Immobilised Ruthenium Complexes for the Electrooxidation of 5-Hydroxymethylfurfural.

Abundantly available biomass-based platform chemicals, including 5-hydroxymethylfurfural (HMF), are essential stepping stones in steering the chemical industry away from fossil fuels. The efficient catalytic oxidation of HMF to its diacid derivative, 2,5-furandicarboxylic acid (FDCA), is a promising research area with potential applications in the polymer industry. Currently, the most encouraging approaches are based on solid-state catalysts and are often conducted in basic aqueous media, conditions where HMF oxidation competes with its decomposition. Efficient molecular catalysts are practically unknown for this reaction. In this study, we report on the synthesis and electrocatalysis of surface-bound molecular ruthenium complexes for the transformation of HMF to FDCA under acidic conditions. Catalyst immobilisation on mesoporous indium tin oxide electrodes is achieved through the incorporation of phosphonic acid anchoring groups. Screening experiments with HMF and further reaction intermediates revealed the catalytic route and bottlenecks in the catalytic synthesis of FDCA. Utilising these immobilised electrocatalysts, FDCA yields of up to 85 % and faradaic efficiencies of 91 % were achieved, without any indication of substrate decomposition. Surface analysis by X-ray photoelectron spectroscopy (XPS) post-electrocatalysis unveiled the desorption of the catalyst from the electrode surface as a limiting factor in terms of catalytic performance.

Solution-Processed Cu2S Nanostructures for Solar Hydrogen Production.

Cu2S is a promising solar energy conversion material due to its suitable optical properties, high elemental earth abundance, and nontoxicity. In addition to the challenge of multiple stable secondary phases, the short minority carrier diffusion length poses an obstacle to its practical application. This work addresses the issue by synthesizing nanostructured Cu2S thin films, which enables increased charge carrier collection. A simple solution-processing method involving the preparation of CuCl and CuCl2 molecular inks in a thiol-amine solvent mixture followed by spin coating and low-temperature annealing was used to obtain phase-pure nanostructured (nanoplate and nanoparticle) Cu2S thin films. The photocathode based on the nanoplate Cu2S (FTO/Au/Cu2S/CdS/TiO2/RuO x ) reveals enhanced charge carrier collection and improved photoelectrochemical water-splitting performance compared to the photocathode based on the non-nanostructured Cu2S thin film reported previously. A photocurrent density of 3.0 mA cm-2 at -0.2 versus a reversible hydrogen electrode (V RHE) with only 100 nm thickness of a nanoplate Cu2S layer and an onset potential of 0.43 V RHE were obtained. This work provides a simple, cost-effective, and high-throughput method to prepare phase-pure nanostructured Cu2S thin films for scalable solar hydrogen production.

Fibrous Structures from Starch and Gluten.

Starch is added to meat analogues for binding and water holding. In this study, we investigate whether starch can have an additional role as a structuring agent. Therefore, different types of starch were combined with wheat gluten at various amounts and sheared in a High Temperature Shear Cell to determine how starch influences the structuring behavior of gluten-starch blends. The starches were chosen based on their diverse amylose contents, leading to different technological properties. Remarkable differences were found between the starches investigated. The addition of Amioca starch (containing 1% amylose) had a strong negative influence on the ability of gluten to form fibers. Maize starch (25% amylose) and Hylon VII (68% amylose) formed fibrous materials up to high starch additions. The pre-gelatinizing of maize starch further increased the ability of gluten-starch mixtures to form fibrous structures. The influence of the different types of starch on the hardness, deformability, and stiffness of the sheared samples was also assessed, revealing a spectrum of achievable properties through the addition of starch. Most remarkable was the formation of a material with anisotropy in Young's modules. This anisotropy is also found in chicken meat, but not in protein-based fibrous materials. Furthermore, it was observed that the pre-gelatinization of starch facilitated fiber formation. A similar effect of pre-gelatinizing the starch was found when using faba bean meal with added wheat gluten, where fibrous structures could even be formed in a recipe that previously failed to produce such structures without pre-treatment.

Quantifying water distribution between starch and protein in doughs and gels from mildly refined faba bean fractions.

The development of novel and sustainable food products, such as cheese- and meat analogues, requires a better understanding of the use of less refined ingredients. We investigated the distribution of water between the protein and starch phase of doughs and heat-induced gels made from air-classified faba bean fractions by developing a method suited for investigation of such multi-component ingredients. The moisture contents of the protein and starch phases in the dough were determined using a method based on partial sorption isotherms of mixed doughs of protein- and starch-rich fractions at high water activity. Water content of the protein phase is higher than that of the starch phase in dough, showing that protein takes up more water than starch at room temperature. Also, the moisture content of the protein phase in the gels was calculated using a model based on the denaturation temperature of legumin. From the experiments and the modelling, it became evident that the moisture content of the protein phase in the gel is lower than the moisture content of the protein phase in the dough, showing the importance of considering moisture migration from the protein to the starch during heating.

Expanding the Chemistry Palette for Radiotracer Synthesis.

The synthesis, characterisation and application of radiolabelled compounds for use in diagnostic and therapeutic medicine requires a diverse skill set. This article highlights a selection of our ongoing projects that aim to provide new synthetic methods and radiochemical tools for building molecular imaging agents with various radionuclides.

Modifying Faba Bean Protein Concentrate Using Dry Heat to Increase Water Holding Capacity.

We investigated the effect of dry-heat treatment on the properties of faba bean protein concentrate using soy protein concentrate as a benchmark. While soy protein-widely used as an ingredient in meat replacers-is recovered through a wet fractionation, protein recovery from starch bearing pulses like faba bean can be done via dry fractionation. This process does not require drying or heating steps and therefore, keeps the original protein functionality intact. This results in differences in properties such as water binding capacity of the protein fraction. Faba bean protein concentrate was dry-heated at temperatures from 75-175 °C, which resulted in higher water-holding capacity and less soluble protein, approaching values of soy protein concentrate. These changes were due to partial denaturation of protein, changing the structure of the protein, and exposing hydrophobic sites. This led to protein aggregation, as observed by light microscopy. Only noncovalent bonds caused the decrease of solubility of dry-heated faba bean protein concentrate. We conclude that dry-heating of dry fractionated faba bean protein can change the functional properties of the protein fraction to desired properties for certain applications. The effect is similar to that on soy, but the underlying mechanisms differ.