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Université de Fribourg

Mechanically induced cis-to-trans isomerization of carbon–carbon double bonds using atomic force microscopy

Radiom, Milad ; Kong, Phally ; Maroni, Plinio ; Schäfer, Mark ; Kilbinger, Andreas F. M. ; Borkovec, Michal

In: Physical Chemistry Chemical Physics, 2016, vol. 18, no. 45, p. 31202–31210

Cis-to-trans isomerization of carbon–carbon double bonds can be induced by the application of mechanical force. Using single molecule force spectroscopy by means of atomic force microscopy (AFM) we pulled polymer molecules which contained cis double bonds in the backbone. In the force versus extension profiles of these polymers, a sudden extension increase is observed which is due to the...

Université de Fribourg

Transient anions of cis- and trans-cyclooctene studied by electron-impact spectroscopy

Regeta, Khrystyna ; Nagarka, Amit ; Kilbinger, Andreas F. M. ; Allan, Michael

In: Physical Chemistry Chemical Physics, 2015, vol. 17, no. 6, p. 4696–4700

The effect which deformation of the double bond in trans-cyclooctene (TCO), compared to cis-cyclooctene (CCO), has on its negative ion – and indirectly on the π* virtual orbital – was studied by electron-impact spectroscopy. Differential elastic and vibrational excitation cross sections were measured at a scattering angle of θ = 135°. The vertical attachment energy (VAE) derived from the...

Université de Fribourg

The role of mass and length in the sonochemistry of polymers

Schaefer, Mark ; Icli, Burcak ; Weder, Christoph ; Lattuada, Marco ; Kilbinger, Andreas F. M. ; Simon, Yoan C.

In: Macromolecules, 2016, vol. 49, no. 5, p. 1630–1636

The ultrasound-induced cleavage of macromolecules has become a routine experiment in the emerging field of polymer mechanochemistry. To date, it has not been conclusively proven whether the molecular weight of a polymer or its contour length is the determining factor for chain scission upon ultrasonication. Here we report comparative experiments that confirm unequivocally that the contour length...

Université de Fribourg

ROMP copolymers for orthogonal click functionalizations

Schaefer, Mark ; Hanik, Nils ; Kilbinger, Andreas F. M.

In: Macromolecules, 2012, p. -

The ring-opening metathesis polymerization using ruthenium carbene initiators developed by Grubbs et al. is one of the most functional group tolerant living polymerization methods known. One of the most used postpolymerization functionalization methods used today is the copper-catalyzed 1,3-dipolar cycloaddition between alkynes and organic azides. Organic azides are, however, not tolerated by...

Université de Fribourg

Toward large tubular helices based on the polymerization of tri(benzamide)s

Schulze, Maren ; Kilbinger, Andreas F. M.

In: Journal of Polymer Science Part A: Polymer Chemistry, 2016, p. -

Herein we present the synthesis and polycondensation of mono- and di-N-protected, bis-substituted tri(benzamide)s with the aim to create large, tubular helices. We synthesized 2,4-dimethoxy and 2,5-bis-TEGylated aminobenzoic acid derivatives as bent and linear monomers and introduced p-methoxybenzyl (PMB) amide protecting groups to the oligobenzamide backbone. An iterative coupling strategy...

Université de Fribourg

Polyethylenimine is a strong inhibitor of human papillomavirus and cytomegalovirus infection

Spoden, Gilles A. ; Besold, Katrin ; Krauter, Steffi ; Plachter, Bodo ; Hanik, Nils ; Kilbinger, Andreas F. M. ; Lambert, Carsten ; Florin, Luise

In: Antimicrobial Agents and Chemotherapy, 2012, vol. 56, no. 15, p. 75-82

Polyethylenimines are cationic polymers with potential as delivery vectors in gene therapy and with proven antimicrobial activity. However, the antiviral activity of polyethylenimines has not been addressed in detail thus far. We have studied the inhibitory effects of a linear 25-kDa polyethylenimine on infections with human papillomaviruses and human cytomegaloviruses. Preincubation of cells...

Université de Fribourg

One-pot synthesis and AFM imaging of a triangular aramide macrocycle

Storz, Christof ; Badoux, Michael ; Hauke, Christopher M. ; Šolomek, Tomáš ; Kühnle, Angelika ; Bally, Thomas ; Kilbinger, Andreas F. M.

In: Journal of the American Chemical Society, 2014, vol. 136, no. 37, p. 12832–12835

Macrocyclizations in exceptionally good yields were observed during the self-condensation of N-benzylated phenyl p-aminobenzoates in the presence of LiHMDS to yield three-membered cyclic aramides that adopt a triangular shape. An ortho-alkyloxy side chain on the N-benzyl protecting group is necessary for the macrocyclization to occur. Linear polymers are formed exclusively in the absence of this...

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

Catalytic living ring-opening metathesis polymerization with Grubbs’ second- and third-generation catalysts

Yasir, Mohammad ; Liu, Peng ; Tennie, Iris K. ; Kilbinger, Andreas F. M.

In: Nature Chemistry, 2019, vol. 11, no. 5, p. 488–494

In a conventional living ring-opening metathesis polymerization (ROMP), an equal number of ruthenium complexes to the number of polymer chains synthesized are required. This can lead to high loadings of ruthenium complexes when aiming for shorter polymers. Here, a reversible chain-transfer agent was used to produce living ROMP polymers from norbornene derivatives using catalytic amounts of...