Philippa L. Jacob

A critical assessment of the current literature on the use of Design of Experiments (DoE) in ring opening polymerisation (ROP) and polycondensation for polyester synthesis with a particular focus on enzymatic polymerisation.

Recent studies have highlighted the limitations of conventional high degrees of PEGylation in drug delivery systems, including immune recognition and reduced efficacy. Approaches such as poly(ethylene glycol) (PEG) isomerization and shortening of PEG chains have emerged as strategies to mitigate anti-PEG immune responses while preserving key physicochemical properties required for drug delivery. Inspired by these advancements, this study aims to enzymatically synthesize new hybrid polymers incorporating a limited fraction of PEG and biosourced polyols, such as glycerol and diglycerol, as the hydrophilic counterpart, minimizing the amount of PEG by 50% (compared to our previous work). These novel adipate-based tetrapolymers, generated using four different starting materials, outperformed previous systems, offering a tunable and sustainable design for nanomedicine. By strategically limiting the PEG fraction, we preserved the functional benefits of PEGylation, including stealth and amphiphilicity, while advancing toward greener chemistry. The resulting biodegradable PEGylated polyesters were formulated from film rehydration of solid dispersions and increased the water solubility of the model drug curcumin via direct encapsulation of the compound in polymeric nanoparticles. The best performing polymer variant consisted of diglycerol, 1,6-hexanediol, and PEG combined with divinyl adipate (PEGDGA-Hex 50%). Its drug interactions, colloidal stability, biodegradability, and biocompatibility, in both in vitro (Caco2, human intestinal epithelial cells MCF-7, human breast cancer cells, and MDA-MB-231 late-stage triple-negative breast cancer cells) and invertebrate in vivo models that align with 3R principles (Caenorhabditis elegans and Drosophila melanogaster), support its potential use in systemic drug delivery.

A new high-throughput enzymatic biodegradation assay has been developed, and the data have been used to train a machine learning model to predict polyester biodegradability and explain how structural features influence biodegradability.

This study presents novel mixed nanosystems composed of 10,12‐pentacosadiynoic acid (PCDA) and biodegradable, enzymatically synthesized polymers—PGA, PGA _HEX , or PGA _BDM — designed to alter and exploit PCDA's chromatic properties. These nanoparticles offer a cost‐effective, non‐leachable tracking system suitable for both in vitro and in vivo biological assays. Notably, they enable real‐time monitoring without the need for additional fluorescent dyes, a common requirement in conventional systems. Fabricated via a simple nanoprecipitation method, the nanoparticles exhibit a narrow size distribution, zeta potential, and spherical morphology. Their enhanced stability in response to temperature and phosphate‐buffered saline (PBS) is attributed to hydrogen bonding, hydrophobic interactions, and π – π stacking within the polymeric matrix. Preliminary cytotoxicity assessments using MCF‐7 human breast cancer cells and the invertebrate model Caenorhabditis elegans —aligned with the 3R principle of replacing higher animals—demonstrated good biocompatibility. Importantly, both cellular and nematode uptake of PCDA and PCDA/PGA nanoparticles was successfully achieved, confirming their utility for both in vitro and in vivo tracking without the need for additional dyes.

A facile and green photocatalytic approach to obtain highly pure α-pinene, allowing total utilization of turpentine as a biomass resource.

Earth abundant catalysis and more sustainable post-polymerisation functionalisation have been applied in the synthesis of β-pinene derived polymeric surfactants.

Here we report the scaled-up synthesis of α-pinene-derived monomers, using less hazardous/toxic reagents. The application of these terpene-derived monomers as high T_g components in copolymer coatings with high biobased content is also investigated.

Volumetric Additive Manufacturing (VAM) represents a revolutionary advancement in the field of Additive Manufacturing, as it allows for the creation of objects in a single, cohesive process, rather than in a layer-by-layer approach. This innovative technique offers unparalleled design freedom and significantly reduces printing times. A current limitation of VAM is the availability of suitable resins with the required photoreactive chemistry and from sustainable sources. To support the application of this technology, we have developed a sustainable resin based on polyglycerol, a bioderived (e.g., vegetable origin), colourless, and easily functionisable oligomer produced from glycerol. To transform polyglycerol-6 into an acrylate photo-printable resin we adopted a simple, one-step, and scalable synthesis route. Polyglycerol-6-acrylate fulfils all the necessary criteria for volumetric printing (transparency, photo-reactivity, viscosity) and was successfully used to print a variety of models with intricate geometries and good resolution. The waste resin was found to be reusable with minimal performance issues, improving resin utilisation and minimising waste material. Furthermore, by incorporating dopants such as poly(glycerol) adipate acrylate (PGA-A) and 10,12-pentacosadyinoic acid (PCDA), we demonstrated the ability to print objects with a diverse range of functionalities, including temperature sensing probes and a polyester excipient, highlighting the potential applications of these new resins.