We report on the physical characterization of a dioctyl‐substituted polyfluorene, both in solution and in the solid state. We focus on studies of chain geometry both by molecular modeling and by gel permeation chromatography coupled with light scattering. We determine experimentally a Kuhn segment length, lk = 17.1 ± 2.1 nm and a characteristic ratio C∞ = 21.5 %plusmn; 4.3 indicative of a stiff polymer chain. The effects on absorption and emission spectra of intermolecular interactions that lead to gelation or precipitation from solution are reported. We discuss these results in the context of the strong current interest in the nature of aggregation phenomena and their role in controlling the emissive properties of conjugated polymers. We further show that a markedly enhanced dichroism can be achieved through suitable control of the polymer microstructure.

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Heterogeneous catalysts are desired for the conversion of glucose, the most abundant sugar in renewable biomass, but presently their synthesis requires highly toxic chemicals with long synthesis times. We report the conversion of glucose into fructose and 5‐hydroxymethylfurfural on a heterogeneous catalyst that is stable and selective and operates in the most environmentally benign solvent, water. We used a bifunctional solid with Lewis and Brønsted acid sites by partially replacing the organic linker of the zirconium organic framework UiO‐66 with 2‐monosulfo‐benzene‐1,4‐dicarboxylate. This catalyst showed high product selectivity (90 %) to 5‐hydroxymethylfurfural and fructose at 140 °C in water after a reaction time of 3 h. It was recyclable and showed only a minor loss in activity after the third recycle, offering a realistic solution for the bottleneck glucose isomerization reaction for scale‐up and industrial application of biomass utilization.

Metal organic framework UiO-66 is studied as an adaptable heterogeneous catalyst for glucose conversion. UiO-66 was modified by; i) partial linker substitution, ii) particle size modulation and iii) linker defects. We studied the effect of crystallinity and functional groups on the glucose conversion and product yields. The main products are: i) fructose from the isomerisation of glucose, ii) mannose from the epimerisation of glucose and iii) 5-hydroxymethyl furfural from the dehydration of fructose. We found that defective and nano crystalline UiO-66 catalyst performs best for isomerisation. When 50 % of the linkers of UiO-66 are replaced by a sulfonate-containing linker, the catalyst shows higher isomerisation activity than other UiO-66 catalysts. Naphthalene-dicarboxylate linkers were introduced to induce hydrophobicity and this catalyst further increased isomerisation activity showing 31 % fructose selectivity. Finally, the promising catalysts were tested in a flow reactor and a bifunctional mixed linker catalyst possessing both hydrophobic and acidic functional groups is shown to be stable in a time-onstream study.

Indium phosphide based quantum dots have emerged in recent years as alternatives to traditional heavy metal (cadmium, lead) based materials suitable for biomedical application due to their non-toxic nature. The major barrier to this application, is their low photoluminescent quantum yield in aqueous environments (typically < 5%). Here we present a synthetic method for InP/ZnS quantum dots, utilizing a controlled cooling step for equilibration of zinc sulfide across the core, resulting in a photoluminescent quantum yield as high as 85% in organic solvent and 57% in aqueous media. To the best of our knowledge, this is the highest reported for indium phosphide quantum dots. DFT calculations reveal the enhancement in quantum yield is achieved by redistribution of zinc sulfide across the indium phosphide core through thermal diffusion. By eliminating the need for a glove box and relying on Schlenk line techniques, we introduce a widely accessible method for quantum dots with a realistic potential for improved biomedical applications.

A ytterbium–organic framework containing Lewis and Brønsted acid sites that effects transformation of glucose to 5-HMF in water at 140 °C.

Multi-objective optimisation algorithms (MOOAs) are, of increasing interest for the efficient optimisation of chemical processes. However, an algorithms performance can vary on a case-by-case basis, depending on the complexity of...

Multifunctional nanoreactors are assembled using hollow graphitized carbon nanofibers (GNFs) combined with nanocatalysts (Pd or Pt) and magnetic nanoparticles. The latter are introduced in the form of carbon-coated cobalt nanomagnets (Co@C n ) adsorbed on GNF, or formed directly on GNF from ferrocene yielding carbon-coated iron nanomagnets (Fe@C n ). High-resolution transmission electron microscopy demonstrates that Co@C n and Fe@C n are attached effectively to the GNFs, and the loading of nanomagnets required for separation of the nanoreactors from the solution with an external magnetic field is determined using UV-vis spectroscopy. Magnetically functionalized GNFs combined with palladium or platinum nanoparticles result in catalytically active magnetically separable nanoreactors. Applied to the reduction of nitrobenzene the multifunctional nanoreactors demonstrate high activity and excellent durability, while their magnetic recovery enables significant improvement in the reuse of the nanocatalyst over five reaction cycles (catalyst loss < 0.5 wt%) as compared to the catalyst recovery by filtration (catalyst loss <10 wt%).