Efficient Protein Encapsulation within Thermoresponsive Coacervate-Forming Biodegradable Polyesters

Cruz, Megan A.; Morris, Daniel L.; Swanson, John P.; Kundu, Mangaldeep; Mankoci, Steven; Leeper, Thomas C.; Joy, Abraham

doi:10.1021/acsmacrolett.8b00118

Cited by 18 publications

(18 citation statements)

References 29 publications

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“…In Mfps and sandcastle worm cement, minerals or enzyme-mediated cross-linking of amino acids such as phosphoserine, 3,4-dihydroxyphenylalanine, lysine, and cysteine are shown to increase the cohesive strength and the overall adhesion strength. , Such cross-linking chemistry when designed into synthetic polymers is either too slow due to the reliance on autocrosslinking , or extremely fast when external oxidizers are applied . For obtaining optimum mixing of the oxidizer with the adhesive and to prevent the dissolution of the adhesive in water, the adherents are often brought out of water. , Cross-linking using photochemical reactions provides an alternative method of cross-linking due to the spatial and temporal control over cross-linking. ,− In our study, we chose photochemical dimerization of coumarin as the cross-linking mechanism due to its autoinitiation and water transparent irradiation wavelength . Coacervation allows delivery of the coumarin-functionalized adhesives underwater.…”

Section: Results and Discussionmentioning

confidence: 99%

“…31 Similarly, our polyester library also shows hydrophobically driven, single-component coacervation. Their nonionic, bioabsorbable, 29 cell-compatible, 30 and modular nature allows the incorporation of various small molecules and biomacromolecules, 32 and hence this platform provides significant advantages over any other reported coacervates to date. In this study, we report a class of nonionic, self-coacervating polyesters that demonstrate rapid, water-tolerant photo-crosslinking, resulting in comparable underwater adhesion strength to that of mussels.…”

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confidence: 99%

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Lower Critical Solution Temperature-Driven Self-Coacervation of Nonionic Polyester Underwater Adhesives

et al. 2020

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To enable attachment to underwater surfaces, aquatic fauna such as mussels and sandcastle worms utilize the advantages of coacervation to deliver concentrated protein-rich adhesive cocktails in an aqueous environment onto underwater surfaces. Recently, a mussel adhesive protein Mfp-3s, was shown to exhibit a coacervation-based adhesion mechanism. Current synthetic strategies to mimic Mfp-3s often involve complexation of oppositely charged polymers. Such complex coacervates are more sensitive to changes in pH and salt, thereby limiting their utility to narrow ranges of pH and ionic strength. In this study, by taking advantage of the lower critical solution temperature-driven coacervation, we have created mussel foot protein-inspired, tropoelastin-like, bioabsorbable, nonionic, self-coacervating polyesters for the delivery of photo-cross-linkable adhesives underwater and to overcome the challenges of adhesion in wet or underwater environments. We describe the rationale for their design and the underwater adhesive properties of these nonionic adhesives. Compared to previously reported coacervate adhesives, these "charge-free" polyesters coacervate in wide ranges of pH (3−12) and ionic strength (0−1 M NaCl) and rapidly (<300 s) adhere to substrates submerged underwater. The study introduces smart materials that mimic the self-coacervation and environmental stability of Mfp-3s and demonstrate the potential for biological adhesive applications where high water content, salts, and pH changes can be expected.

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Section: Results and Discussionmentioning

confidence: 99%

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confidence: 99%

Lower Critical Solution Temperature-Driven Self-Coacervation of Nonionic Polyester Underwater Adhesives

et al. 2020

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“…Complex coacervation, [49,51,52,56,57,[61][62][63][64][65][66][67][68][69][70][71][72][73] whose characteristics mimic the characteristics of cells, is a simple, purely aqueous strategy for encapsulating proteins. Complex coacervation is a liquid-liquid phase separation phenomenon resulting from the association of two oppositely charged macro-ions (e.g., polymer, protein, surfactant micelles).…”

Section: Complex Coacervation Phase Behavior and Biomimicrymentioning

confidence: 99%

Protein Encapsulation Using Complex Coacervates: What Nature Has to Teach Us

McTigue

Perry

2020

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Protein encapsulation is a growing area of interest, particularly in the fields of food science and medicine. The sequestration of protein cargoes has been achieved using a variety of methods, each with benefits and drawbacks. One of the most significant challenges associated with protein encapsulation has been achieving high loading while maintaining protein viability. This difficulty has been exacerbated because many encapsulant systems require the use of organic solvents. In contrast, nature has optimized strategies to compartmentalize and protect proteins inside the cell-a purely aqueous environment. Although the mechanisms whereby aspects of the cytosol is able to stabilize proteins are unknown, the crowded nature of many newly discovered, liquid phase separated 'membraneless organelles' that achieve protein compartmentalization suggests that the material environment surrounding the protein may be critical in determining stability. Here, we focus on encapsulation strategies based on liquid-liquid phase separation, and complex coacervation in particular, which has many of the key features of the cytoplasm as a material. We review the literature on protein encapsulation via coacervation and discuss the parameters relevant to creating protein-containing coacervate formulations. Additionally, we highlight potential opportunities associated with the creation of tailored materials to better facilitate protein encapsulation and stabilization.

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“…There is a growing need in the field of polymer science to develop “smart” materials that can respond to applied stimuli. In particular, thermo‐responsive polymers are attractive for a range of applications 1–14 such as liquid chromatography, 11 self‐healing materials, 13 and most frequently in biomedical applications such as tissue engineering and drug and gene delivery 1–3,10,15 …”

Section: Introductionmentioning

confidence: 99%

“…A majority of the polymers in these areas of application are thermo‐responsive with regards to their solubility, such as polymers that exhibit a lower critical solution temperature (LCST) as a means to impart conformational molecular changes simply by applying a thermal stimulus 12,16–19 . Over a defined temperature range, these solution‐state polymers demonstrate a characteristic change from random coils to collapsed coacervates, which are more condensed, globule‐like structures., 12,15–21 In order to increase the range of applications for such polymers, it becomes increasingly important to predict and control their LCST, 14,19 which has traditionally been achieved through the addition of salts or comonomers 12,17,22–24 …”

Section: Introductionmentioning

confidence: 99%

Exploring polymer solubility with thermally‐responsive Diels‐Alder monomers: Revisiting the monkey's fist

Bisbjerg

Brown

Pham

et al. 2021

Journal of Polymer Science

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Thermo‐responsive monomers were designed to contain a Diels‐Alder (DA) adduct such that cyclo‐reversion would yield either the maleimide or the furan unit attached to the polymer chain. These thermally responsive monomers were then copolymerized with N‐isopropylacrylamide (NIPAM) via reversible addition‐fragmentation chain‐transfer (RAFT) polymerization to yield linear gradient‐copolymer structures as a comparison to existing nanogel/starlike systems to understand how polymer topology and composition influence solution‐state properties. Using UV–Vis spectroscopy, it was determined that solution‐state properties were thermally dependent and influenced by a number of variables such as comonomer feed ratio, polymer chain end functionality, and polymer backbone length and composition. Manipulation of the feed ratio allowed for control over the cloud point, including the breadth and location of phase separation. Thermal treatment of these copolymers revealed tunable and predictable variations in previously observed transitions, directly correlated to cleavage of the DA adducts and change in polymer backbone composition. Finally, on cooling cycles, a double sigmoid was sometimes observed, indicating a complex globule to random coil transition correlated to polymer chain end composition. These studies help understand how to untie the “monkey's fist.”

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Efficient Protein Encapsulation within Thermoresponsive Coacervate-Forming Biodegradable Polyesters

Cited by 18 publications

References 29 publications

Lower Critical Solution Temperature-Driven Self-Coacervation of Nonionic Polyester Underwater Adhesives

Lower Critical Solution Temperature-Driven Self-Coacervation of Nonionic Polyester Underwater Adhesives

Protein Encapsulation Using Complex Coacervates: What Nature Has to Teach Us

Exploring polymer solubility with thermally‐responsive Diels‐Alder monomers: Revisiting the monkey's fist

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