Core integration of novel functional, adaptive materials into a smart, highly sensitive analytical system for point of need environmental applications – SmartMatter

SmartMatter sensors become active, dynamic amplifiers of the target specific reactions that modulate their structure. Nanoparticle/dynameric conjugates are set to play a double role: as framework for optical waveguide and as sites for interaction with the analytes. SmartMatter monitoring and interconnectivity capabilities will support reduction of greenhouse gas emission by providing a flexible network of sentinel sensors. Wider impact is foreseeable for energy field where the novel materials warrants enhanced catalytic power, improved sensitivity, specificity and compatibility with portable formats strengthening European innovation and industrial leadership.

The project started on June 1, 2020. After the first meetings and discussions with the hiring by IEM of two Ais associated with the project. This AIs were actives in the experimental design and characterization of compounds. Several samples have been submitted to our partners in Romania (coordinator) and Italy ) in order to start the sensing experiments and using our constitutional frameworks

During the first 18 months of the project, 2 publications, including one accepted as cover paper in ChemPlusChem in November 2021 and a second one is submitted. Other papers are in preparation. Several invited lectures were presented as part of the project.

IEM Review within SMARTMATTER
Constitutional Dynamic Inhibition/Activation of Carbonic Anhydrases
As one important member of metalloenzymes family, carbonic anhydrase (CA) is involved in the treatment of several diseases. Different approaches have therefore emerged to regulate the activity of CA, mostly acting on inner catalytic active site or outer microenvironment of the enzyme, leading to inhibition or activation of CA. In recent years, gradually increased attentions have been drawn into the adoption of constitutional dynamic chemistry (CDC) strategies for the screening and discovery of potent inhibitors or activators. The participation of reversible covalent bonds enabled the enzyme itself to select the optimal ligands obtained from diverse building blocks with comparatively higher degree of variety, resulting in the fittest recognition of enzyme ligands from complex dynamic systems. With the increasing implantation of CDC for enzyme target, it shows great potentials for the environmental-oriented applications.

IEM paper within SMARTMATTER: Polyethyleneimine-Carbonic Anhydrase Dynamic Constitutional Frameworks with Enhanced Catalytic Turnovers
Carbonic anhydrase is an essential enzyme that catalyze the hydration/dehydration of carbon dioxide, highly relevant to carbon capture processes. Efforts are focused on the development of highly functional to maintain good activity and stability compared to free enzyme in solution. Efficient encapsulation is of outmost importance for the system performance and efficiency. In this paper we demonstrate that Polyethyleneimine-dynamic constitutional frameworks PEI-DCFs, synthesized via reversible imine/amino-carbonyl chemistry, provides efficient host matrixes for bovine Carbonic Anhydrase-bCA encapsulation. This system showed an impressive one-order of magnitude improved catalytic proficiency (kcat/Km = 1610 M-1s-1) as compared to bCA alone (kcat/Km = 264 M-1s-1). The hybrid PEI-DCFs nanoparticles present distinct hydrophobic-hydrophilic regions and seamlessly incorporate bCA for enhanced overall catalytic efficiency. This performance rival the current state-of-the-art systems with equivalent amounts of enzyme, even after heating for a prolonged period to 80 °C, translating into a direct perspective for enhancing carbon dioxide capture and conversion.

Distinguishing bioconjugates with hydrophilic and hydrophobic interiors embedded within cationic shells get spontaneously incorporate b-Carbonic Anhydrase to show well-defined catalytic activity enhancement behaviors. The multivalent DCF-bCA conjugates lead to the formation of nanoparticles that optimally encapsulate the enzyme, thereby accelerating the overall catalytic activity of by 20 times compared with the reference bCA probe.

1. D. Su, Y. Zhang, S. Ulrich, M. Barboiu*, Constitutional Dynamic Inhibition/Activation of Carbonic Anhydrases. ChemPlusChem, 2021, DOI:10.1002/cplu.202100263.
2. D. Su, Y. Zhang, S. Ulrich, M. Barboiu*, Polyethyleneimine-Carbonic Anhydrase Dynamic Constitutional Frameworks with Enhanced Catalytic Turnovers submitted, 2021.