Controlled/living radical polymerization techniques have transformed polymer chemistry in the last few decades, affording production of polymers with precise control over both molecular weights and architectures. It is now possible to synthesize almost an infinite variety macromolecules using nonspecialized equipment, finding applications high-tech industry. However, they several shortcomings. Until recently, living polymerizations could not be controlled by external stimulus, such as...

In this Perspective, we summarize recent progress in polymerization-induced self-assembly (PISA) for the rational synthesis of block copolymer nanoparticles with various morphologies. Much PISA literature has been based on thermally initiated reversible addition-fragmentation chain transfer (RAFT) polymerization. Herein, pay particular attention to alternative protocols, which allow preparation improved control over morphology and functionality. For example, initiation visible light, redox...

The use of metalloporphyrins has been gaining popularity particularly in the area medicine concerning sensitizers for treatment cancer and dermatological diseases through photodynamic therapy (PDT), advanced materials engineering molecular antenna harvesting solar energy. In line with myriad functions metalloporphyrins, we investigated their capability photoinduced living polymerization under visible light irradiation over a broad range wavelengths. We discovered that zinc porphyrins (i.e.,...

In this work, we demonstrate the use of organophotoredox catalysts under visible light to perform photoinduced electron transfer-reversible addition fragmentation chain transfer (PET-RAFT) for polymerization methacrylate monomers.

Biotechnology, biomedicine, and nanotechnology applications would benefit from methods generating well-defined, monodisperse protein−polymer conjugates, avoiding time-consuming difficult purification steps. Herein, we report the in situ synthesis of conjugates via reversible addition−fragmentation chain transfer polymerization (RAFT) as an efficient method to generate homogeneous one step, eliminating major postpolymerization A water soluble RAFT agent was conjugated a model protein, bovine...

We report a new approach for the facile synthesis of high-order multiblock copolymers comprising very short blocks. The entails sequential addition different monomers via an iterative single electron transfer–living radical polymerization technique, allowing nearly perfect control copolymer microstructure. It is possible to synthesize with unprecedented control, i.e., A-B-C-D-E-etc., without any need purification between 24 h block formation steps. To illustrate this concept, we model...

Photoregulated polymerizations are typically conducted using high-energy (UV and blue) light, which may lead to undesired side reactions. Furthermore, as the penetration of visible light is rather limited, range applications with such wavelengths likewise limited. We herein report first living radical polymerization that can be activated deactivated by irradiation near-infrared (NIR) far-red light. Bacteriochlorophyll a (Bachl a) was employed photoredox catalyst for photoinduced electron...

In this paper, we describe the synthesis of asymmetric functional POEGMA-b-P(ST-co-VBA) copolymers in methanol, yielding one-pot polymerization a range nanoparticle morphologies, including spherical micelles, worm-like, rod-like micelles and vesicles. The presence aldehyde group was then exploited to form crosslinks or conjugate chemotherapy compounds, such as doxorubicin, via pH-breakable bonds (Schiff base imine) directly preformed nanoparticles. influence morphologies on MCF-7 breast...

Abstract Reversible addition fragmentation chain transfer (RAFT) polymerization is one of the most extensively studied controlled/living radical methods that has been used to prepare well‐defined nanostructured polymeric materials. This review, with more 650 references illustrates range functional nanomaterials can be accessed using RAFT chemistry. The detailed syntheses macromolecules predetermined molecular weights, designed weight distributions, controlled topology, composition and...

Here, we exploit the selectivity of photoactivation thiocarbonylthio compounds to implement two distinct organic and polymer synthetic methodologies: (1) a single unit monomer insertion (SUMI) reaction (2) selective, controlled radical polymerization via visible-light-mediated photoinduced electron/energy transfer-reversible addition–fragmentation chain transfer (PET-RAFT) process. In first method, precise into dithiobenzoate with high yield (>97%) is reported using an photoredox catalyst,...

This study reports a highly efficient photoredox catalyst, Ru(bpy)3Cl2, capable of controlling the polymerization methacrylates, acrylates, and acrylamides in presence thiocarbonylthio compounds via photoinduced electron transfer–reversible addition–fragmentation chain (PET-RAFT) process. technique was performed closed vessel or absence air. Online Fourier transform near-infrared spectroscopy (FTNIR) employed to monitor monomer conversions methyl methacrylate, acrylate,...

Recent developments in polymerization reactions utilizing thiocarbonylthio compounds have highlighted the surprising versatility of these unique molecules. The increasing popularity reversible addition–fragmentation chain transfer (RAFT) radical as a means producing well‐defined, ‘controlled’ synthetic polymers is largely due to its simplicity implementation and availability wide range compatible reagents. However, novel modes activation can expand technique beyond traditional system (i.e.,...

This work describes a study into thiol–ene based Michael addition reactions. Different catalysts, primary and tertiary amines phosphines, were investigated for the reaction of range thiols with dimers oligomers some (meth)acrylates. Primary are efficient catalysts reaction, although these require several hours to reach high conversion. Moreover, phosphine dimethylphenylphosphine (DMPP) tris-(2-carboxyethyl)phosphine (TCEP), in detail. DMPP is an efficacious catalyst yielding complete...