Recently there have been notable synthetic successes in supramolecular polymerization. By contrast, it has long been known that DNA can undergo supramolecular polymerization (concatemerization). Concatemerization is a step‐like polymerization and consequently suffers from broad molecular weight distributions and generally undesirable cyclization reactions. Here we demonstrate that another supramolecular polymerization of DNA, hybridization chain reaction (HCR), is in fact a living polymerization. After consumption of initial monomer, the polymerization can be continued with further addition of monomer, and the molecular weight can be varied by the ratio of monomer to initiator. In contrast to concatemerization, HCR produces polymers with narrow dispersity while avoiding cyclization. Identification of the living character of this supramolecular polymerization presents new opportunities in structural DNA nanotechnology and molecular biology.
- Award ID(s):
- 1847914
- PAR ID:
- 10224206
- Date Published:
- Journal Name:
- Polymers
- Volume:
- 12
- Issue:
- 6
- ISSN:
- 2073-4360
- Page Range / eLocation ID:
- 1247
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Abstract A nitroso Diels–Alder (NDA) reaction between cyclopentadiene and an in situ generated nitroso compound leads to a new heterocyclic monomer for ring opening metathesis polymerization (ROMP) reactions. This monomer could be polymerized in the presence of Grubbs‐third generation initiator with good control over
M nand decentÐ values. The resulting isoxazolidine‐containing material could undergo further hydrogenation, deprotection, and modification with Dansyl chloride as well as ring opening to provide an amino‐and hydroxyl‐decorated “polyolefin.” -
Abstract The synthesis of high‐molecular‐weight poly(vinyl ethers) under mild conditions is a significant challenge, since cationic polymerization reactions are highly sensitive to chain‐transfer and termination events. We identified a novel and highly effective hydrogen bond donor (HBD)–organic acid pair that can facilitate controlled cationic polymerization of vinyl ethers under ambient conditions with excellent monomer compatibility. Poly(vinyl ethers) of molar masses exceeding 50 kg mol−1can be produced within 1 h without elaborate reagent purification. Modification of the HBD structure allowed tuning of the polymerization rate, while DFT calculations helped elucidate crucial intermolecular interactions between the HBD, organic acid, and polymer chain end.
-
Abstract The synthesis of high‐molecular‐weight poly(vinyl ethers) under mild conditions is a significant challenge, since cationic polymerization reactions are highly sensitive to chain‐transfer and termination events. We identified a novel and highly effective hydrogen bond donor (HBD)–organic acid pair that can facilitate controlled cationic polymerization of vinyl ethers under ambient conditions with excellent monomer compatibility. Poly(vinyl ethers) of molar masses exceeding 50 kg mol−1can be produced within 1 h without elaborate reagent purification. Modification of the HBD structure allowed tuning of the polymerization rate, while DFT calculations helped elucidate crucial intermolecular interactions between the HBD, organic acid, and polymer chain end.
-
Abstract The preparation of functionalized graft copolymers utilizing a combination of ATRP, ROMP, thio‐bromo, and Huisgen‐type click chemistries is described. The construction of these polymeric architectures hinges on the use of a norbornene‐based α‐bromo ester that can act as an ATRP initiator and ROMP monomer (a so‐called
inimer ), as well as a thio‐bromo click partner. This allows for the use of a “grafting‐through” ROMP approach of ATRP‐based macromonomers that can undergo a post‐polymerization thio‐bromo click modification. Additionally, this material can undergo further modifications using archetypal copper‐catalyzed azide/alkyne click reaction as well as metal‐free strain‐promoted azide/alkyne click reactions.