doi.org/10.26434/chemrxiv.9991937.v1 Tropoelastin-Inspired, Non-Ionic, Self-Coacervating Polyesters as Strong Underwater Adhesives Amal Narayanan, Joshua Menefee, Qianhui Liu, Ali Dhinojwala, Abraham Joy Submitted date: 16/10/2019 • Posted date: 21/10/2019 Licence: CC BY-NC-ND 4.0 Citation information: Narayanan, Amal; Menefee, Joshua; Liu, Qianhui; Dhinojwala, Ali; Joy, Abraham (2019): Tropoelastin-Inspired, Non-Ionic, Self-Coacervating Polyesters as Strong Underwater Adhesives. ChemRxiv. Preprint. Inspired from the one-component self-coacervation of tropoelastin and mussel foot protein-3s, we created the first non-ionic, single component coacervates that can coacervate in a all ranges of pH (acidic to basic) and wide range of ionic strengths with degradability, rapid curing and strong underwater adhesion. In contrast to the complex coacervates, these ‘charge-free’ coacervates are potential candidates as tissue adhesives and sealants, adhesives for sensor attachment to wet skin, and as sprayable adhesives. Their potential use in the clinic arises from their enhanced stability to changes in external conditions, cytocompatibility, biodegradability and modular nature in incorporating various functional groups and crosslinkers. File list (5) download file view on ChemRxiv Manuscript.pdf (524.05 KiB) download file view on ChemRxiv Literature Fig.png (645.77 KiB) download file view on ChemRxiv Supporting Information.pdf (1.12 MiB) download file view on ChemRxiv Movie S1.m2ts (28.11 MiB) download file view on ChemRxiv Movie S2.m2ts (98.65 MiB)
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doi.org/10.26434/chemrxiv.9991937.v1
Tropoelastin-Inspired, Non-Ionic, Self-Coacervating Polyesters as StrongUnderwater AdhesivesAmal Narayanan, Joshua Menefee, Qianhui Liu, Ali Dhinojwala, Abraham Joy
Submitted date: 16/10/2019 • Posted date: 21/10/2019Licence: CC BY-NC-ND 4.0Citation information: Narayanan, Amal; Menefee, Joshua; Liu, Qianhui; Dhinojwala, Ali; Joy, Abraham (2019):Tropoelastin-Inspired, Non-Ionic, Self-Coacervating Polyesters as Strong Underwater Adhesives. ChemRxiv.Preprint.
Inspired from the one-component self-coacervation of tropoelastin and mussel foot protein-3s, we created thefirst non-ionic, single component coacervates that can coacervate in a all ranges of pH (acidic to basic) andwide range of ionic strengths with degradability, rapid curing and strong underwater adhesion. In contrast tothe complex coacervates, these ‘charge-free’ coacervates are potential candidates as tissue adhesives andsealants, adhesives for sensor attachment to wet skin, and as sprayable adhesives. Their potential use in theclinic arises from their enhanced stability to changes in external conditions, cytocompatibility, biodegradabilityand modular nature in incorporating various functional groups and crosslinkers.
File list (5)
download fileview on ChemRxivManuscript.pdf (524.05 KiB)
download fileview on ChemRxivLiterature Fig.png (645.77 KiB)
download fileview on ChemRxivSupporting Information.pdf (1.12 MiB)
download fileview on ChemRxivMovie S1.m2ts (28.11 MiB)
download fileview on ChemRxivMovie S2.m2ts (98.65 MiB)
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Table of Content
Non-ionic coacervates: The first non-ionic, single component coacervates that can coacervate in a all ranges of pH (acidic to basic) and wide range of ionic strengths with degradability, rapid curing and strong underwater adhesion.
Tropoelastin-Inspired, Non-Ionic, Self-Coacervating Polyesters as Strong Underwater Adhesives
A. Narayanan, J. R. Menefee, Q.
Liu, Prof. Dr. A. Dhinojwala,*
Prof. Dr. A. Joy*
download fileview on ChemRxivManuscript.pdf (524.05 KiB)
dimethylbenzo[d][1,3]dioxol-5-yl)-N,N-bis(2-hydroxyethyl)propenamide (Mpr),[3] and N,N-
bis(2-hydroxyethyl)-4-((4-methyl-2-oxo-2H-chromen-7-yl)oxy)butanamide (C)[4] were prepared
as per reported procedures.
Instrumentation
1H NMR spectra of the monomers and polyesters were recorded on a Varian Mercury 500
MHz spectrometer. The molar mass (Mn,GPC) and dispersity (Ð) of the polyesters were calculated
from a TOSOH EcoSec HLC-8320 GPC using refractive index detector (RI) detector. Separation
occurred over two PSS Gram Analytical GPC Columns in series using 25 mM LiBr in DMF as
eluent at a flow rate of 0.8 mL/min. The columns and detectors temperatures were maintained at
50 °C. Molar masses were obtained relative to narrow disperse polystyrene standards. The cloud
point temperature (TCP) of the polyesters were analyzed using a Shimadzu UV-1800 UV-Vis
spectrophotometer equipped with a Shimadzu S-1700 thermoelectric single cell holder in a 1 cm
quartz cell with nitrogen chamber. The nanoparticles were imaged with a scanning electron
microscope (SEM JSM7401). The interfacial tension of the coacervate dense phases in water were
measured by pendant drop shape analysis using a Rame-Hart drop shape analyzer. Rheological
experiments were performed on a TA ARES-G2 rheometer. The lapshear and tack adhesion
strength measurements were performed on a TA.XT texture analyzer from StableMicroSystems
with 10 Kg load cell.
Experimental Section
Scheme S1. Schematic representation of the polyesterification reaction and the deprotection of
3,4-acetonide groups.
Table S1. The molar ratio of the monomers, weight average molar mass (Mn,GPC), cloud point
temperature (TCP) of the polyesters used for creating the phase diagram (Figure 1B).
Polymer aE:M:C Mn,GPC (kDa) dTCP (C)
P1 100:0:0 95.7b 55
P2 100:0:0 33.7b 48
P3 95:0:4 56.8b 41
P4 95:6:0 19.6c 39
P5 89:5:6 17.3c 24
P6 90:10:0 48.1c 25
P7 85:17:0 8.1c 17
P8 85:15:0 28.7c 14
HyPPo-20 80:20:0 22.1c 7
HyPPo-10 80:11:9 17.6c 7
HyPPo-15 80:6:14 13.5c 7
HyPPo-20 82:0:18 15.3b 8
aCalculated using 1H NMR. bDetermined from the SEC traces or cfrom the corresponding acetonide
protected copolyesters. Mn,GPC = Mn,GPC of acetonide protected − 44 Da no. of repeating unit of M. dQuantified using temperature-dependent absorbance measurements at wavelength = 500 nm.
(A)
(B)
(C)
(D)
Figure S1. 1H NMR of the polyesters (A) HyPP0-20, (B) HyPPo-11, (C) HyPPo-6, and (D)
HyPPo-0.
Synthesis
Polymerization
The polymerization of the N-functionalized diethanolamides were carried out in similar
method as reported by Gokhale et al.[6] The preparation of prHyPPo-11 is described as an example
(Scheme S1). To a 100 mL round bottom flask (r.b.) equipped with magnetic stir bar, added E