An alkyne-azide addition, i.e., click, reaction in conjunction with an electrostatic self-assembly and covalent fixation (ESA-CF) process has been demonstrated to effectively construct a variety of unprecedented multicyclic polymer topologies. A series of single cyclic poly(tetrahydrofuran), poly(THF), precursors having an alkyne group (Ia), an azide group (Ib), two alkyne groups at the opposite positions (Ic), and an alkyne group and an azide group at the opposite positions (Id) have been prepared by the ESA-CF process. Moreover, a bicyclic 8-shaped precursor having two alkyne groups at the opposite positions (Ie) was synthesized. The subsequent click reaction of Ia with linear (IIa) and three-armed star (IIb) telechelic precursors having azide groups has been performed to construct bridged-type two-way (IIIa) and three-way (IIIb) paddle-shaped polymer topologies, respectively. Likewise, spiro-type tandem tricyclic (IVa) and tetracyclic (IVb) topologies resulted from Ib/Ic and Ib/Ie, respectively. Furthermore, three types of multicyclic topologies that are composed of repeating ring (Va), alternating ring/linear (Vb), and alternating ring/star (Vc) units have been synthesized from Id, Ic/IIa, and Ic/IIb, respectively.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ja103402c | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
The Topology of Poly(2-methyl-2-oxazine) Shells on Nanoparticles Determines Their Interaction with Serum and Uptake by Immune Cells.
Biomacromolecules
December 2024
Laboratory for Macromolecular and Organic Chemistry, Department of Chemical Sciences, University of Padova, Padova 35131, Italy.
Cyclic poly(2-methyl-2-oxazine) (-PMOZI) brush shells on Au nanoparticles (NPs) exhibit enhanced stealth properties toward serum and different cell lines compared to their linear PMOZI (-PMOZI) counterparts. While selectively recruiting immunoglobulins, -PMOZI shells reduce overall human serum (HS) protein binding and alter the processing of complement factor 3 (C3) compared to chemically identical linear shells. Polymer cyclization significantly decreases NP uptake by nonphagocytic cells and macrophages in both complement-deficient fetal bovine serum (FBS) and complement-expressing HS, indicating ineffective functional opsonization.
View Article and Find Full Text PDFBlock Architectures in 2D Polymer Networks Fabricated via Sequential Copolymerization in a Metal-Organic Framework.
Chemistry
December 2024
The University of Tokyo Graduate School of Engineering School of Engineering: Tokyo Daigaku Daigakuin Kogakukei Kenkyuka Kogakubu, Department of Applied Chemistry, 7-3-1 Hongo, Bunkyo-ku, 113-8656, Tokyo, JAPAN.
Two-dimensional (2D) polymer network monolayers with novel block architectures were fabricated via sequential copolymerization within a pillared-layer metal-organic framework (MOF) that served as the reaction template. The MOF provides a confined 2D nanospace, restricting the crosslinking copolymerization of vinyl monomers to two dimensions. Sequential crosslinking copolymerization of methyl methacrylate and styrene, regulated by the reversible addition-fragmentation chain transfer (RAFT) process, resulted in the formation of 2D block architectures with 'patchy' domains consisting of crosslinked poly(methyl methacrylate) and polystyrene segments.
View Article and Find Full Text PDFHalf-integer topological defects paired via string micelles in polar liquids.
PNAS Nexus
December 2024
Department of Mechanical and Energy Engineering, Southern University of Science and Technology, Shenzhen 518055, China.
Ferroelectric nematic (N) liquid crystals present a compelling platform for exploring topological defects in polar fields, while their structural properties can be significantly altered by ionic doping. In this study, we demonstrate that doping the ferroelectric nematic material RM734 with cationic polymers enables the formation of polymeric micelles that connect pairs of half-integer topological defects. Polarizing optical microscopy reveals that these string defects exhibit butterfly textures, featured with a 2D polarization field divided by Néel-type kink walls into domains exhibiting either uniform polarization or negative splay and bend deformations.
View Article and Find Full Text PDFTuning Star Polymer Architecture to Tailor Secondary Structures and Mechanical Properties of Diblock Polypeptide Hydrogels for Direct Ink Writing.
Biomacromolecules
December 2024
Department of Chemistry, RCSI University of Medicine and Health Sciences, Dublin D02 YN77, Ireland.
Hydrogel three-dimensional (3D) printing has emerged as a highly valuable fabrication tool for applications ranging from electronics and biomedicine. While conventional hydrogels such as gelatin, alginate, and hyaluronic acid satisfy biocompatibility requirements, they distinctly lack reproducibility in terms of mechanical properties and 3D printability. Aiming to offer a high-performance alternative, here we present a range of amphiphilic star-shaped diblock copolypeptides of l-glutamate and l-leucine residues with different topologies.
View Article and Find Full Text PDFThermodynamic Perturbation Theory for Charged Branched Polymers.
J Chem Theory Comput
December 2024
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, PR China.
Classical density functional theory (DFT) provides a versatile framework to study the polymers with complex topological structure. Generally, a classical DFT describes the excess Helmholtz free energy of nonbonded chain connectivity due to excluded-volume effects and electrostatic correlations using the first-order thermodynamic perturbation theory (referred to as DFT-TPT1). Beyond first-order perturbation, the second-order TPT (TPT2) captures not only the correlations between neighboring monomers but also the interactions within three consecutive monomers, playing a crucial role in describing the polymer topology.
View Article and Find Full Text PDFWant 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!