As a main synthetic strategy for monodisperse sequence-defined polymers, the known iterative exponential growth (IEG) methods were all developed on protecting-group chemistry, where the additional deprotection reactions increased their synthetic steps and decreased their atom economy. In this study, we developed a protecting-group-free IEG method for the formation of sequence-defined polymers by combining three orthogonal click reactions of copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), sulfur-fluoride exchange reaction (SuFEx), and Ugi four-component reaction (Ugi-4CR). In this approach, oligomer synthesis began with three parallel CuAAC, SuFEx, and Ugi-4CR couplings among three monomers each with two orthogonal clickable end groups. By iteratively applying parallel CuAAC, SuFEx, and Ugi-4CR to couple three resultant oligomers, each having two orthogonal clickable terminals, this approach could exponentially grow three different sequence-defined polymers simultaneously with high efficiency, requiring no protecting-group chemistry. Additionally, each Ugi-4CR coupling reaction could introduce two external side groups to provide the molecular variation and side-chain functionalization for the resultant sequence-defined polymers.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acsmacrolett.0c00812 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
A modular and extensible CHARMM-compatible model for all-atom simulation of polypeptoids.
J Chem Phys
December 2024
Department of Chemistry, University of Chicago, Chicago, Illinois 60637, USA.
Peptoids (N-substituted glycines) are a class of sequence-defined synthetic peptidomimetic polymers with applications including drug delivery, catalysis, and biomimicry. Classical molecular simulations have been used to predict and understand the conformational dynamics of single chains and their self-assembly into morphologies including sheets, tubes, spheres, and fibrils. The CGenFF-NTOID model based on the CHARMM General Force Field has demonstrated success in accurate all-atom molecular modeling of peptoid structure and thermodynamics.
View Article and Find Full Text PDFHigh Molecular Weight Uniform Polymers Encoding Octal Sequences by Passerini Iterative Exponential Growth.
J Am Chem Soc
December 2024
Department of Chemistry, Seoul National University, Seoul 08826, Korea.
Sequence-defined polymers composed of a large pool of chemically distinct monomers (SDPs) have been pursued to achieve the structural and functional precisions exhibited by biopolymers in nonbiological environments. In contrast to the incremental growth of SDPs by sequential addition of individual monomers, the iterative exponential growth (IEG) method allows the synthesis of high molecular-weight SDPs, but their sequences have been composed mostly of binary monomers. Consequently, achieving high molecular-weight SDPs built with a large pool of monomers remains a challenge.
View Article and Find Full Text PDFSwitchable Radical Polymerization of α-Olefins via Remote Hydrogen Atom or Group Transfer for Enhanced Battery Performance.
Angew Chem Int Ed Engl
December 2024
Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
Introducing polar groups into non-polar polyolefins can significantly enhance the important properties of materials. However, producing polyolefin backbones consisting of polar blocks remains elusive, due to the substantial difference of reactivity ratios between polar and non-polar olefin monomers in radical polymerization or the poisoning of transition-metal catalysts by polar groups in coordination polymerization. Herein we present a practical way for the preparation of polyethylene-based polymers with distinct polar groups by radical polymerization of α-olefins.
View Article and Find Full Text PDFUprising Unconventional Nanobiomaterials: Peptoid Nanosheets as a Multi-Modular Platform for Advanced Biological Studies.
Small
December 2024
Department of Science and Environment, Roskilde University, Roskilde, 4000, Denmark.
Peptoids are bio-inspired peptidomimetic polymers that can be designed to self-assemble into a variety of nanostructures. Among these different assemblies, peptoid nanosheets are the most studied. Peptoid nanosheets are 2D highly ordered nanostructures, able to free float in aqueous solutions while featuring versatile chemical displays that can be tuned to incorporate a plethora of functional units.
View Article and Find Full Text PDFBottlebrush Polymers with Sequence-Controlled Backbones for Enhanced Oligonucleotide Delivery.
J Am Chem Soc
December 2024
Department of Chemistry and Chemical Biology, Northeastern University, Boston, Massachusetts 02115, United States.
Article Synopsis
- This study addresses the delivery challenges of oligonucleotide-based therapies by introducing a new type of delivery vehicle made from poly(ethylene glycol) (PEG) bottlebrush polymers with specifically designed backbones.
- The researchers utilized solid-phase synthesis to create these polymer-oligonucleotide conjugates, incorporating modifications like carbon 18 (C) units to enhance cell-material interactions.
- Findings indicate that optimizing the arrangement of the C modifier can significantly improve cellular uptake, pharmacokinetics, biodistribution, and effectiveness of the treatment, suggesting that modifying the polymer backbone can tailor the delivery systems for different diseases.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!