0000000000122113
AUTHOR
Peter J. Roth
Influence of End Groups on the Stimulus-Responsive Behavior of Poly[oligo(ethylene glycol) methacrylate] in Water
The influence of the chemical structure of both end groups onto the lower critical solution temperature (LCST) of poly[oligo(ethylene glycol) monomethyl ether methacrylate] (POEGMA) in water was systematically investigated. POEGMA of Mn = 3550 g/mol and Mw/Mn = 1.14 prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization was equipped with two different functional end groups in a one-step postpolymerization reaction combining activated esters, functional amines, and functional methane thiosulfonates. As end groups, n-propyl, n-hexadecyl, di(n-octadecyl), poly(ethylene glycol)-550 (PEG), 1H,1H-perfluorononyl, azobenzene, and trimethylethylammonium groups were system…
Two-dimensional self-assembly of disulfide functionalized bis-acylurea: a nanosheet template for gold nanoparticle arrays.
A new functional bis-acylurea molecule allows a two-stage self-organization process. It self-organizes--at first--into 2D nanosheets with disulfide groups at the surface, which act--in the second stage--as a template for gold nanoparticle arrays.
A Versatile Grafting-to Approach for the Bioconjugation of Polymers to Collagen-like Peptides Using an Activated Ester Chain Transfer Agent
DepartmentofMaterials Science and Engineering, University of Delaware, 201DuPont Hall, Newark, Delaware 19716,Received February 24, 2009Revised Manuscript Received April 24, 2009Biohybrid materials consisting of synthetic polymers andbiological moieties have gained more and more interest in therecent years.
UCST-type behavior of poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) in aliphatic alcohols: solvent, co-solvent, molecular weight, and end group dependences
Poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) is shown to possess insoluble–soluble transitions (UCST-type phase behavior) in a large variety of aliphatic alcohols. Samples of different molecular weights ranging from 5 kg mol−1 to 23 kg mol−1 prepared by the RAFT process and featuring different end groups at each end were analyzed by cloud point measurements. Transitions occurred sharply and were fully reversible. The UCST was found to increase with an increasing molecular weight. Hydrophobic (alkyl chain) end groups were found to lower the critical temperature in isopropanol, while rigid aromatic end groups raised the transition temperature. In ternary mixtures of isoprop…
Synthesis of Heterotelechelic α,ω Dye-Functionalized Polymer by the RAFT Process and Energy Transfer between the End Groups
The synthesis of a vinyl polymer with two different fluorescent dye end groups using reversible addition-fragmentation chain transfer (RAFT) polymerization is described. Use of a pentafluorophenyl (PFP) activated ester chain transfer agent (CTA) provided a polymer with an R end group that was reactive toward amines and a dithioester ω end group. The R PFP ester was amidated with Oregon Green Cadaverin. This did not harm the ω dithioester, which was subsequently aminolyzed with an excess of n-propylamine in the presence of Texas Red-2-sulfonamidoethyl methanethiosulfonate, resulting in a disulfide bond connecting the second dye to the polymer chain. Excess dyes and side products were removed…
Versatile Synthesis of Functional Gold Nanoparticles: Grafting Polymers From and Onto
Functionalized gold nanoparticles have been prepared in an organic solvent by a two-phase reduction method in ethyl acetate and water using bis(6-hydroxyhexyl) disulfide bis(2-bromoisobutyl) ester, bis(6-acetyloxyhexyl) disulfide, and bis(5-carboxypentyl) disulfide bis(pentafluorophenyl) ester as stabilizing ligands. This procedure features the advantages that no phase transfer agent was necessary during the preparation of the gold nanoparticles and that the reducing conditions were mild enough to utilize functional disulfide ligands. The obtained gold nanoparticles with typical sizes between 2 and 5 nm could be precipitated and redispersed without any irreversible aggregation. Using these nanop…
Post-Polymerization Modification
The synthesis of functional polymers has been enriched dramatically by post-polymerization modifications. Even though it represents a synthetically very appealing approach, different synthetic concepts of organic reactions are utilized in polymer science for the synthesis of architecturally well-defined multifunctional polymers. The different classes of reactions that provide the synthetic polymer chemist with tools of unprecedented precision, thereby opening the doors for materials synthesis in an interdisciplinary world, will be summarized.
Hetero-Telechelic Dye-Labeled Polymer for Nanoparticle Decoration
The synthesis of poly(methyl methacrylate) (PMMA) exhibiting one fluorescent dye (Texas Red) and one methyl disulfide end group is described. It is shown that the latter end group enabled the exchange of both oleic amine on gold nanoparticles (AuNP) and of oleic acid on CdSe/ZnS quantum dots (QD), allowing for a phase transfer of both types of nanoparticles (NP) from hexane into dimethylformamide due to the solubility provided by the PMMA chains. For AuNP, a fluorescence quenching of the dye was found due to fluorescence resonance energy transfer (FRET) from the dye to the AuNP, while QDs caused a fluorescence enhancement by FRET from the QD to the attached dyes. Due to the hetero-telecheli…
A Method for Obtaining Defined End Groups of Polymethacrylates Prepared by the RAFT Process during Aminolysis
Macromolecules is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Communication to the Editor A Method for Obtaining Defined End Groups of Polymethacrylates Prepared by the RAFT Process during Aminolysis Peter J. Roth, Daniel Kessler, Rudolf Zentel, and Patrick Theato Macromolecules, 2008, 41 (22), 8316-8319 • Publication Date (Web): 01 November 2008 Downloaded from http://pubs.acs.org on November 19, 2008
Reactive Surface Coatings Based on Polysilsesquioxanes: Controlled Functionalization for Specific Protein Immobilization
The key designing in reliable biosensors is the preparation of thin films in which biomolecular functions may be immobilized and addressed in a controlled and reproducible manner. This requires the controlled preparation of specific binding sites on planar surfaces. Poly(methylsilsesquioxane)-poly(pentafluorophenyl acrylates) (PMSSQ-PFPA) are promising materials to produce stable and adherent thin reactive coatings on various substrates. Those reactive surface coatings could be applied onto various materials, for example, gold, polycarbonate (PC), poly(tetrafluoroethylene) (PTFE), and glass. By dipping those substrates in a solution of a desired amine, specific binding sites for protein ads…
Double Thermoresponsive Block Copolymers Featuring a Biotin End Group
A poly(oligo(ethylene glycol) monomethyl ether methacrylate)-block-poly(N-isopropyl methacrylamide) (POEGMA-b-PNIPMAM) block copolymer with a biotin end group on the PNIPMAM block as a biotarget was synthesized as a model system for temperature-controlled polymer immobilization. The synthesis was based on RAFT polymerization followed by postpolymerization modification of an activated ester precursor block and an exchange of the dithioester end group within one step. NMR, differential scanning calorimetry (DSC), dynamic light scattering (DLS), and turbidimetry measurements were performed to investigate the stimulus-responsive properties. The double thermoresponsive POEGMA-b-PNIPMAM with biot…
Thermo- and Light-Responsive Polymers Containing Photoswitchable Azobenzene End Groups
Telechelic thermo- and light-responsive polymers based on poly(oligo(ethylene glycol) methyl ether methacrylate) P(OEGMA) with azobenzene functionalities at the end groups were synthesized. In a reversible addition−fragmentation chain transfer (RAFT) polymerization using a functionalized chain transfer agent (CTA) containing a pentafluorophenyl (PFP) activated ester, oligo(ethylene glycol) methyl ether methacrylate (OEGMA, Mn ∼ 300 g mol−1) could successfully be polymerized with good control over molecular weight, very high conversions, and narrow molecular weight distributions. Polymers derived from this CTA possessed an activated ester at the α-end of the polymer chain as well as a dithio…
Versatile ω-end group functionalization of RAFT polymers using functional methane thiosulfonates
Five different polymers, poly[methyl methacrylate] (PMMA), poly[lauryl methacrylate] (PLMA), poly[diethylene glycol methacrylate] (PDEGMA), poly[N-iso-propylacrylamide] (PNIPA), and poly[styrene] (PS) prepared by the RAFT process and thus terminated with dithioesters were aminolyzed in the presence of S-3-butynyl methane thiosulfonate (MTS), which was synthesized in two steps. Analysis of the polymers by 2D NMR, UV–vis absorbance, and gel permeation chromatogra-phy revealed them to quantitatively carry acetylene end groups connected with disul-fide bridges, indicating that functional MTS reagents can be employed for end group functionalization of RAFT polymers. This versatile method is of ad…
Synthesis of Reactive Telechelic Polymers Based on Pentafluorophenyl Esters
A diazo initiator and a chain transfer agent (CTA), both containing a pentafluorophenyl (PFP) activated ester, were synthesized. In a RAFT polymerization using the functionalized chain transfer agent (PFPCTA), methyl methacrylate (MMA), diethylene glycol monomethyl ether methacrylate (DEGMA), poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), and lauryl methacrylate (LMA) could successfully be polymerized into homopolymers and diblock copolymers with good control over molecular weight, very high conversions, and narrow molecular weight distributions. Polymers derived from the PFP-CTA possessed an activated ester at the R-end of the polymer chain, which could be reacted with amines…