Novel Bifunctional Amide-Based Initiator for the Atom Transfer Radical Polymerization of Styrene with Ascorbic Acid Acetonide as Reducing Agent

This study focuses on the synthesis and characterization of a new bifunctional benzamide initiator, CMB2HexDA, for the production of thermostable α,ω-dichloropolystyrene via ARGET ATRP. The motivation behind this research is the need to obtain functionalized polystyrene that can withstand the high temperatures used in industrial extrusion processes, as well as the previous development of a method to obtain α,ω-dialkenepolystyrene by solventless thermal dehydrohalogenation. The commonly used initiators in ATRP undergo thermal fragmentation, leading to chain length reduction and loss of telechelicity. The synthesized initiator was purified and characterized, and the resulting α,ω-dichloropolystyrenes were analyzed through GPC and NMR. The telechelic polystyrene produced with the new initiator exhibited enhanced thermal stability compared to aliphatic-halide ester initiators. Although the specific diamine used does not confer specific functionality, the developed synthetic pathway allows for the introduction of other functionalities into thermostable polystyrenes. Furthermore, the benzamidic function could be exploited to achieve controlled chemical degradation of polystyrene, resulting in more readly degradable oligomeric fragments

Could Olympic Gels of Polystyrene be Produced by ARGET ATRP From Bifunctional Initiators?

The kinetics of gelation in the Activators Regenerated by Electron Transfer Atom Transfer Radical Polymerization (ARGET ATRP) of styrene, using a bifunctional initiator and no crosslinking agents are investigated. By applying the method of moments, we develop a system of differential equations that accounts for the formation of polymer rings. The kinetic rate constants of this model are optimized on the experimentally determined kinetics, varying the reaction temperature and ethanol fraction. Subsequently, we explore how variations in the amounts of catalyst, initiator, and reducing agents affect the simulated equilibria of ARGET ATRP, the emergence of gelation, and the swelling properties of the resulting networks. These findings suggest that favoring ring formation enhances the gelation phenomenon, supporting the hypothesis that the networks formed under the reported reaction conditions are olympic gels.A kinetic model for the ARGET ATRP of styrene from bifunctional initiators shows that higher amounts of ethanol, catalyst, and reducing agents, along with lower temperatures and initiator amounts, enhance the molar fraction of cyclic polystyrene. These trends correlate with the experimental effects on gelation time, yield, and swelling properties, supporting the hypothesized formation of olympic gels. imag

A Trifunctional ATRP Initiator Bearing Adaptable Bonds

Atom Transfer Radical Polymerization (ATRP) allows for the production of polymers with precise control over molecular weight, dispersity, topology, composition, and functionality. Functional groups can be introduced into the polymer through post-functionalization of chain ends, or on the alkyl residue of the initiator, or by introducing functionalized (co)monomers, greatly greatly enhancing the targetable applications. In addition, the desired functional group can also be carried by the ATRP initiator. Some researchers have explored initiators with hydrolysis- or heat-sensitive functionalities to impart self-healing properties to the final polymer. However, the commonly used aliphatic halide ester initiators have shown poor thermal stability. To address this issue, we recently developed a novel bifunctional benzamide-containing initiator employed in ARGET ATRP of styrene, demonstrating enhanced thermal stability. Covalent Adaptable Networks (CANs) have emerged as a solution for improving the recyclability of thermoset materials. CANs can reorganize connectivity between chains upon thermal treatment, enabling reprocessing. Our goal is to modify the structure of the benzamide-containing initiator to develop a trifunctional initiator bearing adaptable bonds

A PETase enzyme synthesised in the chloroplast of the microalga Chlamydomonas reinhardtii is active against post-consumer plastics

Polyethylene terephthalate hydrolases (PETases) are a newly discovered and industrially important class of enzymes that catalyze the enzymatic degradation of polyethylene terephatalate (PET), one of the most abundant plastics in the world. The greater enzymatic efficiencies of PETases compared to close relatives from the cutinase and lipase families have resulted in increasing research interest. Despite this, further characterization of PETases is essential, particularly regarding their possible activity against other kinds of plastic. In this study, we exploited for the first time the use of the microalgal chloroplast for more sustainable synthesis of a PETase enzyme. A photosynthetic-restoration strategy was used to generate a marker-free transformant line of the green microalga Chlamydomonas reinhardtii in which the PETase from Ideonella sakaiensis was constitutively expressed in the chloroplast. Subsequently, the activity of the PETase against both PET and post-consumer plastics was investigated via atomic force microscopy, revealing evidence of degradation of the plastics

A PETase enzyme synthesised in the chloroplast of the microalga Chlamydomonas reinhardtii is active against post-consumer plastics

Polyethylene terephthalate hydrolases (PETases) are a newly discovered and industrially important class of enzymes that catalyze the enzymatic degradation of polyethylene terephatalate (PET), one of the most abundant plastics in the world. The greater enzymatic efficiencies of PETases compared to close relatives from the cutinase and lipase families have resulted in increasing research interest. Despite this, further characterization of PETases is essential, particularly regarding their possible activity against other kinds of plastic. In this study, we exploited for the first time the use of the microalgal chloroplast for more sustainable synthesis of a PETase enzyme. A photosynthetic-restoration strategy was used to generate a marker-free transformant line of the green microalga Chlamydomonas reinhardtii in which the PETase from Ideonella sakaiensis was constitutively expressed in the chloroplast. Subsequently, the activity of the PETase against both PET and post-consumer plastics was investigated via atomic force microscopy, revealing evidence of degradation of the plastics