Activators regenerated by electron transfer atom radical polymerization (ARGET ATRP) was successfully implemented in aqueous media for the first time. A well-controlled of oligo(ethylene oxide) methyl ether methacrylate (OEOMA) conducted with 300 ppm or lower a copper catalyst and tris(2-pyridylmethyl)amine (TPMA) ligand presence an excess halide salts. Ascorbic acid continuously fed into reaction mixture to regenerate activator complex. The effects salt concentration, feeding rate reducing...

Atom transfer radical polymerization (ATRP) methods were developed in water-based media, to grow polymers from proteins under biologically relevant conditions. These conditions gave good control over the resulting polymers, while still preserving protein's native structure. Several reaction parameters, such as ligand structure, halide species, and initiation mode optimized water PBS buffer yield well-defined grown bovine serum albumin (BSA), functionalized with cleavable ATRP initiators (I)....

Initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) with ppm amount of Cu catalyst was successfully developed in water. For the first time, concentrations 100 and lower were used aqueous media to prepare well-defined macromolecules. Polymers oligo(ethylene oxide) methyl ether acrylate synthesized low dispersity (Mw/Mn = 1.15–1.28) using 20–100 an active CuBr/tris(pyridin-2-ylmethyl)amine-based presence excess bromide anions. This technique...

Naturally occurring hemin, an iron-containing porphyrin, and its synthetic derivatives were used as atom transfer radical polymerization (ATRP; see picture) catalysts. The effects of the halide salt concentration, attachment poly(ethylene glycol) moieties, hydrogenation hemin vinyl groups on catalyst performance studied. As a service to our authors readers, this journal provides supporting information supplied by authors. Such materials are peer reviewed may be re-organized for online...

Therapeutic benefits of curcumin for inflammatory diseases have been demonstrated. However, curcumin's potential as a clinical therapeutic has hindered due to its low solubility and stability in vivo. We hypothesized that hybrid carrier incorporates albumin-binding extracellular vesicle (EV) encapsulation could effectively address the current challenges delivery. further postulated using dissolvable microneedle arrays (dMNAs) local delivery curcumin-albumin-EVs (CA-EVs) control skin...

Curcumin, the primary active ingredient in spice turmeric, was converted to reactive monofunctional derivatives (carboxylic acid/azide/alkyne). The were employed produce a 3 + 2 azide-alkyne "clicked" curcumin dimer and poly(amidoamine) (PAMAM) dendrimer-curcumin conjugate. retain biological activity are efficient for labeling dissolving amyloid fibrils. selectively destroys human neurotumor cells. synthetic methodology developed affords general strategy attaching various macromolecular scaffolds.

Despite the importance of protein−polymer bioconjugates, there is no general method for producing homogeneous recombinant protein that contains polymer initiators at defined sites. To address this deficiency, we designed amino acid 4-(2′-bromoisobutyramido)phenylalanine (1) as an initiator in atom-transfer radical polymerization (ATRP) would provide a stable linkage between and growing polymer. We synthesized 1 evolved Methanococcus jannaschii tyrosyl-tRNA synthetase/tRNACUA pair to...

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...

The synthesis of a water/plasma soluble, noncytotoxic, "clicked" sugar-derivative curcumin with amplified bioefficacy in modulating amyloid-β and tau peptide aggregation is presented. Curcumin inhibits at micromolar concentrations; the sugar–curcumin conjugate Aβ concentrations as low 8 nM 0.1 nM, respectively. In comparison to curcumin, this conveniently synthesized Alzheimer's drug candidate more powerful antioxidant.

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...

Anticipated increases in the frequency and intensity of extreme temperatures will damage crops. Methods that efficiently deliver stress-regulating agents to crops can mitigate these effects. Here, we describe high aspect ratio polymer bottlebrushes for temperature-controlled agent delivery plants. The foliar-applied bottlebrush polymers had near complete uptake into leaf resided both apoplastic regions mesophyll cells surrounding vasculature. Elevated temperature enhanced vivo release...

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...

Fluorescein O-methacrylate was copolymerized with n-butyl acrylate by atom transfer radical polymerization in a "grafting from" reaction multifunctional linear macroinitiator to form pH responsive fluorescent bottlebrushes. The brush-like structure of the synthesized macromolecules confirmed through molecular imaging atomic force microscopy. NMR spectroscopy showed that units were successfully incorporated into polymer. bottlebrushes displayed highly properties under basic conditions, yet no...

Using a genetically engineered protein, containing non-natural amino acid bearing an atom transfer radical polymerization (ATRP) initiator, protein–nanogel hybrids (PNHs) were synthesized by activator generated electron (AGET) ATRP in inverse miniemulsion. The route presented is appropriate synthetic strategy to covalently and site specifically incorporate green fluorescent protein (GFP) into well-defined nanogels. These PNHs analyzed using dynamic light scattering (DLS), UV-visible...

Well-defined molecular bottlebrushes with poly(N-vinylpyrrolidone) and poly(N-vinylpyrrolidone)-b-poly(vinyl acetate) (PNVP-b-PVOAc) side chains were prepared via a combination of atom transfer radical polymerization (ATRP) reversible addition-fragmentation chain (RAFT). A macro agent poly(2-((2-ethylxanthatepropanoyl)oxy)ethyl methacrylate) (PXPEM) was by attaching xanthate agents onto each monomeric unit poly(2-hydroxyethyl methacrylate). Subsequently, RAFT procedure used to synthesize...

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...

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 synthesis of a sulfoxide-based water-soluble polymer, poly(2-(methylsulfinyl)ethyl acrylate) (polyMSEA), polymeric analogue DMSO, by atom transfer radical polymerization (ATRP) is reported. Well-defined linear polymers were synthesized using relatively low amounts copper catalyst (1000 or 100 ppm). Two types star either an "arm-first" approach "core-first" biodegradable β-cyclodextrin core. glass transition temperatures both the polymer (16 °C) and (32 determined differential scanning...

Since its introduction in 2014, the sulfur(VI) fluoride exchange (SuFEx) reaction has emerged as a promising new field of polymer chemistry, both polymerization diverse backbones and postpolymerization modification (PPM). Previously, we successfully reported use SuFEx chemistry method for surface derivatization through PPM sulfonyl containing brushes. However, with diversity conditions, substrate scope, catalyst selection afforded by this reaction, it is advantageous to expand on brushes...

Monoclonal antibodies (mAbs) and vaccines have been proposed as medical countermeasures to treat opioid use disorder (OUD) prevent overdose. In contrast current pharmacotherapies (e.g., methadone, buprenorphine, naltrexone, naloxone) for OUD overdose, which target brain receptors, mAbs vaccine-generated polyclonal sequester the in serum reduce drug distribution brain. Furthermore, offer several potential clinical benefits over approved medications, such longer half-life, higher selectivity,...

Abstract Dynamic materials (DMs) or dynamers have potential applications across a broad range of material science challenges. These include sustainable as part the circular plastics economy, advanced with tailored high stress properties and biomedical agents. DMs are comprised polymers that crosslinked through reversible covalent noncovalent linking groups. This group provides bonds, which impart such (re)healing, adaptability, toughness into material. The nature linker dictates dynamer's...

Hydrophilic polymers were attached to lysozyme by a combination of grafting-to and grafting-from approaches using RAFT polymerization. A hydrophilic oligomer was synthesized, the protein. The protein-oligomer hybrid contained end group, enabling chain extension in solution. Lysozyme maintained activity throughout this process.

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...