- and wide-angle X-ray scattering (SAXS and WAXS). In the liquid state many of the FPILs showed an intermediate range order, or self-assembled nanostructure, resulting from segregation of the polar and nonpolar hydrocarbon and fluorocarbon domains of the ionic liquid. In addition, the physicochemical properties of the FPILs were determined including the melting point (T(m)), glass transition (T(g)), devitrification temperature (T(c)), thermal stability and the density ρ, viscosity η, air/liquid surface tension γ(LV), refractive index n(D), and ionic conductivity κ. The FPILs were mostly solids at room temperature, however two examples 2-pyrrolidinonium heptafluorobutyrate (PyrroBF) and pyrrolidinium heptafluorobutyrate (PyrrBF) were liquids at room temperature and all of the FPILs melted below 80 °C. Four of the FPILs exhibited a glass transition. The two liquids at room temperature, PyrroBF and PyrrBF, had a similar density, surface tension and refractive index but their viscosity and ionic conductivity were very different due to dissimilar self-assembled nanostructure.

The thermal phase transitions and physicochemical properties of a series of 21 amino acid-derived protic ionic liquids and four protic molten salts have been investigated. Structure–property comparisons for this series were investigated for alkyl- and cyclic amino acid cations, and ethoxy and methoxy groups on the cation, combined with nitrate or various carboxylate-containing anions. All the protic fused salts were found to be ‘fragile’. Most of the protic fused salts exhibited a glass transition, with the transition temperatures ranging from –90° to –42°C. Viscosities and conductivities ranged from 0.03 to 15.46 Pa s and 0.02 to 2.20 mS cm–1 at 25°C respectively. The protic ionic liquids alanine methyl ester glycolate, proline methyl ester nitrate, and proline methyl ester glycolate were found to be capable of supporting amphiphile self-assembly. Lamellar or hexagonal liquid crystalline phases were observed with the cationic surfactant hexadecyltrimethylammonium bromide and the non-ionic surfactant Myverol 18–99K.

Gadolinium doped mesoporous silica (gadolinosilicate) nanoparticles were synthesized using a novel approach aimed at incorporating Gd ions into a porous silica network. The ionic liquid, gadolinium (Z)-octadec-9-enoate (Gd Oleate) was utilized in a dual role, as a soft template to generate porous silica and also to act as a gadolinium source for incorporation into the silicate. The generated silicate materials were characterized for size, structure and composition, confirming that gadolinium was successfully doped into the silicate network in a mesoporous nanoparticulate form. Proton relaxivity results indicated that the gadolinium doped silicates had slightly lower longitudinal relaxivity and much higher transverse relaxivity than the commercial contrast agent Magnevist®, suggesting that the mesoporous nanoparticulate materials have potential as contrast agents for magnetic resonance imaging.

Potential catalysts for the hydroamination of 2-(2-phenylethynyl)aniline 2 which have been identified through high throughput screening methods were investigated. Two complexes were shown to be highly active hydroamination catalysts in acetone: the in situ combinations of [Rh(CO)2Cl]2–mesBIAN–NaBF4 (mesBIAN = bis(2,4,6-trimethylphenylimino)acenapthene) and [Ir(COD)Cl]2–NaBF4 (COD = 1,5-cyclooctadiene). The isolated complexes [M(N–N)XCl]BF4 (M = Rh, Ir; N–N = bidentate nitrogen donor ligand; X = CO or Cp*) were found to be inactive as catalysts for the conversion of 2 to 3. However, chloride abstraction from these complexes through the addition of AgBF4 was found to generate extremely active catalysts. Particularly active was the complex [Rh(CO)ClmesBIAN]–AgBF4 (5 mol%) which achieved complete conversion of 2 to 3 in 12 minutes at 50 °C. Also identified was the formation of the unusual product, N-(2-methylvinyl)-2-phenylindole 5, catalysed by [IrCp*Cl2]2–NaBF4 from starting material 2via the incorporation of one molecule of acetone.

Characterisation of the multiple pore sizes, or heirarchical porosity, within periodic mesoporous silicas, carbons and carbon silica composites using a combination of standard analysis techniques and also positron annihilation lifetime spectroscopy is reported. The PALS technique was found to complement more standard methods of porous materials characterisation such as nitrogen sorption, small angle X-ray diffraction (SAXRD), and thermogravimetric analysis (TGA). Additional information, particularly on the location of polymer within silica materials, and also on internal surfaces, regardless of surface connectivity or long range order was revealed. The templating process was investigated for the widely employed materials SBA-15, KIT-6 and MCF-2.5. Samples were taken at various times throughout the nanotemplating process. Using commonly reported procedures parent templated silicas, ordered mesoporous carbons, their carbon-silica composite materials and second generation silicas were obtained and have been characterised using the suite of techniques. As a result, new information on the development of pore structure derived from the effectiveness of the templating process is reported. The results obtained highlight the factors that influence the process of pore filling. The new details uncovered regarding the porosity of many materials should be useful in the development of further applications with the characterisation serving as a ready reference for future materials development in this field.