Periodic Reporting for period 1 - RenEcoPol (Sustainable route for circularity of renewable polyesters)
Periodo di rendicontazione: 2021-06-01 al 2023-05-31
The problem addressed by RenEcoPol project and why it is important for society:
Plastic pollution is one of the most challenging environmental issues of the current years. The material and polymer sectors are facing the challenge of integrating the sustainability of both processes and products, including their management after disposal. Renewable bio-based polymers are a solution offered by bioeconomy to solve the environmental emergency connected to fossil-based plastics. It was demonstrated that more than 70 % of the natural capital cost associated with plastic derives from the extraction and processing of fossil raw materials.
The aim of the RenEcoPol project was to develop and implement a new scientific approach for the ecodesign of environmentally safe polymers based on the integration of bioinformatics knowledge, biocatalysis and polymer chemistry data, environmental biotechnology and ecology. The RenEcoPol project objectives were achieved by implementing ecodesign strategies able to rationally select targeted monomers and enzymes.
The RenEcoPol project overall objectives foreseen and achieved were:
• to develop computational procedure able to analyze and evaluate the ability of different hydrolases to interact and to accept short chain substrates either for synthetic or degradative processes.
• to obtain biobased polyesters by using green routes and to perform a complete characterization by using several analytical techniques.
• to evaluate the ecological impact by determination of the ecotoxicity and biodegradation rates in marine environment and the development of reuse and recycle strategies of the monomers obtained after polymer degradation.
Plastic pollution is one of the most challenging environmental issues of the current years. The material and polymer sectors are facing the challenge of integrating the sustainability of both processes and products, including their management after disposal. Renewable bio-based polymers are a solution offered by bioeconomy to solve the environmental emergency connected to fossil-based plastics. It was demonstrated that more than 70 % of the natural capital cost associated with plastic derives from the extraction and processing of fossil raw materials.
The aim of the RenEcoPol project was to develop and implement a new scientific approach for the ecodesign of environmentally safe polymers based on the integration of bioinformatics knowledge, biocatalysis and polymer chemistry data, environmental biotechnology and ecology. The RenEcoPol project objectives were achieved by implementing ecodesign strategies able to rationally select targeted monomers and enzymes.
The RenEcoPol project overall objectives foreseen and achieved were:
• to develop computational procedure able to analyze and evaluate the ability of different hydrolases to interact and to accept short chain substrates either for synthetic or degradative processes.
• to obtain biobased polyesters by using green routes and to perform a complete characterization by using several analytical techniques.
• to evaluate the ecological impact by determination of the ecotoxicity and biodegradation rates in marine environment and the development of reuse and recycle strategies of the monomers obtained after polymer degradation.
To achieve the three main objectives:
• 7 work-packages and 24 tasks: scientific, management, training and dissemination were defined in the project proposal; • the tasks were implemented within the Laboratory of Applied and Computational Biocalalysis, Department of Chemical and Pharmaceutical Sciences, University of Trieste, Italy in collaboration with: Esteco S.p.a for the computational support and Department of Life Sciences of University of Trieste and Bioscience Research Center Srl, Orbetello, for the ecotoxicity evaluation studies.
Objective 1 (month 1-month 8)
In this respect computational studies were performed for a series of polyesters and enzymes by using three different computational approaches:
- for substrates modelling and simulation: • for 30 copolymers the physico-chemical properties were predicted using available platforms based on machine learning and softwares; •for 70 polyesters molecular descriptors from 3D Molecular Interaction Fields (MIFs) were generated and evaluated;
- for enzyme modelling: • MD studies were performed for 6 hydrolases at different temperature conditions.
- for enzyme-substrate modelling: • 2 docking methods were applied to the analysis of the selected substrates; • more than 40 copolymers were docked in the catalytic site of the 6 hydrolases using Lamarckian genetic algorithm search method and free energy estimation based on an empirical free-energy force field; • about 40 terpolymers were docked by using Monte Carlo search and rapid gradient-optimization conformational search coupled with a simple scoring function for free energy estimation;
• an automatic workflow using modeFrontier software was developed by integrating specific modelling software; • a series of bio-based monomers and enzymes were screened up and the computational studies results were correlated with experimental data
Objective 2 (month 8-month 13)
The second objective was achieved by implementing:
• the synthesis of 18 polyesters, by using the monomers and hydrolases selected from Objective 1; • experimental reactions in solvent less system, or novel sustainable solvents for 4 of the targeted products. Reaction yields were in the range of 86 and 96%; • complete characterization procedures for all polyesters;
Objective 3 (month 12-month 24)
The third objective was achieved by studying:
• the biodegradability in marine environment of 25 sample (starting bio-based monomers and the polyesters synthesized within Objective 2)
• the ecotoxicity of 18 samples consisting of starting bio-based monomers and the correspondent polyesters enzymatically synthesized within Objective 2. The ecotoxicity was evaluated in: • fresh water in the presence of microalgae and • marine water in the presence of bacteria and microalgae
• the hydrolysis of the synthesized polyesters by 2 commercially available enzymes, obtaining degradation yields up to ~ 90%.
• the recovery of the monomers at laboratory scale to demonstrate the circularity of the concept and strategy developed within the RenEcoPol project as a proof of concept. Two or three steps protocols were developed as a function of the monomers solubility in water. Monomers recovery yields were in the range of 76-98%.
DISSEMINATION
• PUBLICATIONS: 4 papers published in journals with impact factor as open access, cumulative impact factor WoS 2021: 23.575; 1 paper under revision at Sustainable Chemistry and Pharmacy; 2 manuscripts in preparation for publication.
• INTERNATIONAL CONFERENCES :7 prestigious international conferences in: Italy (2), Germany, Austria, Slovenia, Greece and France; 4 workshops organized in Italy, Romania (2) and one organized by ESAB - European Society of Applied Biocatalysis.
• 7 work-packages and 24 tasks: scientific, management, training and dissemination were defined in the project proposal; • the tasks were implemented within the Laboratory of Applied and Computational Biocalalysis, Department of Chemical and Pharmaceutical Sciences, University of Trieste, Italy in collaboration with: Esteco S.p.a for the computational support and Department of Life Sciences of University of Trieste and Bioscience Research Center Srl, Orbetello, for the ecotoxicity evaluation studies.
Objective 1 (month 1-month 8)
In this respect computational studies were performed for a series of polyesters and enzymes by using three different computational approaches:
- for substrates modelling and simulation: • for 30 copolymers the physico-chemical properties were predicted using available platforms based on machine learning and softwares; •for 70 polyesters molecular descriptors from 3D Molecular Interaction Fields (MIFs) were generated and evaluated;
- for enzyme modelling: • MD studies were performed for 6 hydrolases at different temperature conditions.
- for enzyme-substrate modelling: • 2 docking methods were applied to the analysis of the selected substrates; • more than 40 copolymers were docked in the catalytic site of the 6 hydrolases using Lamarckian genetic algorithm search method and free energy estimation based on an empirical free-energy force field; • about 40 terpolymers were docked by using Monte Carlo search and rapid gradient-optimization conformational search coupled with a simple scoring function for free energy estimation;
• an automatic workflow using modeFrontier software was developed by integrating specific modelling software; • a series of bio-based monomers and enzymes were screened up and the computational studies results were correlated with experimental data
Objective 2 (month 8-month 13)
The second objective was achieved by implementing:
• the synthesis of 18 polyesters, by using the monomers and hydrolases selected from Objective 1; • experimental reactions in solvent less system, or novel sustainable solvents for 4 of the targeted products. Reaction yields were in the range of 86 and 96%; • complete characterization procedures for all polyesters;
Objective 3 (month 12-month 24)
The third objective was achieved by studying:
• the biodegradability in marine environment of 25 sample (starting bio-based monomers and the polyesters synthesized within Objective 2)
• the ecotoxicity of 18 samples consisting of starting bio-based monomers and the correspondent polyesters enzymatically synthesized within Objective 2. The ecotoxicity was evaluated in: • fresh water in the presence of microalgae and • marine water in the presence of bacteria and microalgae
• the hydrolysis of the synthesized polyesters by 2 commercially available enzymes, obtaining degradation yields up to ~ 90%.
• the recovery of the monomers at laboratory scale to demonstrate the circularity of the concept and strategy developed within the RenEcoPol project as a proof of concept. Two or three steps protocols were developed as a function of the monomers solubility in water. Monomers recovery yields were in the range of 76-98%.
DISSEMINATION
• PUBLICATIONS: 4 papers published in journals with impact factor as open access, cumulative impact factor WoS 2021: 23.575; 1 paper under revision at Sustainable Chemistry and Pharmacy; 2 manuscripts in preparation for publication.
• INTERNATIONAL CONFERENCES :7 prestigious international conferences in: Italy (2), Germany, Austria, Slovenia, Greece and France; 4 workshops organized in Italy, Romania (2) and one organized by ESAB - European Society of Applied Biocatalysis.
The research field addressing the study of plastic impact, and bio-based plastic, is evolving very rapidly. Simultaneously, there is a lack of widely recognized benchmarks due to the multidisciplinary nature of the problem. The RenEcoPol project contributed to the progress of the research in this field by:
• connecting several fields of science: bioinformatics, biocatalysis, green chemistry, biodegradation, ecotoxicity and circular economy;• demonstrating the effectiveness of the eco-design and synthesis of polyesters with intrinsic recycling properties as well as the feasibility of the biotechnological recovery of the original monomers; • implementing and testing a computational automatic work-flow, which offers the possibility to adapt this “tool” to different eco-design objectives and integrate experimental data
The social impact of RenEcoPol project is evident from: •the scientific and dissemination activities guided by the EU policy priorities design for environmentally sound and safe product use and reduction amount of plastic material; • the uptake of research and innovation of researchers underage of 40: PI, 1 postdoc researcher; 2 PhD students (one from an ITC country as Erasmus student) and 2 MS students; • the starting of new collaborations between and Italian/ European research institutions and industries, which will lead to new project proposals to address Horizon Europe calls.
The economic impact is related to: • the collaborations with two companies carried out during the RenEcoPol projects, which are confident that the tools and methodologies developed within the RenEcoPol project will open new economic opportunities; • the collaboration with a company producing biobased monomers bioplastics who provided monomers for the experimental part; • involvement of new industrial players in research related to RenEcoPol approach: a company responsible for the management of the public water grid has offered its financial support for continuing the research in the field of microplastics;
• connecting several fields of science: bioinformatics, biocatalysis, green chemistry, biodegradation, ecotoxicity and circular economy;• demonstrating the effectiveness of the eco-design and synthesis of polyesters with intrinsic recycling properties as well as the feasibility of the biotechnological recovery of the original monomers; • implementing and testing a computational automatic work-flow, which offers the possibility to adapt this “tool” to different eco-design objectives and integrate experimental data
The social impact of RenEcoPol project is evident from: •the scientific and dissemination activities guided by the EU policy priorities design for environmentally sound and safe product use and reduction amount of plastic material; • the uptake of research and innovation of researchers underage of 40: PI, 1 postdoc researcher; 2 PhD students (one from an ITC country as Erasmus student) and 2 MS students; • the starting of new collaborations between and Italian/ European research institutions and industries, which will lead to new project proposals to address Horizon Europe calls.
The economic impact is related to: • the collaborations with two companies carried out during the RenEcoPol projects, which are confident that the tools and methodologies developed within the RenEcoPol project will open new economic opportunities; • the collaboration with a company producing biobased monomers bioplastics who provided monomers for the experimental part; • involvement of new industrial players in research related to RenEcoPol approach: a company responsible for the management of the public water grid has offered its financial support for continuing the research in the field of microplastics;