A catalytic living ring-opening metathesis copolymerization (ROMP) method is described that relies on a degenerative, reversible and regioselective exchange of propagating Fischer-carbenes. All characteristics of a living polymerization such as narrow dispersity, excellent molar mass control and the ability to form block copolymers are achieved by this method. The method allows the use of up to 200 times less ruthenium complex than traditional living ROMP. We demonstrate the synthesis of ROMP-ROMP diblock copolymers, ATRP from a ROMP macro-initiator and living ROMP from a PEG-based macro chain transfer agent. The cost-effective, sustainable and environmentally friendly synthesis of degradable polymers and block copolymers enabled by this strategy will find various applications in biomedicine, materials science, and technology. 相似文献
Cell‐based therapies are gaining prominence in treating a wide variety of diseases and using synthetic polymers to manipulate these cells provides an opportunity to impart function that could not be achieved using solely genetic means. Herein, we describe the utility of functional block copolymers synthesized by ring‐opening metathesis polymerization (ROMP) that can insert directly into the cell membrane via the incorporation of long alkyl chains into a short polymer block leading to non‐covalent, hydrophobic interactions with the lipid bilayer. Furthermore, we demonstrate that these polymers can be imbued with advanced functionalities. A photosensitizer was incorporated into these polymers to enable spatially controlled cell death by the localized generation of 1O2 at the cell surface in response to red‐light irradiation. In a broader context, we believe our polymer insertion strategy could be used as a general methodology to impart functionality onto cell‐surfaces. 相似文献
Summary: The combination of enzymatic polymerization with ATRP for the synthesis of branched (block) copolymers was investigated. Heterotelechelic polycaprolactone macroinimer was synthesized in a one‐pot enzymatic procedure by using 2‐hydroxyethyl α‐bromoisobutyrate as a bifunctional initiator. A polymerizable end group was introduced by subsequent in situ enzymatic acrylation with vinyl acrylate. Branched polymers were obtained by subsequent atom transfer radical polymerization (ATRP).
Enzymatic synthesis of heterotelechelic macromonomers and subsequent self condensing vinyl polymerization by ATRP. 相似文献
Strain‐promoted 1,3‐dipolar cycloaddition of cyclooctynes with 1,3‐dipoles such as azides, nitrones, and nitrile oxides, are of interest for the functionalization of polymers. In this study, we have explored the use of a 4‐dibenzocyclooctynol (DIBO)‐containing chain transfer agent in reversible addition–fragmentation chain transfer polymerizations. The controlled radical polymerization resulted in well‐defined DIBO‐terminating polymers that could be modified by 1,3‐dipolar cycloadditions using nitrones, nitrile oxides, and azides having a hydrophilic moiety. The self‐assembly properties of the resulting block copolymers have been examined. The versatility of the methodology was further demonstrated by the controlled preparation of gold nanoparticles coated with the DIBO‐containing polymers to produce materials that can be further modified by strain‐promoted cycloadditions. 相似文献
We report the synthesis of telechelic poly(norbornene) and poly(cyclooctene) homopolymers by ring‐opening metathesis polymerization (ROMP) and their subsequent functionalization and block copolymer formation based on noncovalent interactions. Whereas all the poly(norbornene)s contain either a metal complex or a hydrogen‐bonding moiety along the polymer side‐chains, together with a single hydrogen‐bonding‐based molecular recognition moiety at one terminal end of the polymer chain. These homopolymers allow for the formation of side‐chain‐functionalized AB and ABA block copolymers through self‐assembly. The orthogonal natures of all side‐ and main‐chain self‐assembly events were demonstrated by 1H NMR spectroscopy and isothermal titration calorimetry. The resulting fully functionalized block copolymers are the first copolymers combining both side‐ and main‐chain self‐assembly, thereby providing a high degree of control over copolymer functionalization and architecture and bringing synthetic materials one step closer to the dynamic self‐assembly structures found in nature. 相似文献
Grignard Metathesis polymerization (GRIM) for the synthesis of regioregular poly(3‐alkylthiophenes) proceeds via a “living” chain growth mechanism. Due to the “living” nature of this polymerization regioregular poly(3‐alkylthiophenes) with predetermined molecular weight, narrow molecular weight distributions and desired chain end functionality are now readily available. Allyl terminated poly(3‐hexylthiophene) was successfully used as a precursor for the synthesis of di‐block copolymers containing polystyrene. The addition of “living” poly(styryl)lithium to the allyl terminated regioregular poly(3‐hexylthiophene) generated the di‐block copolymer. Poly(3‐hexylthiophene)‐b‐polystyrene was also synthesized by atom transfer radical polymerization. Integration of poly(3‐hexylthiophene) in di‐block copolymers with polystyrene leads to the formation of nanowire morphology and self‐ordered conducting nanostructured materials. 相似文献
A novel process to produce homo‐ and copolymers by RAFT polymerization in emulsion is presented. It is known that RAFT‐controlled radical polymerization can be conducted in emulsion polymerization without disturbing the radical segregation characteristic of this process, thus leading to polymerization rates identical to those encountered in the corresponding nonliving systems. However, RAFT agents are often characterized by very low water solubility and, therefore, they diffuse very slowly from the monomer droplets, where they are initially solubilized, to the reaction loci, i.e., the polymer particles. Accordingly, when used in emulsion polymerization, they are practically excluded from the reaction. In this work, we show that cyclodextrins, well‐known for their ability to form water‐soluble complexes with hydrophobic molecules, facilitate the transport across the H2O phase of the RAFT agent to the polymer particles. Accordingly, chains grow through the entire process in a controlled way. This leads to the production of low‐polydispersity polymers with well‐defined structure and end functionalities as well as to the possibility of synthesizing block copolymers by a radical mechanism. 相似文献