Segmented block copolymers with adhesive functionality bridges in between are synthesized through the combination of controlled radical polymerization (CRP) and thiol-quinone Michael-polyaddition. CRP provides a set of α,ω-dithiol polystyrenes (PS), which react as telechelics with a low molecular weight bisquinone, resulting in thiol-catechol connectivities (TCCs). By introducing as little as 3 mol % of TCC functionalities, the bonding of the polymer on dry and wet aluminum surfaces is significantly improved while keeping the integrity of the PS segments undisturbed to constitute favorable bulk properties. This improvement is evidenced by reaching up to 3.8 MPa adhesive strength, representing a 600% increase compared to nonfunctional PS.
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http://dx.doi.org/10.1021/acsmacrolett.4c00069 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Humboldt-Universität zu Berlin, Department of Chemistry, Unter den Linden 6, 10117, Berlin, Germany.
Multifunctional ortho-quinones are required for the formation of thiol-catechol-connectivities (TCC) but can be delicate to handle. We present the electrochemical oxidation of the dipeptide DiDOPA, achieving up to 92 % conversion efficiency of the catechols to ortho-quinones. Graphite and stainless steel could be employed as cost-efficient electrodes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of chemistry, Humboldt-Universität zu Berlin, Unter den Linden 6, 10117, Berlin, Germany.
Debondable pressure-sensitive adhesives (PSAs) promise access to recyclability in microelectronics in the transition toward a circular economy. Two PSAs were synthesized from a tetravalent thiol star-polyester forming thiol-catechol-connectivities (TCC) with either the biorelated DiDopa-bisquinone (BY*Q) or the fossil-based bisquinone A (BQA). The PSAs enable debonding by oxidation of TCC-catechols to quinones.
View Article and Find Full Text PDFACS Macro Lett
April 2024
Department of Chemistry, Laboratory for Organic Synthesis of Functional Systems, Humboldt-Universität zu Berlin, Unter den Linden 6, 10099 Berlin, Germany.
Segmented block copolymers with adhesive functionality bridges in between are synthesized through the combination of controlled radical polymerization (CRP) and thiol-quinone Michael-polyaddition. CRP provides a set of α,ω-dithiol polystyrenes (PS), which react as telechelics with a low molecular weight bisquinone, resulting in thiol-catechol connectivities (TCCs). By introducing as little as 3 mol % of TCC functionalities, the bonding of the polymer on dry and wet aluminum surfaces is significantly improved while keeping the integrity of the PS segments undisturbed to constitute favorable bulk properties.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2021
Laboratory for Organic Synthesis of Functional Systems Institution, Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
The formation of cysteinyldopa as biogenic connectivity in proteins is used to inspire a chemical pathway toward mussel-adhesive mimics. The mussel-inspired polymerization (MIPoly) exploits the chemically diverse family of bisphenol monomers that is oxidizable with 2-iodoxybenzoic acid to give bisquinones. Those react at room temperature with dithiols in Michael-type polyadditions, which leads to polymers with thiol-catechol connectivities (TCC).
View Article and Find Full Text PDFMacromol Rapid Commun
January 2020
Laboratory for Organic Synthesis of Functional Systems, Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany.
A previously introduced tyrosinase-activated polymerization of Tyr- and Cys-bearing peptides yielding artificial mussel-glue proteins is realized without the need of the specific enzyme by a chemical activation route. This decouples the sequence of polymerizable peptides (unimers) from the constraints of tyrosinase substrates and enables the polymerization of minimal motifs such as Dopa-Lys-Cys (U ) or Dopa-Gly-Cys (U ). In the polymerization procedure, sodium periodate is used to oxidize Dopa residues of the unimers to Dopa-quinones to which the thiol of a Cys residue is added in a Michael-type reaction.
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