Abstract: A method of synthesizing a polynucleotide composition includes attaching a compound including at least one initiator or at least one transfer agent for a reversible deactivation radical polymerization to an end of a nucleotide chain assembly immobilized upon a solid phase support during a solid phase synthesis of a polynucleotide so that the initiator or the transfer agent is attacked to the end of a nucleotide chain assembly in a manner which is stable under conditions of deprotection of the polynucleotide, and growing a polymer from the initiator of from a site of the chain transfer agent via the reversible deactivation radical polymerization to form the polynucleotide composition.

Abstract: This invention pertains to methods for producing homogeneous recombinant proteins that contain polymer initiators at defined sites. The unnatural amino acid, 4-(2?-bromoisobutyramido)phenylalanine of formula 1, was designed and synthesized as a molecule comprising a functional group further comprising an initiator for an atom-transfer radical polymerization (‘ATRP”) that additionally would provide a stable linkage between the protein and growing polymer. We evolved a Methanococcus jannaschii (Mj) tyrosyl-tRNA synthetase/tRNACUA pair to genetically encode this unnatural amino acid in response to an amber codon. To demonstrate the utility of this functional amino acid, we produced Green Fluorescent Protein with the unnatural amino acid initiator of formula 1 site-specifically incorporated on its surface (GFP-1).

Abstract: A delivery system for delivering oligonucleotides includes a conjugate includes a complexing agent including an oligonucleotide, a peptide nucleic acid or chimera thereof and a polymer covalently attached to the complexing agent. The complexing agent of the conjugate is adapted to complex a biologically active agent thereto after formation of the conjugate.

Abstract: This invention pertains to methods for producing homogeneous recombinant proteins that contain polymer initiators at defined sites. The unnatural amino acid, 4-(2?-bromoisobutyramido)phenylalanine of formula 1, was designed and synthesized as a molecule comprising a functional group further comprising an initiator for an atom-transfer radical polymerization (‘ATRP”) that additionally would provide a stable linkage between the protein and growing polymer. We evolved a Methanococcus jannaschii (Mj) tyrosyl-tRNA synthetase/tRNACUA pair to genetically encode this unnatural amino acid in response to an amber codon. To demonstrate the utility of this functional amino acid, we produced Green Fluorescent Protein with the unnatural amino acid initiator of formula 1 site-specifically incorporated on its surface (GFP-1).

Abstract: A series of ligands with site specific electron donating substituents that form a catalyst complex with a transition metal and are suitable for catalysis of atom transfer radical reactions, including ATRP are described. Faster catalysis rates were observed allowing for low catalyst concentrations and linear increases in molecular weight with monomer conversion, and narrow molecular weight distributions. Cyclic voltammetry revealed that increasing the strength and number of conjugated electron donating groups resulted in more stable complexes and larger ATRP equilibrium constants.

Abstract: The invention generally relates to a method of inhibiting polymerization of vinyl aryl monomers, a process for increasing number average molecular weight of a polystyrene, and to an inhibitor composition useful therein.

Abstract: A process for constructing multi-arm star macromolecules with uniform properties, high molecular weight and narrow molecular weight distribution using free radical polymerization is described.

Abstract: A method of forming a composition includes adding together a plurality of particle brush systems wherein each of the particle brush systems includes a particle and a polymer brush including a plurality of polymer chains attached to the particle. The plurality of polymer chains of the polymer brush exhibit two chain conformations as the degree of polymerization of the polymer chains increases so that the polymer brush includes a concentrated polymer brush region with stretched polymer chains and a semi-dilute polymer brush region with relaxed chains that is radially outside of the concentrated polymer brush region. The degree of polymerization of the polymer brush is no less than 10% less than a critical degree of polymerization and no more than 20% greater than the critical degree of polymerization. The critical degree of polymerization is defined as the degree of polymerization required to achieve a transition from the concentrated polymer brush region to the semi-dilute polymer brush region.

Abstract: A polymer formed by controlled radical polymerization includes groups that can be modified after controlled radical polymerization to form a radical. The polymer can be the reaction product of a controlled radical polymerization of radically polymerizable monomers, wherein at least one of the radically polymerizable monomers includes at least one group that can be modified after the controlled radical polymerization to form a radical.

Abstract: A core-shell composite particle for incorporation into a composite wherein the composite has improved transparency is disclosed. The core-shell composite particle includes a core material having a first refractive index and a shell material having a second refractive index where the core-shell particle has an effective refractive index determined by the first refractive index and the second refractive index. The effective refractive index is substantially equal to the refractive index of the envisioned embedding medium. Methods of forming the core-shell particles are also disclosed.

Abstract: Methods for conducting controlled grafting-from radical polymerizations from biomolecules under conditions that are biologically compatible are described. The methods provide biomolecule-polymer conjugates with highly controlled structures and narrow polydispersities under aqueous reaction conditions and biological temperatures. Biomolecules, such as proteins and nucleotides can be conjugated to polymers with high levels of control.

Abstract: This invention pertains to methods for producing homogeneous recombinant proteins that contain polymer initiators at defined sites. The unnatural amino acid, 4-(2?-bromoisobutyramido)phenylalanine of formula 1, was designed and synthesized as a molecule comprising a functional group further comprising an initiator for an atom-transfer radical polymerization (‘ATRP”) that additionally would provide a stable linkage between the protein and growing polymer. We evolved a Methanococcus jannaschii (Mj) tyrosyl-tRNA synthetase/tRNACUA pair to genetically encode this unnatural amino acid in response to an amber codon. To demonstrate the utility of this functional amino acid, we produced Green Fluorescent Protein with the unnatural amino acid initiator of formula 1 site-specifically incorporated on its surface (GFP-1).

Abstract: Electrochemical reduction of an exemplary ATRP catalyst, C11Br2/Me6TREN, is shown to be an efficient process to mediate and execute an ATRP. The onset of polymerization occurs only through passage of a cathodic current achieved under a reductive potential to form Cu1Br2/Me6TREN, within the reaction medium. Unprecedented control over the polymerization kinetics can be attained through electrochemical methods by modulating the magnitude of the applied potential allowing polymerization rate enhancement or retardation. Additional polymerization control is gained through electrochemical “dials” allowing polymerization rate enhancements achieved by larger applied potentials and the ability to successfully switch a polymerization “on” and “off between dormant and active states by application of multistep intermittent potentials.

Abstract: A polymer formed by controlled radical polymerization includes groups that can be modified after controlled radical polymerization to form a radical. The polymer can be the reaction product of a controlled radical polymerization of radically polymerizable monomers, wherein at least one of the radically polymerizable monomers includes at least one group that can be modified after the controlled radical polymerization to form a radical.

Abstract: The present invention is directed towards a protein-polymer composition having a protein with a site-specifically incorporated unnatural amino acid initiator and a covalently attached polymer.

Abstract: This invention pertains to methods for producing homogeneous recombinant proteins that contain polymer initiators at defined sites. The unnatural amino acid, 4-(2?-bromoisobutyramido)phenylalanine of formula 1, was designed and synthesized as a molecule comprising a functional group further comprising an initiator for an atom-transfer radical polymerization (‘ATRP”) that additionally would provide a stable linkage between the protein and growing polymer. We evolved a Methanococcus jannaschii (Mj) tyrosyl-tRNA synthetase/tRNACUA pair to genetically encode this unnatural amino acid in response to an amber codon. To demonstrate the utility of this functional amino acid, we produced Green Fluorescent Protein with the unnatural amino acid initiator of formula 1 site-specifically incorporated on its surface (GFP-1).

Abstract: The invention generally relates to a method of inhibiting polymerization of vinyl aryl monomers, a process for increasing number average molecular weight of a polystyrene, and to an inhibitor composition useful therein.

Abstract: A polymer formed by controlled radical polymerization includes groups that can be modified after controlled radical polymerization to form a radical. The polymer can be the reaction product of a controlled radical polymerization of radically polymerizable monomers, wherein at least one of the radically polymerizable monomers includes at least one group that can be modified after the controlled radical polymerization to form a radical.

Abstract: A transition metal mediated chain transfer agent controlled polymerization process is described. The process combines the advantages of atom transfer radical polymerization (ATRP) and reversible addition fragmentation transfer (RAFT) polymerization. Synthesis of chain transfer agents useful in the disclosed processes is also disclosed. Other improvements on ATRP RAFT processes are also described.

Abstract: Embodiments of the polymerization process of the present invention are directed to polymerizing free radically polymerizable monomers in the presence of a polymerization medium initially comprising at least one transition metal catalyst and an atom transfer radical polymerization initiator. The polymerization medium may additionally comprise a reducing agent. The reducing agent may be added initially or during the polymerization process in a continuous or intermittent manner. The polymerization process may further comprises reacting the reducing agent with at least one of the transition metal catalyst in an oxidized state and a compound comprising a radically transferable atom or group to form a compound that does not participate significantly in control of the polymerization process.