Synthesis and stability against oxidation of random brush copolymers carrying PEO side chains and catechol moieties

Steponavičiūtė, Medeina; Klimkevičius, Vaidas; Makuška, Ričardas

doi:10.1016/j.mtcomm.2020.101262

Cited by 9 publications

(10 citation statements)

References 43 publications

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“…The copolymerization rate constant calculated from that plot is 5.34 × 10 –5 s –1 and is similar to that of previously studied copolymerization of acetonide‐protected dopamine methacrylamide (ADOPMA) and PEOMEMA. [ 36 ] Thus, the rate of copolymerization of the equimolar mixture of DMAEMA and PEOMEMA is moderately high.…”

Section: Resultsmentioning

confidence: 99%

“…By measuring WCAs, hydrophilicity of the copolymers p(DMAEMA‐ co ‐PEOMEMA) and their quaternized derivatives p(QDMAEMA‐ co ‐PEOMEMA) was evaluated and compared to that of the neutral catechol brush copolymers of similar architecture p(DOPMA‐ co ‐PEOMEMA) described in our previous publication. [ 36 ] WCA of the bare glass surface is ≈25° (Figure S6, Supporting Information). Adsorption of pPEOMEMA increases hydrophilicity of the surface (WCA ≈17°), while adsorption of pDMAEMA and its quaternized derivative pQDMAEMA decreases it (WCA 43° and 37°, respectively).…”

Section: Resultsmentioning

confidence: 99%

“…It was demonstrated in our previous paper [ 36 ] that neutral catechol brush copolymers are relatively stable in acidic aqueous solutions but unstable in neutral and alkaline solutions undergoing coloring because of oxidation reactions involving catechol groups. It was also demonstrated [ 48 ] that underwater wear resistance of the adsorbed layers of cationic catechol brush copolymers is exclusively high and significantly exceeds that of uncharged catechol brush copolymers.…”

Section: Resultsmentioning

confidence: 99%

“…Figure demonstrates changes in color of the copolymer solutions of various pH during storage up to 3 weeks. UV–vis spectra of aqueous solutions of the cationic catechol brush copolymers are similar to those of neutral analogs [ 36 ] with one important difference: changes in absorption start earlier and at lower pH. The most serious changes undergo alkaline polymer solutions, irrespective of polymer charge.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Properties of Cationic Gradient Brush Copolymers Carrying PEO Side Chains and Catechol Moieties

Steponavičiūtė

Klimkevičius

Makuška

2021

Macro Chemistry & Physics

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Synthesis and study of brush copolymers carrying long PEO side chains and catechol moieties are reported. Kinetics of reversible‐addition‐fragmentation chain‐transfer copolymerization of 2‐(dimethylamino) ethyl methacrylate (DMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEOMEMA) is studied by size exclusion chromatography (SEC) and 1H NMR spectroscopy, which allow calculating not only copolymerization rate but also the evolution of copolymer composition during copolymerization. Molecular weight Mn and dispersity Ð of the copolymers are determined by SEC with triple detection. Well defined gradient copolymers p(DMAEMA‐co‐PEOMEMA) of various composition with degree of polymerization close to 100 and Ð less than 1.18 are synthesized. For attachment of catechol moieties and introduction of positive charge, DMAEMA units are quaternized with 2‐chloro‐3,4‐dihydroxyacetophenone. The use of tetrahydrofuran as a solvent for that reaction allows obtaining the degree of quaternization close to 100%. Positively charged catechol brush copolymers and their solutions are characterized by 1H NMR, fourier‐transform infrared spectroscopy), and ultraviolet–visible spectroscopy, potentiometric titration, and water contact angle measurements, and their properties are compared with those of similar neutral catechol brush copolymers.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Synthesis and Properties of Cationic Gradient Brush Copolymers Carrying PEO Side Chains and Catechol Moieties

Steponavičiūtė

Klimkevičius

Makuška

2021

Macro Chemistry & Physics

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“…Catecholic units can be easily protected by a wide variety of protective groups, including acetonides [ 45 ], cyclic carbonates [ 46 ], and cyclic boronates [ 47 ]. However, the orthoformate group has special relevance because the deprotection reaction requires mild conditions in an aqueous medium [ 48 , 49 ].…”

Section: Resultsmentioning

confidence: 99%

Design and Synthesis of Bio-Inspired Polyurethane Films with High Performance

et al. 2020

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In the present work, the synthesis of segmented polyurethanes functionalized with catechol moieties within the hard or the soft segment is presented. For this purpose, a synthetic route of a new catechol diol was designed. The direct insertion of this catechol-free derivative into the rigid phase led to segmented polyurethanes with low performance (σmax ≈ 4.5 MPa). Nevertheless, when the derivative was formally located within the soft segment, the mechanical properties of the corresponding functionalized polyurethane improved considerably (σmax ≈ 16.3 MPa), owing to a significant increase in the degree of polymerization. It is proposed that this difference in reactivity could probably be attributed to a hampering effect of this catecholic ring during the polyaddition reaction. To corroborate this hypothesis, a protection of the aromatic ring was carried out, blocking the hampering effect and avoiding secondary reactions. The polyurethane bearing the protected catechol showed the highest molecular weight and the highest stress at break described to date (σmax ≈ 66.1 MPa) for these kind of catechol-functionalized polyurethanes. Therefore, this new approach allows for the obtention of high-performance polyurethane films and can be applied in different sectors, benefiting from the molecular adhesion introduced by the catechol ring.

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Local Wear of Catechol-Containing Diblock Copolymer Layers: Wear Volume, Stick–Slip, and Nanomechanical Changes

et al. 2021

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Polymers containing catechol groups have gained a large interest, as they mimic an essential feature of mussel adhesive proteins that allow strong binding to a large variety of surfaces under water. This feature has made this class of polymers interesting for surface modification purposes, as layer functionalities can be introduced by a simple adsorption process, where the catechol groups should provide a strong anchoring to the surface. In this work, we utilize an AFM-based method to evaluate the wear resistance of such polymer layers in water and compare it with that offered by electrostatically driven adsorption. We pay particular attention to two block copolymer systems where the anchoring group in one case is an uncharged catechol-containing block and in the other case a positively charged and catechol-containing block. The wear resistance is evaluated in terms of wear volume, and here, we compare with data for similar copolymers with statistical distribution of the catechol groups. Monitoring of nanomechanical properties provides an alternative way of illustrating the effect of wear, and we use modeling to show that the stiffness, as probed by an AFM tip, of the soft layer residing on a hard substrate increases as the thickness of the layer decreases. The stick−slip characteristics are also evaluated.

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Synthesis and stability against oxidation of random brush copolymers carrying PEO side chains and catechol moieties

Cited by 9 publications

References 43 publications

Synthesis and Properties of Cationic Gradient Brush Copolymers Carrying PEO Side Chains and Catechol Moieties

Synthesis and Properties of Cationic Gradient Brush Copolymers Carrying PEO Side Chains and Catechol Moieties

Design and Synthesis of Bio-Inspired Polyurethane Films with High Performance

Local Wear of Catechol-Containing Diblock Copolymer Layers: Wear Volume, Stick–Slip, and Nanomechanical Changes

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