Thermoresponsive polymers with LCST transition: synthesis, characterization, and their impact on biomedical frontiers

Yuan, Yichun; Raheja, Konpal; Milbrandt, Nathalie B.; Beilharz, Sophia; Tene, Steffy; Oshabaheebwa, Solomon; Gurkan, Umut A.; Samia, Anna Cristina S.; Karayilan, Metin

doi:10.1039/d3lp00114h

Cited by 9 publications

(3 citation statements)

References 371 publications

(560 reference statements)

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“…[31,32] While poly(ethylene glycol) (PEG) has been extensively studied for its LCST behavior, it is noteworthy that shorter oligoethylene glycols also manifest LCST characteristics. [33,34,35] Consequently, the incorporation of TEG into BTA may confer a thermoresponsive LLPS phenomenon, possibly culminating in the formation of phase-separated liquid droplets. Preliminary evidence of this LCST phenomenon was detected in an early BTA report almost a decade ago, however, comprehensive investigation to unravel any supramolecular droplet formation was not pursued.…”

Section: Resultsmentioning

confidence: 99%

Unveiling the Liquid‐Liquid Phase Separation of Benzene‐1,3,5‐Tricarboxamide in Water

Kumar,

Hanssen,

Dhiman

2024

ChemSystemsChem

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The intricate interplay between self‐assembly and phase separation orchestrates biomolecular organization inside cells, thereby dictating the formation of vital structures such as protein assemblies and membraneless organelles (MLOs). However, in the context of supramolecular polymerization, these fundamental processes have traditionally been studied separately. This study reevaluates the supramolecular polymerization process to unveil the presence of phase‐separated droplet state. Utilizing the well‐studied benzene‐1,3,5‐tricarboxamide (BTA) supramolecular motif, we explore its thermally driven liquid‐liquid phase separation (LLPS). Thermodynamic and kinetic analysis, employing temperature‐dependent spectroscopic and microscopic techniques, elucidates the distinct BTA states and their evolution towards the thermodynamic fiber state. This research sheds light on the existence of hidden phases of supramolecular monomers, emphasizing the delicate balance of non‐covalent interactions among monomers and with solvents in governing self‐assembly vs. phase separation. This is particularly important in comprehending phase separation in the biological realm such as in MLOs, and for applications such as condensate‐modifying therapeutics.

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Section: Resultsmentioning

confidence: 99%

Unveiling the Liquid‐Liquid Phase Separation of Benzene‐1,3,5‐Tricarboxamide in Water

Kumar,

Hanssen,

Dhiman

2024

ChemSystemsChem

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“…For the preparation of PNPs with unique properties, so-called smart polymers have proven to be very useful [ 11 ]. Such polymers reversibly change their physicochemical properties in response to external stimuli such as temperature [ 12 ], pH [ 13 ], light [ 14 ], and electromagnetic field [ 15 ]. Thermoresponsive polymers, for instance, are fully water-soluble at low temperatures.…”

Section: Introductionmentioning

confidence: 99%

Degradable Nanogels Based on Poly[Oligo(Ethylene Glycol) Methacrylate] (POEGMA) Derivatives through Thermo-Induced Aggregation of Polymer Chain and Subsequent Chemical Crosslinking

Filipek,

Otulakowski,

Jelonek

et al. 2024

Polymers

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Polymer nanogels—considered as nanoscale hydrogel particles—are attractive for biological and biomedical applications due to their unique physicochemical flexibility. However, the aggregation or accumulation of nanoparticles in the body or the occurrence of the body’s defense reactions still pose a research challenge. Here, we demonstrate the fabrication of degradable nanogels using thermoresponsive, cytocompatible poly[oligo(ethylene glycol) methacrylate]s-based copolymers (POEGMA). The combination of POEGMA’s beneficial properties (switchable affinity to water, nontoxicity, non-immunogenicity) along with the possibility of nanogel degradation constitute an important approach from a biological point of view. The copolymers of oligo(ethylene glycol) methacrylates were partially modified with short segments of degradable oligo(lactic acid) (OLA) terminated with the acrylate group. Under the influence of temperature, copolymers formed self-assembled nanoparticles, so-called mesoglobules, with sizes of 140–1000 nm. The thermoresponsive behavior of the obtained copolymers and the nanostructure sizes depended on the heating rate and the presence of salts in the aqueous media. The obtained mesoglobules were stabilized by chemical crosslinking via thiol-acrylate Michael addition, leading to nanogels that degraded over time in water, as indicated by the DLS, cryo-TEM, and AFM measurements. Combining these findings with the lack of toxicity of the obtained systems towards human fibroblasts indicates their application potential.

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“…In this context, although there have been numerous instances of phase-separated droplets composed of synthetic polymers exhibiting low critical solution temperatures (LCST), 19 the potential of synthetic catalysts within such droplets remains unexplored, despite the various strategies that have been proposed for using water as a solvent in catalytic organic reactions, 20,21 including the development of water-soluble homogeneous precatalysts, [22][23][24][25][26][27] on-water synthesis, 28,29 micellar catalysis, [30][31][32][33][34][35][36][37] utilization of organic cosolvents, 33,38,39 and biocatalysis. 40,41 In particular, a single synthetic compound, that can act as both a catalyst and a reaction field like the phaseseparated droplets in an aqueous environment, has not yet been achieved.…”

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confidence: 99%

A bioinspired bifunctional catalyst: an amphiphilic organometallic catalyst for ring-closing metathesis forming liquid droplets in aqueous media

Mori,

Sugai,

Sato

et al. 2024

Chem. Commun.

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Thermoresponsive polymers with LCST transition: synthesis, characterization, and their impact on biomedical frontiers

Abstract: Enhancing our comprehension of the structural influences alongside characterization tools for thermoresponsive polymers will pave the way to design and deploy more advanced biomaterials, holding promise for future applications in public health.

Cited by 9 publications

References 371 publications

Unveiling the Liquid‐Liquid Phase Separation of Benzene‐1,3,5‐Tricarboxamide in Water

Unveiling the Liquid‐Liquid Phase Separation of Benzene‐1,3,5‐Tricarboxamide in Water

Degradable Nanogels Based on Poly[Oligo(Ethylene Glycol) Methacrylate] (POEGMA) Derivatives through Thermo-Induced Aggregation of Polymer Chain and Subsequent Chemical Crosslinking

A bioinspired bifunctional catalyst: an amphiphilic organometallic catalyst for ring-closing metathesis forming liquid droplets in aqueous media

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