Memory Effect in Thermoresponsive Proline‐based Polymers

Badreldin, Mostafa; Scouarnec, Rosanna Le; Lecommandoux, Sébastien; Harrisson, Simon; Bonduelle, Colin

doi:10.1002/anie.202209530

Cited by 14 publications

(24 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In fact, for the later IRI testing, hydrophobicity is known to be crucial, and hence this limit of solubility may be useful, as seen for facially amphiphilic glycopolymers . It was recently demonstrated that polyproline shows large hysteresis in its LCST transitions matching the observations found here …”

Section: Resultssupporting

confidence: 82%

High Molecular Weight Polyproline as a Potential Biosourced Ice Growth Inhibitor: Synthesis, Ice Recrystallization Inhibition, and Specific Ice Face Binding

Judge¹,

Georgiou

Bissoyi

et al. 2023

Biomacromolecules

View full text Add to dashboard Cite

Ice-binding proteins (IBPs) from extremophile organisms can modulate ice formation and growth. There are many (bio)technological applications of IBPs, from cryopreservation to mitigating freeze–thaw damage in concrete to frozen food texture modifiers. Extraction or expression of IBPs can be challenging to scale up, and hence polymeric biomimetics have emerged. It is, however, desirable to use biosourced monomers and heteroatom-containing backbones in polymers for in vivo or environmental applications to allow degradation. Here we investigate high molecular weight polyproline as an ice recrystallization inhibitor (IRI). Low molecular weight polyproline is known to be a weak IRI. Its activity is hypothesized to be due to the unique PPI helix it adopts, but it has not been thoroughly investigated. Here an open-to-air aqueous N-carboxyanhydride polymerization is employed to obtain polyproline with molecular weights of up to 50000 g mol–1. These polymers were found to have IRI activity down to 5 mg mL–1, unlike a control peptide of polysarcosine, which did not inhibit all ice growth at up to 40 mg mL–1. The polyprolines exhibited lower critical solution temperature behavior and assembly/aggregation observed at room temperature, which may contribute to its activity. Single ice crystal assays with polyproline led to faceting, consistent with specific ice-face binding. This work shows that non-vinyl-based polymers can be designed to inhibit ice recrystallization and may offer a more sustainable or environmentally acceptable, while synthetically scalable, route to large-scale applications.

show abstract

Section: Resultssupporting

confidence: 82%

High Molecular Weight Polyproline as a Potential Biosourced Ice Growth Inhibitor: Synthesis, Ice Recrystallization Inhibition, and Specific Ice Face Binding

Judge¹,

Georgiou

Bissoyi

et al. 2023

Biomacromolecules

View full text Add to dashboard Cite

show abstract

“…The secondary structure contributes to the hysterical behavior of polypeptides. Bonduelle and co-workers reported that poly- l -proline exhibits LCST phase separation behavior with unprecedented hysteresis, which is related to the PLPII and PLPI conformation and chirality of the proline units . Different from LCST polymers, the hysteresis of UCST polymers mainly originated from the desynchronized association of inter/intrachain interaction between polymers. − On that account, the transitions of secondary structures during heating and cooling processes were recorded in situ (Figure ).…”

Section: Results and Discussionmentioning

confidence: 99%

Secondary Structure-Governed Phase Separation Behavior in Glutamate-Based Polypeptides

et al. 2023

View full text Add to dashboard Cite

The phase separation behavior of biomacromolecules plays a key role in the fields of biology and medicine. In this work, we gain a deep insight into how the primary and secondary structures govern and regulate the phase separation behavior of polypeptides. To this end, we synthesized a series of polypeptides with tailorable hydroxyl-containing side chains. The secondary structure of polypeptides can be modulated by the local chemical environment and content of side chains. Interestingly, these polypeptides with different helical contents exhibited upper critical solution temperature behavior with marked differences in the cloud point temperature (T cp) and the width of hysteresis. The phase transition temperature is highly relevant to the content of secondary structure and interchain interactions of polypeptides. The aggregation/deaggregation and the transition of secondary structure are completely reversible during heating–cooling cycles. Much to our surprise, the recovery rate of the α-helical structure governs the width of hysteresis. This work establishes the structure–property relationship between the secondary structure and phase separation behavior of the polypeptide and delivers new insight into the rational design of peptide-based materials with tailor-made phase separation behavior.

show abstract

“…The cloud point temperature ( T CP ) of PPro is ca. 67 °C, depending on length and potentially on the polymer endgroup . A conformational shift from PPII to PPI is implicated as a driver of this process.…”

Section: Resultsmentioning

confidence: 99%

“…PPro has an aqueous lower critical solution temperature (LCST) where the polymer is miscible with water below the LCST, but above the LCST aggregation occurs, resulting in two immiscible phases in thermodynamic equilibrium. 54 I.e., above the LCST temperature, polymer solutions become cloudy. The cloud point temperature (T CP ) of PPro is ca.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Clickable Polyprolines from Azido-proline N-Carboxyanhydride

Detwiler,

McPartlon,

Coffey

et al. 2023

ACS Polym. Au

View full text Add to dashboard Cite

Polyproline is a material of great interest in biomedicine due to its helical scaffold of structural importance in collagen and mucins and its ability to gel and to change conformations in response to temperature. Appending of function-modulating chemical groups to such a material is desirable to diversify potential applications. Here, we describe the synthesis of high-molecular-weight homo, block, and statistical polymers of azide-functionalized proline. The azide groups served as moieties for highly efficient click-grafting, as stabilizers of the polyproline PPII helix, and as modulators of thermoresponsiveness. Saccharides and ethylene glycol were utilized to explore small-molecule grafting, and glutamate polymers were utilized to form polyelectrolyte bottlebrush architectures. Secondary structure effects of both the azide and click modifications, as well as lower critical solution temperature behavior, were characterized. The polyazidoprolines and click products were well tolerated by live human cells and are expected to find use in diverse biomedical applications.

show abstract

Memory Effect in Thermoresponsive Proline‐based Polymers

Cited by 14 publications

References 44 publications

High Molecular Weight Polyproline as a Potential Biosourced Ice Growth Inhibitor: Synthesis, Ice Recrystallization Inhibition, and Specific Ice Face Binding

High Molecular Weight Polyproline as a Potential Biosourced Ice Growth Inhibitor: Synthesis, Ice Recrystallization Inhibition, and Specific Ice Face Binding

Secondary Structure-Governed Phase Separation Behavior in Glutamate-Based Polypeptides

Clickable Polyprolines from Azido-proline N-Carboxyanhydride

Contact Info

Product

Resources

About