A Water‐Borne Adhesive Modeled after the Sandcastle Glue of <i>P. californica</i>

Shao, Hui; Bachus, Kent N.; Stewart, Russell J.

doi:10.1002/mabi.200800252

Cited by 233 publications

(254 citation statements)

References 25 publications

Supporting

Mentioning

254

Contrasting

Order By: Relevance

“…Such association can take the form of layer-bylayer assembly of polymers on a charged substrate, 1,2 or it could involve charge complexation in solution. [3][4][5] Examples of emerging technologies that rely on these and related phenomena include wet adhesives for medical, construction, consumer, and military use, 6,7 advanced biosensors, drug and gene delivery vehicles, [8][9][10] and responsive and switchable surfaces. 11,12 When the association takes place in solution, depending on the strength of the polyelectrolyte and the solvent conditions, the resulting polyelectrolyte complex can either be a solid precipitate or a polyelectrolyte-rich liquid phase termed a "complex coacervate."…”

Section: Introductionmentioning

confidence: 99%

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Riggleman

Kumar

Fredrickson

2012

The Journal of Chemical Physics

101

130

View full text Add to dashboard Cite

Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full fieldtheoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments. Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full fieldtheoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.

show abstract

Section: Introductionmentioning

confidence: 99%

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Riggleman

Kumar

Fredrickson

2012

The Journal of Chemical Physics

101

130

View full text Add to dashboard Cite

show abstract

“…5 The first synthetic adhesive to be studied as a complex coacervate was modeled after sandcastle worm cement and consisted of two oppositely charged dopamine-functionalized polyelectrolytes. 6,7 Coacervation benefits adhesion in several important ways: (1) high polymer concentration increases density, (2) the low interfacial energy improves wetting, (3) high diffusivity maintains good mixing, and (4) reduced viscosity eases delivery. 1 Mfp-3s is localized to the plaque−substratum interface ( Figure 1b) together with mfp-3f and mfp-5.…”

mentioning

confidence: 99%

Microphase Behavior and Enhanced Wet-Cohesion of Synthetic Copolyampholytes Inspired by a Mussel Foot Protein

Seo¹,

Das²,

Zalicki³

et al. 2015

J. Am. Chem. Soc.

130

144

View full text Add to dashboard Cite

Numerous attempts have been made to translate mussel adhesion to diverse synthetic platforms. However, the translation remains largely limited to the Dopa (3,4-dihydroxyphenylalanine) or catechol functionality, which continues to raise concerns about Dopa's inherent susceptibility to oxidation. Mussels have evolved adaptations to stabilize Dopa against oxidation. For example, in mussel foot protein 3 slow (mfp-3s, one of two electrophoretically distinct interfacial adhesive proteins in mussel plaques), the high proportion of hydrophobic amino acid residues in the flanking sequence around Dopa increases Dopa's oxidation potential. In this study, copolyampholytes, which combine the catechol functionality with amphiphilic and ionic features of mfp-3s, were synthesized and formulated as coacervates for adhesive deposition on surfaces. The ratio of hydrophilic/hydrophobic as well as cationic/anionic units was varied in order to enhance coacervate formation and wet adhesion properties. Aqueous solutions of two of the four mfp-3s-inspired copolymers showed coacervate-like spherical microdroplets (ϕ ≈ 1−5 μm at pH ∼4 (salt concentration ∼15 mM). The mfp-3s-mimetic copolymer was stable to oxidation, formed coacervates that spread evenly over mica, and strongly bonded to mica surfaces (pull-off strength: ∼17.0 mJ/m 2 ). Increasing pH to 7 after coacervate deposition at pH 4 doubled the bonding strength to ∼32.9 mJ/m 2 without oxidative cross-linking and is about 9 times higher than native mfp-3s cohesion. This study expands the scope of translating mussel adhesion from simple Dopa-functionalization to mimicking the context of the local environment around Dopa. M arine mussels (Figure 1a) attach to hard surfaces, e.g., mineral and metal, in the intertidal zone where waves with and without suspended sand often exceed 25 m/sec velocities. 3,4-Dihydroxyphenylalanine (Dopa), a main constituent in mussel foot proteins (mfps) and substantially contributing to wet adhesion, has been incorporated in synthetic polymers to mimic the bio wet-adhesion. 1−5 However, other constitutional features of mfps, e.g., cationic residues (lysine, K), anionic residues (aspartic acid, D), nonionic polar residues (asparagine, N), and nonpolar residues (alanine, A), have not typically been included in mussel-inspired synthetic wet-adhesion systems. 1,2Here, we studied the microphase behavior and wet-adhesion of copolyampholytes with fixed catechol content and varied other key functionalities. Potential effects of aromatic moieties (Tyr, Trp) besides Dopa in mfp-3s have not been specifically tested in the present structural design of the model copolyampholytes. Conditions for the experiments were adjusted according to the microenvironmental conditions of adhesive protein deposition under the mussel's foot including acidic to neutral pH and ionic strength of ≤100 mM. 3,4 In mussel adhesion, polyelectrolyte adhesive proteins or mfps are presented to target surfaces after being condensed as a dense fluid by complex coacervation, a critical ste...

show abstract

“…1,2014 intended for use as industrial, consumer, or medical adhesives by many authors. [8][9][10][11][12][13][14] This biomimetic anchor strategy seems quite robust for surface modification in many applications.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Gelation of Dopamine-modified Polyaspartamides by NaIO₄

Jeon¹,

Bui²,

An³

et al. 2014

Polymer Korea

View full text Add to dashboard Cite

Novel adhesive polyaspartamides containing catechol and primary amine pendent groups were synthesized through successive ring-opening aminolysis reactions of dopamine (DOP) and ethylenediamine (EDA) with polysuccinimide (PSI). The oxidative gelation of aqueous dopamine-modified polyaspartamide was observed by adding NaIO 4 as the oxidizing reagent. FTIR, UV-vis and oscillatory rheometry was used to elucidate the oxidative cross-linking toward gel formation. The prepared gel was characterized by the swelling degree, thermogravimetric analysis (TGA), and by scanning electronic microscopy (SEM).

show abstract

A Water‐Borne Adhesive Modeled after the Sandcastle Glue of P. californica

Cited by 233 publications

References 25 publications

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Microphase Behavior and Enhanced Wet-Cohesion of Synthetic Copolyampholytes Inspired by a Mussel Foot Protein

Oxidative Gelation of Dopamine-modified Polyaspartamides by NaIO₄

Contact Info

Product

Resources

About

A Water‐Borne Adhesive Modeled after the Sandcastle Glue of P. californica

Cited by 233 publications

References 25 publications

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Microphase Behavior and Enhanced Wet-Cohesion of Synthetic Copolyampholytes Inspired by a Mussel Foot Protein

Oxidative Gelation of Dopamine-modified Polyaspartamides by NaIO4

Contact Info

Product

Resources

About

Oxidative Gelation of Dopamine-modified Polyaspartamides by NaIO₄