Sequence- and stereo-defined macromolecules: Properties and emerging functionalities

Szweda, Róża

doi:10.1016/j.progpolymsci.2023.101737

Cited by 14 publications

(7 citation statements)

References 436 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The precise control of monomer sequence, regio- and stereochemistry of the primary structure of functional polyolefins is crucial as it will further determine the specific secondary and tertiary structures and final properties . As for monomer sequence, most of the reported rare-earth catalyzed polar olefin copolymerization reactions are block or random copolymerization.…”

Section: Introductionmentioning

confidence: 99%

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Zhang,

Xue,

Shi

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

The direct copolymerization of polar and nonpolar olefins is of great interest and significance, as it is the most atomeconomical and straightforward strategy for the synthesis of functional polyolefin materials. Despite considerable efforts, the precise control of monomer-sequence and their regio-and stereochemistry is full of challenges, and the related mechanistic origins are still in their infancy to date. Herein, the mechanistic studies on the model reaction of Sc-catalyzed co-syndiospecific alternating copolymerization of anisylpropylene (AP) and styrene were performed by DFT calculations. The results suggest that the subtle balance between electronic and steric factors plays an important role during monomer insertions, and a new aminodissociated mechanism was proposed for AP insertion at chain initiation. AP insertion follows the 2,1-si-insertion pattern, which is mainly controlled by steric factors caused by the restricted MeO•••Sc interaction. As for styrene insertion, it prefers the 2,1-reinsertion manner and its regio-and stereoselectivities are influenced by steric repulsions between the inserting styrene and the polymer chain or the ligand. More interestingly, it is found that the alternating monomer-sequence is mainly determined by the "steric matching" principle, which is quantitatively expressed by the buried volume of the metal center of the preinserted species. The concept of steric pocket has been successfully applied to explain the different performances of several catalysts and other alternating copolymerization reactions. The insightful mechanistic findings and the quantitative steric pocket model present here are expected to promote rational design of new rare-earth catalysts for developing regio-, stereo-, and sequence-controlled copolymerization of specific polar and nonpolar olefins.

show abstract

Section: Introductionmentioning

confidence: 99%

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Zhang,

Xue,

Shi

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…Originally, chemists embarked upon the exploration of sequence-dened polymers to mimic the extreme control and precision found in biomacromolecules (i.e., proteins and oligonucleotides), and go towards a variety of uniform synthetic polymers, oen completely stereo-controlled. [1][2][3][4][5] Nowadays, these macromolecules, exhibiting by denition a discrete molecular weight, a uniform structure and dened architecture, could be prepared through two main methods, being solid- [6][7][8][9][10] and liquid-phase synthesis. [11][12][13] The rst one makes use of an insoluble polymer matrix that can be functionalized with a cleavable linker from which the iterative attachment of monomers starts.…”

Section: Introductionmentioning

confidence: 99%

Telechelic sequence-defined oligoamides: their step-economical synthesis, depolymerization and use in polymer networks

De Franceschi,

Badi,

Du Prez

2024

Chem. Sci.

View full text Add to dashboard Cite

show abstract

“…The sequence-defined polymer term was recently formulated to describe a macromolecular species whose length is discrete and the order of monomeric units within a chain is strictly specific. − Archetypical representatives of these chemical species are naturally occurring polymers, i.e., proteins and nucleic acids. Non-natural building blocks and backbones broaden the scope of macromolecular structures thanks to advancements in precision polymer synthesis. − Backbone structures may range from bioinspired peptoids , or polyphosphates to novel chemical moieties, i.e., triazoles, − urease, urethanes, − ethers, , esters, , or π-conjugated oligomers. − Applying chiral monomers enables full control over the stereochemistry of macromolecules. ,,− Consequently, primary structure control and stereochemistry are emerging as promising tools to induce functionalities in abiotic macromolecules …”

Section: Introductionmentioning

confidence: 99%

“…12,18,28−31 Consequently, primary structure control and stereochemistry are emerging as promising tools to induce functionalities in abiotic macromolecules. 32 Discrete, abiotic macromolecules have already been proven to display functions such as natural polymers. For instance, sequence-defined polymers are used as binary information carriers similar to DNA storing genetic code.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Revealing the Effect of Stereocontrol on Intermolecular Interactions between Abiotic, Sequence-Defined Polyurethanes and a Ligand

Szatko,

Forysiak,

Kozub

et al. 2024

ACS Biomater. Sci. Eng.

Self Cite

View full text Add to dashboard Cite

The development of precision polymer synthesis has facilitated access to a diverse library of abiotic structures wherein chiral monomers are positioned at specific locations within macromolecular chains. These structures are anticipated to exhibit folding characteristics similar to those of biotic macromolecules and possess comparable functionalities. However, the extensive sequence space and numerous variables make selecting a sequence with the desired function challenging. Therefore, revealing sequence− function dependencies and developing practical tools are necessary to analyze their conformations and molecular interactions. In this study, we investigate the effect of stereochemistry, which dictates the spatial location of backbone and pendant groups, on the interaction between sequence-defined oligourethanes and bisphenol A ligands. Various methods are explored to analyze the receptor-like properties of model oligomers and the ligand. The accuracy of molecular dynamics simulations and experimental techniques is assessed to uncover the impact of discrete changes in stereochemical arrangements on the structures of the resulting complexes and their binding strengths. Detailed computational investigations providing atomistic details show that the formed complexes demonstrate significant structural diversity depending on the sequence of stereocenters, thus affecting the oligomer−ligand binding strength. Among the tested techniques, the fluorescence spectroscopy data, fitted to the Stern−Volmer equation, are consistently aligned with the calculations, thus validating the developed simulation methodology. The developed methodology opens a way to engineer the structure of sequence-defined oligomers with receptor-like functionality to explore their practical applications, e.g., as sensory materials.

show abstract

Sequence- and stereo-defined macromolecules: Properties and emerging functionalities

Cited by 14 publications

References 436 publications

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Telechelic sequence-defined oligoamides: their step-economical synthesis, depolymerization and use in polymer networks

Revealing the Effect of Stereocontrol on Intermolecular Interactions between Abiotic, Sequence-Defined Polyurethanes and a Ligand

Contact Info

Product

Resources

About