Advanced functional polymer colloids with high photo-oxidative properties

Project Information

APOCOLIPS

Grant agreement ID: 893426

DOI

10.3030/893426

Project terminated on 24 May 2023

EC signature date 30 April 2020

Start date 1 June 2021

End date 15 July 2023

Funded under

• EXCELLENT SCIENCE - Marie Skłodowska-Curie Actions

Total cost

€ 196 707,84

EU contribution

€ 196 707,84

Coordinated by

CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE CNRS
France

Periodic Reporting for period 1 - APOCOLIPS (Advanced functional polymer colloids with high photo-oxidative properties)

Reporting period: 2021-06-01 to 2023-05-31

Summary of the context and overall objectives of the project

In recent decades, EU has focused on reducing waste and energy consumption while promoting eco-friendly processes to create advanced materials. APOCOLIPS contributes to these efforts through combining research and engineering to develop environmentally friendly photoactive polymer colloids with advanced properties in safe solvents, which aligns with green chemistry principles. Likewise, there is a growing societal need to reduce bacterial and microbial contamination in healthcare and food packaging sectors due to the growing antimicrobial resistance (AMR) threat. Given the current state of AMR and the EU's objective to address this challenge, this project aims to reduce numerous sources of AMR in healthcare environments.
APOCOLIPS is crucial for society because it develops new polymer colloids with high photo-oxidative properties. These colloids can be used for effective wastewater treatment and offers better separation and recycling of photocatalysts. Secondly, the photo-oxidative properties of these polymer colloids can be applied in the field of healthcare. They have the potential to enhance disinfection processes, aiding in the elimination of harmful pathogens. Furthermore, these advanced polymer colloids can find applications in areas such as catalysis, photochemical production of derivatives and sensors.
APOCOLIPS aims to integrate advanced polymer chemistry strategies to develop innovative photoactive polymer colloids for two primary applications:
1) Development of effective polymer coatings with self-disinfecting and antimicrobial resistance properties: Inorganic materials have been used as substrates for incorporating organic photosensitizers (PSens), however, there is a growing interest in using polymers due to their versatility. The innovation of this research aim is to develop polymer coatings by integrating organic PSens through a safe and straightforward covalent bonding process.
2) Design of stable colloidal dispersions as substrate of photosensitizer that enables the photo-oxygenation of organic molecules for fine chemicals production industry. One of the challenges of this industry is to implement efficient and safe industrial processes. In this context, continuous-flow technologies have recently emerged as alternatives to batch processing. The innovation of APOCOLIPS for this second application involves combining the favorable aspects of flow photochemistry with the benefits of supported photosensitizers (PSens) to create novel stable submicronic photo-active polymer colloids.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

1) Preparation of photoactive polymer colloids by Polymerization‐Induced Self‐Assembly (PISA): core-shell type polymer latexes synthesized by polymerization in dispersed alcoholic media are designed. As the photosensitizer molecule, the nontoxic and commercially available Rose Bengal (RB) dye was chosen. The formation of photo-active polymer colloids was consisting of 3 steps (image 1):
- Synthesis of PSens-based polymerizable methacrylate monomer (EMARB) involving RB group
- Controlled copolymerization, by reversible addition fragmentation chain transfer (RAFT) polymerization, of a hydrophilic monomer such as oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and EMARB dye based comonomer which led to formation of the hydrophilic part called macromolecular chain transfer agent.
-Employing PISA in dispersion that led to create amphiphilic core-shell colloids. The objective in this step was to locate the PSens in the stabilizing hydrophilic shell and the insoluble hydrophobic polymer such as polybenzyl methacrylate (PBzMA) in the core.
This class of photoactive polymer colloids dispersed in alcoholic continuous phase offered additional perspectives for the 2nd objective of APOCOLIPs in terms of applications, ie the process intensification via LED-driven continuous-flow microphotoreactors for photooxygenation of fine chemicals (collaboration with CNRS LGC France).
2) Stable photo-active core-shell submicronic polymer colloids in aqueous dispersed media were also synthesized using completely different monomers and reaction conditions.
3) The photoactivity of polymer colloids was evaluated for singlet oxygen (1O2) production in collaboration with a PhD student. The quantum yield of singlet oxygen production was measured using an indirect method based on the photo-oxidation kinetics of a quencher molecule. As result, these photoactive colloids efficiently produced singlet oxygen at the particle/alcohol interface under visible light irradiation. The average quantum yield of singlet oxygen production approached that of free RB.
4) Results from APOCOLIPS led to collaboration with Laboratoire de Génie Chimique (INP, CNRS, France) and ongoing research related to this subject is being conducted involving the dedicated work of 2 PhD students.
5) The project results were disseminated through manuscript preparation and participation in some scientific conferences such as:
- ECIS 2022 conference, 4 -9 September 2022, Chania, Crete, Greece
- SCM10 conference, 1-3 February 2023, Amsterdam, Netherlands
- APME23 conference, 23-27 April 2023, Paris, France
6) The fellow had the opportunity to co-supervise a master student during his fellowship.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

APOCOLIPS filled a research gap with an innovative strategy that meets multiple criteria simultaneously. The approach aimed to develop a scalable and environmentally friendly process for producing functional colloids without the use of molecular surfactants, which can harm the environment and impact material properties. On the other hand, most studies on singlet oxygen mediated photo-oxygenations in microreactors employ a PSens dissolved in the reaction medium. However, a major drawback of these homogeneous photo-oxygenations is the need for an organic solvent that can dissolve both the dye and target molecule (often hazardous solvents), followed by the extraction of the dissolved PSens through organic solvent distillation. Introducing solid-supported PSens addresses this issue by allowing easy separation of the photo-active compound from the reaction mixture, enabling the use of environmentally friendly solvents.
APOCOLIPS can have several socio-economic impacts and wider societal implications as follows:
-Environmental Benefits: The project develops eco-friendly polymer colloids with robust photo-oxidative properties as alternatives to hazardous materials or processes.
-Enhancing public health quality: The developed polymer colloids with high photo-oxidative properties are beneficial in healthcare as they could enhance disinfection procedures by effectively eliminating drug-resistant microorganisms and reducing infection transmission.
-Sustainable industrial manufacturing: Advanced functional polymer colloids can optimize manufacturing processes, enhancing efficiency and sustainability. They enable the production of coatings, films and materials with improved properties.
-Energy Efficiency: Highly photo-oxidative polymer colloids aid energy efficiency in applications like photochemistry and photocatalysis. They harness light energy more effectively than batch processes, potentially advancing renewable energy tech and reducing carbon emissions.
-Knowledge and Innovation: The project's R&D activities drive scientific knowledge and innovation in polymer chemistry and materials science which can pave the way for new research and collaboration opportunities among academia and industry.

Synthetic pathway for the formation of photo-active polymer colloids