Conversion of Contaminated Post-Consumer Polyethylene Terephthalate into a Thermoset Alkyd Coating Using Biosourced Monomers.

The synthesis of a high-performance oxidative cross-linked thermoset alkyd coating is described that utilizes a novel recycling strategy from contaminated postconsumer waste polyethylene terephthalate (wPET). A single-stage "depolymerization-repolymerization" process has been developed that allows the exploitation of a waste stream from a commercial PET recycling process with 95% efficiency, which, when copolymerized with glycerol and tall oil fatty acid, delivers a sustainable fatty acid-functional polyester suitable for use in thermoset alkyd coatings. Physical drying challenges have been tackled via the development of a convergent polymer formulation strategy from a single source of wPET and the formulation of the resulting fatty acid-functional polymers with commercial alkyd driers, delivering a thermoset alkyd coating suitable for industrial applications.

Use of remote sensing to assess vegetative stress as a proxy for soil contamination.

We report, for the first time, a multimodal investigation of current crude oil reprocessing and storage sites to assess their impact on the environment after 50 years of continuous operation. We have adopted a dual approach to investigate potential soil contamination. The first approach uses conventional analytical techniques i.e. energy dispersive X-ray fluorescence (ED-XRF) for metal analysis, and a complementary metabolomic investigation using hydrophilic liquid interaction chromatography hi-resolution mass spectrometry (HILIC-MS) for organic contaminants. Secondly, the deployment of an unmanned aerial vehicle (UAV) with a multispectral image (MSI) camera, for the remote sensing of vegetation stress, as a proxy for sub-surface soil contamination. The results identified high concentrations of barium (mean 21 017 ± 5950 µg g-1, n = 36) as well as metabolites derived from crude oil (polycyclic aromatic hydrocarbons), cleaning processes (surfactants) and other organic pollutants (e.g. pesticides, plasticizers and pharmaceuticals) in the reprocessing site. This data has then been correlated, with post-flight data analysis derived vegetation indices (NDVI, GNDVI, SAVI and Cl green VI), to assess the potential to identify soil contamination because of vegetation stress. It was found that strong correlations exist (an average R2 of >0.68) between the level of soil contamination and the ground cover vegetation. The potential to deploy aerial remote sensing techniques to provide an initial survey, to inform decision-making, on suspected contaminated land sites can have global implications.

Use of an unmanned aerial vehicle for monitoring and prediction of oilseed rape crop performance.

The flowering stage of oilseed rape (Brassica napus L.) is of vital interest in precision agriculture. It has been shown that data describing the flower production of oilseed rape (OSR), at stage 3, in spring can be used to predict seed yield at harvest. Traditional field-based techniques for assessing OSR flowers are based on a visual assessment which is subjective and time consuming. However, a high throughput phenotyping technique, using an unmanned aerial vehicle (UAV) with multispectral image (MSI) camera, was used to investigate the growth stages of OSR (in terms of crop height) and to quantify its flower production. A simplified approach using a normalised difference yellowness index (NDYI) was coupled with an iso-cluster classification method to quantify the number of OSR flower pixels and incorporate the data into an OSR seed yield estimation. The estimated OSR seed yield showed strong correlation with the actual OSR seed yield (R2 = 0.86), as determined using in-situ sensors mounted on the combine harvester. Also, using our approach allowed the variation in crop height to be assessed across all growing stages; the maximum crop height of 1.35 m OSR was observed at the flowering stage. This methodology is proposed for effectively predicting seed yield 3 months prior to harvesting.

Engineered living photosynthetic biocomposites for intensified biological carbon capture.

Carbon capture and storage is required to meet Paris Agreement targets. Photosynthesis is nature's carbon capture technology. Drawing inspiration from lichen, we engineered 3D photosynthetic cyanobacterial biocomposites (i.e., lichen mimics) using acrylic latex polymers applied to loofah sponge. Biocomposites had CO2 uptake rates of 1.57 ± 0.08 g CO2 g-1biomass d-1. Uptake rates were based on the dry biomass at the start of the trial and incorporate the CO2 used to grow new biomass as well as that contained in storage compounds such as carbohydrates. These uptake rates represent 14-20-fold improvements over suspension controls, potentially scaling to capture 570 tCO2 t-1biomass yr-1, with an equivalent land consumption of 5.5-8.17 × 106 ha, delivering annualized CO2 removal of 8-12 GtCO2, compared with 0.4-1.2 × 109 ha for forestry-based bioenergy with carbon capture and storage. The biocomposites remained functional for 12 weeks without additional nutrient or water supplementation, whereupon experiments were terminated. Engineered and optimized cyanobacteria biocomposites have potential for sustainable scalable deployment as part of humanity's multifaceted technological stand against climate change, offering enhanced CO2 removal with low water, nutrient, and land use penalties.

Self-Assembled, Hierarchical Structured Surfaces for Applications in (Super)hydrophobic Antiviral Coatings.

A versatile method for the creation of multitier hierarchical structured surfaces is reported, which optimizes both antiviral and hydrophobic (easy-clean) properties. The methodology exploits the availability of surface-active chemical groups while also manipulating both the surface micro- and nanostructure to control the way the surface coating interacts with virus particles within a liquid droplet. This methodology has significant advantages over single-tier structured surfaces, including the ability to overcome the droplet-pinning effect and in delivering surfaces with high static contact angles (>130°) and good antiviral efficacy (log kill >2). In addition, the methodology highlights a valuable approach for the creation of mechanically robust, nanostructured surfaces which can be prepared by spray application using nonspecialized equipment.

Applied aerial spectroscopy: A case study on remote sensing of an ancient and semi-natural woodland.

An area of ancient and semi-natural woodland (ASNW) has been investigated by applied aerial spectroscopy using an unmanned aerial vehicle (UAV) with multispectral image (MSI) camera. A novel normalised difference spectral index (NDSI) algorithm was developed using principal component analysis (PCA). This novel NDSI was then combined with a simple segmentation method of thresholding and applied for the identification of native tree species as well as the overall health of the woodland. Using this new approach allowed the identification of trees at canopy level, across 7.4 hectares (73,934 m2) of ASNW, as oak (53%), silver birch (37%), empty space (9%) and dead trees (1%). This UAV derived data was corroborated, for its accuracy, by a statistically valid ground-level field study that identified oak (47%), silver birch (46%) and dead trees (7.4%). This simple innovative approach, using a low-cost multirotor UAV with MSI camera, is both rapid to deploy, was flown around 100 m above ground level, provides useable high resolution (5.3 cm / pixel) data within 22 mins that can be interrogated using readily available PC-based software to identify tree species. In addition, it provides an overall oversight of woodland health and has the potential to inform a future woodland regeneration strategy.

Enzyme-catalysed polymer cross-linking: Biocatalytic tools for chemical biology, materials science and beyond.

Intermolecular cross-linking is one of the most important techniques that can be used to fundamentally alter the material properties of a polymer. The introduction of covalent bonds between individual polymer chains creates 3D macromolecular assemblies with enhanced mechanical properties and greater chemical or thermal tolerances. In contrast to many chemical cross-linking reactions, which are the basis of thermoset plastics, enzyme catalysed processes offer a complimentary paradigm for the assembly of cross-linked polymer networks through their predictability and high levels of control. Additionally, enzyme catalysed reactions offer an inherently 'greener' and more biocompatible approach to covalent bond formation, which could include the use of aqueous solvents, ambient temperatures, and heavy metal-free reagents. Here, we review recent progress in the development of biocatalytic methods for polymer cross-linking, with a specific focus on the most promising candidate enzyme classes and their underlying catalytic mechanisms. We also provide exemplars of the use of enzyme catalysed cross-linking reactions in industrially relevant applications, noting the limitations of these approaches and outlining strategies to mitigate reported deficiencies.

Investigation of the acid/base behaviour of the opium alkaloid thebaine in LC-ESI-MS mobile phase by NMR spectroscopy.

As part of a research programme to establish an analytical method for the simultaneous detection of the five major opium alkaloids in poppy seeds by liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) it was discovered that the inclusion of thebaine produced two peaks for the same compound. This was in contrast to the effective simultaneous detection, by LC-ESI-MS, of morphine, codeine, papaverine and noscapine. The presence of these two peaks for thebaine was investigated using nuclear magnetic resonance spectroscopy with deuterated solvents to emulate the mobile phase conditions experienced. It was found that the presence of 80%, or higher ratios of, water caused two epimeric forms of thebaine to be formed; this explained the presence of two peaks on the chromatogram. In contrast, when a lower water content was used with 1% acetic acid, one stable form of thebaine could be analysed and resulted in a single peak visible in the subsequent chromatography.

An investigation of nitrile transforming enzymes in the chemo-enzymatic synthesis of the taxol sidechain.

Paclitaxel (taxol) is an antimicrotubule agent widely used in the treatment of cancer. Taxol is prepared in a semisynthetic route by coupling the N-benzoyl-(2R,3S)-3-phenylisoserine sidechain to the baccatin III core structure. Precursors of the taxol sidechain have previously been prepared in chemoenzymatic approaches using acylases, lipases, and reductases, mostly featuring the enantioselective, enzymatic step early in the reaction pathway. Here, nitrile hydrolysing enzymes, namely nitrile hydratases and nitrilases, are investigated for the enzymatic hydrolysis of two different sidechain precursors. Both sidechain precursors, an openchain α-hydroxy-ß-amino nitrile and a cyanodihydrooxazole, are suitable for coupling to baccatin III directly after the enzymatic step. An extensive set of nitrilases and nitrile hydratases was screened towards their activity and selectivity in the hydrolysis of two taxol sidechain precursors and their epimers. A number of nitrilases and nitrile hydratases converted both sidechain precursors and their epimers.

A high-throughput screening method for determining the substrate scope of nitrilases.

Nitrile compounds are intermediates in the synthesis of pharmaceuticals such as atorvastatin. We have developed a chromogenic reagent to screen for nitrilase activity as an alternative to Nessler's reagent. It produces a semi-quantifiable blue colour and hydrolysis of 38 nitrile substrates by 23 nitrilases as cell-free extracts has been shown.

Sterol 3ß-glucosyltransferase biocatalysts with a range of selectivities, including selectivity for testosterone.

The main objectives of this work were to characterise a range of purified recombinant sterol 3ß-glucosyltransferases and show that rational sampling of the diversity that exists within sterol 3ß-glucosyltransferase sequence space can result in a range of enzyme selectivities. In our study the catalytically active domain of the Saccharomyces cerevisiae 3ß-glucosyltransferase was used to mine putative sterol 3ß-glucosyltransferases from the databases. Selected diverse sequences were expressed in and purified from Escherichia coli and shown to have different selectivities for the 3ß-hydroxysteroids ergosterol and cholesterol. Surprisingly, three enzymes were also selective for testosterone, a 17ß-hydroxysteroid. This study therefore reports for the first time sterol 3ß-glucosyltransferases with selectivity for both 3ß- and 17ß-hydroxysteroids and is also the first report of recombinant 3ß-glucosyltransferases with selectivity for steroids with a hydroxyl group at positions other than C-3. These enzymes could therefore find utility in the pharmaceutical industry for the green synthesis of a range of glycosylated compounds of medicinal interest.

The identification of synthetic organic pigments in modern paints and modern paintings using pyrolysis-gas chromatography-mass spectrometry.

A collection of more than 70 synthetic organic pigments were analysed using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). We report on the analysis of diketo-pyrrolo-pyrrole, isoindolinone and perylene pigments which are classes not previously reported as being analysed by this technique. We also report on a number of azo pigments (2-naphthol, naphthol AS, arylide, diarylide, benzimidazolone and disazo condensation pigments) and phthalocyanine pigments, the Py-GC-MS analysis of which has not been previously reported. The members of each class were found to fragment in a consistent way and the pyrolysis products are reported. The technique was successfully applied to the analysis of paints used by the artist Francis Bacon (1909-1992), to simultaneously identify synthetic organic pigments and synthetic binding media in two samples of paint taken from Bacon's studio and micro-samples taken from three of his paintings and one painting attributed to him.

A New Generation of "Cholaphanes": Steroid-Derived Macrocyclic Hosts with Enhanced Solubility and Controlled Flexibility.

The macrocyclic "cholaphanes" 3a-c were synthesized from the inexpensive steroid cholic acid. Like earlier relatives they feature substantial cavities with inward-directed hydroxyl groups, suitable for binding polar molecules such as carbohydrates in nonpolar media. New features are the externally directed alkyl chains, promoting solubility in organic solvents, and (in the case of 3b/c) reduced conformational freedom resulting from truncation of the steroidal side-chain. In particular, modeling shows that the smallest macrocycle 3c possesses very little flexibility, preferring an open conformation which is also revealed in the X-ray crystal structure of its pentahydrate. NMR studies indicated that all three cholaphanes form 1:1 complexes with octyl beta-D-glucoside in CDCl(3), with K(a) = 600-1560 M(-)(1). Cholaphanes 3b/c proved able to extract methyl beta-D-glucoside from aqueous solutions into CHCl(3). The transport of methyl beta-D-glucoside across a chloroform barrier was also demonstrated for 3c.