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Université de Fribourg

Mono-telechelic polymers by catalytic living ring-opening metathesis polymerization with second-generation Hoveyda–Grubbs catalyst

Liu, Peng ; Dong, Zhenghao ; Kilbinger, Andreas F. M.

In: Materials Chemistry Frontiers, 2020, vol. 4, no. 9, p. 2791–2796

The second-generation Hoveyda–Grubbs (HG2) catalyst, which has a small initiation to propagation rate ratio (ki/kp) in ring-opening metathesis polymerization (ROMP), was successfully used in a recently developed catalytic living ROMP. This proved that slow-initiating catalysts can enable ROMP in a living fashion to produce polymers with narrow dispersity and controlled molecular weight. The...

Université de Fribourg

Slow-targeted release of a ruthenium anticancer agent from vitamin B 12 functionalized marine diatom microalgae

Delasoie, Joachim ; Rossier, Jérémie ; Haeni, Laetitia ; Rothen-Rutishauser, Barbara ; Zobi, Fabio

In: Dalton Transactions, 2018, vol. 47, no. 48, p. 17221–17232

Herein we report the synthesis of a new biomaterial designed for targeted delivery of poorly water-soluble inorganic anticancer drugs, with a focus on colorectal cancer. Diatomaceous earth microparticles derived from marine microalgae were coated with vitamin B12 (cyanocobalamin) as a tumor targeting agent and loaded with the well- known anticancer agents cisplatin, 5-fluorouracil (5-FU), and...

Université de Fribourg

Photochemical methods in metathesis reactions

Harvey, Freya M. ; Bochet, Christian G.

In: Organic & Biomolecular Chemistry, 2020, vol. 18, no. 40, p. 8034–8057

Metathesis reactions are one of the most reliable and prevalent ways of creating a C– C bond in synthesis. Photochemical variants exist, and they have proven extremely useful for the construction of complex molecules, from natural products to Möbius rings. A variety of starting materials can undergo photometathesis reactions, including alkenes, alkynes, carbonyls, thiocarbonyls, and...

Université de Fribourg

One-step ring opening metathesis block-like copolymers and their compositional analysis by a novel retardation technique

Yasir, Mohammad ; Liu, Peng ; Markwart, Jens C. ; Suraeva, Oksana ; Wurm, Frederik R. ; Smart, Jansie ; Lattuada, Marco ; Kilbinger, Andreas F. M.

In: Angewandte Chemie International Edition, 2020, vol. 59, no. 32, p. 13597-13601

Using a one-step synthetic route for block copolymers avoids the repeated addition of monomers to the polymerization mixture, which can easily lead to contamination and, therefore, to the unwanted termination of chain growth. For this purpose, monomers (M1–M5) with different steric hindrances and different propagation rates are explored. Copolymerization of M1 (propagating rapidly) with M2...

Université de Fribourg

Telechelics based on catalytic alternating ring-opening metathesis polymerization

Pal, Subhajit ; Alizadeh, Mahshid ; Kilbinger, Andreas F. M.

In: ACS Macro Letters, 2019, vol. 8, no. 10, p. 1396–1401

We describe a protocol to synthesize alternating telechelic ROMP copolymers of 7- oxa-norbornene derivatives and cycloalkenes under catalytic conditions. These copolymers were synthesized using Grubbs’ second-generation catalyst. The sterically less hindered backbone double bonds of the resulting alternating copolymers facilitate the chain transfer (secondary metathesis) reactions. In the ...

Université de Fribourg

Functional end groups in living ring-opening metathesis polymerization

Kilbinger, Andreas

In: Synlett, 2019, vol. 30, no. 18, p. 2051–2057

Over the last two decades many synthetic methods have been reported to selectively introduce a number of different functional groups at the chain end of a living ring- opening metathesis polymer. In this personal account, I would like to focus on a few such methods developed in my research group over the last several years and how these led to the discovery of catalytic living ring-opening...

Université de Fribourg

Catalytic living ring opening metathesis polymerisation: the importance of ring strain in chain transfer agents

Liu, Peng ; Yasir, Mohammad ; Kilbinger, Andreas F. M.

In: Angewandte Chemie International Edition, 2019, vol. 58, no. 43, p. 15278–15282

A recently developed catalytic living ring opening metathesis polymerisation (ROMP) was investigated using a series of reversible chain transfer agents (CTA) carrying either cyclopentene or cyclohexene rings, differing only in ring strain. All cyclopentene derivatives examined showed significantly faster reaction rates than the corresponding cyclohexene derivatives. This resulted in lower...

Université de Fribourg

Synthesis and properties of poly(norbornene)s with lateral aramid groups

Kong, Phally ; Drechsler, Susanne ; Balog, Sandor ; Schrettl, Stephen ; Weder, Christoph ; Kilbinger, Andreas F. M.

In: Polymer Chemistry, 2019, vol. 10, no. 16, p. 2057–2063

This paper deals with the synthesis and investigation of comb-like poly(norbornene)s carrying lateral rod-like aramid groups. Two types of norbornene-based monomers were synthesized and copolymerized with a norbornene carrying an aliphatic side chain using ring opening metathesis polymerization (ROMP). The new monomers contain aramid derivatives that display different types of non-covalent...