Photoinduced atom transfer radical polymerization (photo-ATRP) has risen to the forefront of modern polymer chemistry as a powerful tool giving access well-defined materials with complex architecture. However, most photo-ATRP systems can only generate radicals under biocidal UV light and are oxygen-sensitive, hindering their practical use in synthesis biohybrids. Herein, inspired by photoinduced electron transfer-reversible addition-fragmentation chain (PET-RAFT) polymerization, we...

Photoinduced reversible-deactivation radical polymerization (photo-RDRP) techniques offer exceptional control over polymerization, providing access to well-defined polymers and hybrid materials with complex architectures. However, most photo-RDRP methods rely on UV/visible light or photoredox catalysts (PCs), which require multistep synthesis. Herein, we present the first example of fully oxygen-tolerant red/NIR-light-mediated photoinduced atom transfer (photo-ATRP) in a high-throughput...

Hyperbranched polymethacrylates were synthesized by green-light-induced atom transfer radical polymerization (ATRP) under biologically relevant conditions in the open air. Sodium 2-bromoacrylate (SBA) was prepared situ from commercially available 2-bromoacrylic acid and used as a water-soluble inibramer to induce branching during copolymerization of methacrylate monomers. As result, well-defined branched obtained less than 30 min with predetermined molecular weights (36 000<Mn <170 000),...

The copper(I)-promoted azide-alkyne cycloaddition reaction (click chemistry) is shown to be compatible with RNA (with free 2'-hydroxyl groups) in spite of the intrinsic lability RNA. degradation minimized through stabilization Cu(I) aqueous buffer acetonitrile as cosolvent and no other ligand; this suggests general possibility "ligandless" click chemistry. With viability chemistry validated on synthetic bearing "click"-reactive alkynes, scope extended in-vitro-transcribed or, indeed, any...

Abstract A DNA synthesizer was successfully employed for preparation of well‐defined polymers by atom transfer radical polymerization (ATRP), in a technique termed AutoATRP. This method provides homopolymers, diblock copolymers, and biohybrids under automated photomediated ATRP conditions. PhotoATRP selected over other methods because mild reaction conditions, ambient temperature, tolerance to oxygen, no need introduce reducing agents or initiators. Both acrylate methacrylate monomers were...

Atom transfer radical polymerization (ATRP) can be carried out in a flask completely open to air using biocatalytic system composed of glucose oxidase (GOx) and horseradish peroxidase (HRP) with an active copper catalyst complex. Nanomolar concentrations the enzymes ppm amounts Cu provided excellent control over oligo(ethylene oxide) methyl ether methacrylate (OEOMA500 ), generating polymers high molecular weight (Mn >70 000) low dispersities (1.13≤Đ≤1.27) less than hour. The continuous...

Exosomes show potential as ideal vehicles for drug delivery because of their natural role in transferring biological cargo between cells. However, current methods to engineer exosomes without negatively impacting function remain challenging. Manipulating exosome-secreting cells is complex and time-consuming, while direct functionalization exosome surface proteins suffers from low specificity efficiency. We demonstrate a rapid, versatile, scalable method with oligonucleotide tethers enable...

Exosomes are emerging as ideal drug delivery vehicles due to their biological origin and ability transfer cargo between cells. However, rapid clearance of exogenous exosomes from the circulation well aggregation shedding surface proteins during storage limit clinical translation. Here, we demonstrate highly controlled reversible functionalization exosome surfaces with well-defined polymers that modulate exosome’s physiochemical pharmacokinetic properties. Using cholesterol-modified DNA...

Abstract The combination of polymers with nucleic acids leads to materials significantly advanced properties. To obviate the necessity and complexity conjugating two macromolecules, a polymer initiator is described that can be directly covalently linked DNA during solid‐phase synthesis. Polymer then grown from bound initiator, both in solution after DNA‐initiator released solid support as well on support, simplifying purification. resulting polymer‐DNA hybrids were examined by chromatography...

Poly(ethylene glycol) (PEG)-based star polymers with a cationic core were prepared by atom transfer radical polymerization (ATRP) for in vitro nucleic acid (NA) delivery. The synthesized ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and ethylene glycol dimethacrylate (EGDMA). Star characterized gel permeation chromatography, zeta potential, dynamic light scattering. These combined either plasmid DNA (pDNA) or short interfering RNA (siRNA) duplexes to form polyplexes intracellular...

An aqueous electrochemically mediated atom transfer radical polymerization (eATRP) was performed in a small volume solution (75 μL) deposited on screen-printed electrode (SPE). The reaction open to air, thanks the use of glucose oxidase (GOx) as an oxygen scavenger. Well-defined poly(2-(methylsulfinyl)ethyl acrylate) (PMSEA), poly(oligo(ethylene oxide) methyl ether methacrylate) (POEOMA), and corresponding DNA–polymer biohybrids were synthesized by small-volume eATRP at room temperature....

Bright signal outputs are needed for fluorescence detection of biomolecules at their native expression levels. Increasing the number labels on a probe often results in crowding-induced self-quenching chromophores, and maintaining function targeting moiety (e.g., an antibody) is concern. Here we demonstrate simple method to accommodate thousands fluorescent dye molecules single antibody while avoiding negative effects self-quenching. We use bottlebrush polymer from which extend hundreds...

A rapid blue-light-induced atom transfer radical polymerization (ATRP) was conducted in a biologically friendly environment. Well-controlled of oligo(ethylene oxide) methyl ether methacrylate (OEOMA) successfully performed aqueous media (1X PBS) under irradiation by blue LED strips. With 10.0 mW/cm2 intensity output at 450 nm, >90% conversion achieved 2 h the presence system comprising glucose, glucose oxidase, and sodium pyruvate. Poly-(OEOMA) synthesized with predetermined Mn low...

Exosomes are 30–200 nm sized extracellular vesicles that increasingly recognized as potential drug delivery vehicles. However, exogenous exosomes rapidly cleared from the blood upon intravenous delivery, which limits their therapeutic potential. Here, we report bioactive exosome-tethered poly(ethylene oxide)-based hydrogels for localized of exosomes. Using cholesterol-modified DNA tethers, lipid membrane was functionalized with initiators to graft polymers in presence additional and...

Combining synthetic polymers with RNA paves the way for creating RNA-based materials non-canonical functions. We have developed an acylation reagent that allows direct incorporation of atom transfer radical polymerization (ATRP) initiator into both short oligoribonucleotides and natural biomass extracted from torula yeast. The was performed in a quantitative yield. resulting initiator-functionalized RNAs were used grafting polymer chains by photoinduced ATRP, RNA-polymer hybrids narrow...

Nucleic acid-binding dyes (NuABDs) are fluorogenic probes that light up after binding to nucleic acids. Taking advantage of their fluorogenicity, NuABDs have been widely utilized in the fields nanotechnology and biotechnology for diagnostic analytical applications. We demonstrate potential together with an appropriate acid scaffold as intriguing photocatalyst precisely controlled atom-transfer radical polymerization (ATRP). Additionally, we systematically investigated thermodynamic...

Cationic nanogels with site-selected functionality were designed for the delivery of nucleic acid payloads targeting numerous therapeutic applications. Functional cationic containing quaternized 2-(dimethylamino)ethyl methacrylate and a cross-linker reducible disulfide moieties (qNG) prepared by activators generated electron transfer (AGET) atom radical polymerization (ATRP) in an inverse miniemulsion. Polyplex formation between qNG exemplified plasmid DNA (pDNA) short interfering RNA (siRNA...

Polymer biomolecule hybrids represent a powerful class of highly customizable nanomaterials. Here, we report star-polymer conjugates with DNA using "ligandless" Cu(I) promoted azide–alkyne cycloaddition click reaction. The multivalency the architecture allows for concomitant conjugation other molecules along DNA, and method provides control over orientation. nanoparticles are shown to assemble into higher-order nanoassemblies through hybridization. Further, show that strands can be utilized...

The inhibition of biochemical processes requiring S-adenosylmethionine as a co-factor have led to many nucleoside-based medicinal agents. Included in this group are 5′-deoxy-5′-(isobutylthio)adenosine (SIBA), nucleoside with antiparasitic, antiviral and antiproliferative effects, 5′-noraristeromycin, carbocyclic-derived potent properties. This report brings together the structural components these two compounds by describing both enantiomers carbocyclic 5′-nor SIBA (3 4). Owing recent...

Short interfering ribonucleic acids (siRNAs) are important agents for RNA interference (RNAi) that have proven useful in gene function studies and therapeutic applications. However, the efficacy of exogenous siRNAs knockdown remains hampered by their susceptibility to cellular nucleases impermeability cell membranes. We report here new covalent polymer-escort siRNA constructs address both these constraints simultaneously. By simple postsynthetic click conjugation polymers passenger strand an...