Controlled synthesis of cyclic helical polyisocyanides and bottlebrush polymers using a cyclic alkyne–Pd(<scp>ii</scp>) catalyst

Duan, Bing-Hui; Yu, Jia-Xin; Gao, Run-Tan; Li, Shi-Yi; Liu, Na; Wu, Zong-Quan

doi:10.1039/d3cc04095j

Chem. Commun.

2023

DOI: 10.1039/d3cc04095j

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Controlled synthesis of cyclic helical polyisocyanides and bottlebrush polymers using a cyclic alkyne–Pd(ii) catalyst

Bing-Hui Duan,

Jia-Xin Yu,

Run-Tan Gao

et al.

Abstract: A cyclic catalyst was prepared which initiates the living polymerisation of isocyanide monomers and macromonomers, affording various well-defined cyclic polymers with predictable molar mass and low distribution.

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2024

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Cited by 3 publications

References 51 publications

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Effects of Cyclic Glycopolymers Molecular Mobility on their Interactions with Lectins

Jin,

Nagao,

Kumon

et al. 2024

ChemPlusChem

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Cyclic polymers, which are found in the field of biopolymers, exhibit unique physical properties such as suppressed molecular mobility. Considering thermodynamics, the suppressed molecular mobility of cyclic polymers is expected to prevent unfavorable entropy loss in molecular interactions. In this study, we synthesized cyclic glycopolymers carrying galactose units and investigated the effects of their molecular mobility on the interactions with a lectin (peanut agglutinin). The synthesized cyclic glycopolymers exhibited delayed elution time on size exclusion chromatography and a short spin–spin relaxation time, indicating typical characteristics of cyclic polymers, including smaller hydrodynamic size and suppressed molecular mobility. The hemagglutination inhibition assay revealed that the cyclic glycopolymers exhibited weakened interactions with PNA compared to the linear counterparts, attributable to the suppressed molecular mobility. Although the results are contrary to our expectations, the impact of polymer topology on molecular recognition remains intriguing, particularly in the context of protein repellent activity in the biomedical field.

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Effects of Cyclic Glycopolymers Molecular Mobility on their Interactions with Lectins

Jin,

Nagao,

Kumon

et al. 2024

ChemPlusChem

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Complex Cage, Cage-Brush, and Lantern Polymers with Topological-Enhancing Phosphorescence

Wang,

Wang

et al. 2024

Macromolecules

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Cage polymers, a type of special cyclic polymer with an intriguing three-dimensional topology and internal cavity, have attracted increasing attention. However, because of the complicated topological structure, precise preparation of cage polymers is a formidable challenge. Herein, an effective and versatile synthetic strategy was developed to precisely construct complex topological polymers with a well-defined structure and high molecular weight, including three-arm cage, three-arm cage-brush, bi(three-arm) cage, and six-arm cage polymers, by a ring-opening metathesis polymerization-based blocking-cyclization technique using different short polymeric ladderphanes containing multiple living ends as the initial and end-cyclizing motifs, which was the key factor in simply tuning the polymer topology. Moreover, bi-and six-arm lantern polymers were readily derived from the corresponding cage polymers. By comparison of the performance differences between these novel polymers, the dependence of the properties on the topology was revealed. Therefore, this work provided a platform for constructing complex topological polymers with unique topological-enhancing phosphorescent performance and mechanical properties.

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Helical Star-Shaped Bottlebrush Polymers: From Controlled Synthesis to Tunable Photoluminescence and Circularly Polarized Luminescence

Li,

Duan,

Liu

et al. 2024

ACS Macro Lett.

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The controlled synthesis of star-shaped bottlebrush polymers with tunable topologies is a challenge. However, such materials may exhibit distinct photoluminescence properties. Bottlebrush polymers have polymerization-induced emission (PIE) properties due to their aggregated side chains, and aggregation-induced emission (AIE) is also a unique luminescent property. In this work, we prepared a variety of highly active alkyne Pd catalysts and polymerized poly(L/D-lactic acid) macromonomers containing polymerizable phenylisocyanide groups as end groups to obtain a variety of topologically structured bottlebrush polymers with controllable molecular weights and narrow molecular weight distributions. Bottlebrush polymers with tetraphenyl ethylene (TPE) units as the core exhibit tunable photoluminescence and circularly polarized luminescence properties. We propose that such properties are due to the unique AIE characteristics of the TPE unit combined with the PIE characteristics of the bottlebrush polymer.

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Controlled synthesis of cyclic helical polyisocyanides and bottlebrush polymers using a cyclic alkyne–Pd(ii) catalyst

Abstract: A cyclic catalyst was prepared which initiates the living polymerisation of isocyanide monomers and macromonomers, affording various well-defined cyclic polymers with predictable molar mass and low distribution.

Cited by 3 publications

References 51 publications

Effects of Cyclic Glycopolymers Molecular Mobility on their Interactions with Lectins

Effects of Cyclic Glycopolymers Molecular Mobility on their Interactions with Lectins

Complex Cage, Cage-Brush, and Lantern Polymers with Topological-Enhancing Phosphorescence

Helical Star-Shaped Bottlebrush Polymers: From Controlled Synthesis to Tunable Photoluminescence and Circularly Polarized Luminescence

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