Expedient synthesis and ring-opening metathesis polymerization of pyridinonorbornenes

Hancock, Sarah; Yuntawattana, Nattawut; Valdez, Sara M.; Michaudel, Quentin

doi:10.1039/d2py00857b

Cited by 3 publications

(4 citation statements)

References 46 publications

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“…[11][12][13][14][15] In recent years there has been interest in broadening the scope of (macro)monomers used in ROMP to achieve faster polymerizations, as well as larger and better-defined polymers. [16][17][18][19][20][21][22][23] A common cyclic olefin used in ROMP is norbornene, often with substituents, due to its high ring strain providing high propagation rates (k p ) and its facile functionalization with various side chains to make MMs. [24][25][26][27] By tuning MM side-chain identities and sizes to match specific applications, researchers have turned to ROMP to synthesize various bottlebrush polymers for use in several areas, including as nanomaterials with unusual shapes, [28][29][30] photonic crystals, [31][32][33] organic electronic materials, [34][35][36] elastomers, [37][38][39] and in biomedical systems.…”

Section: Introductionmentioning

confidence: 99%

Ring-opening metathesis polymerization of norbornene–benzoladderene (macro)monomers

Scannelli,

Alaboalirat,

Troya

et al. 2023

Polym. Chem.

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Section: Introductionmentioning

confidence: 99%

Ring-opening metathesis polymerization of norbornene–benzoladderene (macro)monomers

Scannelli,

Alaboalirat,

Troya

et al. 2023

Polym. Chem.

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“…Crystallization or melting transitions were not observed by DSC for either polymer suggesting a mostly amorphous behavior. Notably, poly( 1- t Bu + ) exhibited T d and T g values higher than those of the neutral variant poly( 1- t Bu ) ( T d = 281 °C, T g = 157 °C) ( 57 ).…”

Section: Resultsmentioning

confidence: 95%

“…We recently reported the expedient synthesis of monomers 1-H and 1- t Bu from 2,3-pyridyne derivatives. While monomer 1-H was found to resist productive ROMP potentially because of catalyst poisoning, the more sterically hindered 1- t Bu underwent successful controlled polymerization using Ru-1 ( 57 ). We hypothesized that neutral poly( 1- t Bu ) could serve as a platform for the preparation of main-chain cationic polymers via alkylation of the repeating pyridine nitrogen.…”

Section: Resultsmentioning

confidence: 99%

Ring-opening metathesis polymerization of N -methylpyridinium-fused norbornenes to access antibacterial main-chain cationic polymers

Hancock,

Yuntawattana,

Diep

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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Cationic polymers have been identified as a promising type of antibacterial molecules, whose bioactivity can be tuned through structural modulation. Recent studies suggest that the placement of the cationic groups close to the core of the polymeric architecture rather than on appended side chains might improve both their bioactivity and selectivity for bacterial cells over mammalian cells. However, antibacterial main-chain cationic polymers are typically synthesized via polycondensations, which do not afford precise and uniform molecular design. Therefore, accessing main-chain cationic polymers with high degrees of molecular tunability hinges upon the development of controlled polymerizations tolerating cationic motifs (or cation progenitors) near the propagating species. Herein, we report the synthesis and ring-opening metathesis polymerization (ROMP) of N -methylpyridinium-fused norbornene monomers. The identification of reaction conditions leading to a well-controlled ROMP enabled structural diversification of the main-chain cationic polymers and a study of their bioactivity. This family of polyelectrolytes was found to be active against both Gram-negative ( Escherichia coli ) and Gram-positive (Methicillin-resistant Staphylococcus aureus ) bacteria with minimal inhibitory concentrations as low as 25 µg/mL. Additionally, the molar mass of the polymers was found to impact their hemolytic activity with cationic polymers of smaller degrees of polymerization showing increased selectivity for bacteria over human red blood cells.

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“…■ EXPERIMENTAL SECTION Synthesis of Monomers and Polymers. Monomers 1 and 2 were synthesized according to literature procedures 41,42 (see the Supporting Information for more details). To synthesize all-cis block copolymer poly-cis-1-b-cis-2, monomer 1 (73.3 mg, 296.4 μmol, 30 equiv) was first measured into a reaction vial charged with a stir bar inside a nitrogen-filled glovebox.…”

Section: ■ Introductionmentioning

confidence: 99%

Linear and Nonlinear Optical Properties of All-cis and All-trans Poly(p-phenylenevinylene)

Mandal,

Ogunyemi,

Nicholson

et al. 2024

J. Phys. Chem. C

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Poly(p-phenylenevinylene) (PPV) is a staple of the family of conjugated polymers with desirable optoelectronic properties for applications including light-emitting diodes (LEDs) and photovoltaic devices. Although the significant impact of olefin geometry on the steady-state optical properties of PPVs has been extensively studied, PPVs with precise stereochemistry have yet to be investigated using nonlinear optical spectroscopy for quantum sensing, as well as light harvesting for biological applications. Herein, we report our investigation of the influence of olefin stereochemistry on both linear and nonlinear optical properties through the synthesis of all-cis and all-trans PPV copolymers. We performed two-photon absorption (TPA) using a classical and entangled light source and compared both classical TPA and entangled two-photon absorption (ETPA) cross sections of these stereodefined PPVs. Whereas the TPA cross section of the all-trans PPV was expectedly higher than that of all-cis PPV, presumably because of the larger transition dipole moment, the opposite trend was measured via ETPA, with the all-cis PPV exhibiting the highest ETPA cross section. DFT calculations suggest that this difference might stem from the interaction of entangled photons with lower-lying electronic states in the all-cis PPV variant. Additionally, we explored the photoinduced processes for both cis and trans PPVs through time-resolved fluorescence upconversion and femtosecond transient absorption techniques. This study revealed that the sensitivity of PPVs in two-photon absorption varies with classical versus quantum light and can be modulated through the control of the geometry of the repeating alkenes, which is a key stepping stone toward their use in quantum sensing, bioimaging, and the design of polymer-based light-harvesting systems.

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Expedient synthesis and ring-opening metathesis polymerization of pyridinonorbornenes

Abstract: Pyridine-containing polymers are promising materials for a variety of applications from the capture of contaminants to the self-assembly of block copolymers. However, the innate Lewis basicity of the pyridine motif...

Cited by 3 publications

References 46 publications

Ring-opening metathesis polymerization of norbornene–benzoladderene (macro)monomers

Ring-opening metathesis polymerization of norbornene–benzoladderene (macro)monomers

Ring-opening metathesis polymerization of N -methylpyridinium-fused norbornenes to access antibacterial main-chain cationic polymers

Linear and Nonlinear Optical Properties of All-cis and All-trans Poly(p-phenylenevinylene)

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